I HC QUC GIA H NI

TRNG I HC KHOA HC T NHIN

NGUYN NH TRIU

HA HC CC HP CHT
HOT NG B MT
(Bi ging chuyn cao hc ha hu c)

H NI 2005

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 MC LC
Chng 1. nh ngha v ngha ca cc cht hot ng b mt.............................................3
1.1. nh ngha v cc cht hot ng b mt .................................................................3
1.2. Phn loi cc cht hot ng b mt theo s dng....................................................4
1.3. ng dng ca cc cht hot ng b mt trong sn xut v i sng.......................7
Chng 2. Phn loi v cu to cc cht hot ng b mt.......................................................9
2.1. Phn loi cc cht hot ng b mt theo cu to.....................................................9
2.2. Cht HBM anionic..................................................................................................9
2.3. Cht HBM cationic...............................................................................................11
2.4. Cht HBM khng ionic.........................................................................................12
2.5. Cht HBM ampholit (amphotere) phn t cha c nhm baz v nhm axit......15
2.6. Cht HBM a in tch.........................................................................................17
2.7. Cht HBM polime................................................................................................22
Chng 3. Mt s tnh cht ca cc cht hot ng b mt......................................................23
3.1. Sc cng b mt.......................................................................................................23
3.2. S lin quan gia cu to v tnh cht ca cht HBM..........................................28
3.3. Gin pha ca cht lng tnh trong dung dch nc..........................................34
Chng 4. Cn bng hirophin/lipophin (a nc/a du) HLB-RHLB..................................38
4.1. Cn bng hirophin/lipophin (HLB).......................................................................38
4.2. Phng php xc nh RHLB ca nh tng v HLB ca cht nh ha................40
Chng 5. Nng lng tng tc hidrophin v lipophin...................................................46
5.1. Khi nim Winsor v s tng tc trong h nh tng...........................................46
5.2. Cc v d ca s bin i nng lng tng tc.....................................................51
5.3. S la chn cc cht ng hot ng b mt (cotensio-actif) (cht ph tr)..........53
5.4. Mt s v d n gin ng dng thc t. Khi nim winsor...................................58
5.5. Mt s v d v ng dng cht ng hot ng b mt...........................................60
Chng 6. Nh tng v vi nh tng......................................................................................62
6.1. Nh tng................................................................................................................62
6.2. Vi nh tng............................................................................................................66
Chng 7. Phng php tng hp cc cht hot ng b mt.................................................72
7.1. Tng hp cc cht HBM anionic..........................................................................72
7.2. Tng hp cc cht HBM cationic.........................................................................77
7.3. Tng hp cc cht hot ng b mt khng ionic...................................................80
7.4. Tng hp cc cht hot ng b mt da trn cacbohidrat.....................................82
7.5. Tng hp cc cht hot ng b mt lng tnh in tch.......................................86
7.6. Tng hp cc cht hot ng b mt polime...........................................................88
Chng 8. Cc cht git ra tng hp.......................................................................................91
8.1. Thnh phn cc cht git ra tng hp....................................................................91
8.2. Cng thc pha ch cc cht ty ra.........................................................................96
8.3. Du gi u..............................................................................................................99
8.4. Kem nh rng......................................................................................................102
Chng 9. Ph gia du, m bi trn.......................................................................................106
9.1. Du gc..................................................................................................................106
9.2. Ph gia du, m bi trn.......................................................................................107
Chng 10.
TI LIU THAM KHO.......................................................................................................115

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3
 Chng 1. nh ngha v ngha ca cc
cht hot ng b mt

1.1. nh ngha v cc cht hot ng b mt

Cc cht hot ng b mt (HBM) l nhng hp cht ha hc c kh nng lm
thay i tng tc pha (phase) v nng lng mt ranh gii tip gip lng-khng
kh", lng-rn v du-nc v.v. Phn ln cc cht hu c trong iu kin no
u c th biu hin ra l cht HBM. Tc dng ny xut hin do cu to phn t, v d
tnh phn cc v do cc iu kin bn ngoi gy ra nh nhit , dung mi, nng
Thc t tu thuc vo iu kin bn ngoi m hp cht c th l cht HBM cc mc
khc nhau.
Cht HBM c kh nng nm trn lp b mt dung dch c hp ph > 0 tc
l c s hp ph dng. N c cc c im sau:
C sc cng b mt b hn ca dung mi v nh th n mi nm lp b mt,
do tnh cht nhit ng hc. T dn n sc cng b mt ca dung dch dd
nh hn sc cng b mt ca dung mi dm .
C tan tng i nh v nu khng n c xu hng ri khi b mt dung dch
vo trong cht lng.
Ngc li, cc cht khng phi l cht HBM, chng c xu hng ri khi b mt dung
dch tan vo trong dung dch, c hp ph < 0, tc l c hp ph m. N c
cc c im tri ngc nh sau:
C sc cng b mt ln hn sc cng b mt ca dung mi, t dn n sc
cng b mt ca dung dch dd ln hn sc cng b mt ca dung mi dm .
C tan cao v th cht tan mi c th ri khi b mt i vo trong dung dch.
Mt s t cht HBM nh ng khi ha tan vo dung dch th sc cng b mt
ca dung dch khng khc sc cng b mt ca dung mi l my.
Thng thng cht HBM l mt phn t hu c cha gc hirocacbon v mt
hay nhiu nhm hot ng.
Phn hirocacbon (c gi l lipophin hay hirophop) c th l parafin,
isoparafin, benzen, ankylbenzen, naphtalen, vng ngng t hidrocacbon c mch nhnh.
Cc nhm chc cha oxi( COOH, -OH), cha nit (nitro, amin, amit, imit), cc nhm
cha lu hunh(sunphat, sunphonat), photpho(photphat, cacboxylat) u c gi l
hidrophin.

1.2. Phn loi cc cht hot ng b mt theo s dng

Trn c s tinhs cht ca cc cht HBM v cc h thng nh ngi ta phn chia
chng thnh mt s loi sau y:

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1.2.1. Cht hot ng b mt tan trong nc
Cc cht HBM ny gm 2 phn: phn hirocacbon (lipophin hay hirophob) v
phn cha cc nhm phn cc nh COONa, SO 3Na, OH (hirophin hay lipophob)
c tc dng lm cho chng d tan trong nc. Chng c s dng dng dung dch
nc lm cc cht git ra, cht tuyn ni, cht ph nh, cht c ch n mn, cht thm
t
V mt cu to, cc cht HBM tan trong nc c chia thnh cc cht HBM
cationic, anionic v khng ionic. Tnh cht c trng ca cc cht HBM tan trong nc
l tc dng ca n trn b mt phn cch nc - khng kh ngha l lm gim sc cng
b mt ca cht in ly gii hn tip gip khng kh .

1.2.2. Cht hot ng b mt ha tan du nc

Chng c s dng ch yu cho h du-nc. Nhm hirophin lm cho n tan
trong nc cn gc hirocacbon di to cho n tan trong du. Cht HBM tan du nc
c s dng lm cc cht ph nh, to nh v cht c ch n mn kim loi.

1.2.3. Cht HBM tan trong du

Chng l cht khi thm vo du, m lm cht c ch n mn, bin tnh b mt
cht rn, to nh Cht HBM tan trong du, khng ha tan v khng phn ly trong
dung dch nc. Phn lipophin (hay hirophob) l cc gc hirocacbon mch nhnh hay
hirocacbon vng thm to cho n d tan trong du. Cc cht ny l cc cht HBM
yu ranh gii tip gip mi trng lng- khng kh, n lm gim sc cng b mt
ca sn phm du tip gip vi khng kh.
Cc cht HBM tan trong du, trong mi trng hirocacbon t phn cc cng
nh cc cht HBM tan trong nc trong mi trng nc phn cc u to nn cc
mixen gy nn gii hn tng mixen-mi trng. V d cc cht sau l cc cht HBM
tan trong du:

OH
C20 SO3Na

C20 SO3Na C8
C8

C5
SO3Na

S cc phn t to nn mixen v s hnh thnh nng ti hn mixen ca cht

HBM tan trong du trong sn phm du m v trong mi trng t phn cc khc c
lin quan vi tnh cht th tch bi v tnh HBM ca cht HBM tan trong du nm
gii hn kim loi-nc thng quyt nh tnh cht HBM ca n.
Trn bng 1.1 cho s phn loi chung cc cht HBM. Theo tt c cc cht
HBM c phn chia thnh 5 nhm da trn mi quan h gia hirocacbon (lipophin)
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v nhm phn cc (hirophin) ca phn t, c gi l cn bng hirophin-lipophin
(HLB) hay cn bng oleophin-hirophin (O/H). Gi tr HLB s c gii thch r
chng 4.
Ngoi ra, da trn hin tng hnh thnh keo t ca dung dch ngi ta cng phn
chia cc cht HBM thnh hai nhm l cht HBM keo t v cht HBM khng keo
t:
1. Cht HBM keo t (hay to mixen) l nhng cht trong dung dch sau khi t
nng bo ha khng to ra kt ta hay khng phn lp m to ra cc mixen
c kch thc vi nanomet n vi micronmet. S to ra cc mixen ny c li
v nng lng: nhm hirophin bao quanh hirophin, nhm hirophob bao
quanh hirophop, tng t nh h hp ph trong h lng-kh hay lng-lng.
2. Cht HBM khng keo t (hay ha tan phn t) to ra mt dung dch trong.
Cht HBM keo t c ng dng lm bn vng ha h phn tn v cc cht git
ra. Cht HBM khng keo t c dng lm cht phn tn v cht to bt. Tuy nhin
trong mt s trng hp c hai cht ny u c tc dng nh nhau, v d cht HBM
khng keo t c dng lm cht ng nh ha hay cht bn vng ha bt km bn, cn
cht HBM keo t li c dng lm cht to mng.

Bng 1.1. c tnh ca mt s cht hot ng b mt tan trong nc (W), tan trong du
nc (WO) v tan trong du (O)

Ch dn Cht HBM Cht HBM Cht HBM Cht HBM Cht HBM
(W) nhm 1 (W) nhm 2 (WO) nhm 3 (O) nhm 4 (O) nhm5
c tnh Cht HBM Cht HBM Cht HBM Cht HBM Cht HBM
to mixen khng phn phn cc to phn cc to phn cc to khng phn
(nh) cc to ra ra dung dch ra dung dch ra dung dch cc to ra
dung dch mixen trong mixen du v mixen du dung dch
nc tht nc nh nc hay du tht
nh nc/du
hoc
du/nc
HLB
(cn bng > 15 10-15 8-10 <8
hirophin-
lipophin )
O/H
(cn bng <0,5 0,5-30 > 30
oleophin-
hirophin )
Nng > 7g/l 0,1-7g/l < 0,2g/l trong 0,001 -0,8% >0,2 %
mixen ti H2O hay (khi lng) (khi lng)
hn 0,001-0,1% trong du trong du
trong du
ng dng Cht thm Cht git Cht nh ha Cht c ch
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chnh t ra v c ch n n mn
mn

Bng 1.2. Vai tr ng dng ca cc cht hot ng b mt

Cc qu trnh gy ra bi Cc qu trnh gy ra bi cht Cc qu trnh gy ra bi
cht HBM keo t HBM khng keo t c 2 loi cht HBM
Bn vng ha K nc ha Tuyn ni.
nh c ch n mn Thm t.
S to ht (bt Tc dng chu mi mn Khng tnh
bn ) Cht to bt Gim bn
Tc dng git ra S kh bt Ph nh
Ti to du iu ha s ln ln ca tinh Phn tn
th
Kh sng v chy ri
Lm chm s bay hi
Thu gom du m
Bn vng ha th huyn ph

1.3. ng dng ca cc cht hot ng b mt trong sn xut v i

sng
Cc cht HBM c ng dng rng ri trong nhiu ngnh sn xut cng, nng
nghip, xy dng.

1.3.1. Cng nghip ha cht: Trong cng nghip ho cht, cc cht hot ng b mt
c dung lm:
Cht to mng: gim dnh ca cao su, h tr qu trnh nhum mu, k nc
ha ca giy (khng thm nc).
Cht phn tn: tng cht lng ca qu trnh ha trn ca cao su, phn tn cht
mu, nghin xi mng
Cht thm t: qu trnh sn xut nha
Cht bn nh: polime ha th nh, ch to cao su m, to ht sn phm
Cht to bt: ch to cht do xp, s to bt trong cc qu trnh sn xut khc
nhau nh cng nghip sn xut cht git ra, sn xut v pha ch cc thuc bo v
thc vt.
Cht tuyn ni: tuyn ni cc mui v qung

1.3.2. Khai thc v ch bin du m

Cht c ch n mn: ph nh du th
Cht git ra: cht to bt v nh ha
Dch khoan, thm cht nh ha vo dung dch khoanto ra nh tng
Lm sch v bo v cc phng tin cha ng v vn chuyn du m
Bn vng ha cc cht chng oxi ha
Ph nh du th- lm sch du th.

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1.3.3. Cng nghip nh nh dt, da, thc phm, nhum
Cht chng thm t: X l b mt si v sn phm khc
Cht thm t: cng nghip da, si v cht mu
Cht nh ha: bi m du cc da, da c lng, si
Cht git ra

1.3.4. Cng nghip luyn thp v ch to my

Mng mng: cht ph b mt in ha, cht gip chy khi hn thp
Cht thm t
Cht c ch n mn
Cht nh ha
Cht tuyn ni v cht ty ra

1.3.5. Cng nghip v k thut xy dng

Cht to mng v cht k nc: cht ph gia xi mng
Cht phn tn: trn tt hn cc thnh phn
iu ha s pht trin ca cc tinh th trong qu trnh sn xut xi mng
Cht to bt: ch to b tng bt, thch cao mn, bt cha chy
Cht nh ha: nh bitum, nh cha chy
Cht ph gia cho qu trnh nghin xi mng v ng cng xi mng
1.3.6. Nng nghip
Cht phun m: ch to thuc bo v thc vt (tr su, tr c ..) dng sng m
phun bng my bay
Cht to mng v cht k nc: cht chng mt phn bn trong t
Cht nh ha: ch to cc dung dch thuc bo v thc vt dng nh phun tay,
phun my

1.3.7. Cng nghip thc phm

Cht to mng ngn cn s ha cng ca bnh m
Cht iu ha s pht trin ca tinh th trong qu trnh ch bin ng lnh
Cht nh ha trong qu trnh sn xut magarin (b thc vt), sa nhn to,
mayone v cc sn phm khc
Cht bm dnh b mt kim loi khi sn ph cc lp bo v hp ng thc phm

1.3.8. Cng nghip dc phm

Cht thm t lm cho thuc phn tn lan truyn tt hn trong c th
Cht nh ha trong qu trnh sn xut crem bi mt, crem dng da, cc dng
thuc phun st trng
Cht bn nh ch to thuc dng sir
Cht kh bt, cng nghip tng hp vi sinh
Cht git ty
Cht chng vi trng, vi khun

1.3.9. Sinh hc
Ch to mng sinh hc

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 Cht bn vng to nh thin nhin (sa, m cao su)

Chng 2. Phn loi v cu to cc cht

hot ng b mt

2.1. Phn loi cc cht hot ng b mt theo cu to.

Cc cht hot ng b mt (HBM) trong phn t ca chng c cha nhng
nhm a nc (hidrophin) v nhm k nc (hidrophob) do c coi l phn t
lng tnh.
Da trn cu to ha hc ngi ta phn chia cc cht HBM thnh 4 loi:
Cht HBM anionic, k hiu
Cht HBM cationic, k hiu
Cht HBM khng ionic, k hiu
Cht HBM ampholit (amphotere) cha in tch m hay in tch
dng ph thuc pH mi trng, k hiu
Cht HBM a in tch
Cht HBM polime
Ngoi ra chng cng c phn loi theo tnh tan trong nc, chng hn cht
HBM km tan trong nc nh cc axit bo hay cht HBM tan mnh trong nc nh
cc arylsunfonat, cht HBM km bn.
Cht HDBM nm trn mt
ngn cch hai tng lng-kh

2.2. Cht HBM anionic.

Cht HBM anioic l loi cht HBM ph bin v c s dng t lu, gm cc
loi sau:

2.2.1. Cc cacboxylat.
a) X phng c bit n t 2000 nm trc l mui ca axit bo: R COO Na
b) Ete ca axit cacboxylic:
Axit ankyl polioxietilen cacboxylic: RO (C2H4O)nCH2COOH

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Hoc dng mui natri ca n: R O (C2H4O)nCH2COO Na

2.2.2. Cc cc sunfonat.
a) Ankylarylsunfonat, v d ankylbenzensunfonat (ABSs):
R SO3 Na

b) Sunfonat mch thng (ankylsunfonat):

R SO 3 Na
c) Hiroxiankansunfonat:
OH
R CH2 CH (CH2)mSO3 Na
d) Ankenylsunfonat:
R CH CH (CH2)nSO 3 Na
e) Ancolsunfat:
R (O CH2CH2)n OSO3 Na
f) Sunfat du v glixerit:
O
H2C OCR
HC OH
H2C OSO3 Na
g) Sunfat ancanol amit:
O
R C
NH CH2CH2O (CH2CH2O) SO3 Na
n
Amit ete sunfat

2.2.3. Sn phm ngng t ca axit bo.

a) Isothionat:
R C OCH2CH2SO3Na
O
b) Taurat:
O
R C N CH2CH2SO 3Na
CH3
c) Sacosinat:
O
R C N CH2CH2COONa
CH3

d) Axit bo ngng t:
10
 OH
O O
N C
H

O
OH
Ankylamit glutamic

e) Dn xut axit photphoric (axyl ha protein)

O
R C
peptit COO Na
N
H

Axyl ha sn phm thy phn protein

f) Dn xut anionic ca ankylpoliglicosit:

OR

RO O
RO
OR
O
O
RO O
RO
OR
n
OH OH
R= H, CO CH CHCOONa , CO CH2 C CH2COONa , CO CH2 CH COONa
OH COONa SO3Na

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2.3. Cht HBM cationic.
2.3.1. Mui amin bc 1, amin bo axetat hay clorat.

R NH3 X
2.3.2. Mui amoni bc 4. ( X= CH3COO-, ClO3-,)
CH3
Trimetylxetyl amoni bromua C16H33N CH3 Br
CH3

2.3.3. Amit ca amin th c cation ha bng etylsunfat :

CH2 CH2OH
R CONH(CH2)n N CH2 CH2OH SO4 C2H5
C2H5
ietanoletylamino-propylamin : monoetyl sunfat
CH2 CH2OH
H2N (CH2)3 N CH2 CH2OH SO4 C2H5
C2H5
Trietylamino-propylamid :
CH2 CH3
R CONH(CH2)3 N CH2 CH3 SO4 C2H5
C2H5

2.3.4. Amit ca ietylentriamin c vng ha cho imidazolin v dn xut ca n :

C NH
R CONH CH2 CH2 NH CH2 CH2 NH2 N CH2
NH2 CH2 CH2 C H2

2.4. Cht HBM khng ionic.

2.4.1. Este poliglycol:
Monoeste: R C O (CH2CH2O)nH
O
ieste: R C O (CH2CH2O)n C R
O O

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2.4.2. Ete ca mt s nhm phn cc:
R O (CH2CH2O)nH

2.4.3. Este ca poliol

Sorbitol (mono v ieste):
OH H OH OH
HOCH2 C C C C CH2OH CH2O COR
H OH H H
Erythrol hay erythrit:
HOCH2 CHOH CHOH CH2OH CH2O C R
O
Pentaerythrol (mono, i, tri, tetra-este)
HOCH2 CH2OH CH2O C R
C O
HOCH2 CH2OH
Trimetylolpropan (mono, i, tri-este)
CH2OH
CH2O C R
CH3CH2 C CH2OH
CH2OH O

CH2OCOR CH2OCOR CH2OCOR

CH3CH2 C CH2OH CH3CH2 C CH2OCOR CH3CH2 C CH2OCOR
CH2OH CH2OH CH2OCOR
Ancoloxietyl ha (bc 1 v bc 2)
RCH2O(CH2CH2O)nH RRCHO(CH2CH2O)nH
R C8 C18 R, R C10 C14
n: 3 5 n: 3 12
bc 1 bc 2

2.4.4. Cc cht HBM l cc este v amit ca ng.

Cc cht HBM ny c kh nng phn hy do cc vi sinh vt, chng thng l
cc este ca cc axit bo vi ng hoc l amit nh sau :

O O
HOCH2
CH3(CH2)10COCH2 CH3(CH2)10COCH2
O
O OH O
OH
OH OH CH2OH
O
HO HO OH
OH OH
Glucoz 6-oecanoat Sacaroz 6-oecanoat

13
 O
CH3(CH2)10COCH2
O
OH
O CH2 CH3
HO O
OH CH2 N C R
OH H C OH O
HO HO C H
HO O
HOH2C H C OH
O
H C OH
O
CH2OH CH2OH
Rafinozo 6-oecanoat N-Metylglucamit ca axit bo
OH

O
CH3(CH2)10COCH2
O
OH
O CH2
HO O
OH
OH
HO O CH2
HO O
OH
HO
HO O
HOH2 C O
O
CH2OH

OH
Stachyoz 6-oecanoat

2.4.5. Cc cht HBM este ortho- bn vng vi kim nhng b phn hy trong mi
trng axit.
a)
O CH2(CH2)mCH3
O nO
O CH O
CH3(CH2)m O O O OCH2(CH2)mCH3
n n

14
b)
O(C2H4)nCH3 CH3
HO (CHCH2O)m CH O (CHCH2O)mH
q
Oxit amin C12H35N(CH3)2O

2.5. Cht HBM ampholit (amphotere) phn t cha c nhm baz v

nhm axit.
2.5.1. Photpholipit:
O
CH2 O C R
O
CH3
CH O C R
A l: O C2H4 N CH3 OH
O
CH2 O P CH3
A
OH

a) Photphatiylcholin: Lexitin (Lcithines)

O
CH2 O C C15H31
O
CH O C C15H31
O CH3
CH2 O P O C2H4 N CH3 OH
OH CH3

(A) Hiroxit ca trimetylamino etanol hay cholin

CH3
A l: O CH2 CH2 N CH3 OH
CH3
b) Photphatiyletanolamin: cphaline (xephalin)
(A) Etanolamin hay colamin
A l: O CH2 CH2 NH2
O
c) Photphatiylinositol
(A) Hexolxiclic hay inositol CH2 O C C15H31
O
OH OH CH O C C15H31
A l: O H
H HO CH2 A
H OH Cng thc chung ca photphati
yl
OH H
d) Photphatiylserin NH2
(A) Etanolaminocacboxylic hay xerin A l: O CH2 CH
COOH 15
 Axit akylaminocacboxylic O
R NH (CH2)n C
OH

2.5.2. Beten (Btaines) cha nhm amonihiroxit

CH3
CH3 N OH
CH3
CH2 COOH
Dn xut ca glicol nhn c qua oxi ha cholin: H2N CH2 COOH
CH3 [O] CH3
CH3 N OH CH3 N OH
CH3 CH3
CH2 CH2OH CH2 COOH
Cholin Beten
Cc hirat hay hiroxit amoni bc 4 nhn c qua phn ng ca hiroxit kim
loi vi mui amoni bc 4.

CH3 CH3
CH3 CH3
N Br + KOH N OH + KBr
CH3 CH3
CH3 CH3

2.5.3. Ngng t betenic: dng mui clorua.

a) Betenclohirat:
CH3 CH3
CH3 N + ClCH2 COOH CH3 N Cl
CH3 CH3 CH2 COOH
Trimetylamin betenclohirat
b) N-trietanolaminaxeticclohirat.
HOCH2 CH2 HO CH2 CH2
HOCH2 CH2 N + ClCH2 COOH HO CH2 CH2 N Cl

HOCH2 CH2 HO CH2 CH2 CH2 COOH

Trietanolamin

16
c) Este ca axit bo.
O O
R C R C
O CH2 CH2 O CH2 CH2
HO CH2 CH2 N Cl HO CH2 CH2 N Cl
O
HO CH2 CH2 CH2 COOH HO CH2 CH2 CH2 C
CH3
Dng axit Dng este
* Bc trung gian iu ch cc sn phm trn l cc dn xut amit hoc este ca axit
cacboxylic :
O O O
R C CH2 CH2OH R C CH2 CH2OH R C CH2 CH2OH
N N N CH2 CH2OH
CH2 CH2OH CH2 CH2 O C R CH2 CH2 N
amit O CH CH2OH
monoamidoeste amit amin th 2
O O
R C O
CH2 CH2 O C R
R C
N
CH2 CH2 O C R O CH2 CH2 CH2 CH2 CH2OH
O este
amit dieste
d) Cc sunfobeten hay cacboxylbeten:
CH3 CH3
C12H25N CH3 C12H25N CH3
CH2CH2CH2OSO2 CH2COO
(Sunfobeten) (Cacboxylbeten)

2.5.4. Cc arylsunfon: dng mui ni phn t

N C
R NH C2H4NH2 R C N
N C SO3
SO3 NH2

2.6. Cht HBM a in tch

Cht HBM a in tch c bit n v s dng trn 50 nm, c bit ph
bin l dng cation. Trong phn t ca chng c th cha 2, 3 hoc nhiu hn n a tm
mng in tch dng (+) hoc m (-), phn t thng c dng ime, trime hay
polime.V mt cu to cc cht HBM ny cn c th phn chia theo cc loi:
Cht HBM oligome
Cht HBM oligomeric
Cht HBM gemini

17
 Cht HBM monome
Cht HBM oligome, phn t gm cc phn mang in tch ghp li (hnh a), cht
HBM oligomeric gm cc phn mang in tch khc nhau (nh copolime) ghp li
(hnh b), cht HBM gemini gm hai na phn t mang in tch ghp li (hnh c),
cht HBM monome l cc loi phn t mang mt in tch nh trn (hnh d)

a) Cht HBM oligome b) Cht HBM oligomeric

c) Cht HBM gemini d) Cht HBM monome

Hnh 2.1. M hnh cc cht HBM a in tch

Mc oligo ha phn t cc cht HBM tc l s lng cc phn mang in tch

trong phn t cht HBM thay i ty thuc vo yu cu v iu kin phn ng tng
hp. Di y trnh by mt s loi thng gp.

2.6.1. Cht HBM gemini (ime).

a) Cht HBM gemini (ime) dng cation
Trong phn t c cha hai na mang in tch dng (+) i xng vi nhau,
thng gp l cc mui amoni bc 4 nh cc cht di y:
O N N
N (CH2)n N 2Br N N 2Br 2Br
n R R
R R R R
(a) (b) (c)

N N

O O
R S N Y N S R 2Br
HN NH

(e)
O O
O O
R R
(d)
b) Cht HBM gemini dng anion.
Phn ln cc cht HBM gemini dng anion l cc sunfonat (a), sunfat (b),
photphat (c), cacboxylat (d) vi cc phn mang in tch m (-) nh s di y:

18
 X Y X
(a) X = CH2CH2CH2SO3Na
(b) X = OSO3Na
O O (c) X = OPO(OH)(ONa)
(d) X = OCH2CO2Na
R R
Y = O, O-(CH2CH2O)n-

O
O O
O O
NaO3S O s NaO P O O P NaO
R OR OR
R SO3Na
(e) (f)
c) Cht HBM dn xut axit amin.
T cc axit amin iu ch cc cht HBM gemini vi s thay i cu to cc
u phn t khc nhau nh hnh di: cht (a) khng ionic, cht (b) anionic.
KO3S SO3K

CH3[OCH2CH2]n [CH2CH2O]nCH3
N NH HN
O
O
NH HN S S
NH NH
O C C O O
R R
NH HN
(a)
O O

R R
(b)
d) Cht HBM dn xut ng.
Cht HBM gemini da trn cacbohirat l cc sn phm mi, chng c kh
nng phn hy sinh hc, v d cht (a), (b) u l cht HBM khng ionic:

19
 R
OH OH OH OH O
O OH
N OH
nN O
O
OH OH OH R R OH OH OH OH
O HO
O OH
(a)
O

O
HO O (b)
OH O OH
HO
O O
O OH
HO
O
R
e) Cht HBM d ime.
Phn t ca loi ny gm hai na khc nhau, khng i xng, v d phn t (a)
dng cationic v (b) cationic v anionic:

2Br Br
N N N COO
N N
H

(b)
(a)
f) Cht HBM i quang.
Trong phn t ca chng c cha tm i xng, v d:
Na2O3P O OPO3Na2

* *
O O
O O
R R

20
2.6.2. Cht HBM oligome.
Cu to ca oligome c th l trime, tetrame hay polime dng cationic hay
anionic, khng ionic nh cc v d di y:
1) Cationic:
OH OH
(a) N N N 3Br
R R R

(b)
N N
N N 4Br
R R
R R
N
N R
(c) N
3Br
R
N
R
2) Anionic
SO3Na NaO3S

(d) O O
O O O O
R R
O
NaO3S
O

O
R
3) Khng ionic:
OH OH OH
H(OCH2CH)n (CHCH2O)nH (CHCH2O)nH

(e)
n

21
 Cc cht (a), (b) mch thng, (c), (d) mch nhnh, hp cht (e) polime vng thm
benzen.
d) Cht HBM oligomeric, cc phn t khc nhau.
O CH3
CH2 O C
O CH3
X
O CH2 O C
O X OH
O O
O O HO HO O
OH CH3
CmH2m+1 CmH2m+1 O CH2 O C
(a) CmH2m+1 OH
(b)
CH3 O
RCONH(CH2)3N CH2CH(OH)CH2 O P O
CH3 (c) OH

2.7. Cht HBM polime.

Phn t polime c th cha mt hay nhiu in tch m hoc dng hoc khng
mang in tch, c cu to chung:
A A (A)n A B (B)n B B

A A A A A A A A
B B B B n
A v B l nhm hirophil v lipophil. V d :
OH OH
COONa
R CH2
CH2

(a) CH2 CH2

R
COONa
OH OH
Cht HBM anionic
(b) CH3O (CH2CH2O)45 C CH CH COOC12H25
O
Cht HBM khng ionic
CH3 Cl
(c) N CH2 CH CH2
n
C12H25 OH
Cht HBM cationic

22
 Chng 3. Mt s tnh cht ca cc cht
hot ng b mt

3.1. Sc cng b mt.

3.1.1 S hp ph
Hp ph l s cht cha cc phn t cht kh, cht lng hay cht ha tan ln b
mt phn cch pha. B mt phn cch pha c th l kh-lng, kh-rn, lng-lng hay
lng-rn. Hp ph c phn chia thnh hp ph vt l (hp ph Van der waals) v hp
ph ha hc. S hp ph ph thuc vo nhiu yu t, trong ph thuc vo nng C
(hay p sut p) nhit khng i l quan trng nht. y gi l s hp ph ng
nhit.
Mi quan h gia lng cht b hp ph trong lp b mt , nng cht tan
trong dung dch C v sc cng b mt c Gibbs nu ra theo phng trnh sau:
C d
.
RT dC
d
Nu 0 th < 0, tc l nng cht tan trong lp b mt b hn trong th
dC
d
tch dung dch, ta c s hp ph m. Nu 0 th > 0 nng cht tan trong lp
dC
d
b mt ln hn trong th tch dung dch, ta c s hp ph dng. Nu 0 , khng
dC
i khi C tng th nng cht tan phn b u c trn lp b mt v trong th tch dung
dch.
d
i lng c gi l hot ng b mt c k hiu l G, do :
dC

d C
G RT hay .G
dC C RT
Phng trnh ny c gi l phng trnh Gibbs.

3.1.2. ln ca sc cng b mt.

