B CNG THNG

TRNG I HC CNG NGHIP TP.HCM

KHOA TI CHNH NGN HNG

CHUYN MN HC
ti:

GVHD : Th.S Tng Th Thanh Thy

Nhm

:3

Lp

: HTN2

TP. H Ch Minh, ngy 31 thng 12 nm 2010

MC LC
M U............................................................................................................................4
1. Cu to...........................................................................................................................5
2. Tnh cht vt l.............................................................................................................6
2.1. Nhit nng chy v nhit chuyn thy tinh....................................................7
2.2. Khi lng ring......................................................................................................7
2.3. Tnh tan....................................................................................................................9
2.4. To mng...............................................................................................................10
2.5. Kh nng chu du v dung mi.............................................................................14
2.6. Tnh cht dnh keo dn...........................................................................................14
2.7. Kh nng chng thm kh.......................................................................................14
3. Tnh cht ha hc........................................................................................................15
3.1. Phn ng acetal ha...............................................................................................15
3.2. Phn ng ether ha.................................................................................................16
3.3. Phn ng ester ha.................................................................................................17
3.4. Phn ng to phc..................................................................................................17
3.5. Phn ng to mch nhnh......................................................................................18
3.6. Phn ng phn hy.................................................................................................18
4. Tng hp......................................................................................................................18
4.1. Tng hp monomer vinyl acetate...........................................................................19
4.2. Tng hp polyvinyl acetate....................................................................................20
4.3. Tng hp polyvinyl alcohol...................................................................................21
5. ng dng.....................................................................................................................23
5.1. X si tng hp......................................................................................................23
5.2. Keo dn.................................................................................................................24
5.3. Cht kt dnh..........................................................................................................24
5.4. H v ph giy.......................................................................................................25
5.5. H si v hon thin...............................................................................................25
5.6. Tc nhn to nh....................................................................................................26
5.7. Mng PVA.............................................................................................................26
2

5.8. Gm.......................................................................................................................27
5.9. Cc sn phm c..................................................................................................27
5.10. Lp ph bo v.....................................................................................................28
5.11. M phm..............................................................................................................28
5.12. Cc mn giy nn.................................................................................................28
5.13. Ha cht trung gian..............................................................................................28
5.14. Ti thp................................................................................................................29
KT LUN......................................................................................................................30
TI LIU THAM KHO..............................................................................................31

M U

Polyvinyl l nhm hp cht cao phn t c hnh thnh t phn ng polymer ha

cc hp cht vinyl. C th k n y nh: polyvinyl acetate, polyvinyl formate,
polyvinyl benzoate, polyvinyl ether Tuy nhin, trong nhm ny c mt loi polymer
khng th tng hp trc tip t monomer vinyl c. chnh l polyvinyl alcohol
(PVA).
Nh vy, nguyn nhn no lm cho PVA khng th tng hp c trc tip t
monomer vinyl alcohol? PVA c cu to v tnh cht ra sao? Quy trnh sn xut PVA
trong cng nghip nh th no? V n c nhng ng dng g trong i sng cng nh
trong sn xut? Bi tiu lun ny s i su vo tm hiu v lm sng t nhng vn trn.
cng chnh l mc ch v phm vi nghin cu ca bi tiu lun.
Cui cng, em xin chn thnh cm n thy Nguyn Quang Khuyn tn tnh
hng dn v cung cp ti liu, nh m em c th hon thnh bi tiu lun ny trong
thi hn cho php. Mc d c gng ht sc nhng vi s hiu bit cn hn ch nn bi
tiu lun s khng trnh khi nhng thiu st. Em rt mong nhn c s ng gp
kin ca thy v cc bn!

1. Cu to
n v cu trc ca polyvinyl alcohol (PVA) l:
H2
C

H
C
OH

Khi nhn vo cng thc ny, mt s ngi ngh rng monomer ca n phi c
H 2C

C
H

cng thc:

OH

Thc t khng nh vy, PVA c tng hp t qu trnh thy phn polyvinyl

acetate v hp cht vinyl alcohol khng tn ti. Ngay sau khi c to ra, vinyl alcohol
chuyn ha v dng ng phn bn hn l acetandehyde.
Ph thuc vo mc thy phn (mc th, DS) v khi lng phn t (
trng hp, DP) m c th tng hp c mt lot cc hp cht PVA c thnh phn khc
nhau. Da vo mc thy phn, PVA c chia thnh 2 loi: PVA thy phn mt phn
v PVA thy phn hon ton.
Cu trc ca PVA thy phn mt phn nh sau:
H2
C

H
C
OR

Vi R = H hoc COCH3
nhit thng, PVA l cht rn v nh hnh. Khi un nng, PVA b mm ha,
c th ko di nh cao su v khi n s kt tinh.
0

Gin Rnghen ca PVA khi ko c chu k dc theo si l 2.52 A v mng li

tinh th c kch thc:
0

a= 7.81 A , b= 5.51 A , c= 2.52 A

v cu trc n t, gc = 91.410, song cng c ti liu cho l cu trc gi hnh thoi vi
kch thc:
5

a= 7.60 A , b= 5.60 A , c= 2.52 A

0

bao gm hai mch kt hp vi nhau bng cu hydroxyl vi khong cch l 2.8 2.9 A .
Cc mt xch dc theo mch c s kt hp u ui v mch l ziczac.
0

Tnh kt tinh vi chu k cu trc si l 2.52 A , cho thy trong phn t khng c
s phn b u ha cc nhm OH m theo s phn b thng k.
Da vo s khc nhau v cu trc khng gian m ta c PVA cc dng isotactic,
syndiotactic hay atactic. Tng hp PVA bng cch thy phn polyvinyl formate th PVA
to ra dng syndiotactic, thy phn polyvinyl benzoate to PVA dng izotactic, thy
phn polyvinyl acetate (PVAc) to hn hp 3 loi: isotactic, syndiotactic v atactic, trong
atactic chim ch yu.

