BI GING MN K THUT SN XUT CHT DO

GV SON: PHAN TH ANH

PHN 1
CNG NGH SN XUT MT S POLYMER TRNG HP
CHNGI: SN XUT POLYETYLEN (PE)
I.Nguyn liu
Nguyn liu sn xut PE l etylen (C
2
H
4
), ch yu thu c t vic cracking du m.
Tnh cht ca C
2
H
4
:
+ t
o
nc = -169
o
C
+ t
o
s = -103,8
o
C
+ Khi lng ring t
o
si: d
(ts)
= 0,57 g/cm
3

Etylen khng phn cc (
o
=0) nn kh trng hp. Lng nhit to ra khi trng hp cao.
Monome Lng nhit to ra (cal/g)
C
2
H
4
(kh) 800
Stryren (lng) 164
MMA (nh tng) 129
Etylen dng sn xut yu cu :
C
2
H
4
98%
C
2
H
6
1 2%
N
2
0,5 1%
C
2
H
2
0,1 0,3%
II.L thuyt trng hp
Phn ng trng hp etylen thnh PE c th thc hin theo c ch gc hoc ion.
1.Trng hp gc
Peroxit, pesulfat, hp cht azo v cc dn xut alkyl ca cc kim loi khi un nng
to ra gc t do. Cc gc t do mi ny d dng phn ng vi etylen:
R

+ CH
2
=CH
2
R-CH
2
-CH
2


Gc ny tip tc pht trin :
R-CH
2
-CH
2

+ nCH
2
=CH
2
R-(CH
2
-CH
2
-)CH
2
-CH
2


Giai on ny nhit phn ng to ra rt ln do cn phi ly nhit ra khi hn hp
phn ng. Nu khng do s tng cao nhit etylen khng phn ng b phn hu v
thng km theo ting n.
Phn ng pht trin mch ngng l do kt qu kh hot tnh gc polymer
R-(CH
2
-CH
2
-)
n
CH
2
-CH
2


+ CH
2
=CH
2
R-(CH
2
-CH
2
-)
n
CH=CH
2
+ CH
3
-CH
2


Trong qu trnh phn ng, do s kt hp ca cc phn t etylen hoc gia monome
vi i phn t polymer to ra nhnh.
R-(CH
2
-CH
2
-)
m

C H-CH
2
-CH
2
-CH
3
+ nCH
2
=CH
2




nCH
2
=CH
2
+ CH
2
=CH
2
+ mCH
2
=CH
2


2.Trng hp ion
ng ch l trng hp etylen theo c ch trng hp ion c xc tc Xigle-Naptha,
TiCl
3
+ Al(R
1
)
3
R
1
: C
2
H
5

TiCl
3
+ Al(R
1
)
3

0
t

+
Ti Cl
2
Cl

Al (R
1
)
3
+
+
CH
2
=

CH
2

0
t






















+u im:
Trng hp etylen c xc tc Xigle-Naptha c nhiu u im nh polymer t nhnh,
tnh c l cao.
+Nhc im:
R-(CH
2
-CH
2
-)
m
CH-CH
2
-CH
2
-CH
3
(CH
2
-CH
2
)
n-1
-CH
2
-

C H
2

-(CH
2
-CH
2
-)
n
CH-(CH
2
-CH
2
-)
m

CH
3

TiCl
2
Cl

Al (R
1
)
3

+
CH -

C H
2

Xc tc t, d chy n
Sau khi kt thc qu trnh phi tch xc tc ra khi polymer phc tp.
III.Cc phng php sn xut PE
Nha Polyetylen c nhiu loi: HDPE, LDPE, LLDPE, VLDPE, nhng trong th
trng ph bin l 2 loi HDPE v LDPE.
HDPE l PE c khi lng ring ln. C th sn xut theo 2 phng php:
+p sut trung bnh (30 40 atm)
+p sut thp (3 4 atm)
LDPE l PE c khi lng ring b. Sn xut theo phng php p sut cao
(1500 2500 atm).
1.Phng php p sut cao (P=1500 2500 atm)
Phng php trng hp etylen trong pha kh p sut cao v nhit cao
(180 200
o
C) c cht khi u l O
2
l phng php c bn sn xut PE c t trng
thp, trng lng phn t10.000 45.000.
-Cc yu t nh hng n qu trnh trng hp:
+Hm lng O
2
trong kh

