TAP CHI HOA HOC T.

49(3)311-314 THANG 6 NAM 201

NGHIEN CU'U T 6 N G HQP POLYME DAN DIEN POLYANILIN (PANI)

Vu Tien Cong, Pham Manh Thao, Duong Cong Hung
Hpc vien Ky thudt qudn sir
DCMI Tda soan 5-10-2010

Abstract
The paper presents a process of synthcsi/ing conductive polymers from an aromatic amine as aniline. The process
provides simple svnthesizing steps for the polyaniline salt b\ polymerizing aniline in the presence of different protonic
acids as dopants such as hvdrochloric. maleic. and 5-suiri>salicylic acids. The synthesized polyaniline salts have electrical
conductivitv- as high as 4 S.cm"' and the v icld of polvaniline was higher than 61 percent in all cases and up to 90 percent.
A process for preparing of PANI. which dissolves in organic solvent ofchloroform is also presented.

1. GIOl THILL
Polyme dan dien la mdt vat lieu mdi dugc phat
hien va nghien ciru trong vai thap ki gan dav. Vdi
dac diem khac vdi nhimg polyme truven thdng -
nhirng polyme each dien. polyme dan da thu bill su
quan tam cua rat nhieu nha khoa hgc tren the gidi.
cau triic dac trung cua polyme dan dien bao gdm
nhiing ndi ddi lien hgp trong mach chinh va su cd
mat cua dopant. Do dan dien cua polyme dan phu
thudc nhieu > eu td, trong dd dang quan tam la do dai
mach polyme, ban chat cua dopant, ham lugng
dopant tham gia v ao qua trinh polyme hoa.
P.A.N1 la mdt trong nhiing polyme dan dien dugc
nghien ciru nhieu nhat ciing nhu cd nhung irng dung
kha da dang boi uu diem v e do dan dien cao. do ben
mdi trudng. ben nhiet. ben co hoc va nhe. 0 Viet
Nam. da cd mdt sd nghien ciru su dung PANI trong
quan su nhu che tao vat lieu hap thu sdng rada
(RAM) diing trong nguv trang, nghi trang [1.2].
Trong bai bao nay chiing tdi trinh bay ket qua
tdng hgp PANI a dang bdt. dua ra quv trinh tdng
hgp tdi uu ddi vdi timg dopant dugc su dung de dat
do dan dien cQng nhu hieu suat cao nhat. Ngoai ra
ciing dua ra quy trinh co' ban de tdng hgp PANI tan
trong cloroform, san pham PANI tan trong dung mdi
hiru CO khdng dugc khao sat trong bai bao nay.
2. THUC NGHIEM
2.1. Thiet bi va hoa chat
De tdng hgp PANI va ep thanh tam, da su dung
cac dung cu thuy tinh thdng thudng trong phdng thi
nghiem, may khuay tir. thiet bj dn nhiet, khudn va
may ep thuy luc. De do do dan dien, da su dung
phuong phap do bdn cue [8] vdi sai sd ±7,5%o. Ngoai
ra, cdn su dung kinh hien vi dien tu quel (SEM). do
phdng dai su dung tii' 200 + 10000 lan (Jeol JMS
5300 - Japan) va may phan tich phd hap thu hdng
ngoai de phan tich cau triic PANI thu dugc.
cac hoa chat su dung la: Anilin (PA); axit
clohydric. axit maleic, axit 5-sulfoxalixyIic; amoni
pesulfat; benzoylpeoxit; natri laurylsunfat.
2.2. Phu'ong phap nghien cii'u
PANI dang bdt dugc dieu che theo quy trinh sau:
nho gigt dung dich amoni pesunfat vao khdi dung
dich mudi cua anilin va dopant theo ty le khao sat,
duy tri tdc do nho gigt de nhiet do phan irng thay ddi
trong khoang ±0.5"C: khuay trong 2 tieng ddng hd.
Ket thiic khuay, de yen hdn hgp phan img trong 2
gid thu dugc ket tua mau xanh den, cd anh kim bam
tren thanh binh. Tien hanh Igc hiit chan khdng v a rua
vdi nudc cat den pH = 5 -^ 7, sau dd rua lai vdi
axeton thu dugc PANI am. Sav trong 2 tieng ddng
hd a nhiet do thich hgp (tuv tirng dopant) thu dugc
bdt PANI khd, nghien thanh dang bdt min sau dd
dem ep thanh dang tam kich thudc 27 x 19 mm bang
may ep thuy luc, ap suat 50 kG/cm' Mau tbu dugc
cd do day xap xi 2.7 mm.
Che do khao sat:
Theo nhiet do: tai cac nhiet do 5, 15, 25. 35°C.
Theo ty le mol dopant/anilin la 0; 1/2; 1/1; 3/2;
2/1, cac dopant su dung la axit clohydric, maleic, 5-
sulfoxalixylic.
Nhiet do say (T): axit clohydric 110 + 120,
maleic 100 + 105. 5-sulfoxalixylic 110 - 120.
PANI dang tan trong dung mdi hiru co dugc dieu
che theo quy trinh sau: Hda tan natri laurylsunfat
trong nudc cat; hda trdn vao dung dich cua
benzoylpeoxit trong cloroform tao thanh nhu tuong