2. Tnh cht vt l
Tt c cc PVA c alcol phn mt phn v hon ton u c nhiu tnh cht
thng dng, lm cho polymer c gi tr cho nhiu ngnh cng nghip. Cc tnh cht quan
trng nht l kh nng tan trong nc, d to mng, chu du m v dung mi, bn ko
cao, cht lng kt dnh tuyt vi v kh nng hot ng nh mt tc nhn phn tn - n
nh. Tm tt cc tnh cht ca PVA (c trng bi loi Elvanol) c trnh by trong
bng 2.1.
Bng 2.1. Tnh cht ca PVA
Dng
Mu sc
T trng ring
Th tch ring, in3/lb
Ch s khc x, nD25
dn di, mng do ha, %
bn ko, kh, cha do ha, psi
cng, do ha, Shore
Nhit hn gn nhit, kh, cha do
ha, 0C
Nhit c p, do ha, 0C

Bt
Trng ti kem
1.27 1.31
22.9 21.1
1.49 1.53
Di 600
Di 22000
10 100
165 210
100 150
6

 bn nhit, trn 1000C

Lm thm mu chm

trn 1500C

Lm thm mu nhanh

trn 2000C
bn bo qun (mt vi nm)
H s dn n nhit, 0 - 450C
Nhit dung ring, cal/g/0C
Tnh bt chy
nh hng ca nh sng
nh hng ca axit mnh
nh hng ca kim mnh
nh hng ca axit yu
nh hng ca kim yu
nh hng ca dung mi hu c

Phn hy
Khng gy hng
7*10-5 12*10-5
0.4
Chy vi tc ca giy
Khng nh hng
Ha tan hoc phn hy
Chy mm hoc ha tan
Chy mm hoc ha tan
Chy mm hoc ha tan
Khng nh hng

2.1. Nhit nng chy v nhit chuyn thy tinh

Vic xc nh trc tip nhit nng chy ca PVA rt kh v PVA b phn hy
nhit nng chy. Thng thng nhit nng chy ca PVA c xc nh gin tip,
gi tr ny khng c tnh tuyt i v nhit nng chy ca polymer khng l mt im.
Bn cnh , nhit nng chy ca PVA cn ph thuc vo lng nc b hp ph
trong phn t polymer.
Tng t nhit nng chy, nhit chuyn thy tinh ca PVA cng thay i
theo lng nc b gi trong polymer. Do vy, cng mt khi lng phn t, nhit
chuyn thy tinh Tg c th khng ging nhau. Nhiu nghin cu cho thy nhit chuyn
thy tinh ca PVA chia lm 2 nhm: nhm c nhit chuyn thy tinh trn 800C dng
trong sn xut s xi, nhm cn li c nhit chuyn thy tinh khong 80 0C c dng cho
cc ng dng khc.
2.2. Khi lng ring
Khi lng ring ca PVA c xc nh theo phng php tuyn ni. N thay
i ty theo trng hp v nhit ca qu trnh x l nhit. Chng hn, khi nghin
cu trn cc mng PVA (loi thy phn hon ton) c trng hp thay i t 309 (mc
thp nht) n 4570 (mc cao nht), sau khi x l nhit cc nhit khc nhau ta thu
c kt qu sau:
7

Bng 2.2. Khi lng ring ca PVA (thy phn hon ton)
theo nhit x l v trng hp
Nhit x l 0C
trng hp
309
708
1288
2317
4570

40
1.2824
1.2854
1.2879
1.2896

80

120

180

200

1.2893
1.2920
1.2949
1.2954

1.2961
1.2965
1.2987
1.3006
1.3020

1.3044
1.3036
1.3039
1.3050
1.3045

1.3094
1.3062
1.3065
1.3088
1.3088

T bng s liu ta thy, khi lng ring ca PVA ph thuc ch yu vo nhit

x l nhit. S thay i khi lng ring theo nhit x l nhit c gii thch da
trn c s nhit ng hc ca qu trnh bin i pha trong PVA. Nh ta bit, tt c cc
hp cht cao phn t trng thi rn u tn ti mt trong 2 pha v phng din tinh
th hc l pha kt tinh v pha v nh hnh.
Trong pha kt tinh, vt cht c cu trc cht ch, ngc li trong pha v nh hnh,
cu trc ca vt cht khng c cht ch bng. Bi vy trong pha v nh hnh, c nhiu
l xp. Pha kt tinh c cu trc cht ch nn khi lng ring ln. Pha v nh hnh c
nhiu l xp nn khi lng ring nh. Vt liu PVA ni ring, cc hp cht cao phn t
khc dng rn ni chung u cha c pha tinh th ln pha v nh hinh. Do vy, khi
lng ring ca n c tnh theo cng thc:

Trong : x t l pha kt tinh;

khi lng ring ca pha kt tinh.

khi lng ring ca pha v nh hnh.

Gia pha kt tinh v pha v nh hnh c cn bng nhit ng v cn bng ng lc hc.
Qu trnh x l nhit cng iu kin c hc, nhit x l cng cao, phn tinh th trong
PVA tng theo lm tng khi lng ring ca vt liu.