Sc cng b mt ca cht lng c trng cho gi tr nng lng t do b mt ca
cht lng l ni p ca cht lng sinh ra, l lc ko cc phn t trn b mt vo pha
bn trong lng cht lng theo hng vung gc vi b mt thong. Cht lng cng phn
cc, ni p ca n cng ln. Ni p ca nc l 14.800 atm cn ca benzen l 3.800 atm.
Ni p ko phn t vo pha trong lm cho b mt cht lng gim n ti thiu trong
nhng iu kin nht nh.
Lc tc dng ln mt n v b mt i c 1 n v chiu di tch cc phn
t ra khi b mt cht lng gi l sc cng b mt, c th nguyn dyn.cm -1 v c k
hiu l .
F= 1dyn1cm.1cm-2 = dyn.cm-1

23
 lm tng b mt cn tiu ph mt cng thng lc gy ra bi ni p. Cng
lm tng 1 cm2 b mt bng nng lng t do ring, th nguyn erg.cm-2 cng l sc
cng b mt v:
erg.cm-2 = dyn.cm.cm-2 = dyn.cm-1
= 10-7.J.cm-2 = 10-3.J.m-2
Nu nghin cu cht lng trong tr ng lc ng nht theo mi hng
(hirocacbon parafin, benzen, tetraclorua) v pha gii hn khng b trn ln th sc cng
b mt ca cht lng nh vy ch ph thuc vo lc tng tc gia cc phn t c
nh gi theo tnh cht th tch ca cht. Trong trng hp ny n c xc nh bng
hiu s phn cc ca pha v l hm s ca thm in mi.
Rehbinder a ra phng trnh tnh sc cng b mt i vi kiu h thng hai
pha trn ln nh sau :
1
f f( )
2
y l phn cc, l thm in mi.
Nng lng c trng ca s tng tc gia cc phn t l nhit bay hi (Hi).
V sc cng b mt ph thuc vo din tch b mt nn nhit bay hi ph thuc vo th
tch m khng ph thuc mol. S ph thuc ca vo v Hi th hin hnh 3.1.

a) b)

Hnh 3.1. a) S ph thuc ca sc cng b mt vo hiu s phn cc ca h

lng-kh () v lng-lng (o).
b) Quan h v Hi h lng-kh: 1. Phn t i xng
2. Phn t bt i xng dy mch thng,
vng cc im l ca phn t khng i xng dy thm.

Cc hm = f() v = f(Hi) l tuyn tnh i vi cht lng, cc phn t i

xng v trn ln vi pha th hai. S ph thuc tuyn tnh ca c h lng-lng v
lng-kh, c th vit:
= G + I. (3.1)
24
 v = G + I. Hi
G l nng lng t do ca phn t
I l h s
l hiu s phn cc gia hai pha
Hi l nhit bay hi
1 1 2 1
(3.2)
2 2 2 2
1, 2 l thm in mi ca hai pha
i vi h lng-kh th tng kh c 2 = 1 nn :
1 1 1 1 1
1 1 (3.3)
2 2 2 2 2 2
phng trnh (3.1) nng lng t do G bng sc cng b mt khi = 0 v
bng 28.10-3J/m2.

3.1.3. Cc yu t nh hng n sc cng b mt.

1/ Sc cng b mt ca cht lng gm cc phn t khng i xng.
Tt c cc axit, este, ru, xeton, anehit, amin mch thng c p sut hi bo
ha nh hn 100 Pa1, mc d khc nhau rt t v chiu di mch cacbon, gi tr v
Hi thc t cng nh hng n sc cng b mt.

Hnh 3.2. S ph thuc ca sc cng b mt vo s nguyn t cacbon trong mch thng.

Hnh 3.2 cho thy sc cng b mt gim khi s nguyn t C trong mch tng
ln n mt gii hn th khng gim na. iu ny ch ra rng trong cht lng cc phn
t nm gii hn phn chia pha nh hng nhm phn cc vo trong cht lng cn
nhm khng phn cc ra pha kh. Tuy nhin dy cc hp cht vng thm, hiu ng

1
Pa l n v o p sut (Pascan). 1Pa l p sut gy ra bi lc 1N tc dng u n ln
b mt vung gc vi n c din tch 1m2 ; 1atm = 1,01.105Pa, 1mmHg = 1,33Pa.
25
electron t nhm phn cc chuyn sang h lin hp ca vng thm, lm thay i sc
cng b mt trong mt gii hn rng.
Khi s dng yu t nh hng phn t c th tm thy chiu dy lp mng xc
nh sc cng b mt. T cn bng sc cng b mt ca hirocacbon parafin v dn xut
th ca chng ch cn xc nh phn phn t nh hng gii hn trc tip vi pha khc.
S ph thuc ca sc cng b mt vo s nguyn t cacbon trong mch c biu din
trn th hnh 3.2. Cc hp cht trong ch c nhm metyl v etyl nh hng c gi
tr cao hn cc hp cht vi mch cacbon di nhng li thp hn cc gi tr tnh theo
phng trnh (3.1). Ngha l chiu dy lp mng xc nh sc cng b mt c quyt
nh bi 2-3 nguyn t cacbon v bng (5-7).10-10M.
Do sc cng b mt ca cht lng c to ra t phn t bt i xng v cha
mch thng bo ha thc t bng sc cng b mt ca hirocacbon parafin, s mt nh
hng ca phn t ca lp b mt khng tm thy khi nghin cu sc cng b mt. iu
ny c th gii thch nh sau: Mt cch gn ng s phn t mt nh hng b mt
phn chia pha c th tnh theo phng trnh :
nK F
exp K (3.4)
n RT
y nk l s phn t mt nh hng, n l s phn t nm b mt, fk l nng
lng t do ca s mt nh hng, nk/n l t l phn t mt nh hng.
Bng di y cho gi tr nk/n thu c t hm ca fk (bng 3.1).

Bng 3.1. S ph thuc ca t l phn t mt nh hng vo nng lng t do ca n

nk/n fk (KJ/mol) nk/n fk(KJ/mol)

1 0 2,0.10-4 21,0
0,2 4,2 4,5.10-5 25,2
3,6.10-2 8,4 9,2.10-6 29,3
7,0.10-3 12,6 1,7.10-6 33,5
1,3.10-3 16,7 3,2.10-7 37,7

T bng trn c th thy rng cc phn t mt nh hng ca lp b mt quan st

thy khi Fk 8,4 KJ/mol. S tnh ton nh hng chng t rng i vi axit v ru
th Fk l 20 KJ/mol.
Nng lng t do ca cc phn t nh hng lp b mt c tnh theo cng
thc :
f = (L - T)Sm (3.5)
L v T l gi tr sc cng b mt tnh theo l thuyt v thc nghim, S m l din
tch b mt m cc phn t chim lp n phn t.
Ngoi ra , cng nhn thy cc ng phn ca cht HBM vi mch nhnh c
sc cng b mt thp hn cc cht HBM mch thng. Cc phn t c mch nhnh ln,
v d mt s siloxan c sc cng b mt nh [khong (18-20).10 -3J/m2] mc d p sut
hi bo ha khng ln v phn cc cao..

26
2/ S ph thuc ca sc cng b mt vo tng tc pha.
Trong h lng-kh c trng ca s trn ln pha l p sut hi bo ha P. Trong h
lng-lng l s tng tc ca cc cht lng, tc l ha tan c P. Khc vi sc cng
b mt, s trn ln pha ch l hm s ca lc gia cc phn t.
Trn hnh 3.5 s ph thuc ca vo P v cP l tuyn tnh trong h ta lgCpv
v biu th bng cng thc :
H lng-kh: M - = R.T.h.lnP (3.6)
y M v h l hng s.
H lng-lng: M - = R.T.h.lnCP (3.7)

Hnh 3.3. S ph thuc ca sc cng b mt vo p sut hi bo ha ca dn xut

halogenua benzen (1) v hirocacbon parafin (2) vo tan trong nc ca axit mch
thng (3).

Nh vy i vi h lng lng khng ph thuc vo p sut p m ph thuc

nng cht HBM. Tuy nhin, trong dy ng ng hirocacbon parafin t pentan n
hexaecan thay i vi p sut n 14.10-3J/m2 ; trong khi gii hn vi mc sc
cng gia cc pha ca cc hp cht ny lun lun thay i ln 3.10 -3 J/m2. iu gii
thch phn t hirocacbon pha kh nh hng n sc cng b mt tng i mnh
hn nc. So snh lng phn t (mol) ca hirocacbon parafin trong 1 lit pha nc v
pha kh p sut cao ca hi bo ha hirocacbon tinh khit ( 20 0C) thy s mol nm
tng nc v tng kh (bng 3.2).

Bng 3.2. S mol hirocacbon parafin nm pha nc v pha kh.

Cht S mol nm pha nc S mol nm pha kh
Pentan 0,0055 0,0300
Hexan 0,0016 0,0089
Heptan 0,00055 0,0021
Octan 0,00013 0,00082

27
 T bng trn thy rng s phn t hidrocacbon nm pha kh lun lun ln hn
nm pha nc nhng vi hai cht lin nhau trong dy (v d hexan v heptan) th s
lng phn t nm pha nc ca cht ny tng ng vi s phn t ca cht kia
pha kh.
Sc cng b mt gim do lng cc phn t ha tan trong dung dch gy ra l ch
yu, khng phi do lc ht gia cc phn t.

3. nh hng ca nhit n sc cng b mt.

Nhn chung sc cng b mt gim khi nhit tng, i vi cht lng hu c gi
tr h s nhit i vi sc cng b mt gn nhau. Cht lng phn cc c gi tr bng
(0,08-0,12).10-3J/m2.K, cht lng khng phn cc bng (0,1-0,13).10 -3J/m2.K, nc l
0,15. 10-3J/m2.K.

Hnh 3.4. S ph thuc ca sc cng b mt ng p (Pa) vo nhit (T,K)

1- 1,3.102 Pa 4- 1,3.104 Pa
2- 1,3.103 Pa 5- 5,3.104 Pa
3- 5,3.103 Pa 6- 1,0.105 Pa

Hnh 3.4 ch ra s ph thuc ca sc cng b mt ng p ca mt dy ng ng

parafin vo nhit di p sut hi bo ha nht nh. C th tm c h s nhit
theo gc nghing ca cc ng thng biu din bng 0,03.10 -3J/m2.K ngha l bng h
s nhit chung ca h ankan-nc. N sai lch vi cht hu c khng phn cc
0,1.10-3J/m2.K l 0,07.103J/m2 l do khi tng nhit th ha tan ca ankan trong
nc tng ln.

3.2. S lin quan gia cu to v tnh cht ca cht HBM.

Gia tnh cht v cu to ca cht HBM c mi lin quan cht ch vi nhau.
3.2.1 S hnh thnh mixen
Mt tnh cht quan trng ca dung dch cc cht HBM l kh nng lm tng
ha tan ca cc cht hu c thc t khng tan trong dung dch v d du trong nc
hoc nc trong du. dung dch du trong nc cc phn t cht HBM ( v d cc
28
mui axit bo ) c ui a du cm vo trong git du cn u a nc bao quanh pha
ngoi cn dung dch nc trong du th u a nc ca cc phn t HBM chui vo
pha trong git nc cn ui a du bao pha ngoi ,kt qu l cc git du ny tan
c trong nc cn cc git nc ny tan trong du . Chnh cc git du hay git nc
ny l hnh nh ca cc ht mixen c hnh thnh trong dung dch du/nc hay
nc/du ( hnh 3.5 v 3.6).

Git du trong nc Git nc trong du

( Mixen ) ( Mixen )

Hnh 3.5 Cc ht mixen

3.2.2. Nng mixen ti hn (CCM)
Khi tng nng ca cht HBM ti gi tr nht nh, chng lin kt vi nhau
to nn cc mixen. Hnh 3.5 l mt trong cc dng mixen, mixen hnh cu.
Nng ti hn l nng cc i ca mt cht ti p sut P v nhit T
khng i m h vn tn ti ng th.
Hot tnh b mt l t s gia nng ca hp cht b mt cht lng [C s] v
nng ca n trong dung dch [Cv] :
CS
Hot tnh b mt
CV
i vi cc cht HBM th t s ny l 1000 nng mixen ti hn.

Hnh 3.6. Mixen hnh cu

Nng mixen ti hn (CCM) l nng ca mt cht HBM trong dung dch

m trn trn nng th mt phn phn t phn tn trong dung dch t hp li
thnh dng mixen.
i vi mt h cho nu nng cht HBM tng th sc cng b mt s gim
n mt gi tr khng i mc d nng dung dch vn tng (hnh 3.7).
Nh vy, gi tr hot tnh b mt (HTBM) ca mt hp cht c biu th theo
cng thc :

29
 O CCM
HTBM
CCM
O l sc cng b mt mi trng.
CCM l sc cng b mt nng mixen ti hn.
[CCM] nng mixen ti hn

Hnh 3.7. S thay i sc cng b mt theo nng .

i vi phn ln cc cht HBM, sc cng b mt ca chng gn nh nhau nhng nng

mixen ti hn thay i theo cu to ca chng. Cc tnh cht khc nh s thm t,
to bt, nh ha cng lin quan n hot tnh b mt.

Bng 3.3. Nng ti hn mixen ca mt s cht HBM

[CCM] [CCM] [CCM]
Cht HBM
500C 250C 300C
Kali stearat CH3(CH2)16COOK 0,45.10-3
Kali oleat (cis) CH3(CH2)7CH=CH(CH2)7COOK 1,2.10-3
Kali eledat 1,6.10-3
Kali lauryl CH3(CH2)10COOK 12,5.10-3
Kali lauryl sunfat CH3(CH2)11OSO3K 9,0.10-3
Natri lauryl sunfat CH3(CH2)11OSO3Na 8,1.10-3
Laurylamin clohirat 14,0.10-3
Lauryl ancol, 5ml etylenoxit 0,57.10-3
Lauryl ancol, 5ml etylenoxit 0,14.10-3

3.2.2. S thay i nng mixen ti hn.

i vi mt dy ng ng cc cht HBM mch thng mt nhit nht nh
th nng mixen ti hn tng gp i cho s gim i mi nguyn t cacbon mch
thuc nhm k nc (hirophop) gn vi u a nc. Nh vy hai cht HBM c s
nguyn t C hn nhau l n, th nng ti hn ca cht c t s C hn bng nng ti
hn ca cht kia nhn vi 2n nh cng thc sau:
[CCM]2 = [CCM]1x2n

30
 [CCM]1 l nng ti hn mixen ca cht c mch cacbon ln hn, [CCM] 2 l
nng ti hn mixen ca cht c s cacbon t hn.
V d xt phn t C13H27COOK (1) v C9H17COOK (2)
[CCM] ca C13H27COOK = 0,006M (miristat)
[CCM] ca C9H17COOK = 0,095M (caprat)
[CCM]2 = 0,006x24 = 0,096M
Hai mui ny khc nhau 4 nguyn t cacbon.
Tnh cht ny ca cc cht HBM c th vit di dng tng qut:
lg[CCM] = A B.nC (3.10)
A c trng cho dy cht HBM; B l gi tr gii hn, nh hn lg2 = 0,3 ;
nC l s nguyn t cacbon trong mch.
A v B l cc hng s thc nghim. S nguyn t C ca mch hyrophop cng
tng th nng ti hn mixen cng gim (xem bng 3.4).

Bng 3.4. Gi tr A v B ca mt s cht HBM.

Cht HBM Nhit 0C A B
X phng kali 25 1,92 0,290
45 2,03 0,292
Ankyl sunfonat 40 1,59 0,294
50 1,63 0,294
Clorua tetraankyl amoni 45 1,79 0,296
Bromua aryltriankyl amoni 60 1,77 0,292

V d: cht C9H19COOK c lg[CCM] = 1,92 0,290x10 = -1,0

Do [CCM] = 0,10M
xung quanh nng ti hn mt s tnh cht ca cht HBM c s thay i
t bin nh p sut thm thu, sc cng b mt, dn in, kh nng git ra nh
hnh 3.8 ch ra nhng thay i tnh cht ca dung dch oexyl(lauryl)sunfat natri
C12H25OSO3Na.

31
 Hnh 3.8. S thay i tnh cht ca dung dch oexyl sunfat natri sau khi vt qua
nng ti hn CCM.
Phn t cht HBM chu hai lc, mt lc hng n vo trong mi trng nc,
mt lc ko ra. Tnh bn ca b mt pha cn mt cn bng gia hai khuynh hng .
Nu ngi ta kim tra s hot ng ca cc hp phn khc nhau i vi nc, v d cc
hirocacbon khng th cho cc lp phn t bn vng nu to ra cc pha ba chiu. Adam
a ra bng phn loi cc nhm theo tnh cht a nc (bng 3.5).

Bng 3.5. Cc nhm a nc.

Tnh a nc rt yu Tnh a nc yu Tnh a nc mnh Tnh a nc rt mnh
- CH3 - CH2OCH3 - CH2OH - C6H4SO3(-)
- CH2I - C6H4OCH3 - COOH - SO3(-)
- CH2Br - COOCH3 - CN - O-SO3(-)
- CH2Cl - CONH2 - NH3(+)
- NO3 - CH=N OH - O-PO3(-)
- C6H4OH
- CH2COCH2-
- NHCONH2
- NHCOCH3

32
 T bng trn thy rng v tr ca cc nhm chc a nc, s c mt ca lin kt
i trong phn t, s phn nhnh, v tr ca chng nh hng ng k n tnh cht sc
cng b mt, cng nh tnh cht vt l v ha hc ca chng (oxi ha, khng hirolis)

3.2.3. nh hng ca chiu di mch v s phn nhnh.

1/ nh hng ca chiu di mch cacbon n tnh cht hot ng b mt thng thy rt
r.
a. im KRAFT.
ha tan ca cc cht HBM l hm s ca cu to ca chng v nhit . i
vi x phng v mt vi cht HBM khc, im KRAFT l nhit m dung dch
cht HBM tr nn c khi lm lnh. chnh l nhit ti hn ca s ha tan (hnh
3.9).
x phng v cc cht HBM khc s ko di mch cacbon u gy ra s thay
i im KRAFT (hnh 3.10). Theo s ny kh mch cacbon tng th im KRAFT
tng.

Hnh 3.9. Gin im KRAFT Hnh 3.10. S thay i im KRAFT theo

(*) ng cong ca s ti hn chiu di mch cacbon ca axit bo

Tri ngc vi cc cht HBM c in tch ion, cc cht HBM khng ionic
thng th hin im c trong dung dch nc thng ph thuc vo cu to ca hai
phn k nc v a nc. V d dy etilenoxit gn vi gc hirocacbon tng ln th im
c ca cc hp cht khng ionic cng tng.
i vi cc hp cht RO(CH 2CH2O)nH th quy tc chung l cng nhiu s
phn t oxytetilen lin kt vi phn t k nc, im c ca cc cht khng ionic cng
tng. V d, RO(CH2CH2O)nH, khi n tng th im c tng.
Cng vy, trong mt dy cho, s nguyn t cacbon trong mch phn k nc
cng tng th im c cng gim, l trng hp ancol bo etoxyl ha.
Mt s hp cht khng ionic cho im c thp nhit mi trng, ngi ta
phi o n khi c mt dung mi th ba. Phn ln cc hp cht khng ionic c im c
nm trn im si ca nc. i vi h ny ngi ta o mi trng nc mui. hai
h trn r rng im c c cho da trn mi trng o n.
b. Trng lng mixen.
S lng phn t dng mixen v trng lng mixen tng ln cng vi chiu di
mch cacbon. V d ancol bo sunfat cho trng lng mixen tng ln bng 3.6.

33
 Bng 3.6. Trng lng mixen tng theo mch cacbon ancol bo sunfat.
Chiu di mch Trng lng mixen S phn t dng mixen
C8 4600 20
C10 13000 50
C12 23000 80

c. Tnh cht b mt.

Nng lng cn thit ri ch mt phn t b mt tng ln vi chiu di
mch, nng lng gii hp W c cho theo phng trnh:
W = p + n. WC
W : nng lng gii hp
p : ph thuc nhm phn cc
n : s nguyn t C trong mch
WC : nng lng gii hp ca nhm CH2. N bng 600 Calo cho mt nhm CH2
Thc t c tng mt nhm CH 2 ca mch ln th sc cng b mt gim i ba ln. Theo
qui tc Adam, s tng chiu di mch mt nhm CH 2 s lm thay i tnh cht lp b
mt cng nh gim nhit i 8/100C.
d. Tnh cht thm t.
Tnh cht thm t tng ln khi mch cacbon tng ng 8-10 cacbon.
e. Tnh cht to bt.
S to bt cc i 20-400C i vi cc cht c mch cacbon t 12-14 cacbon.
f. Tnh cht nh ha.
Tnh cht nh ha tng ln i vi hp cht c t 16-18 nguyn t cacbon.
g. Tnh cht git ty.
Tnh cht ny thay i ty tng trng hp. V d di im KRAFT, mch di
cho kt qu tt nht. di 600C tc dng git ty tng c bit i vi mch di C18.

2/ nh hng ca nhm th phn nhnh.

Theo qui tc chung s phn nhnh chng li mi lin kt gia cc phn t vi
nhau, iu ny ph ri b mt tip gip, lm gim im KRAFT v sc cng b mt. Do
vy s phn nhnh lm thun li cho s to bt v lm hi bn ca nh.
Cc cht phn nhnh l cht to bt tt nhng l cht git ty km. Bn cht ca cc
nguyn t to thnh mch nhnh c nh hng n tnh cht ca n, l trng hp hp cht
flo, lm tng hot tnh to bt ln mnh.

3.3.Cn bng hirophin/lipophin (a nc/a du) HLB-

RHLB
Nghin cu cn bng hirophin/lipophin hay HLB chi ra kh nng ho tan trong
nc v khuynh hng b hp ph b mt ca cht HBM hay kh nng lm gim sc
cng b mt ca n trong dung dch nc pha phn tn l nc hay mt pha hu c
ph bin nht l du. C mt nh du, y pha phn tn l nc, hay c mt pha phn
tn nc y c nh du.

34
3.3.1. Cn bng hirophin/lipophin (HLB)
1. HLB.
Cn bng HLB ch ra nh hng ng dng cc cht HBM pha ch cc dung
dch nh tng v vi nh tng. Gi tr HLB ca cht nh ha biu th trc tip cn bng
hirophin/lipophin l mi quan h i lc ca nhm a nc c i lc vi nc v chiu
di mch k nc c i lc vi du. Trc tin l phn cc hay khng, hirocacbon mch
di l khng phn cc. Bng 3.7 gii thiu mt s cht HBM v cc gi tr HLB tng
ng.

Bng 3.7 Phn loi tc nhn b mt theo gi tr HLB.

Gi tr HLB
Cht HBM
Cc tiu Cc i
Cht kh bt 1,5 3
Cht to nh nc trong du 3 6
Cht tm t 7 9
Cht to nh du trong nc 8 13
Cht ty ra 13 15
Tc nhn peptit ha-cht ha tan 15 18

Cc cht nh ha c gi tr HLB thp hn 9 c trng cho mt cht nh ha k

nc tiu biu, cn cht nh ha c gi tr HLB trong gii hn 11 v 20 c coi l cht
a nc tiu biu.
Vic s dng h thng HLB cho mt cht nh ha hay hn hp cht nh ha c
th bit n l mt nh du trong nc hay nc trong du.
HLB ca mt cht nh ha hay hn hp cc cht nh ha l ch s nh gi
mt cht nh ha khc c cu to gn vi mt cht nh ha bit.
HLB ca mt cht nh ha lin h vi ha tan. Mt cht nh ha c ch s
HLB thp l cht ha tan trong du cn ngc li n l cht ha tan trong nc.
S phn loi HLB theo Davies gia cc gi tr gii hn 1 v 20; coi axit oleic c
gi tr HLB l 1 v kali oleat c gi tr 20. Khi trung ha axit oleic nhn c cc hn
hp c gi tr trung gian t 1 n 20, so snh vi cc cht hot ng b mt khc tnh gi
tr HLB, cui cng xc nh tnh cht nh ha ca chng.

2. RHLB ca cht to nh.

RHLB hay HLB yu cu ca cht nh ha l gi tr HLB cn thit ca cht nh
ha khi thm n vo ch to mt cht nh tng trong iu kin tin hnh nht nh.
Hai tn gi HLB v RHLB c coi nh l iu kin ch to mt nh tng ca
mt cht lng hu c: HLB ca cht nh ha phi lin h vi RHLB ca n ngha l
HLB phi ph hp tt nht cho mt nh tng bn vng nht.

35
 Mi cht, mi loi cht bo thin nhin c mt gi tr RHLB nht nh. Bng 3.8
cho gi tr RHLB ca mt s vt liu ch to nh tng di dng du trong nc
hay nc trong du hay vi nh.

Bng 3.8 Gi tr RHLB ca mt s cht to nh.

Cht Nh nc trong du Nh du trong nc Vi nh ha tan
Du ht bong 5 10 12-18
Sp ong 4 12 12-18
Du vaslin 5-7 12 12-18
Axit stearic 6 15 12-18
Du khong 8 11 12-18
M lng cu 8 10-11 12-18

Trn bng 3.8 cho thy mt s gi tr RHLB ca vt liu du m ch to nh

tng di dng du trong nc hay nc trong du hay hnh thnh vi nh. i vi
nh tng nc trong du, RHLB thng c gi tr 7 n 9, thp hn nh tng du
trong nc l 10 n 15.

Bng 3.9 cho mt s gi tr RHLB ca mt s sn phm trc khi c nh ha.

S hiu bit chng cho php phn bit mt s ln cht nh ha khng thch hp m
HLB ca chng khc gi tr RHLB ca cc cht m to nh.
Nu tha mn iu kin HLB = RHLB s dn n s kho st vic s dng cc
cht nh ha thch hp trn ln nhau. Kinh nghim ch ra rng hai cht nh ha c HLB
ging nhau v tng ng vi RHLB ca cht du to nh khng phi lun lun cho
cc nh tng c bn nh nhau.
Vy l cn phi so snh cc tnh cht khc ca cc cht nh ha nh: nh hng
cht du to nh, bn cht cc tng c mt, nng mui, im nng chy ca cht
m, pH .v..v.

Bng 3.9 Gi tr RHLB ca mt s pha hu c cho s nh ha nc (du trong nc).

Hp cht RHLB Hp cht RHLB
exylaxetat 11 iisooctylbenzen 15
Axetophenon 14 Xng 14
Axit oleic 17 Etylanilin 13
Axit lauric 16 Du mm ng cc 9,5
Axit linoleic 16 Du 12
Axit rixinoleic 16 Du thong 16
Ancol xetylic 15 Du thu du 14
Ancol dexylic 15 Du vaslin 12
Ancol lauric 14 Du khong thm 12
Ancol tridexylic 14 Du khong parafin 10
Ancol stearylic 14 Krosen (du ha) 14
Benzen 15 Laurylamin 12
Etyl benzoate 13 Poliimetylsilicon 11

36
Benzonitril 14 Nitrobenzen 13
Brombenzen 13 Parafin 10
Clobenzen 13 Parafin clo ha 8
Sp 12 Petrol naphta 14
Xiclohexan 15 Butylstearat 11
ecanhironaphtalen 15 Toluen 18
ietylanilin 14 Vaslin 7-8
iisooctylphtalat 13 Xylen 14

3. S bn vng ca nh tng.
S bn vng ca h nh tng du hay hirocacbon vi nc nh cc cht nh
ha c bit t lu. Ni chung hn hp n gin ca mt cht nh ha vi mt cht
du cho mt s phn tn tt trong nc v thu c mt nh tng dng sa bn hay
km bn v cui cng b tch ra thnh hai, ba pha, khi thm mt cht hot ng b mt
vo d dng chuyn n thnh mt h ng nht trong sut, thng ng hng v bn
nhit ng. H ny c gi l vi nh, c th v d nh du hay hirocacbon (pha hu
c), nc v mt cht nh ha (cht hot ng b mt).

3.3.2. Phng php xc nh RHLB ca nh tng v HLB ca cht

nh ha.
Cc yu t quyt nh s la chn ca cc cht nh ha l nhiu v s xc nh
HLB cng nh RHLB khng ch v phng din cng ngh ca cc cht nh tng. R
rng rng bn cht ca s phn tn nh tng nc trong du (W/O), hay du trong nc
(O/W) hay vi nh l iu kin trc tin do HLB ca cht nh ha phi can thip. Nh
ta thy, RHLB ca s nh ha l khc nhau trong trng hp nh tng nc trong du
hay du trong nc hay vi nh. HLB hay cn bng hirophin/lipophin c th c xc
nh bng tnh ton n gin hay bng phng php thc nghim.
Phng php xc nh HLB thc hin theo DAVIES hay theo GRIFFIN bao gm
xc nh cn bng gia s a nc ca cc nhm ha tan v s k nc ca mch cacbon
phn t lin kt vi nhau.
Cc hp cht hot ng b mt c cu to gm mt hay nhiu nhm a nc ni
vi mt mch k nc. Cn bng hirophin/lipophin xc nh tnh cht ca phn t v n
nm gia 0 v 20.

1. Xc nh cn bng hirophin/lipophin bng cch tnh.

i vi mt cht hot ng b mt c cng thc ha hc bit, gi tr HLB c
th tnh ton theo phng php thc nghim ca GRIFFIN.

V d:
S
1. i vi monoeste ca axit bo v HLB 20 1
A

37
 S = ch s x phng ha ca este
A = ch s axit ca axit bo gn vi glixerin.
154,4
HLB 20 1 201 0,79 4,2
197,1
(cht nh ha nc trong du)
Sn phm c HLB = 4,2 ph hp vi s iu ch nh tng nc trong du.
2. i vi hp cht khng ionic nh este hay ete ca cc hp cht oxietylen
a/ Trng hp este ca ancol polihiric oxietylen:
EP
HLB
5
E = % trng lng ca oxietylen
P = % trng lng ca ancol polihiric.
Phng trnh ny tnh cho este ca sorbitan polioxietylen.
R C R' (CH2CH2O)n H OCH2 CH CH CH CH CH2O = R'
O OH OH OH OH
E P 60 7
HLB 13,4
5 5
y: E = 60 ; P=7
Gi tr ny tng ng vi mt sn phm git ra. Gc mch bo = 33%
b/ Trng hp oxit etylen ni trc tip vi mt mch k nc m mnh n ni
vi mt phn nhm a nc:
E
HLB
5
E l % trng lng ca oxit etylen ca hp cht.
i vi monostearat poliglicol th E = 75
75
HLB 15
5 O
Axit stearic CH3(CH2)16COOH R C
O (CH2CH2O)n H

2. Phng php gia s.

Phng php tnh cn bng hidrophin/lipophin theo phng php gia s l cng cc
gia s ca cc nhm nguyn t ng vi nhm a nc v k nc theo bng 3.10

Bng 3.10 Bng gia s ca cc nhm a nc v k nc.

Nhm a nc gH Nhm k nc gL
-O- 1,3 = CH- 0,475
- OH 1,9 - CH2 - 0,475
- COOH 2,1 - CH3 0,475
- COONa 19,1 CH CH2 O 0,125
- CH2-CH2-O- 0,35 CH3

38
 Theo Davies, phng php ny cho php tnh HLB ca cht hot ng b mt c
cng thc bit gi tr k nc v i nc cho mi nhm ca phn t. C th vit gn nh
sau :
HLB = gH + 7 - gL
gH = gia s ca cc nhm a nc ; gL = gia s ca cc nhm k nc
Cn bng hirophin/lipophin c gi tr 7. Nu HLB nh hn 7 ta c hp cht
hng k nc, nu HLB ln hn 7, ta c hp cht a nc.
V d:
a/ Xc nh HLB ca x phng
O
CH3 C16H30 C Natri oleat
Na
gia s nhm a nc (-COONa) = 19,1
gia s cc nhm k nc = 1(-CH3).0,475 + 14(-CH2-).0,475 + 2(=CH-).0,475
= 8,075
HLB = 19,1 + 7 8,075 = 18,025
i vi oleat natri, gi tr HLB c xc nh bng phng php thc nghim l 18.

b/ Hp cht oxietylen
Gi tr ca mt nhm ( -CH2-CH2-O - ) tnh theo :
2 (-CH2-) 0,475 x 2 = 0,95
1(-O-). 1,3 = 1,30
= gH gL = 1,3-0,95 = 0,35
Gi tr HLB ca ancol lauric etoxyl cha 5 nhm oxit etylen (CH2-CH2-O-) :
CH3-(CH2)10-CH2-O-(CH2-CH2-O)5-OH
- Cc nhm hidrophile (a nc) gH :
1(-O-) = 1,30
5(-CH2-CH2-O-)=0,35.5 = 1,75
1(-OH) = 1,90
cc nhm a nc (gH ) = 1,30 + 1,75 + 1,90 = 4,95
- Cc nhm lipophin (k nc) gL :
1(-CH3) = 0,475
11(-CH2-) = 11.0,475 = 5,225
cc nhm k nc ( gL ) = 0,475 + 5,225 = 5,7
HLB = gH + 7 gL = 4,95 + 7 5,7 = 6,25
i vi ancol lauric ngng t 5 phn t oxit etylen, gi tr HLB c xc nh bng
phng php thc nghim l 7. T s so snh cch tnh ton c th kim tra
chnh xc ca cc phng php khc nhau.