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TCHH, T. 49(3), 201
mau trang sua, hdn hgp dugc khuay bang may khuay
til'. Dung djch mudi ciia anilin vdi axit
5-sulfoxalixylic trong 100 ml nudc cat dugc dua vao
binh nhd gigt. Nhd gigt dung djch muoi ciia anilin
vao khdi phan irng, tien hanh d nhiet dg phdng. Duy
tri tdc do nhd gigt sao cho nhi?t dg thay doi trong
pham vi ±0,5"C. Ket thiic nhd gigt, ticp tyc khuay,
de phan irng dicn ra trong 24 gid. Chiet lay ldp dung
djch mau xanh den nam phia dudi. Rira nhicu lan
bang nudc c£^t, lugng nudc cat can diing la khoang 3
lit. Ldp hiru ca chira PANI dugc tiicb nudc bang
Na2S04 khan sau dd dugc Igc qua giay Igc. San
pham cuoi cimg thu dugc la PANI hda tan trong
cloroform.
De khao sat do dan diC-n, cac mau dugc ep thanh
dan^ tam cd kich thudc 27x19x2,7 mm; sir dyng
ngudn 9V DC, ghi lai cac gia trj do tren Von ke va
Ampe ke. Do dan dicMi ciia mau dugc tinh theo cdng
thirc [8]:
I Nhin chung phan iirng tdng hgp PANI la phan
5= [S.cm'']
U.d.CF,CF,
Trong dd:
7 la cudng do ddng dien do dugc [mA];
U\k hieu dien the do dugc [mV] ;
d la do day ciia mau [cm];
CFj, CFh la he sd hieu chinh theo chieu day va
kich thudc mat (rdng va dai). Cac gia trj nay phu
thudc vao kich thudc mau d tren, tra theo bang
trong [8].
3. KET QUA VA THAO LUAN
3.1. Ket qua tdng hop PANI
Day la phan img toa nhiet, tuy nhien qua trinh
toa nhiet chi dien ra mdt each dot bien trong mdt giai
doan keo dai vai phut. Dd la giai doan polyme hoa,
trudc dd la giai doan oxi hoa tao cac gdc ty do. Ddi
100
15 25
Nhiet do, "C
Hinh 1: Hieu suat phan Orng phy thudc nhiet do va ty le mol dopant/anilin
312
Pham Manh Thao vd cdngsu
vdi cac dopant khao sat, mau hdn hgp ludn cd sir
chuyen bien tir mau vang den nau, xanh la cay rdi
cuoi ciing la xanh den. Ludn can giCr ty le chat oxi
hoa nhd han 1 so vdi chat nen [5] va nen tien hanh
phan irng bang each nhd gigt chat oxi hoa vao khoi
phan irng nhSm khong che nhi?t dg tdt va khdng d^
sinh ra san pham dang penigranilin la PANI d mirc
oxi hoa cao cd mau tim, khdng dan dien.
Doi vdi dang tan trong dung mdi hiru ca, san
pham PANI sinh ra dugc tan trong cloroform, nSm
phia dudi. Tuy nhien viec rira lam sach PANI trong
dung mdi hiru ca kha khd khan do thai gian chd tach
ldp de chiet kha lau, lugng nudc can diing de rira
cung tuang ddi nhieu. PANI dang nay tham rat tot
vao bdng va giay, dieu nay md rdng kha nang dua
PANI vao cac dang vat lieu xop. Day la hudng mdi
dc khao sat.
3.2. Hicu suat phan irng
irng cd hieu sudt cao (hinh 1), dac biet khi sir dung
dopant HCI cho hieu suat len den khoang 90%. Tuy
nhien can phai dua dopant vao tir dau, tire la tao
muoi anilin-dopant thi phan irng mdi thu dugc hieu
suat cao do mudi anilin-dopant tan trong nudc tot
ban anilin khien kha nang khuech tan cua chat oxi
hoa tot ban. Do phan irng toa nhiet nen tien hanh 6
nhiet do thap se tdt ban. Khi pha tap vdi HCl cho ket
qua tuan theo quy luat nay, tuy nhien khi tdng hgp
PANI vdi dopant la axit maleic va 5-sulfoxalixylic
lai dat hieu suat cao khi tang nhiet do. Deu nay dugc
giai thich la do mudi cua anilin va HCI tan trong
nudc nen de tuong tac vdi dung dich oxi hda la
amoni pesulfat. Trong khi dd cac axit
5-sulfoxalixylic va axit maleic la cac axit hiru co,
nen khi tang nhiet do, kha nang phan Orng ciia pha vo
ca (dung djch chat oxi hda) vao pha hiru ca tang len,
vi vay qua trinh oxi hoa tao mach cung nhu khau
mach dien ra tdt hon d nhiet dd cao.
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TCHH, T. 49(3), 2011 Nghien cuu tdng hap polyme...