2.3. Tnh tan

Kh nng tan ca PVA trong nc ph thuc vo thy phn, trng hp, nhit
v nhit x l nhit. Tin trnh ha tan PVA bt u t s trng cng nh tt c
cc polymer khc.
Ph thuc vo thy phn v nhit :
PVA thy phn trn 95% khng tan trong nc lnh m ch tan trong nc
nng (65 700C) dung dch t nng ti a 10 12 %.
PVA thy phn 88% tan trong nc nhit phng.
PVA thy phn 80% ch tan trong nc c nhit khong 10 40 0C, trn
400C dung dch tr nn m v sau PVA kt ta.
PVA thy phn 50% khng tan trong nc lnh v nng m ch trng
nhng tan trong hn hp ru v nc (thng dng CH3OH).
Ph thuc vo trng hp (khi lng phn t): kh nng ha tan trong nc
cng l mt hm ca khi lng phn t, khi lng phn t cng thp th PVA
cng d tan.
Ph thuc vo nhit x l nhit: khi x l nhit PVA, nhit x l nhit tng
s lm tng tinh th ha v gim ha tan trong nc.
Dung dch nc ca PVA chu c lng ng k cc ru n chc nh
metanol, etanol v isopropanol, t l tng khi phn trm thy phn ca PVA gim. V d:
lng isopropanol ti a c th a vo nhit phng m khng lm kt ta phn
PVA, thay i t khong 40% i vi Elvanol 72 60 ti khong 60% i vi Elvanol 50
42.
Ch mt vi loi hp cht hu c c th l dung mi i vi cc loi PVA thy
phn hon ton. V d: cc hp cht ny l cc hp cht cha nhiu nhm hydroxyl nh
glyxerin, etylen glycol v mt s loi glycol polyetylen thp hn; cc amin nh
etanolamin, mui etanolamin v cc amit nh formamit, etanol formamit v etanol
axetamit. Hot ng dung mi ln PVA dng nh c h tr bi cc nhm hydroxyl,
amino v amit. Hu ht cc dung mi k trn u cn nhit ha tan thm ch mt lng
nh PVA thy phn hon ton. V d: PVA thy phn hon ton c th c ha tan
9

trong glyxerin nu gia nhit ti 120 1500C, nhng hn hp to gel khi lm ngui ti
nhit phng. Dietylentriamin v trietylentetramin thuc s t dung mi hu c ha tan
PVA nhit phng.
nht ca dung dch PVA tng theo thi gian lu tr. Nng dung dch cng
ln, s gia tng nht theo thi gian cng mnh. Mt khc, dung dch PVA vi thy
phn cao v khi lng phn t ln cng lm tng nht. S tng nht ny ph
thuc vo nhit , nhit thp c th lm tng nhanh hn. PVA thy phn hon ton c
nht bn. Cc mui hu c, ure hoc cc alcol bo c thm vo dung dch PVA
thy phn hon ton ng vai tr nh cht n nh nht.
2.4. To mng
V PVA thng c ha tan trong nc trc khi s dng nn kh nng to mng
ca chng rt quan trng trong hu ht cc ng dng. Mng v lp ph PVA khng cn
chu k ng rn, s to mng d dng xy ra bng cch cho nc bay hi khi dung dch.
So vi cc loi nha, bn ko ca PVA cao v so vi cc vt liu tan trong nc khc
th n kh ni bt. bn ko ca PVA thay i theo mt s yu t nh phn trm thy
phn (xem hnh 2.1), trng hp, hm lng cht do ha v m.

10

Hnh 2.1. Mi quan h gia bn ko v % thy phn

i vi mng PVA khng do ha
Khi cc yu t khc khng i, bn ko tng theo trng hp. V d: mng
cn t PVA khng do ha c nht cao, trung bnh v thp v trong iu kin m
tng i 35% c bn ko trung bnh tng ng l 18000, 17000 v 9000 psi.

11

Hnh 2.2. Mi lin quan gia bn ko v phn do ha

ca mng PVA

12

Hnh 2.3. Mi lin quan gia dn di v phn do ha

ca mng PVA ( nht cao, dng thy phn hon ton,
iu kin 50 phn RH)
Gi tr bn ko gim khi mc alcol phn gim. V d: vi m tng i
50%, mng cn t PVA c alcol phn hon ton, nht cao th c bn ko cao hn
khong 20% so vi mng cn t PVA nht cao ch c alcol phn 88%.
B sung cht do ha nh glyxerin vo PVA lm gim bn ko ca mng (xem
hnh 2.2), mc d vic b sung cht do ha lm tng cc c tnh dn di ca mng.
dn di thay i t di 10% ti hn 600% l kt qu trc tip ca vic b sung cht do
ha (xem hnh 2.3).

13

2.5. Kh nng chu du v dung mi

PVA khng b nh hng bi du thc vt v ng vt, m v hydrocacbon du
m. Kh nng chu dung mi tng theo mc thy phn. Khng c s khc nhau ng
k trong kh nng chu dung mi gia cc loi c nht thp, trung bnh v cao trong
khong thy phn c th.
Cc loi thy phn mt phn hu ht khng b nh hng bi cc este, ete, xeton,
hydrocacbon bo, thm v cc loi ru cao hn. Ru n chc thp hn c th ha tan
hoc lm trng cc loi thy phn mt phn nhng nh hng ca cc dung mi ny ln
cc loi thy phn hon ton th khng ng k.
2.6. Tnh cht dnh keo dn
Mt trong cc thuc tnh quan trng hn ca PVA l keo dn ca n hay bn
kt dnh. iu ny c th l do kh nng d to mng ca n v thu c bn ko cao
hn. Nh vy, PVA l mt trong nhng loi nha gi tr nht sn xut keo dn v cng
vi nh tng polyvinyl acetate to nn ngnh cng nghip keo dn nha tng hp.
Tng t vi cc thuc tnh keo dn ca PVA l cc tnh cht kt dnh ca n.
Trong cc ng dng keo dn, PVA c s dng lin kt hoc cn mng 2 b mt,
trong cc ng dng lm cht kt dnh, n c dng lin kt mt s loi ht, si hay
cc vt liu khc.
2.7. Kh nng chng thm kh
Mt trong nhng thuc tnh c bit nht ca PVA l kh nng chng thm kh ca
n. Nh trnh by trong bng 2.3 v 2.4, mng PVA hu nh khng thm tt c cc loi
kh, tr hi m v NH3. Cc nghin cu i vi mng PVA thy phn hon ton, loi
nht thp 250C, m tng i 0% khng th hin s truyn kh oxi v nit. Di cc
iu kin tng t, tc truyn kh cacbonic ch l 0.02g/m2 trong 1 gi. chng thm
kh cao c gi tr i vi vt liu thm c bao gi nh x phng v cc lp ph bo v.
Bng 2.3. Tc thm kh ca PVA
Kh