3. Phng php thc nghim.

1/ Phng php phn tn cht nh ha.
Phng php thc nghim da trn s ha tan trong nc ca cht nh ha cho
php s la chn gn ng, nhng phn ln n l tha mn. V d i vi h nc sa

39
bn vng, gi tr HLB t 8 n 10, cn i vi h phn tn nc trong sut th HLB ln
hn 13 (xem bng 3.11).

Bng 3.11 Gi tr HLB ca h phn tn nh tng trong nc.

Tnh trng phn tn Gi tr HLB
Khng phn tn trong nc 1 n 4
Phn tn ht th 36
Phn tn sa t bn 68
Phn tn sa bn 9 10
Phn tn trng c 10 13
Phn tn trong sut > 13

2/ Phng php phn tn mt pha hu c c RHLB bit.

C th trn cht nh ha c HLB cha bit theo t l thay i vi mt cht nh
ha c gi tr HLB bit to ra mt nh tng c du bit RHLB. Hn hp cc
cht nh ha cho mt nh tng bn nht l HLB bng RHLB ca du to nh. D dng
xc nh gi tr HLB ca cht nh ha cha bit bng cch khu tr n gin.
Xut pht t cht hot ng b mt c HLB bit v cht nh ha c RHLB xc
nh c th bng cch so snh bit HLB ca mt cht HBM cha bit hay mt pha
hu c c RHLB cha bit.
Phng php ny da trn thc t l nh tng bn nht thu c theo phng
trnh HLB = RHLB c tha mn.
Gi tr HLB ca cht HBM hay hn hp cht HBM thu c nh tng bn
vng nht vi du hay mt tng hu c m HLB ca chng bng nhau trong iu kin
nhit v tinh khit ca nc xc nh. Trong thc t nc s dng l nc ct
nhit 18-200C (nhit mi trng). Trong mt s trng hp cn thc hin to nh
tng vi nc c cng nht nh.
Gi tr HLB ca hn hp cht hot ng b mt v gi tr
RHLB ca mt hn hp du c th c tnh theo cch:

HLB hay RHLB hn hp = HLB hay RHLB ca FB1 HLB hay RHLB ca FB2

FP1 v FP2 l k hiu trng lng ca hn hp hay cht HBM hay du trong nh ha.
Bng gi tr HLB i vi cht HBM v RHLB i vi pha hu c to nh c
cho chung bng 4.3.
Phng php thc nghim c th kim tra bn ca mt nh tng thu c khi
s dng mt dy cc cht nh ha c HLB bit trong gii hn 10-20%.
Nu to ra nh tng du trong nc, v d du thc vt (ng) trn vi mt dy
cht nh ha khng ionic nh nonylphenol oxietylen loi 2, 3, 4, 5, 6
C9H19C6H4O(CH2CH2O)nH
Phn t oxietylen c gi tr HLB nm gia 1 -15 v khi xc nh bn ca nh
tng nhn c, gi tr HLB th hin loi cht nh ha cho nh tng bn nht
trong iu kin thc hin lun lun ng nht. Nu v d HLB l 10 th mt cht nh
ha khc cng c gi tr HLB l 10 c th thc hin th trong iu kin tng t nhau.

40
 Cc cht nh ha thin nhin khc nhau c cng gi tr HLB ni chung c kt qu
tt. Ta c th chn mt dy cc cht nh ha c nhm a nc v k nc ph hp v
trng lng phn t thch ng tt hn.
V d to ra nh tng m ng vt, cc ancol etoxyl bo cho kt qu tt hn
nonyl hay octyl phenol etoxyl c gi tr HLB cng loi.
3. Xc nh gi tr HLB ca cht nh ha.
V d mt hn hp gm 25% cht nh ha A (gi tr HLB cha bit) v 75% cht
nh ha B (HLB = 12) m RHLB ca du nh ha l 10, gi tr HLB ca cht nh ha A
l:
12 75 HLB 25 RHLB 10
100
(12 75) + (HLB 25) = 1000
25HLB = 1000 12 75 = 1000 900 = 100
100
HLB ca cht nh ha A = 4
25

4. HLB yu cu hay RHLB.

HLB yu cu i vi mt nh tng ca mt hp cht k nc l du, m, glixerit
hay hirocacbon l nh th no?
Theo nh ngha HLB, phi c mt cht nh ha iu ch c mt nh tng
trong mt iu kin nht nh ca hp cht to nh. R rng phi c iu kin ch to
nh (nhit , thi gian, s to mui), loi nh tng c kho st (nc trong du,
du trong nc, vi nh).
Trong phn ln trng hp, hn hp ca cc cht nh ha cho kt qu tt hn. C
th xc nh RHLB nh mt gin n gin cc lng tng ng ca cht nh ha
thu c gi tr RHLB. V d trn hai trc thng ng ca gin , pha tri ghi gi tr
HLB t 4-9 cn pha trc phi ghi tip gi tr 9-14; t l phn trm trng lng ca hai
cht nh ha ghi trc nm ngang, gi d chn hai cht nh ha c HLB la 4 v 12, mt
im nm trn ng ni hai trc (4-12) ch ra RHLB v pha trc ngang cho bit t l
trng lng ca hai cht to nh (hnh 3.11)

41
 Hnh 3.11 Gin xc nh HLB ca cht nh ha.

Xin nhc li rng vic s dng mt cht HBM hng a nc thu c mt

vi nh rt bn sau khi xc nh c hn hp cht nh ha p ng tt nht gi tr
RHLB.
HLB cng nh RHLB cn phi ly mt ch s nh th no l khng th b qua
phn thc nghim.
s to nh ti u: cn la chn cht HBM c gi tr HLB ph hp vi gi tr
RHLB to nh, ngoi ra cng cn ch n cc iu kin khc nh nhit , pH, s
mui ha ca dung dch nc, in tch ion v cui cng tnh n gi thnh. Nhng
yu t trn s gip cho la chn mt cht nh ha ti u. C th s dng mt hn hp
cc cht nh ha, tnh ton t l cho mt gi tr HLB ca chng ph hp vi RHLB
ca s to nh.

42
 Chng 4. Nng lng tng tc
hidrophin v lipophin
bn ca cc nh tng c to ra t hn hp cht nh ha v cht to nh
c thc hin t nhiu nm qua v ngi ta ch to ra nhiu sn phm ph tr c
s dng trong nhiu ngnh cng nghip. S nghin cu v cc cht nh ha v bn
ca chng ch ra rng cc nh tng bn nht c ch to tt nht cui cng cng b
phn tch thnh hai, ba pha c nng cc cht hot ng b mt thay i trong phm vi
ln nhng khi thm vo d ch mt lng nh ca cht HBM cng nh hng n
bn ca nh tng do y s nghin cu su v s tng tc gia cc pha.
4.1. Khi nim Winsor v s tng tc trong h nh tng
4.1.1. S tng tc ca h.
Winsor1 nghin cu nhiu h nh tng v ch ra s chuyn ha t h ny sang
h khc c thc hin nh th no khi ch n s tng tc ca cc cht hot ng
b mt (cht nh ha), pha hu c (cht to nh) v mi trng nc ca s phn tn.
Trong th nghim ny bn cht ca cc hp cht ha tan trong pha ny hay pha khc nh
mui v c, dung mi, cc cht khc thm vo c th phn ng c gia cc mch
cacbon, gia cc u hirophin ca hp cht lng tnh in (amphiphil) l cht HBM
(tensio-actif) v cht h tr HBB (cotensio-actif) (hnh 4.1.).

Hnh 4.1. Tng tc nc du ca mt nh tng giao din hai pha .

43
E00 : Nng lng tng tc gia cc phn t pha du.
Eww : Nng lng tng tc gia cc phn t pha nc.
ELCO : Nng lng tng tc gia cc mch lipophin ca cht HBM v ca phn t
du.
EHCO : Nng lng tng tc gia phn a nc ca cht HBM v ca phn t du.
ELL : Nng lng tng tc gia hai phn k nc ca cht HBM.
ELCW : Nng lng tng tc gia phn k nc ca cht HBM v phn t nc.
EHH : Nng lng tng tc gia hai phn a nc ca cht HBM.
EHCW : Nng lng tng tc gia phn a nc ca cht HBM v phn t nc.
C : phn tip gip hai pha (giao din ) W : pha nc
O : pha hu c E : nng lng tng tc
Nng lng tng tc trong h c th phn thnh hai loi:
1. Nng lng hirophin (a nc)
l tng tc tnh in do cc in tch ion v cc lng cc thun t, cc
lin kt hiro.
2. Nng lng lipophin (k nc)
l tng tc in ng hc do s chuyn ng ca cc electron trong phn
t, chnh l tng tc gia cc phn t.

4.1.2. T s nng lng hirophin v lipophin.

hin i ha quan nim ny, Winsor a ra t s R ca nng lng tng
tc lipophin v hirophin ca cc hp phn khc nhau c mt trong h nh tng:

Eco
}

ELco EHco Eoo Ell

R
ELcw Ecw EHww EHH
}

Ecw

ECO : Nng lng tng tc gia lp tip gip v pha du

ECW : Nng lng tng tc gia lp tip gip v pha nc

T s hirophin/lipophin lp tip gip nc/du.

T s R ,theo Winsor l nng lng tng tc ca mt n v b mt lp tip
gip gia pha du lng tnh (amphiphile) vi nc. Trng hp tnh gn ng
c th vit :

E CO
R
E CW

44
 C s khc nhau v s tng tc gia cc phn t c mt trong pha nc v
trong pha du th hin gi tr ECO v ECW :
Gi tr ECO th hin nng lng tng tc gia phn k nc v phn a nc
ca cht HBM vi cc phn t du :
ECO = ELCO + EHCO
ELCO : Nng lng tng tc gia phn k nc ca cht HBM v phn t
du.
EHCO : Nng lng tng tc gia phn a nc ca cht HBM v phn t
du.
Gi tr ECW th hin nng lng tng tc ca phn k nc v phn a nc ca
phn t cht HBM vi cc phn t nc :
ECW = ELCW + EHCW
ELCW : Nng lng tng tc gia phn k nc ca cht HBM v phn t
nc.
4.1.3 Cu to h WINSOR
Khi trn ln ba cu t du,nc v cht HBM vo nhau ty theo bn cht v t l
cc cu t trong hn hp m c th thu c cc h khc nhau di y ( hnh 4.2) :
1- H WINSOR I gm 2 pha : pha du (O) trn v pha vi nh tng (M) di.
2- H WINSOR II gm 2 pha : pha vi nh tng (M) trn v pha nc (W) di.
3- H WINSOR III gm 3 pha : pha du trn,pha vi nh tng gia v pha nc
di .
4- H WINSOR IV gm mt pha ng nht : pha vi nh tng.

O O
M M M
M
W W
WINSOR I WINSOR II WINSOR III WINSOR IV
Hnh 4.2 Cu to h WINSOR
O - Pha du , W - Pha nc , M - Pha vi nh tng

4.1.4. Cu to cc pha trong h Winsor.

Theo Winsor cu to ca cc pha c mt trong h pht trin theo t s R ca nng
lng tng tc.
Nu R<1 mng lng tnh (amphiphile) tr nn li vi nc, thun li hnh thnh
mixen S1 du trong nc ( hnh 4.3).

45
 Hnh 4.3. Mng lng tnh du trong nc.

Nu t s R>1, mng lng tnh (amphiphile) tr nn lm so vi nc, mt li

i vi pha hu c thun li hnh thnh mixen 2 nc trong du (hnh 4.4)

Hnh 4.4. Mng lng tnh nc trong du.

Hai m hnh cu to ny gp trong pha vi nh tng (winsor IV) trong loi

winsor I v winsor II.
Theo quan nim winsor, R khng c mt gi tr c nh m c s dao ng t mt
im ny sang im khc, t mt khong thi gian ny sang khong thi gian
khc.
Ngoi ra n cn c cu to phao gia dng nc trong du v du trong nc, c
th d dng nhn ra cc im ht nc hay du trong nh hnh di (hnh 4.5).

Hnh 4.5. Cu to phao.

46
 Nu R = 1, nng lng tng tc gia cc pha hirophin v lipophin (interphase)
bng nhau. Trng hp ny cho winsor III hay c ba u c mt. Vi nh tng
cn bng vi pha hu c v pha nc.
Trng hp ny xut hin hai dng cu to:
+ Cu to lp.
Cu to ny c to ra bi s sp xp u n nhiu hay t ca cc phn
t cht HBM trong cc pha hu c hay pha nc to ra cc lp mng nc, du
xen k nhau (hnh 4.6)

Hnh 4.6. Cu to hnh l.

+ Cu to phao.
Trong cu to ny c mixen S1 v S2 tn ti, y mng HBM hoc bao vy du
hoc bao vy nc (hnh 4.7).
S bin i t h ny sang h kia c th thc hin bng cch can thip vo s
tng tc mt pha, ELL- tng tc gia cc mch lipophin ca cht HBM. E HH-
tng tc gia cc u hirophin ca cht HBM. Cc yu t ny lm gim nng
lng ca h dn n mt h mi.

Hnh 4.7. Gin hn n ca h nc/kali laurat (mu V.Luzatti).

Trong thc t, bng cch tng nhit hoc thm vo mt hp cht lng tnh
(amphiphile) nh cc cht HBM (ancol, amin, axit), cc cht ny c kh nng nm
gia cc pha ca cht HBM lp tip gip nhng cn bng pha hu c hay pha nc
v c kh nng thay i nhanh chng gia cc pha mnh hn tc dng ca nhit .
Nh vy c th bin i cu to ca h nh tng (du tan, sa) bng cch
thm vo mt lng nh cht HBM thay i bn ca h.
47
4.1.5. Thay i t s R.
Nhiu yu t khc nhau c th thay i t s R v pht trin h thng nh cho cc
h khc nhau, vi nng lng tng tc khc nhau gy ra s chuyn ha h nh lm
thay i tr s R hot ng dn n s thay i cu to mixen c gii thch v c ch
theo hnh 4.8. V d nh thm ancol vo mt cht HBM

Hnh 4.8. S thay i lng cht HBM dn n s thay i cu to mixen

Trn c s v s thay i nng lng tng tc, ngi ta c th d on c

hiu qu ca m hnh, iu kin vn hnh v la chn bn cht ca cht ph tr b sung
vo h nh.

4.2. Cc v d ca s bin i nng lng tng tc.

Gi tr R c th thay i khi c s can thip sau y:
Thm dung dch mui vo nc dn n R tng

48
 S thay i lng mui ca pha nc lm nng lng tng tc gia u
hirophin ca cht HBM v mi trng nc b gim, n lm thay i mt phn
nh bn ca s phn tn v EHCW suy gim.
Thm vo mi trng gia cc pha (interphase) mt hp cht nhiu u
hirophin dn n R gim.
Trng hp ancol c phn t lng thp, amino-ancol l cht HBM thm
t, nng lng tng tc gia phn k nc ca cht HBM v pha hu c EL CO
gim th h i t winsor II sang winsor III ri sang winsor I.
Thm vo pha nc mt hp cht ha tan, c trng lipophin dn n R gim.
iu ny quan h c bit n s thay i chiu di mch ancol c s dng
lm cht HBM. Trong trng hp ny nng lng tng tc gia mch cht
HBM v pha nc ELCW tng. H i t winsor II sang winsor III ri sang winsor
I.
Gim lng nc dn n R tng
Nng lng tng tc mi trng gia cc pha (interphase) v pha nc
ECW gim, tun theo nh lut tc dng khi lng. H i t winsor I sang winsor
III ri qua winsor II.
Thm dung mi phn cc vo pha hu c dn n R tng
Nng lng tng tc gia u hirophin ca cht HBM v phn t du tng.
H i t winsor I sang winsor III ri qua winsor II.
Thm c trng lipophin ca pha trung gian (interphase) dn n R tng.
y c th tin hnh theo cc cch khc nhau:
+ Bng cch tng di mch ca hp cht HBM, nng lng tng tc gia
mch lipophin ca cht HBM v pha du ELCO tng.
+ Bng cch thay th mt ion kim loi ngc bng mt ion hu c ngc, nng
lng tng tc gia u hirophin v phn t ca mi trng nc EHCW gim.
+ Bng cch phn nhnh mch cacbon lipophin ca cht HBM, tng tc gia
cc mch cht HBM ELL gim.
Trong ba trng hp, h i t winsor I sang winsor III ri qua winsor II theo
s quan trng ca s thay i.
Thm vo pha du mt cht t hirophin dn n R gim.
iu ny lin quan n vi c s dng dung mi bo ha nh mch
hirocacbon no, du th
Nng lng tng tc gia mch lipophin ca cht HBM v pha nc AL CW
gim, trong khi nng lng tng tc gia phn t du E OO tng. H i t winsor
II sang winsor III ri winsor I.
Tng khi lng phn t ca cht to nh dn n R gim.
Trong mt dy cht mch bo ha c cho, nu tng chiu di mch cht to
nh th nng lng tng tc gia phn t du EOO tng v ngc li th nng
lng gim.
Trong trng hp u, n i t winsor II sang winsor III ri sang winsor I: R
gim.
Trong trng th hai, h i t winsor I sang winsor III ri winsor I: R tng.
Thay i pH ca mi trng.

49
 + pH ca mi trng thp dn n R tng
+ pH ca mi trng cao dn n R gim
Mt s cht HBM c axit hu c, mt vi cht h tr HBM (cotensio-actif)
c la chn l axit bo. D l phn cc, cc axit hu c c trng lng phn t
cao cng t tan trong nc v EHCO ca n tng: R tng.
Nhng khi pH ca mi trng ca s phn tn tng, mui axit hu c c hnh
thnh l hirophin mnh v ELCW gim: R gim.
H i t winsor II sang winsor III ri n winsor I.
Bng 4.1 cho mt s v d v s thay i iu kin nh hng n lc tng tc
v gi tr R.

Bng 4.1 Thay i iu kin x l.

Thay i c trng ca h C ch gy ra R
Gim lng nc ECW gim Tng
B xung:
Dung mi phn cc vo cht bo EHCO tng Tng
Vo lp tip gip cht lipophin (ancol nng) EHCW gim Tng
Mui ha tan EHCW gim Tng
Vo tng nc mt ancol nh ELCW tng Gim
Vo lp tip gip hp cht hirophin (thm t) ELCO gim Gim
Vo cht bo hp cht lipophin ELCW gim v EOO tng Gim

4.3. S la chn cc cht ng hot ng b mt (cotensio-actif)

Trong mt dy cc cht HBM c s dng iu ch cc nh tng nh axit,
ancol v glycol, c mt v tr quan trng iu chnh h nh tng, chng c gi l
cht ng hot ng b mt ( HBM ).
iu chnh du ha tan ngi ta thng s dng cht ng hot ng b mt
l axit hu c nh axit oleic, axit naphtenic, axit resimic. Thun li ca cc cht ng
hot ng b mt loi ny l ngi ta c th iu chnh lipophin hay hirophin ca
chng d dng bng cch trung ha hn hp cht nh ha v cht to nh
(mulsifiants/mulsifis).
Cc ancol phn chia nhiu hay t theo trng lng phn t ca n gia cc pha
nc, pha tip gip v pha du, biu l tng i nhy cm theo bn cht v lng s
dng ca n, theo nng lng tng tc can thip t s winsor R v c bit theo nng
lng tng tc gia cc mch lipophin ca cht HBM EL CO v nng lng tng tc
gia u phn cc ca cht HBM v pha nc EH CW.

4.3.1. ng dng ca ancol v glycol.

Trong dy cht ng HBM cha nhm chc ancol, cn phn bit hai nhm
khc nhau: mt nhm rt hirophin v mt nhm lipophin nhiu. Theo tiu chun ny
chng c s dng to ra cc nh tng ti u vi lng s dng mt lng nh
cp cht hot ng b mt v ng hot ng b mt (HBM v HBM).

50
 Tng nng lng tng tc ca cc cp HBM/HBM theo n v b mt
gii hn ca hai pha c cho bi ELCO v EHCW nh ni trn:
EL CO X t ELtCO YC ELcCO
v EH CW X t EH CW
t
YC EH cCW
y Xt v Yc l t l cht HBM v HBM vi Xt + Yc = 1

ELCO ELtCO , ELcCO , EH CW

t
, EH cCW l nng lng tng
tc sinh ra bi cc phn t ca cc cht HBM
Et v ca cc cht h tr HBM EC.

EHCW
Vi cc ancol v glycol theo hng lipophin, ni chung khi mch cacbon ca
chng c nhiu hn 4 nguyn t cacbon th:
ELcCO ELtCO v EH cCW EH CW
t

iu ny dn n lm gim s tng tc gia pha tip gip v du, pha tip gip
v nc, ngay khi tng lng cht HBM vo tng tip gip.
S gim nng lng bng cch s dng ancol theo hng lipophin khng phi v lp
nc m v lp du v lm gim rt nhanh lp nc so vi lp du. S gim nng lng
khng phi cng mt cch khi m XEtLCO - YEcLCO khc vi XEtLCW - YEcLCW.
i vi ancol lipophin XEtLCO - YEcLCO << XEtLCW - YEcLCW v t s R tng,
thay i cc loi winsor I, winsor III v winsor II.
Ngc li khi s dng cc ancol mch cacbon t hn 4 cacbon (metanol, etanol,
propanol) tnh hirophin nhiu hn lipophin, bc chuyn ngc li.
XEtLCO - YEcLCO > XEtHCW - YEcHCW
T l cht HBM/HBM (ng HBM) X t v Yc l hon ton xc nh khi
tng gim hiu qu nhn c. i khi s dng nhiu cht HBM m trong mt vi
cht c hng hirophin v mt vi cht khc hng lipophin nh isopropanol trn vi
octanol. H chuyn t winsor II sang winsor III ri winsor I.

4.3.2. ng dng axit hu c.

Bit rng axit oleic c HLB bng 1 trong khi x phng kali c HLB bng 20, vy l bng
cch thm mt lng no ca tc nhn kim vo nh Natrihiroxit hay Kalihiroxit
(xt hay potat) m c thu c mt dy s thay i ca nng lng lipophin/hirophin
gii hn tip gip pha du v pha nc bi v axit hu c ha tan rt nhiu trong du,
cn x phng ca n tan hon ton trong nc.
Cht HBM cha nhm hiroxyl ancol thng c thm vo h nh tng
phc v hiu qu theo hng hirophin hay lipophin lm tng bn ca nh,

51
 hoc l ha tan ca cc cht gia chng,. Cc ancol tan trong tt c cc axit v
x phng ci thin thm b mt sn phm v bn lnh.
Theo l l ny thc t ch ra rng mi loi cht HBM l cht nh ha u c cho
km thm mt lng nh cht HBM khong 1 n 2%.
V mt kinh t iu ny rt c li v gi cht HBM r hn cht HBM, cho
php gim gi thnh.
Trong cng nghip cc cht HBM hay dng nht l axit oleic, axit bo hoc
hn hp ca cc axit bo tng t nhau nh axit bo ca m ng vt, du thc
vt nhng rt t dng axit mch ngn.
Ty theo pH iu chnh ta c th thy mt cht lipophin axit bo trong mi
trng axit hoc mt cht HBM rt hirophin x phng trong mi trng
kim.
Kt qu nng lng tng tc ca cp HBM/HBM i vi mt n v b
mt gii hn hai pha c cho bi t s ECO/ECW thay i theo pH ca h.
nh hng ca pH
Thc t pH 4, khng c mt x phng cn pH ln hn 8,5 tt c axit bo
chuyn thnh x phng.
T s t (HBM) v c (HBM) khng thay i nhng bn cht ca HBM
khc bit nhau theo gi tr pH trong vng 4 n 8,5.
ELCO = X t ELtCO Yc ELCCO
Nng lng tng tc gia mch lipophin ca cp HBM/HTHBM v cc phn
t du bng tng nng lng ring tng ng bi cht HBM v HTHBM theo
t l chng c mt:
EH CW X t E t H cCW YC E C H CW
Thm ch nng lng tng tc gia u hipophin ca cp HBM/HTHBM
bng tng nng lng ring tng ng bi cht HDBM v HTHBM theo t l
ca chng c mt:
ELCO v EHCW theo gi tr pH trong vng ny bi v hai s hng YcEcLCO v
YcEcHCW ph thuc ln nhau, s hng u gim th s hng sau tng v ngc li.
T s YcEcLCO/ YcEcHCW ch ra gi tr cn bng hirophin/lipophin ca cht
HTHBM, ngha l t l tng ng ca axit bo v x phng c mt (bng 4.2,
hnh 4.9).
Bng 4.2. Axit oleic, t l x phng/axit bo ph thuc vo pH.
pH % x phng natri % axit bo
5,0 0,6 99,4
5,5 2,1 97,9
6,0 8,5 91,5
6,5 19,5 80,5
7,0 37,7 62,3
7,5 59,9 40,1
8,0 78,5 21,5
8,5 91,5 8,5
9,0 97,9 2,1
9,5 99,0 1,0

52
 Hnh 4.9. Nng % x phng natri ph thuc pH.

Khi pH 6,5/7; n c hng lipophin ph hp vi s hnh thnh vi nh

nc trong du v ta c: XEtLCO - YEcLCO < XEtHCW - YEcHCW
Khi R tng c s chuyn ha ln trong h : winsor I chuyn sang winsor III
ri sang winssor II.

Thc t loi du gi l tan cha axit bo nh l cht HBM lun lun c

pH trong nh tng ln hn 7,5 v n c xc nh cho nh tng du trong
nc, i khi c bn ln v chng c ti to thng xuyn. S iu chnh
cc loi ny nh cc tc nhn trung ha c bn cht khc nhau m n ph thuc
vo iu kin la chn to nh tng.
Mt s axit hu c lm cht HBM.
+ Axit bo thng dng
- Axit lauric - Axit palmitic
CH3-(CH2)10-COOH CH3-(CH2)14-COOH
- Axit oleic - Axit stearic
CH3-(CH2)7CH=CH-(CH2)7-COOH CH3-(CH2)16-COOH
+ Ancoliaxit OH
Axit tartric Axit quang hot
H C COOH 0
c 168-170 C
H C COOH Axit khng quang hot
c 1600C
OH

53
+ Ancol triaxit
Axit xitric
CH2 COOH rn, tr
ng
HO C COOH c 1550C
CH2 COOH
+ Axit resinic (thnh phn chnh ca colophan)
H3C COOH n, d20 1,07-1,1
cht r
chs axit: 150-155
chs x phng 150-200
chs iCt 105-115
H3C
CH(CH3)2
+ Axit naphtaleic
HOOC COOH
dng nh o
chs axit: 170-230
c 140-1500C
+ Axit malonic
COOH
rn, tr
ng
CH2 c 1350C
COOH
+ Axit maleic
CH2 COOH rn, tr
ng
CH2 COOH c 1300C
+ Axit sucxinic
COOH
CH2 rn, tr
ng
CH2 c 1850C
COOH
+ Axit aipic
CH2
COOH
CH2 rn, tr
ng
CH2 c 1520C
COOH
CH2

54
4.4. Mt s v d n gin ng dng thc t. Khi nim winsor.
4.4.1. Du sunfat ha hay sunfo ha.
Du sunfat ha hay sunfo ha biu hin tt c c trng ca sn phm h tr c
th cho s phn tn nc hay du theo iu kin c th thc hin; du sunfat ha hay
sunfo ha cha ng tt c cc yu t cn thit iu ch mt h phn tn.
Cht hot ng b mt: Phn t du c gn nhm SO 3 hay OSO3 th hin ra
hm lng SO3 lin hp, phn trm ca sn phm cui. Lng phn t sunfo ha
trong du thng mi l 10-20% ca hn hp.
Cht h tr HBM: Cc axit bo t do c hnh thnh trong qu trnh sunfo ha
hay qu trnh ra axit ca sn phm sunfo ha c mt ng thi sn phm cui.
Cht to nh: Mt phn du khng tham gia vo phn ng sunfo ha, cu to ca
n gn vi loi du ban u, chim 50-60% hp phn.
Nc: Phn nc cn li sau khi ra sn phm sunfo ha v nc dng iu
chnh nng sn phm.
Mui: C mt trong dung dch ra l NaCl hay Na 2SO4. Mui xut hin trong qu
trnh trung ha bt lng axit ca sn phm ty theo tc nhn trung ha.
Nh vy, trong du sunfat ha hay sunfo ha cc yu t cu to ca mt nh
tng hay ca mt vi nh, t l tc nhn h tr HBM hirophin qui c theo s trung
ha sn phm.
Sn phm l vi nh du trong nc, hm lng ca nc chim 12-15%. Sn
phm thng mi thng b xung thm nc t 23-25%.
Du sunfat ha hay sunfo ha thng mi l vi nh nc trong du thng bn
nht nhit 10-500C, i khi c cha mt t axit bo t do hay glixerit bo bo ha
hay x phng do thi gian lu kho di, cn cho thm mt t cht h tr HBM
hirophin.

4.4.2. Du sunfat ha hay sunfo ha v nh tng nc ca n.

Khi pha long du sunfo ha (nh tng du nc trong du) vi nc nhit
khc nhau cho mt nh tng nc du trong nc m dng ca n l sa, thng c
mu trng sa i khi trong sut, dng nh tng nc, nm phn tri ca gin ba
pha i vi nh (nc), ph thuc vo hm lng SO 3 c trong du ngha l lng tc
nhn nh ha c mt cng nh pH trung ha, khi n cao th hm lng x phng cao.
Khi hm lng cht nh ha (SO 3 kt hp < 3%), trung ha sn phm
pH=7 thu c mt vi nh. H i t winsor II sang winsor IV (vi nh), trung ha d c
th chuyn sang winsor I.
C th tng pH khi nh tng nc khng tr thnh trong sut pH > 7. Nhng
khi tng hm lng cht HBM hirophin, x phng tc nhn nh ha hiu qu, h
chuyn t winsor III sang winsor IV.
Du sunfo ha lm sng t ch li ca vic nghin cu t s R ca winsor.
Trong cng nghip sn xut c du sunfat ha hay sunfo ha gm cc loi ty
theo mc sunfat ha hay sunfo ha ca chng. Ngi ta c th chuyn ha nh tng
nc trong du sang nh tng du trong nc ty theo ng dng trong cng nghip (da,
giy, dt).

55
 R rng du sunfo ha v du sunfat ha c th phc v lm cc cht ph tr nu
trn ln vi cc du thc vt v ng vt khc, du khong v c nhng hp cht hu c
khc nh l cht hot ng cho phn tn.
Tt c cc cht to nh ny c th thay i trong gin pha, tng hay gim vng
vi nh theo bn cht ha hc xc nh tnh cht ring ca cn bng hidrophin/lipophin.
Du sunfat ha c tnh cht c bit ring ty theo cu to ca n tc l theo bn
cht v ngun gc ban u ca du.
Glixerit ca axit rixinoleic (du rixin) cho sn phm rt khc du triglixerit oleic
(du hng dng) hay mt loi du bo ha nh du da cho sn phm anpha sunfo
ha bng cch sunfonic ha.
Du sunfat ha hay sunfo ha khc bit nhau mch nhau mch di hay ngn, bn
cht v v tr ca du hydrophile (SO 3) trn mch cacbon, s v loi du hydrophile, bn
cht ca tc nhn trung ha, quan trng ca axit t do v pH iu chnh ( bng 4.3).
Lc nhm sunfonic tng dn theo th t:
O
SO3- M+, - +
C O C SO3 M , CH C O R, CH CH
SO3- M+ - +
H H OH SO3 M
sunfat sunfonat -sunfonat hiroxisunfonat
Bng 4.3. V tr ca mt s nhm SO3H trong du sunfat ha v sunfo ha.
O
CH3 (CH2)7 CH CH2 (CH2)7 C
O SO3- +
M OR

Mch oleic sunfat ha. Tc dng ca axit sunfuric

O
CH3 (CH2)7 CH CH2 (CH2)7 C
SO3- M+ OR

Mch oleic sunfo ha. Tc dng ca bisunfit

O
CH3 (CH2)7 CH CH CH2 (CH2)7 C
OH SO3- M+ OR

Mch oleic hiroxisunfo ha. Tc dng ca anhirit sunfuric

O
CH3 (CH2)9 CH C
SO3- M+ O R

Mch lauric -sunfo ha. Tc dng ca oleum

+
M kim loi kim
R gc iglixeric ca phn du thin nhin

Lc ionic ca nhm sunfonic c nh trn mch hirocacbon ph thuc khng ch

vo v tr v dng lin kt, m cn ng u cc v tr khc nhau c mt trn phn t.