Ddi vdi sy phu thudc cua hieu suat vao ty le
dopant/anilin, khi khdng su dung dopant, phan ung
cho hieu suat thap, hieu sudt phan Orng ddi vdi cac
dopant HCl, axit maleic, axit 5-sulfoxalixylic ldn
nhat lan lugt d cac ty le mol dopant/anilin tuong ung
la 1/1; l/I va 3/2. Cd Xhh thSy ban chat cua dopant
anh hudng ldn den hieu suat phan Orng. Dopant vd co
khien mach PANI de dang tao ra hon. Trong khi
dopant huu co vira khd phan tan, vira cd cau true
cdng kenh nen viec tham gia vao mach cung bj h^n
che, VI vay muc do bao hoa cua dopant hiru co trong
mach PANI se thap hon so vdi dopant vd co.
3.3. Do dan dien
Khi sir dung dopant la axit 5-sulfoxalixylic,
PANI thu dugc cd do dan dien vugt trgi. Theo quy
luat chung la tang ty le dopant se tang kha nang dan
dien do ndng do axit cao, sy proton hda PANI nhieu
hon, lam tang lugng polaron va bipolaron trong
mach PANI din dhn tang do din dien. Quy luat nay
dung vdi HCI, tuy vay do din dien cua mlu cd ti le
dopant/anilin bang 2 so vdi ti le 3/2 chi tang len
0,6%, cd the do da dat do bao hda dopant trong
mach PANI, xet ve tinh kinh te thi thyc hien d ty le
3/2 la toi uu. Trudng hgp pha tap vdi axit
5-sulfoxalixylic cho dg din dien tot nhat d ty le mol
dopant/anilin la 3/2; axit 5-sulfoxalixylic bi oxi hda
tao hgp chat mau tim, do dd khi tang lugng
5-sulfoxalixylic qua nhieu cd the xay ra sy oxi hda
chinh axit nay lam giam lugng chat oxi hda ddng
thai mat dopant. Khi pha tap bang axit maleic lai dat
dg dan dien cao nhlt d ty le 1/1 (hinh 2). Cd the giai
thich la cac axit hiru co cd kich thudc ldn nen mOrc
do pha tap cua chiing vao mach PANI gap can trd,
chi pha tap den mgt gidi ban phu thudc vao ban chat
dopant. Chinh dieu nay cung anh hudng true tiep
den kha nang dan dien cua tirng loai PANI.

2.5

E
u
i/i
c-•• 1 5 -5-S
MO
•a -HCl
•O' 1
O -Mai

05

0
10 15 20 25 30

Nhiet do, "C

Htnh 2: Do dan dien phu thudc nhiet do phan ung va ty le mol dopant/anilin

Vdi mau klidng dua dopant vao va van tien hanh
quy trinh polyme hda nhu tren. Phan Orng xay ra rat
cham do anilin khdng tan trong nudc, qua trinh tiep
xuc giCra cau tur vd co va hiru co bi ban che, liic dau
van cd mau vang xuat hien va chuyen dan thanh mau
nau, phai can thdi gian kha lau sau dd mdi xuat hien
mau xanh. Ve ly thuyet mau nay phai cd do dan dien
rat thap (khoang 10"^ S.cm''), tuy nhien mau thu
dugc van dat do dan dien 5.10"^ S.cm'' Dd la do san
pham cua qua trinh oxi hda cd sinh ra axit H2SO4,
ban than axit nay cung la mdt dopant lam san pham
thu dugc tang do dan dien. Mudn tao PANI bazo
hoan toan khdng cd dopant can phai trung hda PANI
mudi trong dung djch amoniac de loai bd axit.
Anh chup SEM (hlnh 3) cho thay kich thudc bdt
PANI dieu che dugc khac nhau ddi vdi cac dopant
khac nhau. Do kich thudc hat ldn lam tang do linh
ddng cua polaron va bipolaron trong mach PANI
nen do dan dien cang cao khi kich thudc hat
cang Idn.