thm (g/m2/gi)
Mng A
Mng B

Mng C
14

Oxi
Cacbondioxit
Nit
Hydro
Heli

0
0.02
0
0
0.02

0
0
0
0
0.02

0
0
0
0
0

Bng 2.4. Kh nng thm hi m ca mng PVA

(loi thy phn hon ton, nht trung bnh)
dy
(mm)
Mu 1 3
Mu 2 3

g/m2/24 gi

g/100in2/24 gi

g/100in2/24 gi/mm chiu dy

7.0

0.45

1.4

147

9.5

29

3. Tnh cht ha hc
PVA l mt polymer cha nhiu nhm OH, do vy n c tnh cht ca mt ru a
chc. PVA c th tham gia cc phn ng ester ha, ether ha, acetal ha, to phc vi
mui ca kim loi
3.1. Phn ng acetal ha
Phn ng acetal ha thc cht l phn ng cng hp i nhn gia mt aldehyde v
mt ru a chc.
C
H2

H
C
OH

H2
C

O
H
C
OH

+ H 3C

C
H2

C
H

H
C

H2
C

H
C

H
C

+ nH2O

CH 3

C hai nhm hydroxyl gn nhau s tham gia phn ng acetal ha vi mt phn t

aldehyde, kt qu l lng nhm hydroxyl t do trong PVA gim ng k sau khi thc
hin phn ng. Ta c th acetal ha PVA bng nhiu aldehyde khc nhau. Vi mi mt
aldehyde, mc acetal ha ti a cng khc nhau.
Bng 3.1. Mc acetal ha ti a ca mt s aldehyde
15

Aldehyde

Phn trm acetal ha (%)

Acid B-buthylaldehyde sulfonic

57.6

Acid Ortho-benzadehyde sulfonic

44.0

Acid 2,4-benzadehyde sulfonic

36.0

Palmitinaldehyde

85.0

Chloracetaldehyde

85.8

Ortho-chlorobenzadehyde

84.6

Benzadehyde

83.0

Khi dng cc dialdehyde lm tc nhn acetal ha ta s thu c PVA c cu trc

khng gian do d hnh thnh cu ni acetal gia cc phn t PVA ln hn.
Phn ng ca ceton vi PVA chm hn nhiu so vi aldehyde. Tuy nhin, vn tc
phn ng ca ciclohexanon cng bng vi vn tc phn ng ca aldehyde.
Phn ng acetal ha ng vai tr quan trng trong sn xut x PVA.
3.2. Phn ng ether ha
PVA c th hnh thnh ether rt d dng. N hnh thnh ether ni phn t bng
cch loi nc. Thng trong phn ng ny xc tc l acid hoc kim mnh, dn ti sn
phm khng ha tan.
Ether quan trng nht trong thng mi c hnh thnh t phn ng ca alkylen
ocid vi PVA. V d nh PVA c th tham gia phn ng ether ha
OHvi cc ethylene oxide
H2
H 2phm
H
to nn nhng
H sn
H cn d tan trong nc hn c PVA.
H C
CH
C
C
C
C
H2

OH

OH

H2

H2
C

C
H
H2
C

OH

Hydro trong nhm hydroxyl ca PVA kh linh ng n c th tham gia phn ng

vi cc acid chlocarboxylic hnh thnh cc hp cht c nhm chc acid trong mch
nhnh. V d nh phn ng ca PVA vi natri monocloaxetat to thnh ether glyconic:

16

OH
C
H2

H2
C

H
C
OH

H
C

+ ClCH2COONa

C
H2

OH

H
C

H2
C

H2
C

C
H

+ NaCl

COOH

OH
H2
3.3. Phn ng
ha
H ester
H
C
H2

+ CH3COOH

C
H2

H
C

H2
C

C
H

+ H2O

PVA d dng tham gia cc phn ng ester ha vi cc acid v c ln hu c.

OH

OH

CH3

Phn ng ca ester clofocmat vi PVA dn n polyvinyl cacbonat:

C
H2

H
C

+ ClCOOR

C
H2

OH

H
C

+ HCl

OCOOR

Ure v PVA phn ng to thnh cao phn t cacbamat este:

C
H2

H
C

+ H2NCNH2

OH

C
H2

H
C

+ NH3

NH 2

3.4. Phn ng to phc

H

HO

H
2
H
H2
H
H
Cng
khc,
PVA d
to
phc
vi
hp cht v c
C
C nh
C cc
C ru
+ a chc
B
OH
C dng
C
C
C
+ 2Hcc
2O
H2