56
i vi cng mt phn t, nhm sunfat km hot ng hn nhm sunfonat v ngi ta
xc nhn rng i vi mt du sunfat ha, t l ca SO 3 kt hp phi l gp i t l ny
ca du sunfo ha thu c mt vi nh du trong nc. Ta c th kt lun rng phn
t du bo sunfo ha c tc dng nh ha gp hai ln du sunfat ha.

4.5. Mt s v d v ng dng cht h tr hot ng b mt.

4.5.1. ng dng trong iu ch du sunfat ha hay sunfo ha.
thu c mt vi nh xut pht t du c sunfuat ha, du sunfo ha c iu
ch theo tc dng ca bisunfit natri, phi s dng hexyl glicol-(2-metyl-2,4-
pentaiol):
OH OH
CH3 C CH2 C CH3
CH3 CH3
Trong s ioleat glicol, este sunfo ha th butyl iglicol cho kt qu tt thu c
mt vi nh:
CH3 CH CH2 OH CH3 CH2 CH CH2 CH3 (CH2)7 CH CH (CH2)7 COOH
OH OH OH
Propyl glicol 1,2-butyl glicol axit oleic
CH3 (CH2)7 CH CH (CH2)7 C O CH2 CH CH3
O
lng gn trong mi trng axit mnh, mt du c sunfo ha nhiu, vi dung
dch ra c 10% NaCl cho mt nh nc trong du tng i bn, khi thm ancol
etylic vo to ra pha tip gip hirophin mnh v gy ra s lng ng tc thi.
Lng cn thit: 1% ca ancol etylic
gn lc du sunfit ha cui giai on sunfua ha, theo cch trn, thm mt
lng nh (0,1-0,2%) ca ioctylsunfosucxinat natri, sn phm hirophin thm
t mnh.
H17C8OOC CH2 CH COOC8H17
SO3- Na+
thu c mt vi nh xut pht t du gc sunfat ha, pH trung tnh, thm 0,5
n 1% ancol etylic ha tan cc tng khc nhau ang c mt.

4.5.2. ng dng trong s to nh vi cc hp cht baz ca este poliglicol.

i vi baz khng ionic, cc este bo ca polietylen glicol 400, cht nh ha
hirocacbua, nu to ra mt nh tng nc trong du, s dng hexyl glicol.
i vi nh tng du trong nc ancol etylic l thch hp, n cho php thu c
mt nh tng mu xanh, cht thm t, t l este oleic ca PEG 400 l 12-13% trng
lng hn hp.
(PEG: polietilen glicol)

57
4.5.3. ng dng trong cc cht m phm.
Thnh phn ca cc cht m phm rt khc nhau tu theo cng dng ca chng
nh cc cht to bt, x phng tm, cc sn phm sa, kem, nc gi u, cht n
nh .v.v..
Trong phn ln cng thc, ngi ta khng nh s c mt ca cc cht khc nhau,
thng c mt cc cht HBM mt lng nh lm bn vng cc hp phn v s
phn tn ca chng trong nc tt hn.

4.5.4. ng dng trong du ha tan.

Sn phm ny thng c mt cht nh ha anionic trn vi cht nh ha khng
ionic.
S c mt ca axit bo gp phn vo trung ha mt phn baz kim loi kim hay
baz hu c cho mt h nh ha hirophin chng n mn. S thm vo mt lng nh
cc ancol phn t lng thp (etanol, propanol, isopropanol) cho kt qu tt ca cc hp
cht thng mi m c nhng tinh xo v bn vng nh tng nc nng 1-3%.

58
 Chng 5. Nh tng v vi nh tng
Nh tng v vi nh tng l cc hin tng thng gp v c ngha quan
trng trong i sng v trong nhiu nghnh cng nghip nh cng nghip ch bin du
m,cng nghip sn xut sn, mc in, polime ,thuc bo v thc vt

5.1. Nh tng.
Trong phn ln trng hp mt trong hai pha ca nh tng l nc v ngi ta
phn bit hai trng hp:
- Nh tng nc trong du hay a du, l trng hp mi trng phn tn
l du.
- Nh tng du trong nc, l trng hp mi trng phn tn l nc.

5.1.1. S hnh thnh ca nh tng.

Khi cho mt t nc v du vo mt bnh ri khuy mnh ln, thy xut hin cc
ht du l lng trong nc nhng sau khi ngng khuy th cc ht du ny li t li vi
nhau v to thnh hai lp trong bnh, lp nc v lp du.
Nu by gi cho thm mt cht HBM vo ri khuy mnh ln s xut hin li
cc ht l lng to ra mt nh tng. S bn vng ca nh tng ny ty thuc vo loi
cht HBM v t l ca chng.
Mt s cht c sc cng b mt nh nh gm ( nha cy) c th ci thin bn
ca nh, bng cch lm tng mt trong hai pha, lm tng thi gian tn ti ca s phn
tn, lm chm li s phn tch thnh cc pha ring bit.
Cc phn t nh trong mt pha lng di dng siro chuyn ng t do lin tc
c gi l chuyn ng Brawn. Cc phn t nh ny cng gp phn ngn cn s phn
tch thnh cc tng. Hin tng ny c gi l hin tng Duclaux.
Theo cch ny c th thc hin s bn nh tng bng cch thm cc ht nh
cht rn rt mn vo hai pha, n khng c tc dng vi hai pha nhng in tch ca cc
ht ny nh nhau nn y nhau. Mt s cht bn keo ngn cn s t tp li thnh cc ht
ln.

5.1.2. S ca s to nh tng.
Biu din gin ca hai dng nh tng nc trong du v du trong nc l
c trng cho s nh hng ca phn t cht nh ha trong hai mi trng ny (hnh
5.1).

59
 Nc trong du Du trong nc
hay a du hay a nc
Hnh 5.1. Nh tng nc trong du v du trong nc.

Trong nh tng nc trong du, phn k nc (hirophob) ca phn t cht nh

ha nm mi trng phn tn, ngc li trong nh tng du trong nc n nm
trong ht du.
Hai dng nh tng nc trong du v du trong nc c to ra v bn vng
ph thuc vo bn cht ca cht nh ha c s dng theo cn bng hirophin/lipophin
l hirophin nhiu hn lipophin v ngc li.
Ngi ta khng th nhn c nh tng du trong nc bng cch ch cho du
vo nc hoc nh tng nc trong du bng cch cho nc vo du, m phi c t l
gia chng v cht nh ha.
Mt s phn bit cc kiu nh O/W v W/O c th thc hin nh mu tan trong
nc v tan trong du. u tin l mu tan trong pha phn tn ca nh tng du trong
nc v mu ca mi trng, pha th hai l khng ch tan trong pha phn tn ca nh
tng nc trong du v mu. Ngc li khi chp nh micro mu ca nh tng nc
trong du nh mu organol v mu ca nh tng du trong nc l mu xanh ca
nh metylen.

5.1.3. S phn b ca phn t cc cht nh ha.

Nu nh c hai cht lng khng trn ln vi nhau v c mt cht tan c trong
mt trong hai lp cht lng th thnh phn b mt khc vi trong khi th tch.
L thuyt Gibbs cho rng khi nng ca cht tan mt trong hai pha tng ln
nu sc cng gii hn tng, nng b mt phn tch ca hai pha nh hn trong
khi th tch. Nu sc cng gii hn gim, nng b mt tng so vi nng ca khi.
Kt qu l nng rt thp lng phn t cht nh ha b mt cng tng khi
nng cng tng. nng cao th lng phn t b mt b gii hn li.
Cc hp cht c th a thun li vo nh tng ca hai tng phi c trong
phn t mt nhm c i lc vi mi pha khng trn vo nhau v nm lp tip gip
gia hai pha.
Cc hp cht HBM c th c s dng khc nhau trong pha lng phi c cu
to thun li lin kt gia cc pha. Mi lin kt ny pha nc v du lin quan n cn
bng pha hirophin/lipophin ca cht HBM.

5.1.4. Tnh cht nh tng v s phn loi.

60
1. c im nh tng v vi nh tng.
S phn bit gia nh tng, dung dch mixen v vi nh tng da vo c ht
ca h phn tn sau:
Dung dch: cc ht <100 A0 (hay 10nm).
Vi nh tng: cc ht gia 100 v 1000 A0 (hay 10 v 100nm).
Nh tng: cc ht > 1000 A0 (hay 100nm).
Dng nh tng ph thuc v mc phn x ca tia sng truyn qua.
Nu chm tia sng khng phn x khi gp cc phn t ln s c dng truyn qua
to ra dung dch trong sut. Nu kch thc cc ht tng ln, chm tia sng chiu vo b
phn x li mt phn to ra dung dch trng c. Nu chm tia sng chiu vo b phn x
mnh khi kch thc ht tng ln to ra dung dch c dng sa ( hnh 5.2 ).

Hnh 5.2. C ht: 10-1-10 (dng sa), 10-4 -10-1 (trng c), < 10-4 (truyn qua)

Trong nh tng, lp gii hn nc/du to ra mt mng mng cht HBM i

lp vi s kt t ca cc ht, n cng rn v c xung tnh in. Ngc li, trong vi nh
tng lp mng mm hn nhiu.
Nh tng do cc ht ln phn x nh sng nn dung dch c dng sa .Vi nh
tng cho nh sng truyn qua mt phn v phn x mt phn nn dung dch c mu
trng c, cn thu c sau ly tm c kch thc t 50 n 100G. Dung dch tht cc
phn t nh ,nh sng truyn qua gn nh hon ton nn trong sut.
2. Cc loi nh khc nhau.
Nh tng hai pha khng trn ln vi nhau:
Nc trong du hay du trong nc khc bit nhau do mn ca cc ht v nh
nhau v tnh ng nht ca pha phn tn trong nh tng.
Nh kp nc/du trong nc hay du/nc trong du .
3. Phn loi nh tng theo mn.
Nh tng l mt h phn tn lng/lng, kch thc ca ht khong 1000nm. Khi
kch thc nh i 10 ln tr thnh h keo, khi bn knh ht c 50nm tr thnh dng sa,
nu nh hn na c dung dch tht (bng 5.1).

Bng 5.1. Cc loi nh tng.

Dng phn tn V d ca h phn tn ng knh trung bnh ca ht
Microm () Nanomet Angstron
10-6m 10-9m (A0) 10-10m

61
Nhn bng mt Huyn ph t st 500 500.000
Nhn gii hn h bt 100 100.000
Sa c sa 10 10.000
Sa trng sa ng nht 1 1.000 10.000
Sa xanh gii hn nh tng 0,1 100 1.000
Trong nh xanh Vi nh 50m 50 500
Trng c Vi nh 10m 10 100
Trong sut Dung dch mixen 2-6m 2-6 20-60

4. bn v gin pha ca nh tng.

Nu kim tra bn ca mt nh tng mt nhit xc nh cn quan st n
thay i th no vi nng ca mi hp phn trong h (xem gin tng ca h
phn tn nc).
Biu din trn mt tam gic u ba h: nc/cht nh ha/cht to nh, c th bn
ha h ny khi thay i nng mi hp phn. Mt s h cn bng c th c to ra,
mt s c Winsor m t. Cn bng c th phn loi theo winsor I, II, III, IV
(bng 5.2 ).

Bng 5.2. Cc pha khc nhau ca Winsor.

Phn loi Xc nh Hnh v
Winsor I Hai pha (du trong nc). Vi nh cha du,
nc v phn ln cht HBM v ph tr,
cn bng vi du.
Winsor II Hai pha (nc trong du). Vi nh cha
phn ln cc thnh phn cn bng vi
nc.
Winsor III Ba pha. Vi nh nc trong du nm gia
tng du v tng nc.

Winsor IV Mt tng. Vi nh nc trong du hoc

du trong nc ty trng hp.

Nu c mt h bn cu t gm pha hu c phn tn, pha nc v hn hp hai

cht nh ha c th d dng thit lp gin pha ng nhit bit c tnh cht ca
h phn tn ph thuc cc thng s khc nhau v xc nh iu kin thc t ng dng ti
u v d nng ca mui pha nc, nhit v..v.
Nh vy bn ca nh tng ph thuc lng ca cc hp phn khc nhau c
mt v nng mui ca pha nc. V vy thu c mt h phn tn ti u phi ch
thit lp t l cc cu t khc nhau c t l tt nht cc cht nh ha s dng (hay
hn hp cc cht nh ha), hiu qu ln nht l loi du to nh tng ng vi iu kin
pha ch nh nhit , nng mui trong nc, bn cht v lng cht to nh.

62
 Trong thang cht nh ha, s khng chn cht m ha tan ca n tng mnh
vi s tng nhit hay c mt mui ha tan. Khi thay i t l nng ca cht nh
ha thit lp gin ngi ta c th thay i ng k ca vng bn vng. V d khi
tng tnh a nc ca h nh s lm gim kh nng thu c mt nh bn.
Hnh 5.3 gii thiu gin pha ca mt hn hp hirocacbon, cht nh ha v
nc nhit xc nh. Trong trng hp ny xem vng vi nh 1 tng i t m
rng, n c th quan trng hn trong h khc, nhng khng tn ti trong h ba cu t.
y quan trng l xt bn cht ca cc pha gn vi cc hp phn.

Hnh 5.3. Gin pha ba cu t hirocacbua-cht nh ha-nc.

5.2. Vi nh tng.
5.2.1. Gin ba cu t ca h ba nh tng.
Vi nh tng xut hin khi phn t cht phn tn thit lp vi cc phn t nc
v cht nh ho to thnh h phn tn lng/lng trong sut ca nc v du hay nc v
mt dung mi hu c. Chng t nht, s hnh thnh chng l t nhin v khng cn cung
cp nng lng nhiu.
V d nu kho st cc vng khc nhau to ra mt gin ng nhit i vi mt
hn hp c t l thay i: hirocacbua (oecan)/HBM (p-octylbenzen sunfonat
natri)/ph tr (pentanol) v nc: winsor I, II, III v IV (vi nh tng) ph thuc vo t
l ca cc hp phn khc nhau c mt (hnh 5.4).

63
 Hnh 5.4. Cc vng winsor trong h: nc (NaCl 3g/l), oecan, natri p-octylbenzen
sunfonat , pentanol (t l 1/37).

Trong vi nh tng, lc cng gii hn nc/du l lc ko vung gc vi mt tip

gip theo n v chiu di rt nh, thc t bng khng.

5.2.2. Cc yu t nh hng n s hnh thnh v bn vng ca vi nh tng.

1. nh hng ca mn.
Cc mui v c ha tan c nh hng n tng tc tnh in.
- Lm gim s y nhau gia cc ht nc.
- Lm gim s cng ca lp gii hn t l HBM/ph tr.
- Ci thin kh nng ha tan ca pha hu c th hin ra s tng vng tn ti
ca vi nh qua s c mt mt lng nh mui (t hn 1%) trong khi mt
lng d lm gim s ion ha ca phn t cht HBM, hu qu lm gim
vng tn ti vi nh (hnh 5.5). iu ny ch c hiu qu i vi cht HBM
ionic, cn khng c gi tr i vi cht HBM khng ion ha .

64
 Hnh 5.5. Gin pha ca h nc, toluen, butanol v oexylbenzen sunfonat natri.

2. nh hng ca nhit .
Nhit nh hng n s hnh thnh ca vi nh tng v n ph thuc vo
ha tan ca cht nh ha. V d in hnh l trng hp hai pha vi nh ca este
sunfosucxinic, trong ng knh ht l 10 n 30 m khi nhit gia 150C v
360C.
Trong trng hp tc nhn HBM ionic, bn l khong rng ca nng v
nhit .
Trng hp tc nhn HBM khng ionic, mt s trong chng c im c ngha
l chng ri khi dung dch khi nhit tng, trong s ln trng hp xy ra s o pha.
Nhit ca s o pha l nhit di nhit ca h du/nc tn ti trong
khi trn nhit o pha th vi nh nc/du l duy nht.
S chuyn ha ny thay i rt nhy hnh dng ca gin ba cu t v din tch
vng tn ti ca vi nh (hnh 5.6).

65
Hnh 5.6. Gin ph thuc nhit . Dung dch isotropic (ng hng) ca oexyl ete
vi 4 mol OE-oxit etylen.

Phng php kim tra nhanh bn nh theo nhit .

Khi iu chnh nh tng nc trong du v du trong nc, mt phng
php n gin kim tra nhit thch hp tin hnh nh sau: Dng mt a thy
tinh khuy nhanh dung dch ri thm cht iu chnh nh vo. Quan st mi
trng thy c im c hay s pht sng th dng li.
Phng php ny kim tra trc tip bn ca nh ti nhit ca n khng
phi mi trng xung quanh.
Cn bng nhit ca cc hp phn ca mt h bc ba.
Pha nc v du m ngi pha mong i s phn tn ca chng nh cht
HBM khng tan ln vo nhau. Bit rng tan tng h ca hai cht lng c
th thay i nh s dng mt cht lng th ba (benzen, nc, ancol) v cn bng
nhn c c th nhy cm vi nhit . V nguyn tc khi thm mt cht lng
trn ln trong thnh phn ca hn hp ban u lm gim vng phn lp cho n
khi bin mt, ngc li, khi thm mt cht lng tan nhiu trong mt trong s cc
hp phn ca hn hp s hn ch vng trn ln. V d khi s dng mt cht thm
t (natri toluensunfonat) s lm tng vng trn ln ca nc v pha hu c,
khng v th m to ra mixen.
ni n iu kin tt kim tra mt h bc ba, trc tin cn nghin cu
tnh cht ca h bc hai nh nc/du, du/nh ha, nh ha/du.
Nu cht nh ha l hirophin, n tan trong nc, nu l hirophob, n tan trong
du.
Nu h bc hai nc/ nh ha c mt nhit ti hn ca s ha tan (trng
hp tc nhn khng ionic) gin pha c th biu din di y ( hnh 5.7 ):

66
 Hnh 5.7. Gin hai pha lng ph thuc nhit ti hn ha tan (im c) TCD.
C
Nhit ti hn ca s ha tan cht HBM trong du THS v nhit ti hn
C
ca s ha tan cht HBM trong nc TES ph thuc vo nng hp phn
c kim tra trong mi trng.
Ph thuc vo nhit , cht HBM khng ionic ha tan trong nc di im
c (TCD), cn ha tan trong du trn im c ( hnh 5.8 ).

Hnh 5.8. Gin pha ca hai cht lng khng trn ln nhau nhit ti hn ca cht
HBM khng ionic.

5.2.5. Tnh cht ca h vi nh tng

1. Hnh dng.
Theo mn ca cc ht phn tn, vi nh tng biu hin ra di dng cht lng
mu xanh ( 100nm), hay trong sut ( 50nm) c tnh cht c bit i vi s phn x
nh sng.
2. Hiu ng Tyndall.
Khi chiu mt chm nh sng vo mt bnh ng vi nh tng, mt phn nh
sng b hp th v mt phn b khuch tn ra mi hng xung quang.
nh sng khuch tn nhn c c mu xanh v tm nhiu hn mu vng v ,
chnh mu xanh biu hin phn tn ca vi nh tng.
3. Tnh dn in.
Tnh dn in ca vi nh tng thng thay i theo loi ca n. Tnh dn in
tng ln theo th tch nc trong h.

67
4. S thm tch (percolation).
S thm tch l s chuyn ha t pha a nc sang dng kt t k nc ca nh
tng. H s t khuch tn ca nc v cc thnh phn khc trong h tng ln, khng
tch bit hon ton gia vng a nc v k nc, lp gii hn mm do v d bin
dng.
Vng mt s thm tch, dn in gim, l trng hp cu to tnh vi ht
nhn nc c gii hn xc nh. H s t khuch tn ca nc yu cho mt s phn tch
hon ton trong vng a nc v k nc.
5. nht.
nht xut hin trong vi nh tng rt khc nhau. nht l hm s ca gi tr
gii hn ca s thm tch nhng khng phi l mi lin h trc tip gi tr ny vi
nht bn trong.
Cn thy rng trong h vi nh tng kch thc ca cc git l hm s ca nng
ca cht HBM v cht h tr HBM, t l cht nh ha cng nhiu th s ng nh
ha cng tng, kch thc cc git cng gim.
6. Nng lng b mt.
Vi nh tng th hin ra cc git, kch thc ca chng nh hn hng trm ln
kch thc git nh tng. Kch thc ca chng nh hn bc sng nh sng. S hnh
thnh vi nh tng din tch mt cc ht tng ln nhiu.
V d khi 1 cm3 du vo 1 cm3 nc th mt tip gip gia hai tng du-nc
l cm2. Nu to nh tng, kch thc git l micron th b mt tip gip git l m 2, nu
to vi nh tng cc git c kch thc milimicron th b mt tip gip gia cc git tnh
l hecta.
V mt nng lng m xt thy rng nng lng cung cp cho s nh ha 1cm 3
trong 1 cm3 nc to ra nh tng c din tch b mt tip gip l 1m 2 l mi ngn
ln ln hn nng lng ban u, cn to ra mt vi nh tng c b mt tip gip gia
cc git l hecta th nng lng gp mt triu ln nng lng ban u.

68
Chng 6. Phng php tng hp cc cht
hot ng b mt
Cc cht HBM c s dng trong nhiu ngnh cng nghip v trong nhiu
lnh vc khc nhau cho nn hng nm c sn xut mt lng ln. Theo thng k,
mt s nc cng nghip pht trin hng nm s lng cc cht HBM c sn xut
tng khng ngng (xem bng 6.1).

Bng 6.1. Khi lng cc cht HBM c sn xut mt s nc cng nghip pht trin
Cht 1970 1975 1980 1985 1990
HBM Ngn T % Ngn T % Ngn T % Ngn T % Ngn T %
Anion 1914 61,8 2284 56,1 2640 52,8 2988 50,6 3350 49,1
Khng ion 900 29,0 1338 32,9 1750 35,0 5145 36,3 2538 37,2
Cation 280 9,0 440 10,8 600 12,0 763 12,9 925 13,5
Lng tnh 6 0,2 8 0,2 10 0,2 11 0,2 13 0,2
Tng s 3100 4070 5000 5907 6826

Nhn bng trn thy t nm 1970 (3100T) n nm 1990 (6826T) lng cht
HBM tng ln gp i, trong cc cht HBM anionic chim 70% tng s.
Nguyn liu chnh sn xut cc cht HBM l cc ngun sn phm ha du ch
yu l parafin, theo thng k nm 1975 th lng n-parafin tiu th cc nc nh sau:
Ngn tn
Ty u 855
M 450
Nht 135
Phng php chung tng hp cc cht HBM c th trnh by di y:

6.1. Tng hp cc cht HBM anionic.

Cc cht HBM anionic ch yu l cc ankylbenzensunfonat, ankansunfonat v
cc ancoloxyetyl ha sunfat.
6.1.1. Tng hp cc mui axit bo
1/ Thy phn du m ng thc vt
Cc mui axit bo ca kim loi kim RCOO- l cc cht hot ng b mt ph bin c
bit n t lu v c s dng rng ri trong nhiu lnh vc nh sn xut cc cht git ra ,
cc cht ph gia du m, cc cht ph gia cho thuc tr cn trng gy hi ,tr nm u im
ca cc cht HBM ny l ngun nguyn liu ri ro l cc du m ng thc vt v cng
ngh sn xut khng phc tp c pht trin t lu.
Axit bo c c cha trong du m ng thc vt gm axit no v cha no c mch cacbon di
n 20 cacbon,t l ca chng thay i ty theo mi loi du m t nhin nh ch ra bng 6.2
v bng 6.3 di y.

69
 Bng 6.2 S gam axit bo trong 100 g triglixerit ca cc loi du m
Axit bo no Axit bo cha no
----------------------------------------------- -------------------------
M hay du Lauric Panmitic Stearic Oleic Linoleic
(12:0) (16:0) (18:0) (18:1) (18:2)
M ngi - 24,0 8,4 46,9 10,2
M b - 27,4 14,1 49,6 2,5
M b 2,5 29,0 9,2 26,7 3,6
Du da 45,4 10,5 2,3 7,5 vt
Du ng - 10,2 3,0 49,6 34,3
Du oliu - 6,9 2,3 84,4 4,6
Du c - 40,1 5,5 42,7 10,3a
Du lc - 8,3 3,1 56,0 26,0
Du u tng 0,2 9,8 2,4 28,9 50,7

Bng 6.3 Cng thc ha hc v im chy ca axit bo

Tn gi Cng thc ha hc S nguyn t C im chy

0
Axit v ni i C
Lauric CH3(CH2)10CO2H 12:0 44
Miristic CH3(CH2)12CO2H 14:0 58
Panmitic CH3(CH2)14CO2H 16:0 63
Stearic CH3(CH2)16CO2H 18:0 70
Arachidic CH3(CH2)18CO2H 20:0 77

Panmitoleic CH3(CH2)5CH=CH(CH2)7CO2H 16:1 0,5

Oleic CH3(CH2)7CH=CH(CH2)7CO2H 18:1 16
Linoleic CH3(CH2)4(CH=CHCH2)2(CH2)6CO2H 18:2 -5
Linolenic CH3CH2(CH=CHCH2)3(CH2)6CO2H 18:3 -11
Arachidonic CH3(CH2)4(CH=CHCH2)4(CH2)2CO2H 20:4 -49

Cc axit bo c iu ch bng cch thy phn cc du m ng thc vt vi natri

hiroxit ,phn ng c gi l x phng ha theo s sau :

CH2 O C R1 CH2 OH R1 COOH

O 1/ NaOH
CH O C R2 CH OH + R2 COOH
2/ H+
O
CH2 O C R3 CH2 OH R3 COOH
O
Cng thc chung ca du m Glixerin Axit cacboxylic
R1, R2, R3 c th l gc axit no nh axit panmitic C 16 (15-50%), axit stearic C18 (25%) hay
axit cha no nh axit oleic C18 (50%). V d triaxylglixerol (triglixerit) c cng thc sau:

70
 CH2 O CO (CH2)14 CH3 (Axit panmitic)

CH O CO (CH2)16 CH3 (Axit stearic)

H H
C C
CH2 O CO (CH2)7 (CH2)7CH3 (Axit oleic)

2/ Oxiha paraffin
Cc axit bo c th thu c bng cch oxiha paraffin,phng php ny c
thc hin M v cc nc chu u. Phn ng oxiha parafin c tin hnh bng oxi
khng kh nhit 150oC c mt mt lng nh KMnO4 lm xc tc.Cc hirocacbon
mch thng v mch nhnh b oxiha d dng hn mch vng. Ngi ta cng c th thc
hin phn ng ny c mt mt s mui kim loi khc lm xc tc nh cc mui
cacboxylat coban,st,km,ng v ch. Sn phm ca qu trnh oxiha du ngoi axit
bo cn ancol bc cao v mt vi cht khc na. iu kin oxiha du nh nhit , thi
gian ,lng tiu th oxi khng kh v sn phm hnh thnh cng thay i ty theo phn
on du c im si khc nhau,iiu ny th hin trn bng 6.4 di y .

Bng 6.4 iu kin oxi ha cc phn on khc nhau ca du khong

Phn on kl. mol. Nhit Lng oxi Thi gian Ch s axit sp.
o
du khong (g) phn ng C tiu th l/h oxiha (h) mgKOH/g

AC-6 360 190 200 3 58

AC-9,5 430 175 150 3,5 42
DC-8 400 200 125 3,5 7,8
DC-11 420 190 125 4 20
MC-20 610 200 125 5 8,4
MK-22 520 225 125 4 13,4

3/ Oxi ha iankylbenzen
Cc axit cacbonic thm nh axit p- tert-oexylbenzensunfonic c th iu bch
qua conng oxi ha iankykbezen trong mt nhm ankyl l bc 3 cn mt nhm
ankyl l bc 1 hoc bc 2.Khi oxiha bng oxi khng kh c mt xc tc kim loi nh
xc tc mangan,coban th nhm ankyl bc 1 v bc 2 s b oxi ha thnh nhm cacboxyl
COOH cn nhm ankyl bc 3 c gi nguyn . V d oxi ha p-tert-nonyl
metylbenzen cho axit p-tert-nonylbenzoic nh s sau :
O2 / xt
t -C9H19 CH3 t- C9H19 COOH

p- tert-nonyl metylbenzen Axit p-tert-nonylbenzoic

4/ Clo ha parafin thnh ankyl clorua ,sau cho phn ng vi Mg theo phn ng
Grinha ri cho phn ng tip theo vi CO 2 v cui cng thy phn thu c axit
cacboxylic v kim ha cho natri cacboxylat theo s di y :

71
 as Mg/ ete khan 1/ CO2 NaOH
R H Cl2 R Cl RMgCl R COOH R COONa
HCl 2/ H3O Axit cacboxylic Natri cacboxylat
Parafin Ankylclorua

Mt phng php khc cng thu c hiu xut cao l t ankylclorua cho phn ng
vi kalixianua KCN thnh ankyl xianua RCN ri thy phn axit v kim ha cho natri
cacboxylat RCOONa .

6.1.2. Tng hp ankylbenzensunfonat.

Phng php chung iu ch ankylsunfonat thc hin qua 3 giai on: iu
ch ankyl benzen, sunfonic ha ankyl benzen v cui cng trung ha
ankylbenzensunfonat theo s sau:
Bc 1. Ankyl ha benzen theo phng php t parafin clo ha c mt nh sang
thnh ankyl clourua sau cho phn ng vi benzen c mt xc tc kim loi clorua nh
AlCl3 khan theo kiu phn ng Frien Crap . Cch th hai l chuyn parafin thnh anken
ri ankyl ha benzen c mt xc tc HF .Phn ng xy ra theo s sau :

R Cl R
xuc tac
R H
Parafin
R' CH CH R'' R' CH2 CH
anken R''
Bc 2 . Sunfo ha ankylbenzen bng oleum SO 3/H2SO4 vi t l 100% H2SO4 v
20% SO3 :
SO3H
SO3
R R
H2SO4
Bc 3. Chuyn dng axit sunfonic thnh dng mui natri sunfonat bng cch cho
axit sunfonic phn ng vi dung dch NaOH :
SO3H SO3Na
NaOH
R R

Cc parafin s dng thu phn on si 190-255 0C tng ng vi C10- C13 hoc

phn on rng hn tng ng 190-2600C tng ng vi C10- C15.
Lin x trc y, iu ch ankyl benzene, ngi ta s dng phn on
kerosin (du ha) bng cch loi b vng benzen theo cc bc:
- Tch cc vng benzen khi kerosin
- Clo ha kerosin tch benzen
- Ankyl ha benzen bng kerosin clo ho trn
- Sunfonic ha ankyl benzen bng SO3 trong SO2.
- Trung ha axit ankylbenzensunfonic
- Tch kerosin cha phn ng khi sn phm ankylbenzensunfonat.

72
 i vi cc axit ankylsunfonic c cc nhm th khc vng benzen nh RCONR- ,
RCOOCH2NH- , RNHCO- ,RCONHNH- .. cng c iu ch bng cch sunfo ha
cc ankylbenzen th tng ng nh phng php trn vi oleum . Mt vi sn phm nh
sau :

RCOOCH2CONH SO3Na RNHCO SO3Na

RCONH -NH SO3Na RCONR SO3Na

Tng hp ankylbenzensunfonat (ABS ): Trc tin polime ha propen cho

polipropen ,sau cho phn ng vi benzen c mt AlCl 3 khan theo phn ng
Frien Crap quen thuc ,cui cng sunfo ha bng axit sunfuric c thu c
ankylbenzensunfonat (ABS ) nh phn ng di y :

CH3 CH3 CH3

H
4CH3CH=CH2 CH3 CH ( CH2 CH )2 CH=CH
Polime ha AlCl3
CH3 CH3
1
) H2SO4
CH3 CH ( CH2 CH )3 H
2)Na2CO3

CH3 CH3 Sunfo ha

CH3 CH ( CH2 CH )3 SO3Na

Natri ankylbezensunfonat ( ABS )

Tng hp natri p-(2-doxyl)benzensunfonat (LAS) : T benzene cho phn ng

vi 1-oeken c mt AlCl3 khan cho sec-oexylbenzen,tip theo sunfo ha vi
axit sunfuric c nhn c LAS theo s phn ng sau :

73
 CH3
CH3(CH2)9CH=CH2 AlCl3
CH3(CH2)9CH

CH3
(1) H2SO4
CH3(CH2)9CH SO3Na
(2) Na2CO3
LAS

6.1.3. Tng hp ankyl sunfonat.

Ankylsunfonat c sn xut u tin c trong i chin th gii ln 2 bng
cch sunfoclo ha parafin C11- C18 c mt nh sng :
+ NaOH
RH + Cl2 + SO2 RSO2Cl - NaCl RSO3Na
- HCl
Parafin nhn c trc kia qua s hiro ha oxit cacbon theo phn ng Fisher-
Trops, hin nay c tch ra t phn on kerosin (du ha).
c sn xut ankansunfonat theo con ng sunfoclo ha quang ha parafin
vi cng sut 25 ngn T/nm.
Mt phng php khc iu ch ankylsunfonat bng cch sunfo oxiha quang
ha parafin C11-C18 c mt nh sng :
+ NaOH
RH + SO2 + 0,5O2 RSO3H - H2O RSO3Na

Phn ng tin hnh c mt ca nc, ng thi sinh ra axit sunfuric n 30%.