3.4. Phan tich cau true pho hap thu hong ngoai

Bdng 1: Mdt sd vach phd IR quan trgng ciia cac mau PANI
Cac mau PANI va ti le pha tap Mau PANI chuan theo [1,5]
Cau tnic 5-suIfoxalixylic ti Maleic HCl
PANI doped PANI bazo
16 3/2 Ti le 4/1 Ti le 1/1
Quinoit 1567 1556 1571 1561 1587
Benzenoit 1474 1473 1487 1488 1494
N-H 3475 3450 3440 3360
C-N (benzenoit) 1297 1113 1296 1280 1299

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TCHH.T 49(3). 2011 Phgm Mgnh Thao va cdng su

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IUS44Kl>IOM3E(MlA(ll

(a) (b) ^ (c)

Hinh C Anh Sl M cac mau PANI dicn hinh
(a) Mau 5-sull'oxali\vlic: b) Mau maleic; (c) Mau kich tap bang HCl;
tl lc mol diipant anilin: 3 2 li lc mol dopant/anilin: 1/1 ti le mol dopant anilin: 3 2
Nhiet dd 35"( Nhict do 35"C Nhiet do ^"C
Do dan dien 4.05 1 Dd dan dicn 0.353 Dd dan dien 0.345

Dac trirng vc cau triic cua PANI la gdm cac pic 4, K E T L L A N

hdng ngoai cd sd song trong khoang 155(> - 1570
cm ' va 1474 -^ 14S7 cm irng voi ciiu triic cua vong
quinoit vii benzenoit tuong irng. Cac gia tri nav kha
triing voi cac mau chuiin trong tai lieu [4]. Thco [1],
PANI bazo do it bi proton hda hon nen dai phd cua
nd dich chuven ve phia sd sdng cao ban so vdi PANI
da dugc proton hda.
Da lien banh tong bcrp PANI vcVi cac 3 loai dopant
trong cac dieu kien khac nhau. Ket qua khao sat su
phu thudc cua hicu suiit phan img va dd dan dien cua
PANI vao nhiet do phan irng, tv le dopant anilin cho
thin cac PANI co do dan dien cao dugc tdng hgp
tron" cac dieu kien duoc dua ra trans bans 2.

Bang 2 ' Dieu kien phan irng cho do dan dien tdt nhat ddi vdi tung dopant
1

Nhiet dd phan img. Tv le mol Hieu suat. Do dan dien (S.cm

Dopant
dopant anilin % 1 \
1

Axit 5-sulfoxalixylic 35 32 61.0 4.051 j

Axit Maleic 35 1/1 ~3.(t 0.353
HCl 5 32 S'-).9 0.345

Khi oxi hda anilin bang benzoylpeoxit trong
cloroform vdi chat pha tap la axit 5-sulfoxali\v lie cd
the thu dugc PANI tan trong dung mdi hiru co,
TAI LIEL THAM KHAO
1. Nguyen Viin Bac. ""Nghien ciru che um viu lieu \a
phuong lien nguv trang. nghi trang chong trinh sal
radar" Bao cao long ket Khoa hpc - C ong nghe. Dc
tai KCB 01-08. nhanh KCB 01-08-02. Trunu tam
KHKT & CNQS. Ha Npi (2006),
2. Nguyen The Nghiem. Nghien ciru cong nghe che lao
vai lieu polymer hap thu song rada \ a irng dung v ao
ket cau nguy Irang. Phan vien cong nghe vat lieu
Vien hoa hpc vat lieu/Trung lam KHKT & CNQS.
HaNpi.tr. 63 73(2006).
3. Truang Van Tan. Vat lieu lien tien: Tir polyme dan
dien den ong than nano. Nxb. Tre. Tp. HCM (2008).
4. Pham Minh Tuan (2ii()M. Nghien ciru long hpp va
khao sat polyanilin iren nen mpt so vat lieu vcS ca.
Luiin van thac si hda hpc. Hoc vien KTQS - Tmng
tam KHKT c^ C NQS. Ha Ndi (2()()cSi.
5 Trisha A Huber. .A literature survev of polyaniline.
part 1. Polvaniline as a Radar absorbing material.
Dclcncc R&D Canada - Atlantic (2003).
6 Falemeh Masdarolomoor. Novel nanostmctured
conducting polymer svsiems based on sulfonated
polyaniline. Laiiversitv of Wollongong (2006).
Suck-Hyun Lee. Chan-Woo Lee. Conductive
polvmers having highly anhanced solubility in
organic solvent and electrical conductivity and
synthesizing process thereoL United States Patent N '
11120082(2005).
X http: vveevvave.mer.utexas.edu/DPN_fiIes/courses/Fa
bLab/Fab_Lab_Manual/lab_man_2003/OPH_4PTPR,
pdf (Dai hpc long hpp Texas - My).

Lien he: Pham Manh Thao

Hgc vien Ky thuat quan su, 100 Hoang Qudc Viet, Cau Gily, Ha Ndi
Email: thaapm2003(aiyahoo.com

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