nh acid boric:
OH

OH

HO

H2

O
B
OH

17

H
PVA hnh thnh phc
trung tnh hoc base yu. Phc
H 2C vi ng trong mi trng
CH2
O

CH c
O th ha
O tan
HC
ny khng ha tan pH nhng
trong amoniac.
H 2C

Cu
CH

H 2C

O
H

O
H

CH2
O
H

HC
CH2

Mt khc, iod cng phn ng vi PVA thy phn hon ton cho phc c mu xanh
c trng ging nh mu ca phc gia iod v amylose. Iod cho phc mu vi PVA
thy phn mt phn.
3.5. Phn ng to mch nhnh
PVA d tham gia phn ng to thnh mch nhnh khi c mt cc cht sinh gc t
do nh peroxide, persulfate. Phn ng to thnh mch nhnh ca PVA c th c thc
hin khi PVA dng lng hay dng rn. Cc nh sn xut li dng tnh cht ny
sn xut x PVA bin tnh.
3.6. Phn ng phn hy
PVA l mt polymer km bn nhit. Khi b un nng ti 2000C trong chn khng,
PVA b phn hy sinh ra nc v bt c g mu nu hnh thnh. Tip tc un nng ti
4000C PVA li b phn hy ln th hai cho ra cc sn phm l cc hydrocarbon thp phn
t v mt t sn phm nha ha. Cc cht oxy ha mnh nh KMnO4, K2Cr2O7, O3 c kh
nng gy ra phn ng oxy ha ct mch cng nh oxy ha u mch PVA.

4. Tng hp
Polyvinyl alcohol c th nhn c t qu trnh thu phn cc polyvinyl ester khc
nhau nh polyvinyl acetate, polyvinyl formate, polyvinyl benzoate hoc t qu trnh thu
phn polyvinyl ether. Tuy nhin, tt c cc PVA thng mi u c sn xut t qu
18

trnh thu phn polyvinyl acetate. Vic tng hp PVA c tin hnh qua nhiu bc, c
th c minh ha nh sau:
Vinyl acetate

Trng hp

Thy phn

Polyvinyl acetate

Polyvinyl alcohol

4.1. Tng hp monomer vinyl acetate

T acetylene v acid acetic
Phn ng tng hp vinyl acetate t acetylene v acid acetic khng ph bin do c
chi ph nguyn liu cao nn ch cn mang tnh lch s cng ngh ha hc. Acetylene phn
ng vi acid acetic khong nhit t 160 200 0C pha kh trong thit b phn ng tng
si c mt acetate km tm trn than hot tnh lm xc tc. Hn hp sau phn ng c
lm ngui tr v trng thi lng. Kh khng ngng t ch yu l acetylene c lm
sch hon lu li thit b phn ng. Dng lng c em chng ct thu cc sn
phm c nhit si thp l acid acetic v mt phn acetylene cn trong hn hp, t y
thu c vinyl acetate trong sn phm y.
HC

CH

H 3C

COOH

xt

H 2C

C
H

CH3

T ethylene v acid acetic

Vi s pht trin ca cng ngh ha hc, acetylene dn dn b ethylene thay th.
Phn ng tng hp vinyl acetate t ethylene v acid acetic cng xy ra pha kh. u tin
dng kh ethylene c sc vo trong b cha acid acetic nhit 1200C. Sau khi ra
khi pha lng ethylene mang theo hi acid acetic c trn vi oxy ri np vo thit b
phn ng. Xc tc cho phn ng ester oxy ha ethylene l paladi phn b cht mang
Al2O3. Nhit
vo
khongxtt 175H2C 200C0C di
p
5 9 bar.
O
C sut
CHt
H 2C ca
CH2 phn
+ Hng
COOH
3
3C
H

Sau khi ra khi thit b phn ng dng sn phm c lm ngui ri i xuyn qua
glycol tch vinyl acetate sau tip tc i qua dung dch Na2CO3 tch acid acetic.
19

Phn cn li c a qua thit b tch CO2 ln trong ethylene cha phn ng ri quay v
vi nhp liu. Phn lng c chng ct thu cc hp cht c nhit si thp c cha
vinyl acetate. Sn phm chng ct c em i chng phn on s thu c vinyl
acetate sn phm nh.
4.2. Tng hp polyvinyl acetate
Phn ng trng hp vinyl acetate xy ra theo c ch gc chui. Tng t cc phn
ng trng hp theo c ch gc chui khc, phn ng trng hp vinyl acetate c th tin
hnh theo 4 dng l: trng hp khi, trng hp dung dch, trng hp huyn ph v trng
hp nh tng. Phn ng trng hp vinyl acetate l phn ng ta nhit rt ln. Trng hp
khi c nhit ta ra rt ln nn rt kh kim sot, trng hp khi t c s dng v to ra
khi polyvinyl acetate gy kh khn cho cc cng on x l tip theo. Trng hp huyn
ph gp kh khn khi tch v lm sch cc ht polymer ra khi hn hp sau phn ng cn
trng hp nh tng th cc cht to nh v cht lm bn nh ln bn trong polymer. Do
vy, ch c trng hp dung dch l ph hp cho qu trnh sn xut polyvinyl alcohol.
Bng 4.1 Nhit trng hp ca mt s monomer
Monomer
Ethylene
Vinyl acetate
-Vinyl pyridin
Methyl acrylate

H (kcal/mol)
22.7
21.3
18.7
18.6

Monomer
Acrylonitrile
Styrene
Methyl metacrylate
-Methyl styrene

H (kcal/mol)
17.3
16.7
13.6
8.4

Dung mi thch hp trng hp dung dch vinyl acetate l methanol hay acetone.
Nhng ch c methanol l ph hp vi qu trnh chuyn ha t polyvinyl acetate thnh
polyvinyl alcohol. Khi lng phn t c kim sot trong qu trnh ch to v rt quan
trng trong vic xc nh cc thuc tnh ca sn phm cng nh li ch ng dng. Qu
trnh ny thng c iu chnh bng cc cht ct mch trong qu trnh trng hp
polyvinyl acetate. Qu trnh trng hp dung dch thng c dng li khi t chuyn
ha thch hp. Phn vinyl acetate cha phn ng c thu hi, cn dung dch polyvinyl
acetate trong methanol c chuyn qua thit b thy phn.