Hin nay hng Hoescht (Phn Lan) sn xut khong 24 ngn T/nm.

Oxi ha sunfit, mecaptan, ankylisunfit bng HNO3:

HNO3
R S S R RSO3H

6.1.4 . Tng hp olefinsunfonat.

Olefinsunfonat nhn c bng cch sunfon ha vi anhirit sunfuric SO 3 cc -
olefin C12-C20. Khi sunfonic ha xy ra hai phn ng chnh to ra axit olefinsunfonic v
sunton:
40% RCH2 CH CH CH22H
axit olefinsunfonic
R CH2 CH2 CH CH2 RCH2 R
60%
O + O
SO2
SO2
sunton

74
 Axit sunfonic c trung ha (ng thi thy phn sunton) bng dung dch kim
natri nhit cao hn 1000C. Sn phm cui cng l hn hp 50-60% olefinsunfonat
v 40-50% hiroxiankansunfonat.
Olefinsunfonat it nhy cm vi cng nc hn cc ankylbenzensunfonat v
ankansunfonat.

6.1.5. Tng hp ankylsunfat v sunfat ancoloxietyl ha (sunfoete) ROSO 3Na v

RRCHO(CH2CH2O)OSO3Na.
Nhm hp cht HBM ny c ngha thc t ln, cc cht ny c kh nng phn
hy sinh hc cao n 100% cho nn c dng trong cc cht git ra; ng thi n
cng t nhy cm vi nc cng.

Phng php chung tng hp cc ankylsunfat v sunfoete :

1. Sunfo ha ancol : y l phng php ph bin v n gin iu ch cc ankylsunfat trong
c s dng iu ch laurylsunfat ,mt cht HBM quan trng v ph bin dng trong
cng nghip sn xut cc cht git ra v chm sc c th hin nay .

Phng php chung l cho cc ancol bo phn ng trc tip vi axit sunfuric 90%
hay vi axit clorosunfunic ClSO3H ri trung ha sn phm:
NaOH
R OH + H2SO4 R O SO3H R OSO3Na
- H2O
NaOH
R OH + ClSO3H R O SO3H R OSO3Na
- HCl
Phn ng iu ch natri laurylsunfatc thc hin theo s sau :
0
t
CH3(CH2)10CH2OH + H2SO4 CH3(CH2)10CH2OSO3H + H2O
Lauryl ancol
CH3(CH2)10CH2OSO3H + Na2CO3 CH3(CH2)10CH2OSO3- Na+ + NaHCO3
Natri laurylsunfat

2. Phn ng ca cc este vi SO3:

SO3Na
O 1) SO3 (1:1,2) O
R 2) NaOH/H2O R
O
O
C ch phn ng nh sau:

75
 O O OH O
O
R CH3 SO3 R S
O O OCH3 R O S OCH3
O
Este
O O
H
S O O HO3S O
O O
O S OCH3 R
O O S OCH3
O O

SO3

NaO3S O HO3S O
NaOH/H2O

R R O CH3
O CH3
3. Sunfonic ha ieste ca axit maleic cho ieste sunfosuccinat nh sau:
O O
HC C H2C C
OR OR
+ NaHSO3
OR OR
HC C HC C
OR OR
SO3Na

4. Cho ancol tc dng vi axit sunfamic H2NSO3H nhit 1400C:

ROH + H2NSO3H ROSONH4
Cc amit dng ixianiamit, ur, aminisunfat c mt mt lng nh lm xc tc
cho phn ng tin hnh nhit khng cao (1150C).

5. Phn ng ca ancol vi anhiritsunfuric SO 3: Cc ancol bo v monoglyxerit c th

phn ng vi SO3 ha tan trong SO2 lng mt cch d dng vi hiu sut ton lng,
SO2 c gii phng d dng bay hi ra:
NaOH
R OH + SO3 R O SO3H R OSO3Na
- SO2
Ancol Ankylsunfat Natri ankylsunfat
Phng php ny rt thun li iu ch cc ankylsunfat.
Cc dn xut monoglixerit sunfoeste c th nhn c qua phn ng mt giai on
gia glixerin bo vi oleum nhit 30-500C.
CH2 CH CH2OH + SO3 CH2 CH CH2OSO3H
OH OH OH OH
Glixerin Monoglixerinsunfat

76
6. Cc fomiat este ca ancol bo d dng phn ng vi axit closunfonic cho ankylsunfat:
HCOO R + ClSO3H ROSO3H CO HCl
Fomiateste Axit closunfonic Ankylsunfat
7. Este sunfoha du bo
Phng php este ha du bo trc y khng c ch nhng ngy nay sn phm
ca qu trnh c ng dng rt ln.Qu trnh sunfoha du bo c thc hin 300 oC thu c
dng monohidrat c mi d chu.
CH2OCOR CH2OSO3H
CHOCOR + H2SO4 CHOCOR + RCOOH
CH2OCOR CH2OCOR
Du bo Sunfat du bo

Cc du bo c gc R l anken th ni i c th b ph v. V d sunfoha du bo c
gc R l ca axit oleic CH3(CH2)7CH=CH(CH2)7COOH, ni i c th b ph v.
8. Sunfo ha ancol cha nhm trung gian gia gc ankyl v OH
Cc hp cht oxi dng R-(A)-(B)-OH y R l gc ankyl, A l nhm trung gian nh
COO, CONH, O cn B l mch hirocacbon (thng 1-3 nguyn t C) c s dng
sunfo ha cho sn phm l cc cht HBM c gi tr.
Cc loi sn phm nh glixerin este khng hon ton (v d monolaurat glixerin) hay l
akanolamit (v d monoetanolamit ca axit lauric CH3(CH2)10COOH) c s dng ph bin.
Arylpolioxietilen sunfat cng l mt cht HBM c s dng rng ri, n c tng hp
theo con ng sau :

R OH n CH2 CH2 R (OCH2CH2)nOH

O
Ankylphenol Etilenoxit
H2SO4
R (OCH2CH2)nOSO3H

Arylpolioxietilensunfat

6.2. Tng hp cc cht HBM cationic.

Cc cht HBM cationic thuc cc dy:
1) Cc amin thng, cc amidoamin, cc iamin dng mui amoni bc 4.
2) Cc amin vng, imiazolin v piridinium bc 4
3) Cc hp cht photphonienic v sufonienic.
Phng php chung l trc tin tng hp cc amin, sau tng hp cc mui
amoni bc 4 qua phn ng ca cc amin vi dn xut ankylhalogenua.

6.2.1. Tng hp cc amin bc 1 v mui amoni.

Phng php cng nghip iu ch cc amin bc cao l phn ng ca axit
cacboxylic vi amoniac nhit v p sut cao c mt xc tc (Al 2O3). Giai

77
 on u tin ca phn ng l to ra nitrin sau kh ha thnh amin, ri cho
phn ng vi HX to ra mui amoni:
+2H2 HX
RCOOH + NH3 RCN RCH2NH2 RCH2NH3 X
-2H2O
Cc axit cacboxylic c iu ch t du thc vt nh du da hoc oxi ha
parafin.
Nitro ha parafin ri kh ha.
HNO3 [H] HX
R H R NO2 RNH2 RNH3 X
Clo ha parafin thnh dn xut clo ri cho phn ng trc tip vi amoniac :
Cl2 HX
R H R Cl NH3 RNH2 RNH3 X
Clo ha parafin c cha khong 15% mch nhnh thng nhn c 2-3% clorit
bc 1, 20-22% clorit bc 2 v 1-3% policlorit, tuy nhin trong qu trnh ny vic
tch amin ra khi cht u tng i kh.
Qu trnh amin ha cc clorit bc 2 c km theo phn ng tch loi hnh thnh
olefin. Sn phm ca phn ng thng l hn hp amin bc nhnh c 1, 2 n 3
gc th ankyl.
Cc sn phm amin thu c dng mui v c cng l cc cht HBM.

6.2.2. Tng hp cc amin bc 2, bc 3 v mui amoni.

Cc amin bc 2 v bc 3 cng c th hnh thnh trong qu trnh tng hp cc
amin bc 1. Phng php iu ch amin t amin bc 1 vi ankylhalogen l ph
bin, sau cho phn ng vi HX to ra mui amoni :
CH3Cl HX
R NH2 + CH3Cl - HCl RNHCH3 R N(CH3)2 RNH(CH3)2X
- HCl
T amin bc 1 cho phn ng vi fomanehit v hiro :
HX
R NH2 + HCHO R N(CH3)2 + 2H2O RNH(CH3)2X
T amin bc 2 cho phn ng vi ancol :
HX
R OH + NH(CH3)2 R N(CH3)2 + 2H2O RNH(CH3)2X
T amin bc 1, bc 2 cho phn ng vi etilenoxit :
(CH2CH2O)xH (CH2CH2O)xH
HX
R NH2 nH2C CH2 R N R NH
(CH2CH2O)y H X (CH2CH2O)y H
O
R NH CH2CH2CN H2C CH2 R N CH2CH2CN CH2 CHCN + R N C2H4OH
O C2H4OH H
HX

RNH2C2H4OH.X

78
6.2.3. Tng hp cc amin cha lin kt ete, este v amit.
Cc cht HBM l cc amin cha lin kt ete v este cng c s dng kh
nhiu nh :
C2H4
R NH CH COOC2H5 R COOC2H4 N O
CH2COOC2H5 C2H4
ietyleste N-ankyl sucxinic Este etanolmopholin ca axit cacboxylic
CH3
RNH(C2H4NH)xC2H4OH CH3(CH2)7CH CH(CH2)7CO N CH2CH2SO3Na
Poliamin
iu ch c cc phng php ring nh :
1/ Phn ng ca axit cacboxylic vi trietanolamin :
C2H4 HX C2H4
RCOOH + (HO C2H4)3N RCOOC2H4 N O RCOOC2H4 NH O .X
C2H4 C2H4
Trietanolamin

2/ Phn ng ca ankylamin vi ietyleste malonat :

CH COOC2H5 COOC2H5 COOC2H5
R NH2 + HX R NH2 CH .X
R NH CH
CHCOOC2H5 CH2COOC2H5
CH2COOC2H5

3/ Phn ng ca etanolamin vi ankylsunfat ri vi etanolamin , tip theo vi axit oleic v

cui cng vi axit :
HOC2H2NH2 + RO SO3Na RNH(C2H4NH)xC2H4OH
-H2O HOC2H2NH2
HX
RNH2(C2H4NH)x+1C2H4OH.X RNH(C2H4NH)x+1C2H4OH
CH3
CH3(CH2)7CH CH(CH2)7COOH + NH CH2CH2SO3Na
Axit oleic N-metyaurin

CH3
CH3(CH2)7CH CH(CH2)7CO N CH2CH2SO3Na
igenon T HX
CH3
CH3(CH2)7CH CH(CH2)7CO NH CH2CH2SO3Na.X

6.2.4. Tng hp cc arylamin v arylankylamin.

79
 Cc cht HBM cationic cha nhm amonium c nhm th l cc aryl hay
arylankyl cng c s dng nh :
RCOOCH2CH2 N (CH2CH2OH) R OH
CH2C6H5
CH2NHCOCH2Cl
CF3

C12H25N(CH3) CH2 OC2H4OC2H4O C CH2 N

R
CF3 O
Mi cht c phng php iu ch ring, nhng trc tin c th iu ch cc amin
thm hoc arylankylamin theo cc phng php nu trn. Sau cho phn ng vi
HX to mui amoni dng R3NHX

R OH + ClCH2CONHCH2OH R OH

CH2NHCOCH2Cl
HX

R OH

CH2NH2COCH2Cl.X

6.2.5. iu ch mui amoni bc 4.

Cc mui amoni bc 4 c iu ch i t amin khi cho chng phn ng vi

ankylhalogen.
R N(CH3)2 + R'Cl R N(CH3)2R'Cl

Ar CH2Cl + N(CH3)3 Ar CH2N(CH3)3 Cl

Cc mui amoni bc 4 phn t lng thp, anion thng l Cl -, cc mui c phn t

lng cao anion c th khc. Phn ng to mui amoni xy ra d dng.

6.3. Tng hp cc cht hot ng b mt khng ionic.

Cc hp cht hot ng b mt khng ionic l nhng ancol bo hay poliete, c th iu
ch theo cc phng php di y.

6.3.1. Tng hp cc ancol bo :

i t anken xc tc nhm triankyl :

(C2H5)3Al + 3nCH2=CH2 3C2H5(CH2=CH2)nOH

80
 Tng hp oxo t -olefin:

+CO, +H2
R CH CH2 R CH2 CH2OH + R' CH CH3
xc tc
CH2OH
Tng hp oxo t olefin vi ni i gia mch:

+CO, +H2
R CH CHR R' CH2CH2OH + R'' CH CH3 + R''' CH CH2CH3
xc tc
Fe(CO)5, Co(CO)8 CH2OH CH2OH

6.3.2. Tng hp cc este polioxietylen v polioxietylenancol:

Phn ng ca ancol vi oxietylen :

NaOH
R OH + nH2C CH2 R O (CH2CH2O)n H
O
Phn ng ca phenol v ankylphenol vi oxietylen :
NaOH
C6H5 OH + nH2C CH2 C6H5 O (CH2CH2O)n H
O
Phn ng ca mecaptan vi oxietylen :
NaOH
R SH + nH2C CH2 R S (CH2CH2O)n H
O
Phn ng ca axit cacboxylic vi oxietylen :
R COOH + nH2C CH2 RCO(OCH2CH2)n OH
O

6.3.3. Cc cht hot ng b mt cha lu hunh

Cc cht hot ng b mt cha lu hunh thng c dng lin kt S, SS hay

SCH2CH2S nh di y .
1. Bis (- clometylbenzyl)-sunfit (A) l mt cht HBM cha lu hunh lm ph gia
cho c tng hp t phn ng ca stiren vi sunfuaiclo nh sau :

2C6H5CH=CH2 + SCl2 C6H5CHClCH2SCH2CHClC6H5

Stiren Bis (-clometylbenzyl)sunfit

2. Bis (ankylbenzyl)isunfit (C) cng l cht HBM cha lu hunh ph gia cho du
khong c tng hp t ankylbenzen v natri sunfua theo mt dy phn ng sau:

81
 Trc tin clometyl ha ankylbenzen (A) cho clometylankylbenzen (B), cui
cng cht ny cho phn ng vi natrisunfit cho sn phm (C) theo s di y :

H2O
R + HCHO + HCl R CH2Cl

(A) (B)

Na2S R CH2S SCH2 R

2 NaCl

Bis(ankylbenzyl)disunfit (C)

3. Bis (ankylbenzylthio) etan cng l mt cht HBM cha lu hunh c iu ch

theo s sau :

H2O
R + HCHO + HCl R CH2Cl

(A) (B)

ClCH2CH2Cl
R CH2SCH2CH2SCH2 R
2 Na2S
Bis (ankylbenzylthio)-etan

4. D vng cha lu hunh: khi cho lu hunh phn ng vi anken iu kin c bit
( 160-320 oC ,c mt xc tc ) to ra d vng cha hai nguyn t lu hunh :
R C CH3 R C C S
nS C S
R' CH R' H2S + (n - 4)S

5/ iu ch xangtogenat , phn ng thc hin theo hai bc sau :

Bc 1 . Tc dng dung dch kim NaOH m c vi ancol v CS2 20-25oC :
20 - 25 o
C
ROH KOH CS2 ROCSK H2O

S
Bc 2. Tc dng dung dch nc caxantogenat vi icloetan 70oC:

S S S
RO C ClCH2CH2Cl RO C C OR KCl
SK SCH2CH2S

82
6.3.4. Cc cht hot ng b mt cha photpho ,oxi , lu hunh v nit

Cc cht HBM cha photpho hoc photpho v lu hunh c iu ch thng

xut pht t photphotriclorua PCl3 nh mt s v d di y :
1./ iu ch ibutyleste ca axit triclometylphotphonic nh sau :
Trc tin iu ch tributylphotphit t ancol butylic v photphotriclorua :

3C4H9OH + PCl3 + 3(C2H5)3N (C4H9O)3P + 3(C2H5)3N.HCl

Tributylphotphit
Tip theo tributylphotphit phn ng vi cacbontetraclorua cho sn phm cui cng :

(C4H9O)3P + CCl4 CCl3P(O)(OC4H9)2 + C4H9Cl

ibutyleste ca axit
Triclometylphotphonic
2/ iu ch tri-p-ankylphenoxiphotphin t phn ng trc tip ca ankylphenol vi
photphticloru theo s sau :

3R R O P 3 HCl
OH PCl3 3

3/ iu ch 2,6-itert-butyl-4-metylphenyleste (A) ca axit pirocatechinphotphoric

bng cch este ha pirocatechinphotphomonoclorit theo s sau :
OH O
PCl3
PCl
2 HCl
O
OH
Pirocatechin Pirocatechinphotphomonoclorit

( CH3)3C (CH3)3C
O 30 - 40 oC
O
PCl HO P O CH3
O HCl O
(CH3)3C (CH3)3C
(A)
4/ T phn on hirocacbon iu ch axit O-ankyl( O-aryl)ithiophonic theo s
sau :

R PCl2
R S S R
PCl3, O2 P2 S5 S R'OH
RH R PCl3 P S Me S P
S Me(OH)2 R''O OR''
O R P P R
S S S Axit O-ankyl (O-aryl)dithiophotphonic

83
 5/ iu ch cc hp cht cha P,S v N . T cc amin thm cho phn ng vi P2S5 nhn
c cc hp cht cha P,S v N di y :

S S

R NH P S P NH R
2P S
R NH2 2 5 S S
H2S
R NH P S P NH R

S S

6.4. Tng hp cc cht hot ng b mt da trn cacbohirat.

Cacbohirat l ngun nguyn liu thin nhin c s dng lm nguyn liu tng
hp cc cht hot ng b mt. u im ca cc cht hot ng b mt ny l c th b
phn hy trong thin nhin di tc dng ca vi sinh vt. Mc d cacbohirat bao gm
nhiu loi nhng n nay dng ph bin vn l ng glucoz, sacaroz, sorbitol. Bng
6.5 cho sn lng v gi trung bnh ca cc nguyn liu ny.

Bng 6.5 Ngun nguyn liu cacbohirat.

Nguyn liu Sn lng (tn /nm) Gi trung bnh (USD/kg)
Sacaroz 130.000.000 0,70 0,80
Glucoz 16.000.000 0,55 1,12
Sorbitol 8.000.000 0,53 1,70

6.4.1. Sorbitan este

Sorbitan este c sn xut cng nghip bng cch ehirat ha ni phn t sorbitol
trong s c mt ca axit (v d NaH 2PO4) nhit 150 2000C v c mt xc tc (v
d Na2CO3), este ha vi axit bo 200 250 0C. Sn lng hng nm ca sobitan este
l 20.000 tn (xem bng 6.6). Qu trnh phn ng theo s sau:
CH2OH
HO CH CH2 HO CH CH2
HO CH
O O
HO CH + RCOOH
HO CH CH HO CH CH O
-H2O -H2O
HC OH CHCH2OH sorbitan este CHCH2OC R
HO CH OH OH
CH2OH nCH2 CH2 Etilenoxit
O
Polietilenglicol sorbitan este
(Polisorbat, R = C12, C18, C18:1)

84
HO CH CH2 HLB
O
HO CH CH O
1-8
CHCH2OC R
OH R = C12, C18, C18:1

(O CH2CH2)xOH O
O
H2C CH CH CH2 (OCH2CH2)y OCC17H35
10-17
HO (CH2CH2O)w CH CH (OCH2CH2)z OH (w + x + y + z = 20)
Polietlenglicol-(20)-sorbitan stearat este

Bng 6.6. Sn lng cht hot ng b mt t ng

Cht HBM Ni sn sut ng dng Sn lng
(tn/nm)
Sorbitan este Akros, Dai-ichi Kogyo Seiyaku, Dc, thc 20.000
cognis, Kao, ICI, Montedison, phm, ha
PPG, Riken, Vitamin, SEPPIC, nng, cht n,
Witco si vi
Saccaroz este Croda, Dai-ichi Kogyo Seiyaku, Thc phm, < 4000
Goldschmidt, Mitsubishi, sisterna, dc phm,
weixi spark Personal Care
Ankyl poliglicosit Akzo Nobel, BASF, cognis, ICI, Cht git ra, 80.000
Kao, Nihon Seika, SEPPIC, Union ha nng
Carbide
Axit bo Pfizer/Hatco, clariant Cht git ra 40.000
N-metylglucamit
Metylglucosit este Amerchol, Goldschmidt Dc phm 10.000
Dn xut ankyl Pilot chemical Co, Lamberti Spa Personal Care
poliglicosit anionic

6.4.2. Saccaroz este.

Sn phm c sn xut cho cng ngh thc phm, dc phm, m phm, cht
git ra.
Tng hp saccaroz este bng este ha xc tc (K 2CO3) saccaroz vi metyleste
ca axit bo (RCOOCH3) trong dung mi (v d dimetylfomamit) ~ 90 0C nh s
sau:

85
 CH2OH CH2OR
CH2OH CH2OR
O O O
O + R'COOMe
OH HO OR RO
-MeOH O
HO O RO
CH2OH CH2OR
OH OH OR OR

Saccaroz R = R'CO; H Saccarozeste

R' = C12, C16, C18, C18:1

Sn phm thc t ca phn ng l hn hp nhiu loi este mono-, i-, tri-, tetra-
v pentaeste nh s di y:
CH2OH
CH2OH
O O
OH HO
O CH3
CH2OH HO CH2O C
CH2OH OH OH
O O O
OH HO CH3 Monoeste
O CH2O C
HO CH2OH CH2OH
OH OH O O O
OH HO
O CH3
CH3O CH3 HO CH2O C
C OH OH
O ieste
O CH3
CH2O C CH3
CH2O C
O O O O
OH HO
O CH3
HO CH2O C
OH OH
O Trieste

6.4.3. Dn xut glucoz.

1. Ankylpoliglicosit.
Tng hp ankylpoliglicosit c th hin t 100 nm trc, phn ng ca
glucoz vi ancol mch di C8-C16, kt qu sn phm ca phn ng l mono-, i-, tri- v
oligoglicosit hn hp - v -anome nh s di y:

86
 CH2OH
+
O H
HO
+ HO -H2O
HO OH
OH
CH2OH
O
HO
CH2OH
O HO O
HO OH
+ CH2 + (Glucoz)x
HO O O
OH HO
HO O
OH y
Phn ng c thc hin c mt xc tc l axit p-toluensunfonic vi lng d
ancol bc cao (2 n 6 ln) ui nc di p sut thp 100-1200C.
2. Glucamit axit bo.
Tng hp glucamit axit bo da trn phn ng ca glucoz vi metylamin di
iu kin kh (H2/Ni) hnh thnh N-metylglucamin. Cht ny cho phn ng tip vi
metyleste ca axit bo cho N-metylglucamit ca axit bo theo s sau:
CH3 CH3
CH2 NH CH2 N C R
CH OH O CH OH O
HO CH + CH3 OC R HO CH
-CH3OH
CH OH CH OH
CH OH CH OH
CH2OH CH2OH
N-metyl glucamin N-metyl glucamit axit bo

3. Tng hp metyl glucosit este.

Este ha metyl glucosit vi metyl este ca axit stearic hay oleic tng cng tnh k
nc (lipophilic), sau cho metylglucosit phn ng vi etilenoxit nhn c
polietilenglicolmetylglucosit este.

87
 CH2OH CH2OR
O R'COOMe O
HO RO
-MeOH
HO OH RO OCH3
OH OR
(R = R'CO) Metyl glucosit este
n (Etylen oxit)
O
CH2OR
O
RO
RO (OCH2CH2)n OCH3
OR
Polieylenglicol metyl glucosit este

6.4.4. Dn xut ca lactoz.

Cc cht hot ng b mt t ng galactoz nh N-ankylamino-1-deoxilactitol, N-

axetyl-N-ankyllactosylamin l cc cht c hot tnh sinh hc, c iu ch trc tip t
phn ng ca lactoz vi amin hoc anhirit nh s sau:
CH2OH OH
CH2OH OH
HO
HO O O
O O H2O
+ RNH2 OH OH NHR
OH OH OH 2-propan
O
O t0 phng
OH CH2OH
OH CH2OH
Lactoz [H]

CH2OH OH
HO
O O
OH OH CH2NHCnH2n+1
OH
OH CH2OH
N-ankylamino-1-deoxilactitol

CH2OH OH OH
O CH2OH
HO CH3 C HO
O O (C2H5)3N O O
OH OH NHR + O OH OH
DMF NR
O CH3 C t0 phng O
O COCH3
OH CH2OH OH CH2OH
Anhidritaxetic

6.5. Tng hp cc cht hot ng b mt lng tnh in tch.

Cc cht hot ng b mt lng tnh trong phn t cha c nhm baz v nhm
axit, tuy nhin n ch chim mt t l nh so vi cht hot ng b mt anionic v

88
 cationic. Cc cht c s dng nhiu nh oexyl--analin
C12H25NHC2H4COOH c iu ch t amin bo v este ca axit acrylic:
RNH2 + CH2 CH COOCH3 RNHC2H4COOCH3 R NH C2H4 COOH
Dng chung: R NH R COOCH3
Gc R c t 8-16 nguyn t cacabon v R c t 1-8 nguyn t cacbon.
Dn xut este ca axit photphoric vi glixerin cng l mt cht hot ng b mt
lng tnh c iu ch nh sau:
CH2 O COR CH2 O COR CH2 O COR
CH O COR' + POCl3 ClCH2CH2 N(CH3)3OH
CH O COR' CH O COR'
Cl NaOH O CH3
CH2OH CH2 O P CH2 O P
Cl O CH2CH2N CH3
O O
CH3
Lexitin

Tng hp betainic: i t amin bc ba hay trietanolamin:

CH3 CH3
CH3 N + Cl CH2COOH CH3 N CH2 COOH Cl
CH3 CH3

HOCH2CH2 HOCH2CH2
HOCH2CH2 N + Cl CH2COOH HOCH2CH2 N CH2COOH Cl
HOCH2CH2 HOCH2CH2
Trietanolamin
Tng hp ankylolamit t phn ng ngng t ca ietanolamin vi axit bo:
CH2CH2OH O
R COOH + H N R C CH2CH2OH
CH2CH2OH O N
CH2CH2OH

Tng hp cht hot ng b mt dy axit aminosunfonic axit:

R NH CH2CH2OH + H2N RNH CH2CH2 HN

SO3H SO3H
Dy aminosunfonic axit mch thng c th thu c qua phn ng ca etanolamin
th vi halogenoamkansunfonic axit nh sau:
RCONHC2H4 NH CH2CH2OH + ClCH2CH2SO3H RCONHC2H4 N CH2CH2OH
CH2CH2SO3H
Hoc khi cho este ca axit maleic phn ng vi taurin s xy ra phn ng ca nhm
amino ca taurin vi ni i ca axit maleic cho sn phm thuc dy axit
aminosunfonic:

89
 R OOCCH CHCOOR + H2N CH2CH2SO3H ROOCCH2 CH COOR
NHCH2CH2SO3H

6.6. Tng hp cc cht hot ng b mt dy polime.

Nhiu cht hot ng b mt dng polime c s dng lm cht nh ha, trong
phn t ca chng cha c nhm a nc (hirophin) v k nc (hyrophob) c
dng:
A A (A)n A B (B)n B B

A A A A A A A
B B B n
A- nhm k nc B- nhm a nc
R

Dy cht HBM khng ionic

CH2
n
OH
HN C2H4 NH C2H4 N C2H4 NH C2H4 NH CH2 CH CH2
R C O OH
n
R
Cht HBM cationic
iu ch c th thc hin polime ha cc monome, v d:
R R
polime ha
n + HCHO CH2
n
OH OH
CH3 CH3
polime ha
CH3 NH C12H25 + CH2 CH CH2Cl n N CH2 CH CH2Cl N CH2 CH CH2
O C12H25 OH Cl C12H25 OH n

Tng hp cht hot ng b mt polimeflo

Nm 1922 thng bo tng hp c cht hot ng b mt poli (1,1-
ihiropeflooctylacrylat) bng phn ng polime ha c mt cht AIBN trong kh
quyn CO2 59,40, p sut 207 bar theo s sau:

90
 CH2 CH CH3 CH3
C O + CH3 C N N C CH3
OCH2(CF2)6CF3 CN CN
1,1-dihidropeflooctyl acrilat 59,40C AIBN
CO2
207 bar
48h

CH2CH
n
C O
OCH2(CF2)6CF3
Poli (1,1-dihidropeflooctyl acrilat) (PFOA)
Cht PFOA c s dng ng trng hp vi cc monome khc nh
metylmetacrilat (MMA), styren, etilen, butylacrilat (BA), v d trng hp vi stiren
c mt tetrahirothiuram isunfit cho polistiren-b-poli FOA nh s di:

Phn ng to este ca axit 2 chc, sau phn ng to mui amoni bc 4 vi

etilenoxit theo s sau:
+ 2H2O
n H(OH4C2)xN(C2H4O)y H + n HOOC(CH2)4COOH OC(H4C2)4CO(OC2H4)xN(C2H4O)y
R R n
CH2 CH2 nHCl
O

C2H4OH
OC(H4C2)4CO(OC2H4)xN(C2H4O)y
R n

Tng hp polistiren-b-poli FOA (FOA-1,1-ihiropeflooctyl acrylat) trng hp

copolime nh s sau:
S S S S CH2CH3
CH2 CH CH3CH2 un nng CH3CH2
CH2CH3
+ N C S S C N N C S (CH2CH)q S C N
CH3CH2 CH2CH3 CH3CH2 CH2CH3

Tetrahrothiuram isunfit
CH2 CH
C O UV, h
OR
CH3CH2 S S CH2CH3
N C S (CH2CH)q (CH2CH)n S C N
CH3CH2 C O CH2CH3

OR
R = -CH2(CF2)6CF3 Polistiren-b-poli FOA

Mt s cht hot ng b mt polime:

91
 CH3 H3C
O3S (CH2)n O C C N N C C O(CH2)n SO3
O CH3 H3C O
n = 1, 2, 3
Mui amoni bis [2-(4-sunfophenyl)ankyl]-2,2-azoiisobutirat
CH2 (OCH2 CH)n (O CH2CH2)m O CH2CH2CH2SO3K
CH2
CH3 VB n, m-SO3K

CH2 (OCH2 CH)n (O CH2CH2)m O CH2CH2CH2SO3K

CH2
CH3 MB n, m-SO3K
CH3O(CH2CH2 O)45COCH CH COOC12H25
Maleat ieste
CH3(CH2CH2O)45 (CH2CHO)9 CO (CH3)2C N N R
C2H5 CN
Copolime

CH3(CH2CH2O)45 [(CH2)4O]10 C O CH CH COOH

Copolime O
CH3
CH3(CH2CH2O)45 [(CH2)4O]10 C NH C C6H4 C CH2
O CH3 CH3
Copolime

Chng 7. Cc cht git ra tng hp

Cc cht git ra c ngha quan trng khng phi ch trong i sng hng ngy
m c trong cng nghip, vic lm sch cc thit b, thng cha v mi trng xung
quanh u i hi phi c cc cht git ra. Hng nm trn th gii tiu th hng triu
tn cc loi cht git ra khc nhau, to ra mt ngnh cng nghip sn xut cc cht git

92
ra rt pht trin, sn lng u tng ln hng nm. Nguyn liu cung cp cho ngnh
cng nghip ny chnh l cc sn phm ha du.