Oxi l cht khi u trng hp, tc phn ng ph thuc vo lng O
2
trong kh,
nhng v nhit v p sut cng nh hng nhiu n n nn s ph thuc ny rt phc
tp.
Nu nng O
2
qu cao, etylen s b phn hu thnh C, H v CH
4
.
VD: 2000 at v 165
o
C phn hu xy ra ngay 0,075% O
2
so vi lng monome.
Trong 2 th trn ta thy tt c cc nhit v p sut u c hiu sut cc i v
hng v pha O
2
t.
+Nhit :
Tng nhit phn ng n gi tr nht nh s lm tng nhanh qu trnh trng
hp v tng hiu sut polymer, trng lng phn t gim.
0,01 0,02 0,03 0,04
170 C
160 C
150 C
o
o
o
1350 atm
0,04 0,03 0,02 0,01
1150 atm
1000 atm
100 atm
5
10
15
Hiu sut (%)
% Oxi % Oxi
15
10
5
Hiu sut (%)
Tng nhit phn ng ph cng tng theo.
+p sut:
p sut tng th vn tc phn ng v hiu sut to thnh polymer ln.

nh hng p sut n vn tc trng hp
-Thit b phn ng loi ng c dng d
tng
=10 30mm
-c im ca loi trng hp cao p:
+C lin kt i cui mch nhiu (do chuyn mch, t mch)
+C nhnh CH
3
, (-C
2
H
5
) ln hn cc phng php khc hm lng tinh th
khng cao.
K-(CH
2
-CH
2
-)
x
CH
2
-

C H
2
+ CH
2
=CH
2
K-(CH
2
-CH
2
-)
x
CH
2
-CH
2
-

C H-CH
3
K-(CH
2
-CH
2
-)
x

C H-

C H
2
+ CH
2
=CH
2



-u, khuyt im:
+u im:
Sn phm sch (v khng dng cht khi u hu c), tnh cch in cao.
+Khuyt im:
V p sut cao: kch thc thit b b nn nng sut b.
Nng lng tiu hao nhiu do qu trnh nn kh.
Thit b t, lm t thp c bit, vn lm kn thit b, vn chuyn etylen p sut
cao c nhiu kh khn.
phng php cao p t sn xut.
2.Phng php sn xut trung bnh (30 40 atm)
Trng hp etylen trn xc tc oxit crom c th tin hnh theo phng php gin
on v lin tc trong dung mi hoc trong pha kh trng hp cation.
1000
2000
3000
300 1100 1500 2500
Vp khi p= 1atm
p (atm)
V
5000
4000
K (CH
2
CH
2
)x CH CH
2

CH
2
C
H
2

-Cc giai on chnh ca qu trnh:
+Chun b xc tc: Trn CrO
3
vi cht mang alumino silicat. Yu cu ca xc tc l
phi c th tch t do v b mt ca mao qun phi ln V
td
= 1cm
3
/g
F = 400 500m
2
/g
Xc tc s dng dng huyn ph l 0,2-0,6%.
+Chn dung mi: Dung mi ch ho tan C
2
H
4
v khng ho tan polymer, ru
metylic, xiclohecxan, xng tinh khitCH
3
OH l dung mi tt nhit no cng
khng ho tan polymer nhng ho tan monome.
+Tch xc tc ra khi hn hp sn phm: Mun tch xc tc th phi ho tan PE
trong dung mi thch hp ri tch xc tc bng my li tm. Sau sy tch dung mi ta
c PE em i to ht.
-Cc yu t nh hng :


























p
40 30 20 10
1,8
0,6
110
10
10 20 30 40
p
[]
Lng PE (g/g xc tc)

t(pht)
20 15 10 5
15
10
5
115-120 C
125-130 C
100-105 C
135-140 C
135-140 C
PE (g/g xc tc)
o
o
o
o
o
0,6
1,8
50 10 15
[]
t
p
o