20

4.3. Tng hp polyvinyl alcohol

Phn ng thy phn polyvinyl acetate c th c xc tc bng cc acid v c hay
kim, thng thng s dng xc
tc kim trong dung mi l methanol. Dung dch
NaOH
H2 C

CH

+ CH3OH

H2 C

+ CH3COOCH3

CH

polyvinyl acetate di tc dng ca xc tc kim s tham gia phn ng thy phn:

OCOCH 3

OH

Thng thng lng nc c trong methanol dng lm dung mi rt nh, nu

methanol b ln nc, lc nc
NaOHs tham gia phn ng thy phn cnh tranh vi
H2 C

methanol:

CH

+ HOH

H2 C

OCOCH 3

CH3COOH +

+ CH3COOH

CH

OH

NaOH

CH3COONa

H 2O

Acid acetic mi sinh ra phn ng vi NaOH:

Khi ton b NaOH phn ng ht tc dng xc tc khng cn, qu trnh thy phn
b ngng. Cng nh bt c polymer no thu c t qu trnh trng hp gc, polyvinyl
acetate c mch nhnh do s chuyn mch ca gc t do. Khi thc hin phn ng thy
phn, cc mch nhnh xut pht t cc nhm acetyl s b phn hy lm gim trng hp
ca polymer. Phn trm alcol phn c iu chnh bng cch cho php phn ng alcol
phn din ra hon ton hoc dng li mc mong mun.
Do phn ng thy phn lm tch cc nhm acetyl nn n thng c gi tn l
qu trnh deacetyl ha. Ngay khi kim c cho vo dung dch polymer, s thy phn xy
ra to nhng bng polyvinyl alcohol kt ta. Cc bng ny bao bc cc nhm acetyl cha
phn ng nn hiu sut chuyn ha khng cao. V vy, trc khi cho kim, dung dch
polymer c lm lnh hn ch tc phn ng. Khi t n nhit cn thit,
kim c cho vo dung dch, hn hp c khuy u v c a ln bng ti dng
gel. Phn ng deacetyl ha bt u xy ra. Gel c thu gm ri em i mt thi gian
qu trnh xy ra trit hn. Dng lng tch ra khi bng ti bao gm methanol v
methyl acetate c thu hi tch methanol. Polyvinyl alcohol c p tch hon
21

ton cc cht lng, sau c ra bng nc ha tan NaOH v mt phn methanol

cn li trong hn hp. Sau khi p, polyvinyl alcohol c em i sy nhit t 60
800C v cc tinh th PVA xut hin trong lc sy. Qu trnh sy kh s ngng li khi cc
tinh th PVA cha mt lng nc va phi.

22

Hn hp polyvinyl
acetate v methanol

NaOH

My trn

Thy phn

My p

Khuy
Polyvinyl alcohol kh

Bng ti gel ha

My sy

My nghin gel
Khu gel
My ry
Bn cha
ng bao

Dung mi thu
hi
Lng thu hi

Polyvinyl alcohol
thnh phm

Hnh 4.1 S dy chuyn tng hp PVA.

5. ng dng
5.1. X si tng hp
PVA l loi x c i lc vi nc rt ln trong s cc x tng hp. c tnh ny
em li cho n nhng ng dng c bit, m khng mt loi x no c th thay th, cng
nh l mt trong nhng im bt li ln nht ca x. Loi PVA tan c trong nc
c dng dt nhng loi vi dng lm vi nn cho cc sn phm thu, ng ten hay
23

vi d cho cc thy li th t my bay. Loi PVA c x l khng tan trong nc c

dng lm ch thu, loi c cng lc ln c th dng lm lp lt trong v bnh xe cao su
do kh nng lin kt vi cao su kh ln. Nhc im khc ca PVA l kh nng khi
phc bin dng n hi ca n vo hng nh nht trong s cc x tng hp.
5.2. Keo dn
bn ko cao v c tnh keo dn ca PVA khin chng c ng dng rng ri
trong sn xut keo dn vi cc th loi a dng t keo dn t cho giy ti keo dn hot
ha m.
PVA dng ring hoc kt hp vi cht n, cht mu v cht chng tan c s
dng rng ri lm keo dn t cho giy. Kt hp PVA vi tinh bt hay st em li hiu
qu c bit v tit kim. Mt t l nh PVA lm tng bn v kh nng chu nc ca
keo dn tinh bt v dextrin. Khi cn kh nng chu nc ti a th nn s dng PVA loi
alcol phn hon ton.
Loi keo dn nh m t trong U.S Patent 2.413.570 v 2.487.488 ca cng ty Du
Pont c kh nng chu nc vt tri. Cc loi keo dn ny, c bit l hn hp ca PVA
v tinh bt n vi st loi acid c u th v kh nng gia cng trn my tt hn nha
ureformaldehyde. ng dng ca keo dn chu nc trn c s PVA l trong ba giy, giy
dn tng v ti giy.
Cc loi PVA thy phn mt phn thng c la chn dng cho keo dn hot
ha m do chng nhy nc lnh hn loi thy phn hon ton. Khi PVA c s dng
lm keo dn hot ha m, xu hng qun li s gim bt v t b vn cc nhit cao.
5.3. Cht kt dnh
PVA l cht kt dnh hiu qu cao i vi nhiu loi vt liu khc nhau trong c
si vi. N cng c s dng kt dnh cc ht xc tc, nt chai, va v sn phm ph
thi. Vi vai tr l cht kt dnh trong gm, PVA to ra cc tnh cht p n v bn
mu cao v vy gim nt v.
PVA c s dng lm cht kt dnh cho vi v ruy bng khng dt, th hin kh
nng bm dnh tuyt vi vi c si bng v si t tm. Trong hu ht cc ng dng
24