7.1. Thnh phn cc cht git ra tng hp.

Thnh phn chnh ca cc loi x phng trc y l mui natri hay kali ca axit
bo, thu c qua thy phn cc loi du thc vt (ch yu l du da), n chim
khong 70-80% cn li l cc cht n nh s a Na 2CO3 (~4%), thy tinh lng (~6%)
v mt vi cht khc. Thnh phn ca cc cht git ra tng hp bao gm cc cht
HBM, cc mui v c v mt s cht hu c h tr tng cng tc dng ca cc cht
HBM. Ty thuc vo yu cu s dng, thnh phn ca cc cht git ra c thay i. V
d cc cht git ra dng ht cha 12-25% (theo khi lng) cc cht HBM hu c,
25-40% trinatripolyphotphat hay cht thay th, 0-25% natri peborat, 3-10% natri
metasilicat, 0,5-1% mui natri ca cacboxymetylxenluloz v 5-25% natrisunfat. Ngoi
ra cn cho thm mt t cht men, cht ty trng, cht thm, cht mu, lng nc m v
mt vi ph gia khc.
Di y s trnh by r thm v cc thnh phn ny.

7.1.1. Cc cht HBM.

Cc cht HBM bao gm cc cht HBM anionic, cationic, khng ionic v
lng tnh.
Cht HBM anionic thng dng l ankylbenzosunfonat (1), ankansunfonat (2),
olefinsunfonat (3), hiroxiolefinsunfonat (4), este sunfonat ca axit bo (5),
ankylsunfat (6), sunfat ca oxietylancol bo (7).
1. RC6H4SO3Na.
2. RRCHSO3Na.
3. RCH2CH=CHCH2SO3Na.
4. RCH2CH(OH)(CH2)nCH2SO3Na.
5. RCH(SO3Na)COOCH3.
6. RCH2OSO3Na (R=C11-C17)
7. RRCHO(CH2CH2O)2OSO3Na
Cht HBM cationic nh mui amoni bc 4.
Cht HBM khng ionic.
1. RCH2O(CH2CH2O)nH (R= C8-C18) ancol oxietyl ha.
2. C12H25N(CH3)2O oxit amin
Cht HBM lng tnh nh :
1. C12H25N+(CH3)2(CH2)3OSO2-
2. C12H25(CH3)2CH2COO-

7.1.2. Cc mui natriphotphat.

Thnh phn mui natriphotphat trong cc cht git ra chim 30-50%; n c tc
dng to phc vi cc ion kim loi nng trong nc; ty theo loi mui photphat m t
l cc ion kim loi nng (Ca 2+, Mg2+, Fe3+) c th to ra khc nhau (bng 7.1). Mui
photphat l mt hn hp gm nhiu loi nh pyro-, meta-, ortho- v polyphotphat.

93
 Bng 7.1. T l cc ion kim loi to phc.
S gam kim loi to phc vi 100 gam photphat
Natriphotphat
Ca2+ Mg2+ Fe3+
Tetranatripyrophotphat 4,7 8,3 0,273
Hexanatrimetaphotphat 19,5 2,9 0,031
Tetranatrioliphotphat 18,5 3,8 0,092
Trinatripoliphotphat 13,4 6,4 0,184

Cc mui photphat c tc dng lm mm ha nc v iu chnh pH ca dng dch

git ra.
Metaphotphat b phn hy trong my git v to ra mt sn phm nht, ortho- v
pyrophotphat c tc dng git ra km v to kt ta canxi vi nc cng. Trinatri-
polyphotphat to phc vi in canxi v ngn nga mui canxi bm vo si, vi khi git.
Mt vi loi photphat ngng kt to ra cho cht git ra b vn cc, iu ny c
th trnh c khi trong thnh phn cht git ra c t l hn hp tetranatripyrophotphat
v hexanatrimetaphotphat t 4:1 n 1:1.
Mui trinatripoliphotphat c kh nng to phc vi ion kim loi kim th v phn
tn cht mu nhng trong dung dch nc d b thy phn cho axit pyro- v
orthophotphat.
Na5P3O10 + H2O Na4P2O7 + NaH2PO4
pyro- orthorphotphat
Mui trinatripoliphotphat lm tng bn ca nc v do thiu s c mt ca
n trong thnh phn cht git ra s lm gim cht lng ca sn phm.

7.1.3. Silicat.
Silicat kim loi kim ha tan l mt h ha hc phc tp. Dung dch ca n c th
cha monome, ime v polime vi khi lng phn t cao. S c mt ca silicat c th
lm thay i tnh cht ca mui photphat. N c tc dng lm gim s n mn thit b.
N c kh nng lm tng cht lng ca cc cht git ra. Nng ti thiu ca silicat
natri Na2SiO3 l 700g/ml, c tc dng c ch n mn kim loi. Hn hp silicat- photphat
lm tng nng ti hn mixen (CCM) ca cht HBM v lm tng hot tnh b mt.
Silicat c tc dng lm n nh pH, c tc dng st trng yu, gim s to bi ca
cht git ra, lm tng phm cht ca n v lm gim s ht m.

7.1.4. Cacboxymetylxenluloz (KMX).

Cacboxymetylxenluloz l este ca xenluloz v axit glycolic:
[C6H7O2(OH)3-x(OCH2COOH)x]n n = 300 1000
Mc polime ha n xc nh mm ca dung dch KMX trong nc v cc
tnh cht khc. Cc cht git ra c KMX dng mui natri.
ngha c bn ca KMX l ngn nga s lng ng v lm bn trn si, KMX
c kh nng gi duy tr cc cht bn trong dung dch v lm tng trng ca si ln
1,6-1,7 ln. KMX cn phi dng ht n d dng phn tn v khng b ha tan.

94
7.1.5. Mt s mui khc.
Natri sunfat c tc dng in li, n lm tc dng hot ng b mt tt hn. Trong
1 lt cht git ra c khong 1 gam natri sunfat, n thng c phn ng axit.
Canxicacbonat lm tng phn ng kim v lm tng kh nng to huyn ph. Tuy
nhin hin nay n ch c s dng mt lng gii hn.

7.1.6. Cht ty trng.

Hin nay trong bt git lun lun c pha trn cht ty trng, thng dng l cc
cht hu c nh stilben, cumarin, pyrazolin ty theo yu cu ca sn phm. Cht ty
trng ch chim mt lng nh, khong 0,5% khi lng.
Cht ty trng l cc cht mu pht quang c kh nng hp th nh sng vng t
ngoi 300-400nm v thay i n sang vng kh kin 400-500nm. Trng hp khng c
vng tia t ngoi th tc dng ty trng vn c bo tn. Khi ng thi cho vi cht ty
trng khc nhau vo cht ty ra s cho kt qu tt hn v ph hp th nh sng rng
hn, si hoc vi git trng hn. Hng nghin cu hin nay l tng hp cc cht ty
trng c tc dng bn vi nh sng v ty trng hn.
Cht ty trng hin nay hay dng l trans-triazinaminostiben v -
metylumbeliphenon. Ngoi ra cng dng cht v c nh natripeborat NaBO 2.H2O2.3H2O
lm cht ty trng. N c th chim mt lng ln (20-30% trng lng) lm tng
trng ca si khi git v lm sch cc vt bn ca qu chn, da, cacao, c ph, ru nho.
Tc dng ty trng ca natripeborat l phn ng oxi ha, trc tin l ca H 2O2 sinh ra
oxi hot ng x l si vi. Trong iu kin nhit 90 0C, pH=1010,5 cc borat b
phn hy nhanh to ra oxi cho phn ng oxi ha ni trn.
Cc cht ty quang
R1 R1
N N
N NH CH CH NH N
N N
R2 R2
SO3Na NaO3S
Dn xut stiben 4,4'-bis(4-anilin-6-mopholin-s-triazin-2-ylamino)-
-2,2-stilben isunfonat natri

R1 NH

R2 O N

CH CH CH CH

SO3Na NaO3S
Tinopal-CBS-X (Ciba Geigy)
(Dn xut iphenyl)

95
 N N
N CH CH N
N N
SO3Na NaO3S
Blankopho BHC (Bayer)
(Dn xut stilben)
CH3 CH3
CH3 CH3

NaO3S O O SO3Na

4,4'-bis(3,5-dimetyl-6-sunfonat natri benzo furan) diphenyl (Ciba-Geigy)

7.1.7. Cht lm gim nht.

Vi mc ch lm gim nht ca cc hp phn cht git ra, lm tng cht
lng ca n, ngi ta thm vo cc cht ph gia. Cc cht ny thng dng l
ankylbenzosunfoaxit (ch yu l toluen- v xylensunfoaxit).
Cc cht phn t nh khng phi l cht HBM, tc dng ca n l lm thay i
thnh phn hn hp.
CH3 C2H5

SO 3Na
Natri benzensunfonat SO 3Na SO3Na
Natri p-toluensunfonat Natrietylbenzensunfonat
CH3 CH3 HC(CH3)2
H3C

CH3 CH3
SO3Na SO3Na SO3Na
Natri (NH4, K, Mg, Ca) Mui cumensunfonat
1,3-imetylbenzensunfonat Mui ca
1,3,4-trimetylbenzensunfonat
C(CH3)3

SO3Na
Natri t-butylbenzensunfonat

96
7.1.8. Cc enzim.
Cc cht git ra vi thnh phn trn (cht HBM, photphat, borat,
cacboxymetylxenluloz, cht ty trng) khng lm sch c cc vt bn nh mu,
sa v cc cht protein khc. lm sch cc cht ny phi dng cc loi enzim vi sinh.
Cc enzim l cc phn t protein sinh hc ph bin trong thin nhin, phi trn
thm cc enzim (proteaza) vo thnh phn cht ty ra, xc tc phn hy protein thnh
cc hp cht tan trong nc. Cc loi enzim ny thu c qua ln men sinh hc.
Cc cht l cc enzim amilaza thy phn hirocacbon v lipaza phn hy
cht bo. Cc enzim trn vo cht ty ra trng thi kh hoc phun dung dch nng
cao vo natripolyphotphat, to ra cc dng ht.
C ch hot ng ca enzim c th nu ra theo s sau:
E + S ES E + PP
E- enzim S-c cht ban u P-sn phm
Phn ng c thc hin theo hai giai on, ban u enzim gp c cht to ra mt
cht phc hp, sau n gii phng enzim v to ra sn phm.
Qu trnh lm sch vt bn ca enzim c th m t theo s sau:

Vt bn Enzim
Enzim tin li vt bn Enzim bm vo vt bn Vt bn b ph Vt bn tan vo nc
gii phng enzim

Nng ca enzim, cc yu t vt l, ha hc bn ngoi u c nh hng n

hot ng ca enzim. Tc ng ca enzim b suy gim, chng hn cc mui khan khng
nh hng n tc ng ca enzim nhng mui ngm nc (v d Na 2SO4.10H2O;
Na2CO3.10H2O; NaBO2.4H2O) li lm suy gim tc ng ca enzim.

7.1.9. Cht bo v chng nh nng mt tri.

bo v s thay i ca mu sc v cu trc si ca qun o, vi vc phi ngoi
nng trc tc ng ca nh sng mt tri ngi ta thm vo cht ty ra cc cht chng
tc ng ca nh sng mt tri c bit l cc tia t ngoi. V d cht di y:
R2 NH N NH

SO3Na
O
C NH SO3Na NH
R1
NH
C O
Ciba (95) N R1
NH R2

97
7.2. Cng thc pha ch cc cht ty ra.
Mi hng sn xut u c cng thc pha ch cc cht ty ra ring ca mnh, tuy
nhin chng cng c thnh phn gii hn chung cho mi loi cht ty ra.

7.2.1. Bt git v x phng dng bnh.

Thnh phn ca bt git bao gm cc cht HBM nh ABS,LAD ,cc cht lm
mm nc v n nh pH nh TPP ( trinatri poliphotphat), natri silicat, Na cacbonat, Na
sunfat,cc cht ty quang,cht mu v cht thmV d c th xem cc bng 7.2 di
y.

Bng 7.2. Thnh phn cc cht.

Loi thng thng Loi c cha enzim
Cc cht HBM 15-20% 17
Trinatripolyphotphat 40-45% 35
Tetranatripyrophotphat --
Natrisilicat 3-8 5-8
Cacboxymetylxenluloz 0,9-1 1
Natripeborat 20-25 0-20
Mui peoxit n nh 0,3-2 0-2
Natri toluensunfonat 0-2
Cht ty quang 0,3-0,4 0,2
Natrisunfat 10-25 33
Cht m 5-10 5

Loi x phng git c s dng ph bin trc y l x phng dng bnh ,cc
git nh qun o, chn mn ,khn mt c ngm t sau st x phng , v
bng tay v ngm mt thi gian ri mi x nc .X phng dng cng c p khun
c trng lng v kch thc thay i ,nguyn liu chnh l mui natri ca axit bo thu
c qua thy phn du bo ng thc vt nh m b,du da,du c ngoi ra cn
cc ph gia khc nh silicat ,t st.
7.2.2. Cht git ra dng lng.
Cc cht git ra dng lng l cc sn phm ang thu ht ngi tiu dung hin
nay,cng thc pha ch chung c mt s im khc so vi cc cht git ra dng bt. Kh
khn cn gii quyt y l vn lm du nc vic git gi t hiu qu tt v
khng th a mt cht ty tng vo dung dch.Ngi ta khc phc bng cch thay bi
thnh phn v t l mt s cht nh nu ra bng 7.3.

Bng 7.3. Thnh phn cc cht.

Ra bng tay Ra bng my
Ankylbenzensunfonat 6,5-8,5 6

98
 X phng kali 1,5-2,2 2,6
Cht HBM 2,5-3,5 3,5
Toluensunfonat - 1
Trinatripolyphotphat 27-30 25
Natrisilicat 2 -
Cht ty quang 0,1 0,1
Enzim - 9Gu/mg
Pentaborat - 2
Glixerol - 5
Du thm 0,4 0,2
Nc 100 100

7.2.3. Cht lm mm si vi.

Cc vi si git nhiu ln thng b s cng li, lm mm chng ngi ta pha
ch dung dch cht lm mm sau khi git ty bng cc cht ty ra. Bng 7.4 ch ra cng
thc chung ca cht lm mm si vi.

Bng 7.4. Cng thc chung ca cht lm mm si vi.

Cng thc A
isterylimetylamoni clorua (DSDMAC) 6-9%
Du thm 0,2-0,5%
Mu 0,0001%
nc 100
Cng thc B
Diankyl imidazolin (75%) 6-9%
Du thm 0,2-0,5%
Mu 0,0001%
Nc 100

Tc dng ca cht lm mm si vi:

Si vi trc khi git nhiu ln rt mt m nhng sau khi git nhiu ln th b
s, c cht ng bm ca cc loi mui trong nc vo cc x ny thnh cc cng, c
khuynh hng ngn cn dung dch git ra thm vo.

S i vi ban u S i vi bs S i vi bsv c mui ng

bm vo sau khi gi t nhiu ln
Trong cc dung dch nc git, si cha in tch m cho nn c khuynh hng
ht cc phn t DSDMAC mang in tch dng lm trung ha in v tan vo nc,
cc si vi c gi sch v tr nn mm mi.

7.2.4. Cht ra chn, bt, knh, men s.

99
 Cc cht ra chn bt,ni soong ,bn tm,bn ra bt, bp gas, vi nc,knhl lau
chi b mt vt rn c cc vt bn du m , r st i hi phi c thnh phn cc cht ty
sch du m, ty sch r st,ty vt m trn knh . Bng 7.5 l mt v d v thnh phn
cc cht pha ch cht ty ra chn ,bt,knh ,men s

Bng 7.5. Thnh phn cc cht.

Ankylbenzen mch thng 13-15%
Ankyletesunfat (Na) RO(CH2CH2O)n-SO3 0-3
+
Ankyletesunfat (NH4 ) 0-7
*
AOS 0-3
ietanolamit 1-2
Xilensunfonat Na 0-3
Ur 2-3
Etanol 1
Du thm, cht mu, nc 100
*
Anpha olephinsunfat (AOS)

7.2.5. X phng tm.

Thnh phn chnh ca x phng tm l mui natri ca axit cacboxylic mch di
R-COONa, n thu c qua thy phn du m thc vt.
R C O CH2 CH2OH
O
NaOH
R C O CH CHOH + 3RCOONa
O
R C O CH2 CH2OH
O Glixerin
Cc cht bo chnh c dng l du da, du c, m b v m d cu. Thnh phn axit
cacboxylic trong cc loi du m ny thay i t C10 n C20 nh bng 7.6.
pha ch c x phng tm, ngoi mui natri ca cc axit bo mch di cn
i hi cc cht ph gia khc (bng 7.7).

Bng 7.6. Thnh phn axit trong du, m cng nghip (%).
Mch cacbon <C10 C10 C12 C14 C16 C16 C18 C18 C20 C20* >C20**
Axitcacboxylic Capric myristic Palmitoleic Oleic
lauric Palmitic Stearic linoleic
Du ci da 9,5 6,0 47 18 9,4 0,1 2,0 5,5 2,5 0,0 0,0
Du c (ht) 3,5 3,0 47 16,2 8,6 0,2 2,3 16,1 3,1 0,0 0,0
M 0,0 0,0 0,0 3,4 25,6 4,7 22,3 38,4 3,2 0,5 0,5
Du c (v) 0,0 0,0 0,0 1,4 56,9 0,4 5,1 28,5 7,2 0,1 0,1
* arachidic, gardoneic
** axit no v khng no
Ngoi ra trong x phng tm cn c cc cht khc nh cc cht bo qun, cht mu, cht
thm, cht ty quang, cht dit khun.
100
 Bng 7.7. Thnh phn ph gia ch yu ca x phng tm.
Thnh phn cc cht Tc dng
Axyl coco isothionat Na Hot cht to bt v ty ra.
LAS Na Tc ng tc to bt v khi lng bt
X phng Cho bt mt cm gic kem lm do ha
Isothinat Na Cht lm rn li
Stearat Na Cht lm rn li
Oxit titan (TiO2) Chn sng, sc trng
Axit stearic Cht do ha, mm mi
Du khong cht Du tm
Hng liu To mi thm
Bng 8.8. Cng thc pha ch x phng tm.
Thnh phn cc cht T l phn trm (%)
Axyl coco isothionat Na 44-60
Alkyl benzen sunfonat Na 0-2
X phng 7-8
Isothinat Na 2
Axit stearic 15-19
Natrisunfat 5
Cht bo qun +
7.2.6
Oxit titan (TiO2) 0,2 Nc
Du thm + tm
Nc Va 100 v sa
tm
Nc tm
Trong my nm gn y lm du nc tm to ra cm gic d chu ngi ta thng cho
thm mt cht ph gia vao nc tm ,cc cht ny thng l hn hp mt s mui v cht thm
nh cng thc cho bng di.Cc mui ny c tc dng lm mm nc v gim kimv
vy cc dung dch ny cn c gi l mui tm. Cng thc (II) l sn phm c cht lng
cao hn ,c thm cc cht HBM to bt nh x phng tm ( bng 7.9 v 7.10 ) .

Bng 7.9 Cng thc pha ch dung dch ph gia nc tm (I)

Ph gia/ Cng thc A B C
Na Tripoliphotphat 45-55 45-55 -
Na Sesquitcacbonat 45-50 -
Na Clorua - 45-55 75-90
Borax - - -
Du thm + + 5-20
Cht mu + + +
+

101
 Bng 7.10 Cng thc pha ch dung dch ph gia nc tm (II)
Cht ph gia T l
Na bicacbonat 40-50
Axit tactaric 35-45
Natri Hexametaphotphat 8-15
Cacboxylmrtyl xenlulose 1,5-3
Na Laurylsunfat 2,5-7
Du thm +

Sa tm
Sa tm l sn phm s dng khi tm bn hay di vi hoa sen c dung thong dng hin
nay ,thnh phn ca n thay i ty theo hng sn xut tuy nhin c th phn lm hai loi : loi
khng cha x phng ( mui natri miristat,oleat,laurat ..),v loi c cha x phng. Khng k x
phng,thnh phn ca chng bao gm cc cht HBM khc, cht chng oxiha,cht bo
qun ,du thm c bit l cht to nhn l silicon nh cc cng thc nu ra bng 7.11 v
7.12 di y.

Bng 7.11 Cng thc pha ch sa tm ( I )

Cht / Cng thc A / T l B / T l

Na Isothionat 9 5
LES - 2
Cocobetain 6 -
Cocoamidopropyl betain - 8
Du silicon 5 5
Jaguar C-13-5 (+) 0,1 0,1
Fomol 0,1 0,1
Cht bo qun + +
Du thm,nc 100 100

Bng 7.12 Cng thc pha ch sa tm ( II )

Cht / Cng thc A(sn phm trong) B ( sn phm c )

T l T l

Axit miristic 5-8 58

Axit lauric 58 58
Axit oleic 2 4,5 2 4,5
Glixerin 10 - 15 10-15
NaOH 49% 7 10 7 10
Fomol 0,05-0,25 0,05-0,025
Coco amidopropyl betain 12 20 12-20

102
Silicon(th sa) - 2- 6
EDTA Na 0,05- 0,15 0,05-0,15
BHT (+) 0,02-0,07 0,02-0,07
NaCl + +
Cht mu + +
Du thm + +
Nc 100 100

(+) BHT - 2,6 -i-tert-butyl 4-metyl phenol

7.3. Du gi u
Du gi u l loi x phng gi u dng lng ng chai, chc nng ca n l
gi sch tc, ty ht cc cht bn do bi bm, du v cc t bo da cht bm trn tc
v da u gi l gu. Du gi u m bo mt s tnh cht sau:
- D dng ha tan trong nc cng hay mm.
- To bt nhanh v tiu tan nhanh khi x nc.
- C trung tnh cao, khng n da.
- Lm sch tc, sch gu, to cho tc mm, trn mt, trnh rng tc nhiu.
- C mi thm d chu.
c c cc tnh cht nh vy, du gi u bao gm cc thnh phn cht sau
y: cc cht HBM, cht iu ha, cht chng gu, cht dng tc v cht thm.

Thnh phn cc cht trong du gi u:

1. Cht hot ng b mt.
Cht HBM gi vai tr quan trng trong thnh phn du gi u, n bao gm
nhiu loi, mi loi c u, nhc im ring.
a. Cht hot ng b mt anionic.
- X phng hay mui Na, K ca axit bo, thu c qua thy phn du m.
Chng c u im l gi r, khng ty i nhiu vt du m trn da u, lm
tc mm nhng c nhc im l kim hi cao, b gim bt trong nc
cng.
- Cc cht ankyl v arylsunfonat c tc dng ty ra tt, ty d cao, kh nng
to bt tt, gi khng t..
- Sunfat (ankylsunfat PAS, ankyleste sunfat LES) c tc dng ty ra tt, to
nh tng tt, to bt tt.
- Amit th, v d axylsacosinat R-CO-N(CH3)CH2COO- c c tnh ty ra tt,
ha tan trong nc cng d hn x phng, to cho tc v da mm mi.
- Polioxietilen R(OCH2CH2)nOCH2COO- c tc dng ty ra tt, d x, d ha
tan pH thp, tuy nhin t to bt.
b. Cht hot ng b mt cationic; v d:
*
R C NH(CH2)3 NH CH2CH2O
O CH2CH2O

103
 To bt tt, lm mm tc sau khi gi nhng v mt sinh l lm cay nga.
c. Cc cht HBM lng tnh, v d ankyl amidobetain, c kh nng tc ng trc
tip mnh, t c hi, t lm rt da hn cc cht HBM cationic, chng thng
kt hp vi cc cht HBM khc lm du gi u du i.
d. Cc cht HBM khc: ngoi ra cn dng mt s loi cht HBM khc nh
monoetanolamit, cc este poliol, cc oxit amin cc cht ny c tc dng to bt,
ty ra tt.
2. Cht iu ha.
Mt s cht ty ra thng c tc dng mnh trn cht du da u, da tay v
trn tc, l iu khng tt cho du gi u, ngi ta phi cho thm mt s cht vo
iu ha tc dng ny lm v hiu ha tc dng ny du gi u.
Cc cht cho thm vo nh lanolin, lexitin (c trong lng trng trng), polime
cationic, silicon hay este sorbitan polietoxi ha:
HO Si(CH3) O Si(CH3) O Si(CH3) OH
n
imeticonol
3. Cht chng gu
Cht chng gu c ba cch tc ng:
- Gim tc thay th t bo mi
- Ngn cn s tng trng ca loi men nm, nguyn nhn chnh sn sinh ra
gu.
- Gim phn trm axit bo trn da u, chng to ra mt mi trng nui cc
vi sinh vt trong c men nm.
gim cc tc ng trn ngi ta cho thm vo du gi u mt s cht nh
selen sunfua, piriinthion, piroctonolamin, etanolamin, hiroxipiridon,
imiazolylxeton.

N O S CH3 CH3
CH3 C CH2 CH CH2
Zn
S O CH3 N
O
Piri
inthion Piroctonolanin

CH3
O
R O CH C R
N
R N O
OH N
Hiroxipiriinon Imiazolylxeton
4. Cc thnh phn khc
Ngoi ba thnh phn trn, trong du gi u cng cn mt s thnh phn khc nh:

104
- Cc cht lm c v cc cht lm ng nh, thng s dng cc cht sau:
ancolamin ca axit bo, ru cacbon mch di, este etilen glicol, glixeron.
- Cht lm st v iu chnh nhn: thng dng cc cht in gii v c nh
NaCl v cc cht c th ha tan xenluloz, cht polime cacboxyvinylic c
dng di ci tn Carpopol l cht lm st tt.
- Cht bo qun, cht chng oxiha, cht dng thng dng l fomanehit hoc
brnpol (2-brom-2-nitropropan-1,3-iol)
NO2
HO CH2 C CH2 OH
Br
Cht chng oxiha l 2,6-i-t-butyl-u-metylphenol
OH
(CH3)3C C(CH3)3

CH3

- Vitamin A, B, C v D chng can thip vo vic kim sot hin tng oxiha
kh lm cho mu ca da u lu thng hn.
- Cc cht lm n nh bt, cc cht thng dng l mono v ietanolamit, n
cng c tc dng lm thay i cc c tnh v nhn ca sn phm.
Bng 7.13 cho cng thc chung ca cc du gi u tc thng v bng 7.14
cho cng thc chung du gi u c x.

Bng 7.13 Thnh phn cc loi cht c trong du gi u.

Thnh phn cc cht A (Trong) B (c)
Cht hot ng b mt (LES) 10-15 10-15
Cht ng hot ng b mt (CAPB) 2-4 2-4
Mono hay ietanolamit 0-1 0-1
Cht n nh lm c 0 0,5-2
Cht chng oxi ha + +
Cht bo qun + +
Cht thnh phn iu chnh nhn -/+ -/+

Bng 7.14. Cng thc chung ca thnh phn du gi vi cht x.

Thnh phn cc cht T l %
LES 10-15
CAPB 1-4
Nh tng silicon 0-1,5
Polime cacboxyvinyl (Carbopol) 0-0,3
Stearat etilenglicol 0,5-1,5
Clorua hiroxipropyl trimonium (Guar) 0,1-0,5
105
 Du thm +
Fomol 0,05-0,15
BHT 0,025-0,06
NaCl 0,5-1,5
Cht mu +
Axit xitric/NaOH +
Vitamin +
Nc va 100

7.4. Kem nh rng.

Kem nh rng c chc nng lm sch v bng rng, thnh phn ca n gm
nhiu loi c chc nng khc nhau. Kem nh rng c hai loi: loi c mu trng v
loi trong do thnh phn ph gia khc nhau to thnh. Thnh phn cc cht trong kem
nh rng, t l pha ch chng quyt nh cht lng ca kem nh rng. Thnh phn
chnh ca kem nh rng nh di y.

7.4.1. Nc v tc nhn lm t.
Nc c tc dng ha tan cc tc nhn tr liu, ty ra, lm st v lm du. Cc
tc nhn lm t gip lm gim khi lng nc trong cng thc pha ch. Cc cht
thng dng l sorbitol HOCH2[CH(OH)]4CH2OH ; glixerin HOCH2CHOHCH2OH,
sorbitol v glixerol c tc dng lm du.

7.4.2. Cc cht ty ra.

Cc cht ny c tc dng to bt, gip ty trng rng v ha tan, phn tn mi
hng khng tan trong nc.
Cht to bt thng dng l:
Na-laurylsunphat: CH3-(CH2)11SO3(-)Na
Na-ankylbenzensunfonat: CH3-(CH2)11C6H4SO3(-)Na(+)

7.4.3. Cc cht mi mn.

Cc cht mi mn c tc dng c xt lm sch, bng rng, m bo nhn ca
kem nh rng. Cc cht mi mn chnh c dng l: oxitsilic SiO 2, canxicacbonat
CaCO3, hiroxit nhm Al(OH)3; icanxiphotphat CaHPO4.2H2O, natrimetphotphat
NaPO3, canxi pyrophotphat Ca2P2O7. Cc cht ny khng lm h hi men rng nhng c
kh nng lm sach vt bn.

7.4.4. Cc cht lm st.

Chng cho php trnh s lng ng ca cht mi mnv lm thay i cc c tnh
nhn cho sn phm; n to cu trc pha lng ca sn phm, lm l lng cht mi
mn. Cu trc ny bin mt khi bp ng kem v c ti to li khi p sut ln ng
ngng.

106
 Cc cht c dng lm st l cc cht hu c hay khong, nhng polime nh
cacboxymetyl xenluloz, gm xantan (polime thin nhin).

7.4.5. Cc cht to cu trc.

C th s dng polime glicol to cu trc v ha tan ng thi c mi hng
v cht hot ng b mt.

7.4.6. Cc cht lm du
C tc dng to v gic d chu, che du cc v ng ca mt s cht. Cht c
dng nhiu nht l ng Sacarin:
O

N Na
S
O O
Sacarin

7.4.7. Cc cht lm c v cht mu.

Cht thng dng l oxit Titan (TiO2) lm kem trng hn.
Cc cht mu pha vo phi m bo an ton thc phm, gi thnh khng cao.

7.4.8. Cht n nh v iu chnh pH.

Cc cht lm n nh v iu chnh pH khi n mn v kim loi nhm, thng
l iu chnh pH ca cht. Cc cht thng dng l Natrimonophotphat NaH 2PO4, citrat
km.

7.4.9. Cht to hng thm.

Cc cht to mi thm thng dng nh menthol, vanilin, metylsalisilat, engenol,
mint
CH3 CHO
COOCH3
OH
OH CH3
OH
H3C CH3

Methol Vanilin Metylsalisilat

107
 CH3 CH3
OH
O
OCH3
O

CH2CH=CH2 CH3 CH2 H3C CH3

Eugenol Mint Eucaliptol

7.4.10. Cc cht bo qun.

Cht lm m mang li bo qun kem nh rng khong b cng khi ct gi. Cc
cht thng dng fomol, natribenzoat, kalisorbat, metyl p-benzoat.

7.4.11. Cc tc nhn t liu.

Cc cht chng cao rng thng dng l natri pyrophotphat, kali tetraphotphat.
Cc tc nhn chng nhy cm l stroti, stronti axetat, cc mui kaliclorua, nitrat, xitrat..
Cc tc nhn dit khun, lm sch ba rng thng dng km xitrat, tricloxan (Irgasan
DP 300 ca Ciba Geigv).

Cl O Cl

Cl HO
Triclosan

7.4.12. Cht bo v men rng

Cht bo v men rng, thng gi l cht chng su rng, thng dng l cc mui flo
nh natriflorua, NaPO3F (Natri monoflorophotphat), florua amin.