p sut cng ln th [ ] cng ln P M cng cao
Nhit phn ng cng ln [ ] cng gim P M cng gim.
p sut cng tng, hiu sut to PE cng ln.
Nhit thp th hiu sut phn ng thp, nhit cao th hiu sut cao nhng khi
tng nhit ln na (125 130
o
C) th hiu sut gim v khi nhit (135 140
o
C) th
hiu sut rt thp.
Khi nhit cng cao th xy ra nhiu phn ng ph nh: ngt mch, oxi ho,.. nn
hiu sut gim.
-u, nhc im:
So vi phng php p sut cao:
+u im:
-Khng dng cc thit b t tin
-Th tch thit b ln nng sut cao gi thnh h.
-% tinh th ln (>85%) do t phn nhnh
-Khi lng ring d ln hn PEHD
So vi phng php p sut thp:
+u im:
-Xc tc r, an ton khi s dng (t c, khng gy chy n)
-D ti sinh dung mi.
+Nhc im:
-V xc tc l cht rn (CrO
3
) nn tch xc tc kh khn, mun tch phi ho tan PE
ri lc, sau sy tch dung mi phc tp.
3.Phng php p sut thp (3-4 atm)
Trng hp etylen trong dung mi c th thc hin c vi cc loi xc tc v cc
cht khi u khc nhau, ph thuc vo h thng khi u m cc iu kin trng hp v
tnh cht ca polymer thu c s thay i.
Dung mi s dng c th ho tan hoc khng ho tan polymer, thng dng: ru
metylic, xiclohecxan, n-hecxan, n-heptan, benzen,.. trong ru metylic l dung mi tt
trng hp etylen v n ho tan etylen m khng ho tan PE.
Xc tc c s dng rng ri trng hp etylen l Xigle-Naptha
(TiCl
4
+Al(C
2
H
5
)
3
)
Qu trnh tin hnh:
Cho dung mi bezin + xc tc to thnh hn hp huyn ph, cho monome etylen
p sut 3-4atm vo thit b phn ng. Nng nhit t t ln 75-80
o
C, gi t
o
=80
o
C n khi
kt thc phn ng, hiu sut 92 95% . nhit ny PE khng ho tan trong benzin,
khi t hiu sut ngi ta tch PE ra khi huyn ph bng li tm. Sau ra sch bng
CH
3
OH ( tch cc xc tc cn ln li) ri ra li bng nc. Sau PE c sy kh
vi hm m W=0,25 0,5%, c to ht, ng bao.
Benzin c cha polyetylen t trng thp v hn hp benzin, rc c em i chng
tch, lm sch, s dng li.
u, nhc im:
+u im:
-Tin hnh p sut thp nn nng lng tiu hao b nht nng xut sn xut ln
gi thnh thp.
-Trng lng phn t ca PE ln nn bn c hc, bn nhit cao hn phng php
p sut cao.
+Nhc im:
-Phi hon nguyn dung mi nn dy chuyn sn xut phc tp tn km.
-PhI tch ht xc tc ra khi PE ra
-Xc tc d chy n khi tip xc vi khng kh
IV.Cu to, tnh cht v ng dng ca PE
1.Cu to
Phn t polyetylen c cu to mch thng di gm nhng nhm etylen, ngoi ra cn
c nhng mch nhnh. PE l polymer khng phn cc, monome lng cc 0
0
.
Nu mch nhnh cng nhiu v cng di th kt tinh cng km. PE c kt tinh
tng i cao v khc nhau i vi mi loi. Trong PE phn tinh th lm cho mch cng
nn bn nhit , bn vi tc dng c hc, cn phn v nh hnh lm cho mch mm.
Cu to ca PE ph thuc vo phng php sn xut.
HDPE LDPE





S lng nhm -CH
3
(nhnh) trong 1000 nguyn t C
Loi
Tng lng
nhnh
cui mch
Nhnh
CH
3

Nhnh C
2
H
5

PE cao p 21,5 4,6 2,5 14,4
PE p sut thp 3,0 2,0 - 1
PE p sut trung bnh 2,5 1,5 - 1

Ta thy hai phng php sau nhnh t do c s iu chnh bi xc tc.
Lng nhm khng no tnh trn 1000 nguyn t C;
Loi PE

Tng lng
ni i

PE p sut trung
bnh
1,1 1,3 87% 7% 6%
PE p sut thp 0,4 0,5 52% 31% 17%
PE p sut cao 0,3 0,4 17% 71% 12%
2.Tnh cht ca PE
n gin y ta nu ra mt s tnh cht quan trng ca 2 loi PE thng dng l
HDPE v LDPE.
HDPE
+T trng d= 0,95 0,96
+Khng ht m, mc hp th nc trong
24h<0,01%
+ kt tinh 85 95%
Sn phm c m
+ ho mm thp (120
o
C), d gia cng
+Chu ho cht tt
+Cch in tt
+Lc ko t 220 300 kg/cm
2
, c loi
tt cng ko t t 600kg/cm
2

+ dn di 200 400%
+Nhit gin, gy: -80
o
C

LDPE
+d=0,92 0,93 (g/cm3)
+Khng ht m
Mc hp th nc <0,02%
+ kt tinh 60 70%
Sn phm trong hn PEHD. 110
o
C
LDPE hon ton trng thi v nh hnh
trong sut.
+im ho mm thp (90
o
C), rt d gia
cng.
+Chu ho cht tt
+Cch in tt
+Lc ko t 114 150kg/cm
2
+ gin di 400 600%
+Nhit gin, gy: -80
o
C
* HDPE
+Lc un 170kg/cm
2
+ cng shore (theo phng php th ASTM-D2240): 60 65
+ cng Brinel: 4 5kg/cm
2

