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Hóa học các hợp chất hoạt động bề mặt (Bài giảng chuyên đề Cao học Hóa hữu cơ) - Nguyễn Đình Triệu
Hóa học các hợp chất hoạt động bề mặt (Bài giảng chuyên đề Cao học Hóa hữu cơ) - Nguyễn Đình Triệu
NGUYN NH TRIU
HA HC CC HP CHT
HOT NG B MT
(Bi ging chuyn cao hc ha hu c)
H NI 2005
1
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
2
3
Chng 1. nh ngha v ngha ca cc
cht hot ng b mt
4
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 .
OH
C20 SO3Na
C20 SO3Na C8
C8
C5
SO3Na
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
6
chnh t ra v c ch n n mn
mn
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
7
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
1.3.9. Sinh hc
Ch to mng sinh hc
8
Cht bn vng to nh thin nhin (sa, m cao su)
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
9
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
d) Axit bo ngng t:
10
OH
O O
N C
H
O
OH
Ankylamit glutamic
O
R C
peptit COO Na
N
H
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
11
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
12
2.4.2. Ete ca mt s nhm phn cc:
R O (CH2CH2O)nH
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
CH3 CH3
CH3 CH3
N Br + KOH N OH + KBr
CH3 CH3
CH3 CH3
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)
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)
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
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
22
Chng 3. Mt s tnh cht ca cc cht
hot ng b mt
d C
G RT hay .G
dC C RT
Phng trnh ny c gi l phng trnh Gibbs.
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 3.2 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).
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)
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.
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
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).
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).
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)
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
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.
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.
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).
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
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.
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).
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
41
Hnh 3.11 Gin xc nh HLB ca cht nh ha.
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.).
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.
Eco
}
Ecw
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
45
Hnh 4.3. Mng lng tnh du trong nc.
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)
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.
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
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.
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.
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.
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
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.
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.
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.
5.1.2. 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.
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)
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
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.
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).
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.
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.
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:
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
70
CH2 O CO (CH2)14 CH3 (Axit panmitic)
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 .
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
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 .
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
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 :
73
CH3
CH3(CH2)9CH=CH2 AlCl3
CH3(CH2)9CH
CH3
(1) H2SO4
CH3(CH2)9CH SO3Na
(2) Na2CO3
LAS
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.
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
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
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 :
Arylpolioxietilensunfat
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.
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
CH3
CH3(CH2)7CH CH(CH2)7CO N CH2CH2SO3Na
igenon T HX
CH3
CH3(CH2)7CH CH(CH2)7CO NH CH2CH2SO3Na.X
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
R OH + ClCH2CONHCH2OH R OH
CH2NHCOCH2Cl
HX
R OH
CH2NH2COCH2Cl.X
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
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)
Bis(ankylbenzyl)disunfit (C)
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
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
3R R O P 3 HCl
OH PCl3 3
( 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
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
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
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
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
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
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
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
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
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
A A A A A A A
B B B n
A- nhm k nc B- nhm a nc
R
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:
C2H4OH
OC(H4C2)4CO(OC2H4)xN(C2H4O)y
R n
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
Copolime O
CH3
CH3(CH2CH2O)45 [(CH2)4O]10 C NH C C6H4 C CH2
O CH3 CH3
Copolime
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.
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
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.
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.
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
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
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.
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.
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
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 7.6. 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 ) .
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.
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
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
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.
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.
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.
106
Cc cht c dng lm st l cc cht hu c hay khong, nhng polime nh
cacboxymetyl xenluloz, gm xantan (polime thin nhin).
7.4.6. 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
107
CH3 CH3
OH
O
OCH3
O
Cl O Cl
Cl HO
Triclosan
108
Hng v 1,3
Nc kh khong 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
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
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
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
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
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
C13 40,0 50
C9 315,0 -120
C18 50,0 70
C10 60,0 0
C3 250 -325
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
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%.
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
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
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
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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
- Polimetacrilat
- Ankylsunfonat
- Glixerolmonostearat
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- 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.
S
CH3 C CH2
- Sunfonat kim loi
- Benzothiazol
H
N
N
N
- Sunfua phenolat kim loi
- Dn xut mecaptothiothiazol
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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.
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- Alumoferit c cng thc 4CaO.Al2O3.Fe2O3 thy ha chmnn xi mng c
hm lng alumoferit cao s c cng thp.
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
CH2OH
O
OH
O O
OH
n
Polisacarit ( 4)
CH2=CH-C6H4-O-(CH2)12SO3Na
(SSDSE)
CH2=CH-CONH-(CH2)10COONa
( SAU )
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.
Bng PL1 .
SC CNG B MT CA DUNG DCH
127
CC CHT HOT NG B MT
A- Cht HBM anionic
A1/ Mui cacboxylat
2/ Natri hexanoat-heptan-nc
C6H11O2Na - C7H16-H2O
128
Hm lng (NH4)2SO4 (mol/l) 0,4 (1) , 2,5 (2) , 3,0 (3)
T l mol .10-3N/m
N.104
4,1 25,3
8,1 25,5
24,4 25,7
A2 / Mui ankylsunfat
3/ Natriecansunfonat - heptan - nc
C10H21SO3Na - C7H16 H2O
6/ Natri hexaecansunfonat - nc
C16H33SO3Na H2O
1/ inatri monooexylsucxinatsuonat - nc
C16H28O7SNa2 H2O
Phng php Diu Nui , t = 200C ,C mol/l
2/ inatri monotetraexylsucxinatsunfonat - nc
C18H32O7SNa2 H2O
3/ inatri monohexaxylsucxinatsunfonat
C20H36O7SNa2 - H2O
4/ inatri monoheptadexylsucxinat - nc
C21H38O7SNa2 - H2O
1/ Octylamoni clorua - nc
C8H20NCl H2O
Phng php Diu Nui , = 0,2 , t = 200C ,pH = 5 ( axit ho HCl ) , C mol/l
2/ oexylamoni clorua - nc
C12H28NCl H2O
3/ Tetraexylamoni clorua - nc
C14H32NCl H2O
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
2/ Octaexylamoniclorua octan - nc
C18H40NCl - C8H18 - H2O
137
4/ ibutylhexaexyl propylamoni ioua octan - nc
C27H58NI C8H18 H2O
B3 / Mui ankylpiriini
3/ Tetraexylpiriini EP - nc
C21H38NBr - EP - H2O
1/ Propanol (1) - nc
2-Propanol (2) - nc
C3H8O H2O
2/ 2-Metylpropanol - nc
C4H10O - H2O
4/ Metanol - ecanol
CH4O - C10H22O
Phng php p sut cc i bt , = 0,03 , t = 25 0,010C , N -t l mol metanol.
5/ Etanol - ecanol
C2H6O - C10H22O
6/ Propanol - ecanol
C3H8O - C10H22O
7/ 2 Propanol - ecanol
C3H8O - C10H22O
8/ Butanol - ecanol
C4H10O - C10H22O
1/ Axit propionic nc
C3H6O2 H2O
2/ Axit butiric nc
C4H8O2 H2O
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
5/ Axit hexanoic - nc
C6H12O2 - H2O
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
144
145
TI LIU THAM KHO
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