Bng 8.11. Cng thc kem nh rng c

Thnh phn cc cht T l phn trm (%)
Natriflorua 0,22
Km clorua 2,0
Sorbitol (70%) 35,0
Glixerol 10,0
Silichirat ha 23,0
Taurat Na 3,75
Gm xanthan 1,0
Hiroxietyl xenluloz 1,0
Na Gluconat 0,8
Titan oxit 0,8
Na saccarinat 0,7
Saccarin 0,1
Natri benzoat 0,2

108
 Hng v 1,3
Nc kh khong va 100

Bng 8.11. Cng thc kem nh rng trong

Thnh phn cc cht T l phn trm (%)
Glixerol (99,5%) 9,95
Sorbitol (70%) 33,88
CMC Na 0,4
Caragen 0,4
Natriflorua 0,243
Na saccarinat 0,3
Anhirit polivinyl ete maleic 2,0
Sa 50% 0,6
Silica kt ta 2,2
PAS Na 1,5
Hng v 1,5
Triclosan 0,3
Nc va 100

7.5 Du thm
Du thm c ngha quan trng trong vic pha ch cc cht git ra nh cc loi x
phng, sa tm,kem nh rng ,du gi u ,n to ra mi thm cho sn phm. Do cc nguyn
liu sn xut cc cht git ra c cc mi kh chu khc nhau nh mui axit bo c mi hi
ca du, mui amin bc bn c mi tanh c , mui ankylsunfat c mi hi ,enzym mt vi loi
c mi kh chu ...v th cn thm cc cht thm vo to mi d chu. Mi thm dng cho cc
loi sn phm cng khc nhau v d x phng tm,du gi u thng c hng thm ca cc
loi hoa nh hoa hng , hoa nhi,hoa hu,hoa violet .. .c bit to ra cc mi thm khng c
trong t nhin nhng lai rt quyn r , kem nh rng thng c mi hoa qu nh mi
cam,chanh,l,to.... pha ch cc loi du thm ny rt phc tp v n phi dng nhiu loi
ha cht pha trn vi nhau theo cc t l khc nhau v nhn mi i hi phi c cc chuyn
gia ngi mi nh gi, thng l b quyt ring ca cc hng sn xut.V cc loi ha cht pha
ch trong nc thm thng c cc cht c th phn ng vi cht HBM cng nh cc thnh
phn khc c trong cht git ra cho nn khi pha ch cht thm vo cng phi la chn loi cht
thm thch hp khng gy phn ng lm mt mi thm hoc i khi bin n thnh mi kh
chu. Ngoi ra cng cn ch n tnh cht bm mi ca cc loi du thm, pha vo x
phng sa tm, du gi u ...cn loi du thm gi c mi lu nhng pha vo thuc nh
rng ,nc ra chn bt ...cn loi mt mi nhanh.
Di y nu ra mt s cng thc du thm c pha ch tuy nhin cngch c tnh cht
tng trng.

Du hoa hng ( I )

Geraniol 50 g
Ancol phenyletilic 10-
Roinol 20-
Butyl isoeugenol 20-
109
Axetat paracresyl 5-
Nha geranium 45-

Du hoa hng ( II )

Tinh du hoa c 50 g
Geraniol 100-
Tinh du inh hng 20-
Tinh du Miobe 20-
B 100-
Axetat benzyl 20
X hu 10-
Citral 10-
Tinh du hoc hng 10-
Tinh du qu 20-

Du hoa cm chng

Eugenol hoc isoeugenol v ete 100g

Axetat benzyl 25-
Pelagoniol 25-
Nha cy hoa hng 50-

Du hoa hu hng

Terpineol 200g
Tinh du rau mi 5-
Propinat benzyl 100-
Salixilat benzyl 10-
Linalol 200-
Cumarin 20-
X hng 5-

Du hoa hu d hng

Tinh du hoa hu d hng 20g

Tinh du qu hnh ng 1-
Vanilin 0,5-
Tinh du geranium 6-
Thuc nhum x 5-

Du hoa violet

Tinh du bergamo 6g
Linalol 2-
Tinh du cy irit 2-

110
Nha thm peron 10-
Thuc nhum x 5-
Terpineol 4-

Du hng nhi

Benzyl axetat 5 phn

Linalyl axetat ca g hoa hng 2-
Ancol benzilic 15-
Dung dch ecylic anehit 1/10 0,5-
-Amylxinamic anehit 10-
Metylanthrnilat kt tinh 0,60-
Tinh du lng iris 1/10 0,50-
Tinh du hoa nhi lng 0,50-
Tinh du y lng Manila 1,0
- Ionon trng 0,5
Nerol 1,0
Rhoinol 1,5-
Rhoinyl axetat 0,5-
Linalol t tuyn ca g cy hoa hng
Guyam va 100 phn

Nc hoa cologne

Nc ct hoa hng 50 ml
Cn 90o 900-
Tinh du chanh 6-
Tinh du inh hng 0,10-
Tinh du ht nh 0,10-
Tinh du hung 0,50-
Tinh du thanh yn 0,40-
Cn x hng thin nhin 0,60-
Cn cnh kin Thi lan 1/10 10-
Nc ct 50-
Tinh du Bergamot 6-
Cn long din hng 5-

Du mi cam

Ancol phenyl etilic 10 %

Linalol 10 -
Nerol 10 -

111
 Nerolidol 10 -
- Naphtyl metyl xeton 1 -
- Naphtyl etyl ete 1 -
-Naphtyl metyl ete 1 -

Du mi chanh

Tinh du chanh 10 %
ecanal 0-1-
Metyl anthranilat 1-
Metyl N-metylanthranilat 1-
Limonen 10-
ipenten (racemic ) 10-

Chng 8

Ph gia du m,vt liu xy dng,cao su

v cht do

Ph gia du m c ngha quan trng nng cao cht lng ca du m bi

trn, phn ln cc cht ph gia l cc cht hot ng b mt, chng c pha ch vo
du gc. Ngoi ra cn nhiu lnh vc khc nh sn xut vt liu xy dng, vt liu cao
phn t, cht mu , cng ngh dc phm,cng ngh thc phmcng cn cc cht ph
gia trong cc cht HBM ng mt vai tr nht nh.

8.1. Du gc.
Hu ht cc cht bi trn nhm lm gim s mi mn ca cc vt ma st l cht
lng v dng m, thnh phn chnh l hirocacbon thng hoc mch vng v pha thm
cht ph gia.
Phn hirocacbon c gi l du gc, c sn xut t du khong, chng cha
cc thnh phn hirocacbon sau :
- Parafin mch thng v mch nhnh.
- Hirocacbon no n v a vng cha mch nhnh.
- Hirocacbon thm n v a vng cha mch nhnh
Trong du bi trn thnh phn parafin mch thng di phi gim ti mc thp
nht v n l mch sp rn, trong khi parafin mch nhnh li rt tt cho mc ch bi
trn v n c n nh nhit v tnh nhit nht tt. Cc hirocacbon vng thm ngng
t cng nhiu v mch nhnh cng ngn th tnh nhit nht cng km v cng khng
thch hp dng lm du m bi trn (bng 8.1).

112
 Bng 8.1. nht v ch s nht ca mt s hirocacbon.
Cng thc cu to nht (VSO.mm2/s) Ch s nht
2-Metyleicozan (C21) 165
2,2-Metyltricozan (C24) 163
2,4,6-Trimetylheneicosan (C24) 118
Iso-C28H58 6,9 148
C24 17,5 130

C17 20,0 100

C13 40,0 50

C9 315,0 -120

C18 50,0 70

C10 60,0 0

C3 250 -325

Du khong bi trn no cng u l hn hp cc hiroccbon, mi phn on c

cc tnh cht ha l ring (bng 8.2).
p ng yu cu v thnh phn, du gc cn c sn xut t du th qua cc
giai on tinh luyn nh chng ct hon thin, chit bng dung mi, dng dung mi tch
sp v x l tinh ch. Vic la chn du gc pha ch cht bi trn ph thuc vo
nht, mc tinh ch, n nh v kh nng tng hp vi cc cht ph gia v vt liu
m du bi trn s tip xc trong qu trnh s dng.

Bng 8.2. Tnh cht vt l v ha hc ca cc loi du gc khong.

Tnh cht/Thnh phn ha hc Du parafin Du naphten Du aromat
0 2
nht 40 C, mm /s 40 40 36
0 2
nht 100 C, mm /s 6,2 5,0 4,0
Ch s nht 100 0 -185
T trng d420 0,8628 0,9194 0,9826
Nhit chp chy, 0C 229 174 160
0
im anilin, C 107 73 17
0
Nhit ng c, C -15 -30 -24

113
 Phn t lng 440 330 246
Ch s khc x 1,4755 1,5068 1,5503
Phn tch qua t st
% hp cht phn cc 0,2 3,0 6,0
% hp phn thm 8,5 43 80
% thnh phn no 91,3 54 14
Loi nguyn t cacbon
% CA (aromat) 2 19 41
% CN (naphten) 32 37 36
% CP (parafin) 66 44 23

8.2. Ph gia du m bi trn.

Ph gia du m bi trn l nhng hp cht hu c, c kim v v c. Cc cht ny
c thm vo du gc vi nng 0,01 n 5%. Phn ln cc loi du nhn cn nhiu
loi ph gia p ng yu cu tnh nng v cht lng ca du m bi trn. Cc loi
ph gia khc nhau c th h tr cho nhau nhng cng c khi dn n hiu ng i
khng. V th vic t hp cc ph gia cho mi loi du cn nghin cu th nghim cn
thn. Mt khc, du gc cng nh hng n ph gia do hai tnh nng chnh l tnh ha
tan v tnh tng hp. Du gc c tnh ha tan cao c th gi ph gia dng ho tan m
khng cho php n hp th, ngc li nu ha tan km c th ph gia b tch trc khi
n hon thnh chc nng nh.
Cc cht ph gia c nhiu loi ty thuc vo chc nng ca n. C th nu ra cc
chc nng chnh sau:
- Lm tng bn oxi ha (cht c ch oxi ha).
- Ngn chn hiu ng xc tc ca kim loi trong qu trnh oxi ha v n mn
(cht kh hot tnh kim loi).
- Chng n mn (cht c ch n mn).
- Chng g (cht c ch g).
- Chng s to cn bm v cn bn (ph gia ra).
- Gi cc tp cht bn dng huyn ph (ph gia phn tn).
- Tng ch s nht (ph gia tng ch s nht).
- Gim nhit ng c (ph gia lm gim nhit ng c).
- Lm du c th trn ln vi nc (ph gia to nh).
- Chng to bt (ph gia chng to bt).
- Ngn chn s pht trin ca vi sinh vt (ph gia dit khun).
- Lm cho du c kh nng bm dnh tt (tc nhn bm dnh).
- Tng kh nng lm kn (tc nhn lm kn).
- Lm gim ma st (ph gia gim ma st).
- Lm gim v ngn chn s mi mn (ph gia chng mi mn).
- Chng s kt xc cc b mt kim loi (ph gia cc p).
Thc t cho thy cc cht ph gia trn y phn ln thuc dy cc cht hot ng
b mt, phn t chng u c cha cc nhm hirophin nh OH, -COOH, -SO 3H, este

114
v cc nhm lipophin l cc gc ankyl mch di hay cc vng thm c th gc ankyl,
ngoi ra c c cc cht khng ionic cha nhm polyoxietilen ca cc hp cht photphat.

8.2.1. Cht c ch g.
G l s hnh thnh st hiroxit, l mt dng c bit quan trng ca n mn b
mt kim loi. Cc cht c ch g ngn nc thm qua mng hu c bn v, n phi l
cc cht phn cc hp ph chn lc trn b mt kim loi v tc dng nh mt mng ngn
cch chng m. Cc cht c ch chng g in hnh l:
- Axit ankenylsucxinic v cc dn xut, cng nh axit ankylthioaxetic v dn
xut, dng cho du tuabin, du thy lc.
- Cc imiazolin dng cho du bnh rng.
- Amin photphat dng cho du bo qun.
- Sunfonat, amin, photphat, este dng cho du ng c.
- Cc sunfonat trung tnh hoc kim yu dng cho du bo qun ng c.
Sunfonat canxi v natri dng ph bin vi nng 0,1-2%, cc amin bo t 1,5-
2%, axit ankylsucxinic 0,2%, monobutyl este ca stearylglioxan 0,05%.

8.2.2. Cc cht ty ra.

Tc nhn quan trng lm ph gia ty ra l cc cht:
- Sunfonat c gc ankyl.
- Phenolat c gc ankyl.
- Salixylat c gc ankyl.
- Photphat c gc ankyl.
Dng mui canxi v magie ca chng c s dng lm cht ty ra cha kim
loi. V cu trc phn t cc cht ny c nhm hirophin SO 3(-),COO(-),O(-) v c
phn lipophin l gc ankyl mch di hay vng benzen th gc ankyl nh cu to di
y:
O Ca O O
S S S O Ca OH
O O O O
R R O R

canxi sunfonat canxi sunfonat kim

trung tnh
M M
O O O O
CH2

R R R R
Ankylphenolat kim loi ankylphenolat kim loi c cu metylen

115
 M
O O A M O O M A
(S)x Sx

R R R R
Sunfua ankyl phenolat kim loi Sunfua ankyl phenolat kim loi
O C O Ca O C O O C O Ca OH

HO OH HO

R R R
canxi ankylsalixylat trung tnh canxi ankylsalixylat kim

M
O O O O
R P M R P M R P S P R
S O O O O O
Thiophotphat kim loi Photphonat kim loi Thiopyrophotphat kim loi
C ch tc dng ca cc cht hot ng b mt ny l to mixen, ht nhn l
cacbonat kim loi MCO3, nh ui k nc nn cc ht mixen ny tan vo lp du bi
trn v ty ra sch ch bn. Thng thng nhng ph gia ny l loi kim cao c cha
cacbonat kim loi kim phn tn trong du do chng c kh nng trung ha axit to
thnh trong qui trnh chy v tip xc vi nc. Cu trc n gin ca mt mixen cht
ty ra cacbonat kim cao th hin hnh 9.1.

M
M

M (MCO3)n M

M M

Hnh 9.1. Cu trc mixen ca ph gia kim cao.

Cc sunfonat trung tnh, kim, kim cao l nhng ph gia c in nht, sunfonat
kim cao c hnh thnh bi phn ng gia mt sunfonat kim loi trung tnh v
hiroxit kim loi. Phn ng thng xy ra trong ancol, n ha tan mt lng nh
hiroxit kim loi, sau khi tip xc vi CO2 s to thnh cacbonat kim loi.

116
 Sunfonat kim loi kim cao c s dng rng ri trong cc du ng c v du
xylanh tu bin nh l cc tc nhn ty ra. Phenolat kim loi kim c s dng rng
ri lm cht ty ra, chng oxi ha v tc nhn kim trong cc du ng c.
Ankylsalixilat kim loi cng c dng nhiu cho du ng c nh cht ty ra v cht
chng oxi ha. Nhm cc cht photphonat khng c s dng rng ri nh sunfonat,
phenolat v salixilat lm cht ty ra, cc cht ny c cu to:
O O
R P M R P M
S O O O
Thiophotphat Photphat

8.2.3. Cc cht phn tn.

Cc cht phn tn l cc ph gia c kh nng ngn nga hoc lm chm qu trnh
to cn v lng ng trong iu kin lm vic nhit thp. Chng c mt i lc mnh
vi cc tiu phn gy bn du v chng bao quanh mi tiu phn bng cc phn t tan
trong du, nh gi cho cc cn du khng b kt t v ng cn li trong ng c.
Cc cht phn tn l nhng cht c mt u phn cc cha O, N hoc P v mt
mch hirocacbon, thc cht chng l cc cht hot ng b mt. Cc ph gia phn tn
quan trng nht l:
- Ankenyl poliamin sucxinimit.
- Ankyl hiroxibenzyl poliamin.
- Este polihiroxisuxinic.
- Poliaminamit imidazolin.
- Poliamin suxinamit.
- Este photphonat.
O A
R CH C
N CH2 CH2 NH CH2 n CH2 NH2
CH2 C
O
Ankenylpoliaminsuxinimit
O O
R CH C C CH R
N CH2(A)x CH2 N
CH2 C C CH2
O O
Ankenylpoliaminbisuxinimit
R-ankenyl t isobutenyl c trng lng phn t 500-2000 v n = 1-4

117
 OH
O
R CH C
CH2 (NH CH2 CH2)n NH2
OH CH2OH
CH2 C O CH2 C CH2OH
R O CH2OH
Hiroxibenzyl poliamin (R-poiisobutenyl) Polihiroxisuxinic (R-poiisobutenyl)
H2C CH2 H2C CH2
S
N N CH2 CH2 N CH2 CH2 N N
C C R P O (CH2 CH2 O)n H
C
R O R R O (CH2 CH2 O)n H

Poliaminamitimiazolin Estephotphonat (R-poiisobutenyl)

8.2.4 Cht ci thin ch s nht.

Cc cht ci thin ch s nht hay gi tt l ci thin nht l cc polime tan
trong du c tc dng lm tng nht ca du. Cc polime ny c phn t lng t
10.000 n 500.000.
Cc cht ny c chia thnh hai nhm: dng hirocacbon v dng este. Cc
hirocacbon l:
- Copolime etilen-propilen.
- Poliisobutilen.
- Copolime stiren-butaien.
- Copolime stiren-isopren.
Cc este l polimeacrilat, poliacrilat, copolime ca este stirenmaleic.
O Polimeaclirat
C
OR
C CH2
CH3
n
CH2 CH2 n CH2 CH n Copolime etilen-propilen
CH3
Poliisobutilen
CH3
CH2 C
CH3
n

118
 O O Copolime ca stiren v este maleic
C OR C OR
CH CH2 CH CH
n

O Copolime ca ankylmetacrylat v
C vinylpirolydon
OR
CH2 C CH2 CH
n n
CH3 N
H2C C O
CH2 CH2

8.2.5. Cht to nh v kh nh.

Khi du m bi trn lm vic c mt ca nc cn s dng cht to nh hoc kh
nh phn tn nc trong du hay du trong nc. Cht to nh hay kh nh u l
cc cht hot ng b mt nh:
- Cc ankenyl sucxinimic.
- Mui ankyl sunfonat.
- Axit bo v mui ca chng.
- Este ca axit bo.
- Cc poliankylen glicol.
- Cc phenol v phenol este.
- Cc amit ca du tallo.
- Etanol amin.
Cc cht HBM ny u thuc ba nhm l anionic, cationic v khng ionic di y :
- Anionic : mui axit R-COO(-)Na(+) (x phng) ; mui sunfonat R-SO3(-)Na(+)
- Cationic: mui amoni bc 4 (R4N)(+)X(-)
- Khng ionic: ancol polihiric hoc polioxietilen (CH2CH2O)n

8.2.6. Ph gia chng to bt.

S to bt c th gy ra nhiu rc ri khi vn hnh h bi trn, n nh hng xu
ti tnh cht bi trn ca du v lm tng s oxi ha. chng s to bt thng dng
mt s cht:
CH3
- Poliimetyl siloxan Si O
CH3 n

- Polimetacrilat
- Ankylsunfonat
- Glixerolmonostearat

119
 - Ankylankenylithiophotphat.
Cc cht ny bm vo bt khng kh lm gim sc cng b mt, khin cc bt
bong bng nh t hp thnh bt ln, ni ln mt v b ph v.

8.2.7. Cht c ch n mn.

Cc cht c ch oxi ha ng thi cng c tc dng chng n mn. Cc cht c
ch n mn to thnh mt mng bo v trn b mt kim loi, ngn cn s tip xc gia
cc tc nhn n mn nh axit, peoxit v cc cht khc vi mt kim loi. Mng hp ph
bo v cng gim ti thiu tc dng xc tc oxi ha ca kim loi.
Cc cht c ch n mn c s dng rng ri l:
- ithiophotphat kim loi, c bit l km.
- iankylithiophotphat
- Cc ankensunfua ha
- Cc tecpensunfua ha nh limonensunfua
CH3

S
CH3 C CH2
- Sunfonat kim loi
- Benzothiazol
H
N
N
N
- Sunfua phenolat kim loi
- Dn xut mecaptothiothiazol

8.2.8. Ph gia bin tnh ma st.

Ph gia bin tnh ma st l cht lm gim h s ma st v t c s trt
phng. Ph gia loi ny lm tng bn ca mng du v nh gi c bn mt
kim loi. Cc cht ph gia loi ny l cc cht HBM c nhm phn cc v mch
hirocacbon di; chng c th l este, amit hay axit bo; v d:

X (nhm phn cc)

CH3CH2(CH2)nCH2- X vi - OH -CONH2
- COOH - CN
- COOR - NH2

Bng 8.3 ch ra s so snh tc dng ca cc loi ph gia. Bng 8.4 cho v d t l

ph gia trong du SAE30, SAE40.

Bng 8.3. So snh chung v cc chc nng ca ph gia

120
 Chc nng Sunfonat Phenolat Salixilat Photphat
Ty ra Rt tt Tt Rt tt Tt
Tr s kim tng Tt Rt tt Rt tt Trung bnh
Chng oxi ha Khng Rt tt Rt tt Tt
bn thy phn Trung bnh Tt Tt Tt
c ch g Tt Km Km Tt
Gim ma st Khng Trung bnh Tt Trung bnh
Bn nhit Tuyt i Tuyt i Tuyt i Trung bnh

Bng 8.4. Thnh phn du ng c SAE30, SAE40.

Thnh phn % trng lng
Du gc 71,5-96,2
Cht ty ra 2-10
Cht phn tn khng no 1-9
Km iankylithiophotphat 0,5-3,0
Ph gia chng oxi ha v chng mi mn 0,1-2,0
Cht bin tnh ma st 0,1-3,0
Cht h im ng 0,1-1,5
Cht c ch to bt 2-15ppm

Cc cht hot ng b mt c ng dng rng ri trong nhiu nghnh cng nghip

,ngoi cng ngh sn xut cc cht git ra,cc cht ph gia du m ni trn cn
nhiu lnh vc khc nh sn xut vt liu xy dng, vt liu cao phn t, cht mu ,
cng ngh dc phm,cng ngh thc phm

8.3 Sn xut vt liu xy dng

8.3.1 At phan v nh ha
Lnh vc quan trng nht ca atphan l bao ph b mt ca cc con ng beton
atphan. y n cn phi lin kt gia atphan v cc vt liu khc nh dm mt
cch cht ch to ra mt lin kt bn vng ca con ng.Nhng trn b mt vt
liu thng khng sch c bit lun c mt nc do atphan khng th bm cht
c Cc nghin cu thy rng tnh axit hay tnh kim ca cc khong v pH ca
mi trng nc c nh hng n tnh bm dnh ca atphan. Theo quy tc cc b
mt axit th atphan d b bc ra hn b mt kim nhng pH thp li lm tng tnh
bm dnh ca atphan trn b mt axit .Ngc li trn b mt kim gi tr pH cao li
lm tng tnh bm dnh . S b xung cc cht hot ng b mt c th lm tng kh
nng bm dnh ca atphan. Cc vt liu v c c che mt lp x phng ng s
lm tng kh nng bm dnh bitum.
Atphan thng c s dng di dng nh tng nc trong du hay du
trong nc . a s cc loi atphan d dng to nh tng khi thm vo mt lng
nh cc cht x phng kim loi lm cht nh ha. Cng c th thm vo cc cht
HBM cationic nh mui amin bc 4 . Cc mui kim loi nng v cc axit
ankylsunfonic tan trong du cng c dng lm cht nh ha to nh nc ca
atphan. Cc nh tng c nc l tng ngoi c th s dng cc cht HBM tan

121
 trong nc lm cht nh ha.S la chn cht nh ha ph thuc vo yu cu bn
ca nh tng v vo bn cht loi atphan.C l c tnh ca atphan l quan trng v
c th loi x phng kim loi ny l cht nh ha thch hp cho mt loi atphan ny
nhng li khng thch hp cho loi atphan khc . Cc loi ankylsunfonat kim loi
cng l cht nh ha thch hp cho mt s loi atphan.

8.3.2 Xi mng pooclng v b tng

V mt cng ngh, s ch to v s ngng kt xi mng pooclng c lin quan
n hin tng ha hc b mt do vic s dng cc cht HBM trong cc giai
on khc nhau ca qu trnh sn xut ny l cn thit. do ca ximng tng ln
khi c mt cc cht HBM nh ankyl- hay ankylarylsunfonat ,ligninsunfonat ,cc
cht to phc nh axit etilendiamintetraaxetic l cc cht ha do tt.
Natri tripolophotphat l cht HBM thm vo c tc dng lm lng ha nguyn
liu ,thun li cho qu trnh bm nguyn liu ximng pooclng vo l nung . Hiu
ng chy lng ny cho php s dng cc bn c cha cht rn l cht lm gim tui
th ca l t nng.
ngn nga s mt nc ca bn ximng c th s dng cc cht
cacboxymetylxenluloz , oxietilenxenluloz,sunfoxenluloz v cc dn xut tng t
ca tinh bt. Betonit v canxi ligninsunfonat cng c s dng vi mc ch ny.
Ph gia ha hc cho va v b tng c vai tr ht sc quan trng trong xy
dng.Ph gia ha hc thch hp ng vai tr kim sot tnh cht cng ngh ca hn
hp b tng ti nh do ,thi gian ng kt ,kh nng thi cng v tnh cht c
trng ca b tng khi ng rn. Ph gia ha hc c phn thnh cc loi nh :
- Ph gia gim nc
- Ph gia chm ng kt
- Ph gia lm nhanh ng kt
- Ph gia gim nc v lm chm ng kt
- Ph gia gim nc v lm nhanh ng kt
- Ph gia gim nc mc cao ( ph gia siu ro )
- Ph gia gim nc mc cao v lm gim ng kt ( ph gia siu ro v lm
chm ng kt ).

Thnh phn ha hc v khong ca clanke xi mng pooclng : trong clanke xi

mng pooclng c cha 4 oxit chnh l CaO , SiO2 , Al2O3 v Fe2O3 vi hm lng
ca chng chim t 95 -97% . Ngoi ra cn mt lng nh cc oxit khc nh
MgO,TiO2,SO3,Mn2O3 ,Cr2O3,P2O5.BaO,K2O v Na2O . Khi nung phi liu nhit
cao ,tng ng vi 4 oxit chnh c 4 loi khong chnh c to thnh l :
- Alit l loi khong c hm lng ln nht trong clanke xi mng pooclng c
to thnh nhit ln hn 12500C .Thnh phn ha hc ch yu ca alit l
3CaO.SiO2. N lm cho xi mng c cng cao v pht trin nhanh chng.
- Blit c cng thc 2CaO.Al2O3 c to thnh nhit thp hn so vi
alit.Khi thy ha n ng kt chm ,pht trin cng chm.
- Aluminat canxi c cng thc 3CaO.Al2O3 . Aluminat canxi l khong quan
trng cng vi alit to nn cng ban u ca xi mng.

122
- Alumoferit c cng thc 4CaO.Al2O3.Fe2O3 thy ha chmnn xi mng c
hm lng alumoferit cao s c cng thp.

Phn ng thy ha ca cc khong clanke xi mng thc cht l cc phn ng

ha hc ca oxit kimloi vi H2O to ra cc dng oxit kim loi ngm nc ,v d thy
ha alit v belit xy ra nh sau :

3CaO.SiO2 + 3H2O = 2CaO.SiO2 . 2H2O + Ca(OH)2

2CaO.SiO2 + 3H2O = CaO.SiO2 . 2H2O + Ca(OH)2

S thy ha aluminat canxi xy ra ph thuc vo iu kin phn ng cho cc sn

phm khc nhau nh :

2 (3CaO.Al2O3) + 21H2O = 4CaO.Al2O3.13H2O + 2 CaO.Al2O3.8H2O

2 ( 3CaO.Al2O3) + 27H2O = 4CaO.Al2O3.19H2O + 2CaO.Al2O3.8H2O

S thy ha alumoferit xy ra theo cc phn ng sau :

4CaO.Al2O3.Fe2O3 + 13H2O = 4CaO.Al2O3.Fe2O3.13H2O

4CaO.Al2O3.Fe2O3 + 10H2O = 3CaO(Al,Fe)2O3.6H2O + Ca(OH)2 +
+ Fe 2O3.H2O

Ph gia siu do :
Ph gia siu do l cc hp cht t nhin hoc tng hp c trng lng phn t
cao.Ph gia siu do cho php gim mt lng ln nc trn m it nh hng n
thi gian ng kt,lng li kh,tch nc,phn tng cng nh cc tnh cht khc ca
vt liu xi mng ng rn.Ph gia siu ro thc t c th gim ti 30% lng nc
trn trong khi ph gia ha do thng ch gim khong 10-15% lng nc.
Cc loi ph gia siu do c s dng l cc polime nh melaminsunfonat
fomanehit (1) , naphtalen- sunfonat fomanehit (2) , lignosunfonat (3), polisacarit
thin nhin..(4).

H OH2CHN N NHCH2 O

N N

NH
n
CH2SO3Na

Melaminsunfonat (1)

123
 SO3Na

CH2
n

Naphtalensunfonat fomanehit (2)

CH2OH

O
OH
O O
OH
n

Polisacarit ( 4)

Ph gia tr nghin ximng

Trong cng nghip xi mng ,cng on nghin xi mng l mt trong nhng cng on
quan trng quyt nh cht lng xi mng . Vic nghin xi mng lin quan trc tip n cht
lng ca xi mng do t lu th gii quan tm n qu trnh ny,t nhng nm u th
k trc nhiu hng trn th gii nghin cu s dng ph gia trong qu trnh nghin xi
mng ( gi l ph gia tr nghin ) ,hng Grace ( M ) a vo s dng ph gia tr
nghin TDA da trn cht HBM natri naphtalensunfonat , HEA-2 trn c s dn xut ca
amin axetat v gn y l cc ph gia tr nghin TDA-7, WGA-2 ,CBC,RGA,CBA t
trietanolamin bin tnh. Lin x trc y ,cc nc SNG ngy nay,Php,,Trung quc
cng u s dng hiu qu cc ph gia tr nghin xi mng trn c s trietanol bin
tnh,poliol ...Chng u l cc cht HBM.

8.4 Ph gia trong sn xut cao su tng hp v cht do

iu ch cao su tng hp v cht do

1/ Polime ha nh tng
Qu trnh polime ha nh tng trn c s to ra nh tng ca monome hay hn
hp monome trong mi trng nc ri giai on khi mo v pht trin , cui cng
l m bn vng. Nh tng ban u khng ch cha monome ,cht nh ha m c
cht xc tc v cht iu chnh cho php iu chnh qu trnh polime ha ch to
ra polime vi trng lng phn t c ln thch hp. Cht nh ha trong qu trnh
polime ha l cht hot ng b mt tan trong nc thng dng hn hp.
124
 Cc cht hot ng b mt ng vai tr quan trng trong qu trnh polime ,trc
tin to ra cc ht mixen m cc monome khuch tn trong thun li cho qu trnh
polime ha nht l cc monome khng tan trong nc. y cc phn ng ha hc
xy ra v cc monome kt hp vi nhau thnh hng chc ri hng trm phn t cui
cng to ra phn t polime c ln mong mun.
Chng hn khi polime ha nh tng stiren s dng cht HBM l cc
ankylarensunfonat , ancol sunfoesteha , sunfoete . Thc nghim thy rng khi iu
ch m polisiren s dng hn hp cc cht HBM nh x phng hay
oexylsunfonat cho hiu qu cao.
Cc nh tng bn vng polime v copolime ca vinyleste nh s c mt ca
cc cht nh ha nh axit ankylsunfonic v axit oxiankylsunfonic
,iankylsunfosuccinat v sunfosuccinamit . Nh tng vi phn tn rt bn thu
c khi s dng cht nh ha l iankylsunfosuccinat vi keo hidrophin ca cc cht
ngun gc thc vt hay oxietilenxenluloz.Khi polime ha cc vinyleste mch di cn
s dng cht nh ha l hn hp l ankylsunfonat v ete sorbitan .
iu ch cc polime acrylic v etilenic : Cc polime acrylnotrin v copolime
c iu chh dng nh tng vi s c mt ca cc cht nh ha nh ankylsunfat
bo v du m . Cc esteacrylic , axit metaacrylic v cc copolime ca chng d dng
c polime ha dng nh tng khi c mt cc cht hot ng anionic,cationic ,
khng ion ha v hn hp ca chng. Polime ha etilen trong nh c thc hin
bng cch dn kh di p sut vo dung dch natri olein p-aniziinsunfonat v mui
amoniaqc ca axit metaacylic . iu ch nh polietilen cn s dng hn hp cht
nh ha hot ng anion v cht in li cacboxylha. Cc polome v copolime ca
triflocloetilen c iu ch dng nh c mt cht nh ha l este ankylpoliglicolic
bo .
Polime ha dng nh stiren s dng cht nh ha l natri dodexylete sunfonat
(SSDSE) c nng ti hn 2x10-3 M v natri acrylamido undecanoat (SAU ) c
nng ti hn 25oC l 5x10-3 M .