PVA hot ng nh cht kt dnh, c th thu c cc kt qu tuyt vi nh s dng ch 3

5% PVA rn.
5.4. H v ph giy
PVA cung cp cho cc nh sn xut giy mt loi nha tan trong nc lm tng
bn, trong, chu du m, khng thm kh v nh nng cao cht lng in ca cc sn
phm giy. Thit b ph v h truyn thng c th c s dng p dng dung dch
nc vo giy.
Giy chu du m c th c to ra bng cch h b mt bng PVA. Nu cn kh
nng bn du m tuyt i th mt lp ph lin tc c th c p dng. Din tch in trn
giy c h bng PVA cho bng cao hn l do gim kh nng thm ca mc in cng
nh phng mn hn do mc phn tn u hn. i khi n c ng dng trong hp
giy thng thng.
ng ngc nhin l ch cn mt lng nh PVA l c th tng bn v mm
do ca lin kt, k ngang, ch s, bn in phi v nhiu loi giy cht lng cao khc.
Giy Glassine c h bng PVA ci thin bn, trong, bng, kh nng chu du
v bn kch thc. N t b nh hng bi m v lo ha v PVA ht m t hn mt
s tc nhn lm trong v khng bay hi.
5.5. H si v hon thin
bn ko cao, mm do, bn mi mn tt v bm dnh cng vi tan
trong nc chng t tnh c ch ca PVA nh mt tc nhn h si. Qu trnh h c th
c p dng bng cc phng php h si thng thng, cun ch vi si dc v si
an.
Cc kt qu tt cng thu c vi tt c cc loi si nh v si xe bao gm c si
tng hp t cng n h. D tan trong nc, PVA c th d dng loi b khi cc vt
mu xm. Trong mt s trng hp n c th c loi b trong b nhum m khng kh
h.
Mt trong nhng u im quan trng nht ca vic s dng PVA nh mt h ph
l nh cu oxy sinh ha thp (BOD). Cc kt qu kim tra cho thy rng PVA c BOD5
ch l 200ppm so vi BOD5 ca tinh bt l 5000.
25

PVA cng c s dng rng ri nh mt cht hon thin vi, c bit khi kt hp vi
nha nhit rn.
5.6. Tc nhn to nh
Mt tnh cht quang trng ca PVA l kh nng hot ng nh mt tc nhn to
nh khng ion. Nh th, n c mt s u im so vi nhiu cht to nh khc. N hot
ng ch yu nh mt keo bo v v dung ha dn nng cc cht in ly, c bit l
acid. Hn na, n to thnh hn hp cht nh ha h tr vi mt s tc nhn hot ng b
mt. Hot ng to nh tng cng v s kt hp cng thng t lm c hn.
PVA c th s dng to nh hay phn tn mt s lng ln cc vt liu nh du
thc vt, du khong, dung mi, cht do ha, sp v nha. Cho d n hot ng va nh
tc nhn hot ng b mt va nh keo bo v v l tc nhn to nh tt khi s dng
ring th cc kt qu i khi cng c ci thin nh thm mt lng nh sn phm nh
tc nhn hot ng b mt kh dng bt Duponol. ME c bit hiu qu trong vic lm
gim sc cng b mt. Nh tng bn c th c to ra t PVA trong c mi trng acid
v kim. Trong mt s ng dng n c dng nh mt cht kt dnh v cht lm c
cng nh tc nhn to nh.
Ni chung, loi PVA thy phn mt phn l tc nhn to nh hiu qu hn so vi
loi thy phn hon ton, loi nht cao hiu qu hn loi nht thp.
Thng th 2 5% PVA trn tng khi lng nh tng c th c s dng cho
nh tng kiu du trong nc cha 30 50% pha phn tn. Vi nhng th nghim ban
u, ch 3% PVA hay 2.5% PVA v 0.5% tc nhn hot ng b mt l .
5.7. Mng PVA
Nhiu ng dng trong sn xut bao gi gm ti v ng giy cha du, m, sn v
ha cht nn s dng mng PVA. Bao gi mt lng n v cc vt liu x phng, cht
ty trng kh, h l, thuc tr su v cht kh trng trong cc ti cha nha tan trong
nc to thun li cho vic ng dng chng.
Lng cn trc c th thm vo nc m khng lm v bao gi hay loi b giy
gi, nh tit kim thi gian v gim vt liu mt mt. Cc ti hn gn lm t mn ny
26

c th c s dng bao gi chn khng hay kh cc vt liu cn trnh oxy bo

qun cc tnh cht ca n.
Mng PVA c s dng lm cc liu oxy, trong c chn khng hay c
ti, nh mt lp ph cho kim loi nh bng cn bo v trnh kh nh oxy v hydrosulfur.
Khi c nh hng bng cch ko cng, mng phn cc nh sng. Tnh cht u vit ny
l u im khi sn xut knh mt, n bn v mt s k thut chp nh. Do mc bm
dnh thp vi mt s vt liu nha khc, mng PVA ngn chn s bm nm mc.
Khi cn bn mng v kh nng chu dung mi ti a, loi thy phn hon ton
c nht cao hay trung bnh c s dng. Vi mng tan trong nc lnh nn s dng
loi thy phn mt phn.
5.8. Gm
Mt s ng dng trong gm s dng PVA. Mt trong nhng ng dng l sn
xut b n. Ch 0.1% PVA, trn c s khi lng kh ca t st, khi thm vo nc
o khun c th ci thin cc c tnh lm vic.
Mt ng dng khc ca gm l cht kt dnh tm thi. V d: 2 3% PVA trn c
s khi lng kh ca gm cho kt qu tt trong sn xut cc ng Steatite. tan trong
nc m bo s phn b ng nht ca cht kt dnh. S dng PVA lm cht kt dnh
cn t p lc hn n Steatite v to thnh ng c thnh nhn hn. bn siu cao t
cht kt dnh lm gim s mt mt do gia cng v vn hnh my mc.
Cc cng b ch ra rng mt lng nh PVA c thm vo Steatite to ra cc ht
mm d gia cng trong cc my t ng c kh v thng cho cc c tnh c tt.
PVA cng cho cc kt qu tt khi lm cht kt dnh cho thnh phn men bng. Trong ng
dng ny, 1% PVA (trn c s khi lng kh ca thnh phn men bng) l .
5.9. Cc sn phm c
PVA c do ha c th c c thnh cc chi tit dng cao su c cng t 10
100. bn cao, mm do v chu du m, dung mi hu c, khng thm kh,
bn lo ha tt c trng cho cc chi tit ny. Chng khng thch hp cho nhng ng
dng i hi mc chu nc cao. PVA sn c dng ng, que, tm v cc chi tit c
khc nhau.
27

5.10. Lp ph bo v
PVA c s dng nh mt lp ph bo v tm thi chng xc cho cc kim loi
c bng cao v cc vt liu nha trong qu trnh sn xut v vn chuyn. C bm
dnh rt thp i vi cc vt liu ny v tan trong nc, lp ph c th bc hay ra d
dng bng nc m khng mt nhiu thi gian. PVA cng c ch bo v kim loi khi
nhng nh hng lm m ca kh. Cc lp ph trn c s PVA c s dng bo v
cc di vch tng mu trng khi b bn v to mng x khi vn chuyn. Lp ph c
loi b nh bc hay ra.
5.11. M phm
Cc tnh cht to nh, kt dnh, to mng v lm c ca PVA u c ng dng
trong sn xut m phm. Nh tng c bn cao ca cht bo v du t nhin c th
c tng hp t PVA loi thy phn mt phn. Kem lnh, kem lm sch, mt n dng
da trn c s PVA c ch to. Cc thuc v Thc phm M khuyn co rng i vi
m phm bi ngoi, khng nn s dng PVA vi nng trn 7.5%.
5.12. Cc mn giy nn
PVA c p dng t dung dch nc cha mui dicromat nh amoni dicromat s
khng tan trong nc khi tip xc vi nh sng t ngoi. Tnh cht ny c s dng
trong vic tng hp cc mn giy nn v bn in quang hc.
Mn giy nn c tng hp t PVA c s dng rng ri trang tr cc sn phm
gm. Nh mt lp ph nhy sng cho mn giy nn, PVA c mt s u im nh tnh
ng nht, d p dng, bn kch thc tt v thi gian s dng lu.
5.13. Ha cht trung gian
Mt trong nhng ng dng tiu th nhiu PVA nht l ha cht trung gian.
Polyvinyl butyrate thng l mt acetal thu c khi cho PVA phn ng vi
aldehyde.Phn ng ca PVA vi acrylonitrile thu c mt sn phm dng gm c ng
dng lm keo dn nhy p. Vic s dng PVA nh mt polyol sn xut cc ester ca
acid bo c tnh cht kh nhanh, tnh cht mi mn bt thng c thc hin t nm
1952.
28

5.14. Ti thp
Dung dch long ca PVA loi thy phn mt phn c nht cao cho tc lm
mt trung bnh gia du v nc. Khi c trn ti nng 0.05 0.3% khi lng,
dung dch ti PVA loi b s nt gy din ra do nc v lm cng hiu qu (yu t cn
thiu khi s dng du). C qu trnh ti phun v ti trong b u c tha mn.

29

KT LUN
PVA khng th tng hp trc tip t monomer vinyl alcohol v hp cht vinyl
alcohol khng bn, ngay khi c to ra, vinyl alcohol chuyn v dng ng phn bn
hn l acetandehyde. V vy, trong thc t, PVA c tng hp t qu trnh thy phn
polyvinyl acetate. Phn ng thy phn polyvinyl acetate c th c xc tc bng acid v
c hay kim, thng thng s dng kim trong dung mi methanol.
PVA c c trng bi mc thy phn v mc trng hp (hay khi lng
phn t) ca polyvinyl acetate ban u. Nh s kt hp 2 yu t ny m mt lot cc hp
cht PVA c thnh phn khc nhau c th c tng hp nn. Tnh cht ca cc polymer
ny cng thay i ty thuc vo khi lng phn t v phn trm alcol phn. Chng hn
nh khi khi lng PVA gim, nhy nc hay kh nng d tan trong nc tng. Khi
tng khi lng phn t th thu c bn ko, bn x, dn di v mm do
cao hn. Khi phn trm alcol phn tng, bn ko, bn x v dn di cng tng
PVA l mt polymer cha nhiu nhm OH. Do , n c tnh cht ca mt ru
a chc. N c th tham gia vo cc phn ng nh: ester ha, ether ha, acetal ha
PVA c rt nhiu ng dng trong cng nghip cng nh trong i sng. PVA c
th c dng lm keo dn, lm cht kt dnh hay cht to nh, c s dng trong sn
xut bao gi, trong m phm hay c dng lm x si trong dt may
Vi mc ch i tm hiu v polyvinyl alcohol, bi tiu lun ny c bn gii
quyt c nhng vn nu ra phn m u v gip chng ta c mt ci nhn tng
qut v PVA.

30

TI LIU THAM KHO

[1] Nguyn Vn Khi, Polymer a nc Ha hc v ng dng, NXB Khoa hc t nhin
v cng ngh, H Ni, 2007.
[2] Thi Don Tnh, Ha hc cc hp cht cao phn t, NXB Khoa hc v k thut, H
Ni, 2000.
[3] Hunh Vn Tr, Cng ngh gia cng si ha hc, NXB i hc Bch Khoa TP.HCM,
2006.
[4] F. L .Marten, Encyclopedia of polymer science and technology, vol 8 Polyvinyl
alcohol, Air Products and Chemicals, Inc.

31