CH2=CH-C6H4-O-(CH2)12SO3Na
(SSDSE)

CH2=CH-CONH-(CH2)10COONa
( SAU )

2/ Polime ha dng huyn ph

Polime ha dng huyn ph khc nhiu vi polime ha dng nh . Kch thc
ca cc phn t polime bt k thu c ca dng huyn ph thng ln hn ca
polime ha dng nh v th dng huyn ph cc m khng to ra , polime c th
c tch ra t hn hp lc n gin. C hai kiu polime ha dng nh v dng huyn
ph khc nhau khng nhiu v mt c ch nhng polime ha dng huyn ph
thng cho dng khi . Cc cht HBM c s dng l cc cht c kh nng to
huyn ph, chng thuc hai nhm , nhm u l cc keo hu c hirophin nh
polivinylancol ,dn xut xenluloz tan trong nc cn nhm khc l cc cht v c v

125
d cao lanh ,betonit.. Polime ha stiren dng huyn ph s dng cht ph gia l
polivinyl ancol v tricanxiphotphat phn tn cao. Polivinyl ancol cng vi cc cht
bn vng ha c s dng polime ha vinylclorua, vinylaxetat v hn hp ca
chng.

3/ Bn vng ha dng m v s hnh thnh vng sa

tng bn ca cc m cao su thin nhin v tng hp phi s dng cc cht
HBM tan trong nc v cc cht keo bo v hirophin t nhin hay hn hp.
X phng bo , natri ligninsunfat l cc cht bn vng ha m tt ,nh n m cao su
ng t li , tch phn nc d v to ra dng phn tn. Dng m cng c th c
bn vng ha bng cc cht HBBM mui amoni bc bn nh xetylpiriinbromua .

4 / S phn tn cc vt liu khc nhau trong cao su v m

Ngi ta thng trn mui nc phn tn vi m cao su n ng t,vic ny phi
tin hnh cn thn theo tiu chun k thut nu khng cc cht phn tn khng ng
nht dn n m b kt t hay keo t li . Qu trnh polime ha cng nh s ng t
m cao su c th thm cc ci mui cht ph gia l x phng v cc cht HBM phn
tn khc nh cc dn xut ca lignin , axit stearic , mui amoni bc bn .
Mt trong nhng vn quan trng sn xut lp t ,xe my l phi lm sao to
ra s kt dnh bn chc gia lp m cao su vi lp mnh si vi . Trn thc t cn
phi thm t lp vi si bng cc cht HBM trc khi ph cao su. Cc cht
hay dng i vi loi si bng l cc cht HBM cationic nh cc mui amoni th
bc bn hay cc loi x phng amin.
Trong s cc cht thm t v cht HBM anion c th s dng ankkylsunfonat,
ankylnaphtalinsunfonat ,chng lm tng bn lin kt si v cao su.
Bng 8.5 ch ra mt s cc cht HBM thuc cc dy anionic,cationic v khng
ionic c s dng hin nay trong qu trnh polime ha dng nh . Tt c cc cht
ny c th nghim vi qu trnh polime ha dng nh stiren nhng mi ch s t
c th nghim vi dng phn tn . l trng hp cc cht nhm metacrilic
(A3) ,nhm crotonic (A4) ,nhm maleic ( A2) . T stiren butylacrilat cc ht
copolime ( nh hn 40 nm ) c iu ch vi s c mt ca natri oexyl sunfat
( SDS ) . Copolime dng phn tn ( core shell copolimer ) theo t l 49,5:49,5:1 ca
stiren / butyl acrilat / axit acrilic v cha n 50% dng rn . S chuyn ha tt c
cc monome k c cc cht HBM c xc nh. Thc nghim cho thy nhm
cht maleic ( A2 ) c tc dng tt nht cho qu trnh copolie ha stiren dng phn tn
trong s ba cht trn.

Bng 8.5 Mt s cht HBM dng cho qu trnh polime ha

K hiu Tn cht Cng thc cu to

1/ Cht HBM anionic :

A1 Hemieste ca anhidrit maleic CnH2n+1OCOCH=CH-COO-COONa

n = 8,10,12,14,16,18
126
 A2 Ankyl maleat propyl sunfonat CnH2n+1OCOCH=CH-COO-(CH2)3SO3Na
n=8-14
A3 Natri 11-metancryloyl-undecan- CH2= CH-COOC11H22-SO4Na
-1-oyl sunfat CH 3
A4 Natri 11-crotonoyl undecan- CH3-CH=CH-COOC11H22SO4Na
-1-oyl sunfat
2/ Cht HBM cationic

C1 Ankylmaleat trimetylamino CnH2n+1OCOCH=CH-COO -CH2-CH2- B

etyl bromit B : -CH 2N(CH3)3+Br- , n= 12
C2 Ankylmaleat anlyl piridini- CnH2n+1OCOCH=CH-COOCmH2mNC5H5Br
bromua
3/ Cht HBM khng ionic

N1 Maleic ieste CH3O(CH2CH2O)15COCH=CH-COOC12H25

N2 Copolime CH3O(CH2CH2O)45-[ CH2CH(C2H5)O]mH
(EO)n (BO)m m = 8, 9, 12
EO l -CH2CH2O-
BO l -CH2CH(C2H5)O-
N3 Me EO 45-BO9-CO-C(CH3)2-C(CN)-N=N-R
N4 Me EO 45-BO12-OCOCH2SH
N5 Me EO 45-BO9-S-C(C6H5)-CH=CH2

Bng PL1 .
SC CNG B MT CA DUNG DCH
127
 CC CHT HOT NG B MT
A- Cht HBM anionic
A1/ Mui cacboxylat

1/ Natri valeriat heptan - nc

C5H9O2Na C7H16 H2O
C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m
0 51,0 2,0 46,3 4,0 44,5
0,5 49,2 2,5 45,8 4,5 44,2
1,0 48,1 3,0 45,0 5,0 43,95
1,5 47,0 3,5 44,8

2/ Natri hexanoat-heptan-nc
C6H11O2Na - C7H16-H2O

C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m

0 51,0 2,0 44,4 4,0 41,2
0,5 48,6 2,5 43,4 4,5 40,8
1,0 46,8 3,0 42,6 5,0 40,2
1,5 45,3 3,5 41,8

3/ Natri octanoat heptan - nc

C8H15O2Na C7H16 - H2O

C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m

0 51,0 2,0 40,0 4,0 37,2
0,5 45,6 2,5 39,0 4,5 36,8
1,0 43,2 3,0 38,4 5,0 36,4
1,5 41,3 3,5 37,6

4/ Natri lauraan - heptan - nc

C12H23O2Na C7H16 H2O

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0 51,0 2,0 40,0 4,0 37,2
0,5 45,7 2,5 39,0 4,5 36,8
1,0 43,1 3,0 38,4 5,0 36,5
1,5 41,4 3,5 37,7

5/ Natri laurat heptan - nc vi (NH4)2SO4

C12H23O2Na-C7H16-H2O

128
Hm lng (NH4)2SO4 (mol/l) 0,4 (1) , 2,5 (2) , 3,0 (3)

C.105 mol/l .10-3N/m C.105 mol/l .10-3N/m

(1) (2) (3) (1) (2) (3)
0 51,6 51,8 52,2 1,5 48,8 45,0 33,6
0,5 50,6 49,6 42,6 2,0 48,0 43,0 32,6
1,0 49,7 47,0 36,0 2,5 47,4 41,4 31,6

6/ Liti hexanoat metanol

C6H11O2Li - CH4O

C.104 mol/l .10-3N/m C.104 mol/l .10-3N/m C.104 mol/l .10-3N/m

4,1 22,1 24,6 23,5 57,5 25,6
8,2 22,5 32,8 24,1 6 8,5 26,0
16,4 22,9 46,0 25,2

7/ Liti octanoat metanol

C8H15O2Li - CH4O

T l mol .10-3N/m T l mol .10-3N/m T l mol .10-3N/m

N.104 N.104 N.104
4,0 22,5 24,5 23,6 41,0 24,5
8,2 22,7 32,7 24,1 49,2 25,2
16,3 23,1

8/ Liti decanoat - metanol

C10H19O2Li CH4O

T l mol .10-3N/m T l mol .10-3N/m

N.104 N.104
8,1 25,1 32,8 27,5
16,4 25,7 41,0 27,8

9/ Liti laurat - metanol

C12H23O2 Li - CH4O

T l mol .10-3N/m T l mol .10-3N/m

N.104 N.104
4,0 25,0 16,2 25,8
8,1 25,3 24,3 26,4

10/ Liti oleat - metanol

129
 C18H33O2Li - CH4O

T l mol .10-3N/m
N.104

4,1 25,3
8,1 25,5
24,4 25,7

11/ Natri tridecanoat heptan - nc

C13H25O2Na C7H16 H2O

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0 51,0 0,31 43,9 2,48 31,0
0,07 48,2 0,61 40,8 4,90 22,0
0,15 46,7 1,25 39,2

12/ Natri oleat octan -nc

C18H33O2Na - C8H18 H2O

C.106 mol/l .10-3N/m C.106 mol/l .10-3N/m C.106 mol/l .10-3N/m

0 51,4 1,0 43,1 2,5 38,8
0,25 47,4 1,5 27,1 3,0 37,9
0,5 45,3 2,0 39,9

A2 / Mui ankylsunfat

1/ Natri octinsunfat - heptan - nc

C8H17SO4Na - C7H16 H2O
t = 500C

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0 48,2
1 45,4 10 35,9 60 16,7
2 43,8 15 32,9 80 12,5
3 42,7 20 30,4 90 10,9
5 40,4 30 25,7 100 9,6
7 37,9 40 22,3 120 9,6

2/ Natri dexylsnat heptan - nc

C10H21SO4Na C7H16 H2O

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,25 45,7 5 32,8 25 13,3
0,5 44,2 7 29,2 30 10,1
1 42,4 10 25,2 35 9,2
130
2 39,6 15 20,2 40 9,2
3 37,2 20 16,5 60 8,9

3/ Natri tetradexylsunfat heptan - nc

C14H29SO4Na C7H16 H2O

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,025 43,4 0,4 30,3 2,0 7,3
0,05 41,3 0,7 24,0 2,25 5,8
0,10 39,2 1 18,3 2,5 5,7
0,15 36,6 1,4 13,7 3 5,9

4/ Natri hexadexyl sunfat - heptan - nc

C16H33SO4Na C7H16 H2O

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,02 40,3 0,20 24,0 0,60 7,1
0,03 39,2 0,25 20,7 0,65 5,8
0,04 37,1 0,30 18,3 0,7 5,5
0,06 34,4 0,40 13,2 0,8 5,7
0,10 31,5 0,50 10,3 1,0 5,2
0,15 26,3 0,55 8,8

5/ Natri octadexylsunfat heptan - nc

C18H37SO4 Na - C7H16 H2O

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,010 37,7 0,08 19,5 0,18 5,3
0,015 35,3 0,10 15,2 0,20 4,1
0,02 33,2 0,13 11,4 0,25 4,0
0,03 30,5 0,15 9,1 0,3 3,8
0,06 22,3

6/ Natri icoxylsunfat heptan - nc

C20H41SO4Na C7H16 H2O
t = 600C

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,010 33,2 0,020 25,0
0,015 28,1 0,025 20,1

7/ Natri dexylsunfat - heptan - nc vi NaCl

C10H21SO4Na C7H16 H2O
131
Lc ion ca dung dch 3,2.10-2 mol/l

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,15 41,6 1,5 32,0 15 16,2
0,25 39,9 2,5 29,1 20 13,7
0,4 38,2 4 26,1 25 11,8
0,7 35,7 7 22,1 32 10,0
1,0 34,5 10 19,3

8/ Natri oexylsunfat - heptan - nc vi NaCl

C12H25SO4Na C7H16 H2O
Lc ion ca dung dch 8.10-3 mol/l

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,03 41,8 0,7 26,8 4 13,5
0,05 40,2 1,0 24,4 5 11,2
0,06 39,8 1,5 21,2 6 10,1
0,1 36,9 2 19,0 7 8,9
0,2 34,0 3 15,8 8 8,3
0,4 30,0

9/ Natri tetradexylsunfat - heptan - nc vi NaCl

C14H29SO4Na C7H16 H2O
Lc ion ca dung dch 2.10-3 mol/l
C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m
0,015 39,5 0,15 27,9 1,0 14,2
0,025 37,1 0,25 24,5 1,3 11,5
0,04 35,0 0,4 21,4 1,6 9,9
0,07 32,0 0,7 16,9 2,0 8,0
0,10 29,8

10/ Natri oexylsunfat - nc

C12H25SO4Na - H2O
Phng php p sut cc i
= 0,13% , t = 200C

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0 72,75 1,1 52,61 3,5 39,21
0,2 67,31 1,2 51,78 4,0 38,10
0,3 64,98 1,3 50,71 4,5 37,28
0,4 63,01 1,4 49,89 5,0 36,78
0,5 61,02 1,6 48,02 6,0 36,55
0,6 59,41 1,8 46,70 7,0 36,36
0,7 57,82 2,0 45,15 8,0 36,31
0,8 56,43 2,5 42,41 10,0 36,29
132
 0,9 55,25 3,0 40,60 15,0 36,29
1,0 53,99

11/ Natri oexylsunfat - nc

C12H25SO4Na - H2O
Phng php vng Diu Nui , t = 200C , hot chtb 99,9%

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,005 72,2 0,5 64,7 5 41,0
0,01 72,2 1 59,6 6 38,9
0,05 71,8 2 52,9 7 38,8
0,1 71,2 3 48,2 10 38,8

12/ Natri 2-triexylsunfat - nc

C13H27SO4Na - H2O
Phng php vng Diu Nui, t = 200C , hot cht 100,4%

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,001 72,3 0,1 69,3 2,5 45,8
0,005 71,8 0,5 59,8 3 43,5
0,01 71,8 1 54,4 5 38,3
0,05 70,3 2 48,2 10 38,0

13/ Natri 5-tetraexylsunfat - nc

C14H29SO4Na - H2O
Phng php vng Diu Nui , t = 200C , hot cht 99,8%

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,001 72,3 0,1 63,8 2 40,3
0,005 72,3 0,5 52,6 2,5 38,5
0,01 71,7 1 47,0 5 37,6
0,05 66,4 1,5 42,7 10 37,5

14/ Natri 7-pentadexylsunfat n][cs

C15H31SO4Na - H2O
Phng php Diu Nui, t = 200C cht hot ng 100,3%

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,001 71,4 0,1 60,2 2 36,7
0,005 70,0 0,5 50,6 3 36,7
0,01 68,1 1 43,1 5 36,5
0,05 62,9 1,5 37,3 10 36,4

15/ Nat ri 2-hexaexylsunfat - nc

C16H33SO4Na H2O
133
 Phng php Diu Nui , t = 200C , cht hot ng 99,4%

C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,001 71,8 0,15 44,6 1 37,4
0,005 69,9 0,25 40,5 2 37,0
0,01 65,0 0,3 39,0 3 36,9
0,05 57,7 0,5 37,1 5 37,1
0,1 49,5

A3/ Mui ankan- v ankylarylsunfonat

1/ Natri hexansunfonat - heptan - nc

C6H13SO3Na C7H16 H2O

C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m

0 51,0 1 46,2 2 43,2
0,5 48,6 1,5 44,4 3 30,8

2/ Natri octasunfonat heptan - nc

C8H17SO3Na C7H16 H2O

C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m C.102 mol/l .10-3N/m

0 51,0 1,5 37,0 2,5 35,0
0,05 41,6 2 35,8 3 34,3
1 38,6

3/ Natriecansunfonat - heptan - nc
C10H21SO3Na - C7H16 H2O

C.104 mol/l .10-3N/m C.104 mol/l .10-3N/m C.104 mol/l .10-3N/m

0 51,0 0,6 46,4 1,5 42,7
0,2 49,1 0,8 45,3 2,0 41,4
0,4 47,5 1,0 44,5

4/ Natri oekansunfonat heptan - nc

C12H25SO3Na - C7H16 H2O

C.104 mol/l .10-3N/m C.104 mol/l .10-3N/m C.104 mol/l .10-3N/m

0 51,0 0,6 41,2 1,2 36,8
0,2 46,4 0,8 39,6 1,4 35,7
0,4 43,2 1,0 38,3

5/ Natri hexaecansunfonat heptan - nc

C16H33SO3Na C7H16 H2O
134
C.105 mol/l .10-3N/m C.105 mol/l .10-3N/m C.105 mol/l .10-3N/m
0 51,0 0,3 31,7 0,5 29,4
0,1 41,2 0,4 30,1 0,6 29,1
0,2 34,7

6/ Natri hexaecansunfonat - nc
C16H33SO3Na H2O

C, %(khi lng ) .10-3N/m C, %(khi lng ) .10-3N/m

0,0010 55,1 0,015 35,2
0,0025 44,7 0,025 34,5
0,005 36,9

A4/ Mui sunfonat ca este axit cacbonic

1/ inatri monooexylsucxinatsuonat - nc
C16H28O7SNa2 H2O
Phng php Diu Nui , t = 200C ,C mol/l

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

3,5 71,3 3,1 70,3 2,8 65,9
3,4 71,2 3,0 69,6 2,7 63,1
3,3 71,1 2,9 68,1 2,6 60,2
3,2 70,8

2/ inatri monotetraexylsucxinatsunfonat - nc
C18H32O7SNa2 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

4,0 70,8 3,5 69,4 3,2 63,3
3,8 70,2 3,4 68,3 3,1 60,3
3,7 70,0 3,3 66,3 3,0 57,3
3,6 69,8

3/ inatri monohexaxylsucxinatsunfonat
C20H36O7SNa2 - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

4,8 71,8 4,4 69,9 4,15 64,4
4,7 71,7 4,35 68,9 4,1 63,2
4,6 71,6 4,3 67,8 4,0 61,0
4,55 71,5 4,25 66,7 3,9 58,7
135
4,5 71,2 4,2 65,5 3,8 56,4
4,45 70,7

4/ inatri monoheptadexylsucxinat - nc
C21H38O7SNa2 - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

5,7 71,9 5,2 69,2 4,8 64,2
5,6 71,9 5,1 68,0 4,7 62,9
5,5 71,7 5,0 66,8 4,6 61,5
5,4 71,0 4,9 65,5 4,5 60,2
5,3 70,2

B / Cht hot ng b mt cationic

B1/ Mui ankylamin

1/ Octylamoni clorua - nc
C8H20NCl H2O
Phng php Diu Nui , = 0,2 , t = 200C ,pH = 5 ( axit ho HCl ) , C mol/l

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

1,9 66,8 1,4 54,0 1,0 40,8
1,8 65,5 1,3 50,8 0,9 37,4
1,7 60,4 1,2 47,5 0,8 33,8
1,5 57,5

2/ oexylamoni clorua - nc
C12H28NCl H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

4,0 63,0 3,0 52,8 2,4 41,5
3,8 61,8 2,9 51,3 2,3 38,8
3,5 59,0 2,8 49,8 2,2 36,0
3,3 56,8 2,7 48,2 2,1 33,2
3,2 55,5 2,6 46,5 2,0 30,5
3,1 54,1 2,5 44,2 1,9 27,8

3/ Tetraexylamoni clorua - nc
C14H32NCl H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

3,7 57,0 3,3 52,2 2,9 40,1

136
 3,6 56,1 3,2 50,2 2,8 35,2
3,5 55,0 3,1 47,5 2,7 30,3
3,4 53,8 3,0 45,0

4/ Hexaexylamoni clorua - nc
C16H36NCl - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

5,1 64,0 4,0 45,8 3,5 34,5
4,9 61,2 3,9 43,8 3,4 32,0
4,7 58,0 3,8 41,9 3,3 29,4
4,4 52,8 3,7 39,7 3,25 28,0
4,2 49,2 3,6 37,0
5/ Octaexylamoni clorua
C18H40NCl H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

5,1 70,2 4,7 65,5 4,3 57,3
5,0 69,3 4,6 63,8 4,2 52,5
4,9 68,2 4,5 61,9 4,1 48,8
4,8 67,0 4,4 59,8 4,0 42,9

B2/ Mui bas amoni bc 4

1/ Hexaexyltrimetylamoni clorua octan - nc

C19H42NCl C8H18 H2O
Phng php Diu Nui , = 0,2 10-3 , t = 200C

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 50,5 2 42,3 7 34,8
0,5 47,1 3 40,5 10 32,6
1 48,1 5 37,3

2/ Octaexylamoniclorua octan - nc
C18H40NCl - C8H18 - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 50,4 2,0 47,8 4,0 46,3
0,5 49,6 3,0 46,9 5,0 45,7
1,0 48,8

3/ imetyliunexylamoni bromua - octan - nc

C24H52NBr - C8H18 - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 50,5 2 41,2 5 35,5

137
4/ ibutylhexaexyl propylamoni ioua octan - nc
C27H58NI C8H18 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 50,5 0,75 41,9 1,5 38,4
0,25 45,9 1,0 40,5 1,75 37,4
0,5 43,6 1,25 39,4

5/ imetylipentaexylamoni bromua - octan - nc

C32H68NBr C8H18 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 51,2 6 36,9 18 21,2
2 49,3 10 29,4 20 16,5
4 42,9 12 26,4

6/ Hexaexylioctylpropylamoni ioua octan - nc

C25H74NI C8H18 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 51,0 3 34,0 8 28,2
1 40,2 4 32,2 10 27,0
2 36,4 6 29,9

7/ imetyloctaexylamoni clorua - octan - nc

C38H80NCl - C8H18 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 51,6 8 28,6 14 20,2
2 44,2 10 24,9 16 16,3
4 37,2 12 21,7 20 12,4

8/ imetylioctaexylamoni clorua - nc vi NaCl

C38H80NCl - C8H18 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

0 51,4 1,0 43,5 2,5 38,3
0,25 49,0 1,5 41,3 3,0 37,4
0,5 46,8 2,0 39,6

B3 / Mui ankylpiriini

1/ oexylpiriini clorua - bezen - nc

C17H30NCl C6H6 H2O
138
 Phng php tnh trng lng,th tch git , t = 200C

C.105 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

1,12 31,83 4,80 29,11 11,2 27,27
1,60 31,06 8,0 27,62 16,0 26,85
3,20 29,82

2/ Tetraexylpiriini bromua ete petrol ( EP) - nc

C19H34NBr - EP - H2O.

C.105 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,1 17,93 5,0 9,49
0,5 17,50 10 6,57
1,0 13,87

3/ Tetraexylpiriini EP - nc
C21H38NBr - EP - H2O

C.105 mol/l .10-3N/m C.103 mol/l .10-3N/m C.103 mol/l .10-3N/m

0,01 20,44 0,5 20,43 5,0 8,70
0,05 20,76 1,0 17,60 10,0 3,84
0,10 20,76

C / Cht hot ng b mt khng ionic

C1/ Ancol

1/ Propanol (1) - nc
2-Propanol (2) - nc
C3H8O H2O

C,mol/l .10-3 N/m C,mol/l .!0-3.N/m

-------------------------- --------------------------
1 2 1 2
-------------------------- --------------------------
0,03125 68,9 68,9 0,25 67,8 58,7
0,0625 66,9 66,8 0,5 50,7 52,2
0,125 63,3 63,8 1,0 42,5 45,3

2/ 2-Metylpropanol - nc
C4H10O - H2O

C,mol/l .10-3 N/m C,mol/l .!0-3.N/m C,mol/l .!0-3.N/m

0,0156 67,5 0,0625 59,0 0,25 44,1
0,03125 64,5 0,125 52,8 0,5 35,4
1,0 26,5
139
3/ 3-metylbutanol - nc
C5H12O H2O
C,mol/l .10-3 N/m C,mol/l .!0-3.N/m C,mol/l .!0-3.N/m
0,0078 66,0 0,03125 54,6 0,125 38,5

4/ Metanol - ecanol
CH4O - C10H22O
Phng php p sut cc i bt , = 0,03 , t = 25 0,010C , N -t l mol metanol.

N .10-3 N/m N .10-3 N/m N .10-3 N/m

0,1294 28,26 0,3952 28,09 0,6587 26,52
0,2092 28,24 0,4741 27,61 0,7744 25,16
0,3502 28,12 0,5454 27,32 0,9136 23,42

5/ Etanol - ecanol
C2H6O - C10H22O

N .10-3 N/m N .10-3 N/m N .10-3 N/m

0,1073 28,16 0,4778 27,01 0,7021 25,40
0,2905 27,85 0,5474 26,61 0,7960 24,57
0,3773 27,66 0,6025 26,30 0,8944 23,35

6/ Propanol - ecanol
C3H8O - C10H22O

N .10-3 N/m N .10-3 N/m N .10-3 N/m

0,1569 28,09 0,5015 27,04 0,7964 25,29
0,2624 27,95 0,5958 26,56 0,9003 24,28
0,4150 27,40 0,7004 25,96

7/ 2 Propanol - ecanol
C3H8O - C10H22O

N .10-3 N/m N .10-3 N/m N .10-3 N/m

0,1495 27,72 0,5117 25,89 0,7973 23,41
0,2846 27,29 0,5930 25,25 0,8974 22,19
0,4070 26,61 0,6929 24,40

8/ Butanol - ecanol
C4H10O - C10H22O

N .10-3 N/m N .10-3 N/m N .10-3 N/m

0,1513 28,11 0,5079 26,92 0,7918 25,60
0,2824 27,76 0,5952 26,59 0,8980 24,84
0,3982 27,40 0,6927 26,09
140
 9/ Hexanol - ecanol
C6H14O - C10H22O

N .10-3 N/m N .10-3 N/m N .10-3 N/m

0,1538 27,87 0,5002 27,27 0,7963 26,52
0,2782 27,68 0,6057 27,06 0,8907 26,25
0,3953 27,48 0,7033 26,09

10/ Butanol heptan - nc

C4H10O - C7H16 - H2O
Phng php Diu Nui , = 0,2 10-3 N/m ,t = 200C

C .10-2,mol/l .10-3 N/m C.10-2mol/l .!0-3.N/m C.10-2mol/l .!0-3.N/m

0 51,0 2, 0 45,5 4 ,5 40, 0
1,0 48,0 3,0 42,9 5,0 39,0
2,0 45,4 3,5 42,0

11/ Hexanol - heptan - nc

C6H14O - C7H16 - H2O

C .102,mol/l .10-3 N/m C.102mol/l .!0-3.N/m C.102mol/l .!0-3.N/m

0 51,0 0,75 34,0 1,25 28,5
0,5 39,5 1,0 30,3 1,5 27,0

C2/ Axit cacboxylic

1/ Axit propionic nc
C3H6O2 H2O

C ,mol/l .10-3 N/m C.mol/l .!0-3.N/m C.mol/l .!0-3.N/m

0,0156 70,7 0,125 64,5 0,5 54,0
0,0312 69,5 0,25 60,2 1,0 47,0
0,0625 67,7

2/ Axit butiric nc
C4H8O2 H2O

C .102,mol/l .10-3 N/m C.102mol/l .!0-3.N/m C.102mol/l .!0-3.N/m

0 71,5 3,125 65,8 25,0 47,9
0,78 70,0 6,25 61,6 50,0 39,9
1,56 69,1 12,5 54,3 100 32,3

3/ Axit isobutiric nc
C4H8O2 - H2O

141
C .102,mol/l .10-3 N/m C.102mol/l .!0-3.N/m C.102mol/l .!0-3.N/m
0 71,5 3,125 65,3 25,0 47,3
0,78 70,0 6,25 60,7 50,0 39,6
1,56 68,3 12,5 54,3 100 31,8

4/ Axit valeric - nc
C5H10O2 - H2O

C ,mol/l .10-3 N/m C.mol/l .!0-3.N/m C.mol/l .!0-3.N/m

0,008 67,4 0,060 55,6 0,80 42,0
0,016 64,8 0,080 52,8 0,200 43,5
0,024 62,5 0,100 50,6 0,240 42,1
0,040 59,2 0,120 48,6

5/ Axit hexanoic - nc
C6H12O2 - H2O

C ,mol/l .10-3 N/m C.mol/l .!0-3.N/m C.mol/l .!0-3.N/m

0,005 66,2 0,031 49,4 0,062 40,8
0,008 63,6 0,039 46,8 0,069 38,9
0,016 56,5 0,047 44,5 0,078 37,4
0,024 52,8 0,054 42,4

6/ Axit valeric nc vi 0,01M HCl

C5H10O2 - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

2,58 69,9 1,80 62,0 1,60 57,2
2,32 68,1 1,75 61,3 1,52 55,3
2,05 65,5 1,71 60,4 1,45 53,5
1,90 63,5 1,66 59,2 1,32 50,6

7/ Axit hexanoic - nc vi 0,01M HCl

C6H12O2 H2O

C .103,mol/l .10-3 N/m C.103mol/l .!0-3.N/m C.103mol/l .!0-3.N/m

1,0 70,7 5,0 61,4 7,0 58,1
2,0 67,1 5,5 60,7 8,0 57,2
3,0 65,5 6,0 60,2 9,0 55,6
4,0 62,9 6,5 58,8 10,0 54,5

8/ Axit heptanoic nc vi 0,01M HCl

C7H14O2 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

3,61 69,4 2,94 62,0 2,76 57,8
3,25 66,5 2,90 61,7 2,61 55,1
142
3,08 64,8 2,88 61,2 2,56 52,9
3,00 63,0 2,82 59,7 2,48 50,6

9/ Axit octanoic - nc vi 0,01M HCl

C8H16O2 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

4,1 71,1 3,45 64,0 2,92 49,2
3,85 69,6 3,39 61,9 2,80 45,4
3,70 67,8 3,23 57,6 2,61 40,1
3,52 65,0

10/ Axit nonannoic nc vi 0,01M HCl

C9H18O2 - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

4,84 70,9 4,16 65,6 3,78 57,6
4,68 70,0 4,00 63,8 3,70 55,0
4,50 69,0 3,95 62,4 3,60 52,5
4,34 67,5 3,88 60,3 3,48 49,1

11/ Axit ecanoic - nc vi 0,01M HCl

C10H20O2 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

5,30 72,0 4,70 65,0 4,30 53,6
5,00 71,0 4,62 62,0 4,26 52,8
4,88 68,7 4,50 58,0 4,23 51,3
4,80 67,2 4,40 56,1 4,15 49,9
4,75 66,1 4,36 55,1 4,10 48,2

12/ Axit lauric nc vi 0,01M HCl

C12H24O2 H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

6,52 72,3 5,75 64,0 5,40 53,9
6,22 72,2 5,65 62,5 5,30 50,7
6,05 70,8 5,60 60,8 5,23 48,8
5,90 68,2 5,49 57,1

C3/ Amin

1/ Anlylamin - nc
C3H7N H2O

143
C .102,mol/l .10-3 N/m C.102mol/l .!0-3.N/m C.102mol/l .!0-3.N/m
0 71,5 12,5 66,7 50 58,3
3,125 70,2 25,0 63,2 100 52,8
6,25 69,1

2/ Propylamin nc
C3H9N - H2O

C .102,mol/l .10-3 N/m C.102mol/l .!0-3.N/m C.102mol/l .!0-3.N/m

0 71,5 12,5 62,4 50 51,6
3,125 68,6 25,0 58,0 100 45,5
6,25 66,7

3/ Hexylamin nc vi 0,01M NaOH

C6H15N H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

2,7 68,9 2,3 62,9 1,9 52,2
2,5 66,3 2,1 57,8 1,8 49,6
2,4 64,7 2,0 55,0

4/ Octylamin - nc vi 0,01M NaOH

C8H19N H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

3,7 66,5 3,2 61,3 2,9 54,8
3,5 64,7 3,1 60,0 2,8 52,3
3,3 62,5 3,0 57,6

5/ oexylamin nc vi 0,01M NaOH

C12H27N - H2O

-lg C .10-3N/m -lgC .10-3N/m -lg C .10-3N/m

5,7 70,0 5,0 62,8 4,5 51,5
5,6 69,6 4,8 58,2 4,4 49,1
5,2 67,0 4,6 53,8 4,2 44,6

144
145
TI LIU THAM KHO

1. .H.extep, c.keH, .H.TeTepuHa

Macopactbopume nobepxHoctHo aktubHe beectba
Mockoba ug. xumue 1978
2. B.X.apo, B.T. u
Texoou cutetueckux Mou cpegcba
Mockoba ug. xumue 1984
3. Jean Por
Emulsions micro-emulsions, emulsions multiples.
Les Editions Techniques des Industries des Corps Gras, Neuilly 1992
4. Louis H TN TI
Cc sn phm ty ra v chm sc c nhn.
NXB uno Paris 2000
5. Martin J.Schick
Rections and synthesis in surfactant systems.
Marcel Dekker, inc. Newyork.Basel 2001

nn
6.
7. nn
8. C.Kajdas.
Du m bi trn.
NXB Khoa hc v k thut, H ni 1993.

146
Ti liu ny ang trong giai on chnh sa ln, chc hn cn
nhiu sai st, rt mong cc bn hc vin ng gp kin. Xin
chn thnh cm n!

147