+Ch s chy MI: 0,1 20gr/10 pht
+Tnh bm dnh km, d chy, khng mi, khng v, khng c
* LDPE
+Lc un 60kg/cm
2

+ cng shore (theo pp th ASTM-D2240): 30 35
+ cng Brinel 1,8 2,5 kg/cm
2

+Ch s chy MI: 0,1 60gr/10 pht
H-C=CH
2

R
R
1
-C=CH
2

R
2

C=C
R
2

H
R
1

H
+Tnh bm dnh km, d chy, khng mi, khng v, khng c
* ng dng ca PE:
Ta ch quan tm n 2 loi nha PE thng l HDPE v LDPE
HDPE
+Sn xut loi mng (ti xp, ti ng ho cht, thc phm,..)
sn xut mng , ch s chy (MI)<0,05 0,35gr/10 pht
+Sn xut si dt, si n (Yarm v monofilament) lm bao dt, bao che ph (0,8 1,0)
+Sn phm thi cc loi (thng cha, chai, l,..) (0,05 0,3)
+Sn xut cc loi ng dn nc, ho cht.
LDPE
+Sn xut cc loi mng trong, mng che ph, mng co, mng che nh vn,..
sn xut mng, ch s chy 0,3 6gr/10 pht.
+Sn phm thi cc loi nh chai, l, mng co (0,8 1)
+Sn xut cc loi ng























CHNG II: SN XUT POLYPROPYLEN (PP)
I.Nguyn liu
Nguyn liu sn xut PP l propylen, c tch t kh cracking du m hoc t
sn phm du m. Khng ch iu kin cracking (t
o
, p, t, cht xc tc,) ta c th thu
c propylen v etylen. Dng phng php lm lnh tch v lm sch propylen.
Tnh cht ca propylen:
CTCT: C
3
H
6


2
CH =
+
CH CH
3
Propylen l cht kh c t
s
= -47,7
o
C v tnc= -185,2
o
C. nhit si, t trng ca n
0,610g/cm
3

Do nh hng ca nhm CH
3
nn phn t Propylen c s phn cc, momen lng
cc 0,35 debai.
II.L thuyt trng hp propylen
iu ch PP trng lng phn t cao tin hnh trong iu kin c xc tc d th. Cu
to b mt kt tinh ca cht xc tc c vai tr quan trng trong vic iu ch phn t
polymer c cu trc khng gian u n.
Ngi ta cho rng, trc ht cc phn t monome b hp th ln b mt cht xc tc
v nh hng, sau dnh vi mch ca polymer nh m ni i. Kt qu thu c
polymer kt tinh c cu to thng, u n.
Bng cch thay i h thng xc tc, c th loi tr tc dng khng gian ca cht
xc tc v thu c polymer v nh hnh, c th thay i t l gia polymer c cu trc
u n. Xc tc dng huyn ph cho polymer c cu trc khng u n.
C ch:















Tu thuc vo iu kin trng hp, loi xc tc khc nhau m ta thu c polymer
c cu trc khc nhau iu ho hay khng iu ho.
V d: + PP c cu to khng gian khng cao c th thc hin trong h xc tc: dung
dch TiCl
4
+ Al(C
2
H
5
)
3
nhit 35 80
o
C, p = 3 5atm.
+ PP c cu to khng gian cao th dng h xc tc: TiCl
4
nghin mn + dung
dch dietylalumin clorit nhit 70 - 80
o
C, p = 5atm.
+ Hoc dng dung mi n-heptan, cc cacbuahydro khc c nhit si thp hn
nhit nng chy ca polymer kt tinh n 50 80
o
C tch PP c kt tinh cao ra
khi PP v nh hnh v PP c kt tinh thp.
Nhit thp vn tc phn ng gim, thi gian phn ng tng, hiu sut gim, hm
lng izotactic v trng lng phn t trung bnh tng.
Nhit cao th ngc li v hu ht to ra atactic.
3. Cc phng php sn xut PP.
3.1. Phng php c
p sut lm vic ca thit b phn ng l 4 6atm v nhit 50 55
o
C.
Cho dung mi (benzin) v lng xc tc cn thit (TiCl
3
+ Al(C
2
H
5
)
3
) vo thit b
phn ng. Sau cho propylen lc sch O
2
vo, duy tr nhit 50 55
o
C cho n
khi hiu sut t 95%, em lm lnh n 10
o
C tch PP dng huyn ph bng phng
php ly tm ri em x l xc tc bng CH
3
OH trong dung dch HCl. Ra PP bng nc
v sy trong iu kin chn khng nhit 60 - 70
o
C n m 0,25 0,5% ri em i
to ht.
3.2. Phng php mi ( do Naphta ra)
Dng hn hp propan (C
3
H
8
) propylen (C
3
H
6
) vi t l theo khi lng 30/70. H
xc tc l TiCl
3
+ Al(C
2
H
5
)
3
p sut phn ng 6 - 8atm v nhit phn ng 50 55
o
C.
u tin C
3
H
8
ho tan C
3
H
6
ng vai tr nh l dung mi ca phn ng. Khi trng
hp xong a v p sut thng hoc thp, C
3
H
8
khng ho tan c PP c ho hi
thu hi. Mt t C
3
H
8
hp th vo PP ta dng hi nc qu nhit ko ra. Sau ra tch
xc tc bng CH
3
OH trong dung dch HCl, ra li bng nc, sy chn khng v to ht.
3.3. Trong cng nghip
Cho propylen vo trng hp trong ni phn ng p sut n 100atm v khuy u.
Cht xc tc phn tn trong cacbuahydro lng. Duy tr nhit phn ng thp hn nhiu
so vi nhit chy mm ca polymer. Sau khi c 40% hn hp phn ng chuyn
thnh polymer th chuyn dung dch huyn ph cha: dung mi, polymer v cht xc tc
vo thit b bc hi tch ( p sut thp ) propylen khng phn ng v hon nguyn
n v sn xut. Sau nh my ly tm hoc my lc tch polymer dng bt v dung mi
ra. Ra polymer bng CH
3
OH trong dung dch HCl long. Giai on ny phc tp i hi
thi gian khuy trn nhiu, sau mi ln ra phi dng my lc ly tm, dng nhiu ru v
tiu hao nhiu dung mi.
IV.Cu to, tnh cht v ng dng ca PP
1.Cu to
Phn ln l isotactic, mt phn nh l syndiotactic v atactic. Khi nhit phn ng
t=50
o
C v dng xc tc TiCl
3
-Al(C
2
H
5
)
3
th hm lng isotactic: 85 95% hm lng kt
tinh ln.
V mi mc xch c mt nhm CH
3
nn mch cng hn PE v th bn c, bn
nhit ln hn PE.
Cng thc cu to:

Ta thy cng thc ca PP c nguyn t H C bc 3 rt linh ng do PP d b oxi
ha, lo ha.
2.Tnh cht
Tnh cht l nhit ( bn nhit)
+Nhit nng chy cao t
nc
= 160 170
o
C
+n nh 150
o
C khi khng c ngoi lc
+Chu c nc si lu, khng b bin dng.
+ 155
o
C, PP vn cn th rn, nhng n gn nhit nng chy PP chuyn sang
trng thi mm cao (nh cao su).
+Khi gim t nhit nng chy n 120
o
C, PP bt u kt tinh nhit kt tinh
cao


150 100 50
150
50
0
100
1
2
3
4
5

dn di ca cc vt liu khc nhau nhit cao
1 PE t trng thp
2 Polymetylmetaacrylat
3 PE t trng cao
-(CH
2
-CH-)
n

CH
3

dn di tng i (%)
Nhit (
o
C)
4 PVC
5 PP
+Cc tp cht v khi tip xc vi cc kim loi nh: Cu, Mn hoc cc hp kim cha
kim loi , c nh hng ln n tnh chu nhit ca vt liu. Do phi ht sc trnh.
Kh nng chu nh sng mt tri:
Do c nguyn t H C bc 3 linh ng nn d b oxi ho, lo ho.
+PP khng c cht n nh
-Di nh sng khuyt tn vn n nh tnh cht trong 2 nm.
-C nh sng trc tip th ch sau vi thng s b gin v ph hu ngay.
+PP c cht n nh (hoc dng mui than 2%) di nh sng trc tip (tia cc tm)
th sau 2 nm tnh cht khng thay i, bn trong 20 nm.
bn ho hc
+ nhit thng, PP khng tan trong cc dung mi hu c, ngay c khi tip xc
lu, m ch trng trong cc cacbuahydro thm v clo ho. Nhng nhit trn 80
o
C
th PP bt u tan trong hai loi dung mi trn.
+Polymer c kt tinh ln bn ho cht hn polymer c kt tinh b.
+PP thc t xem nh khng ht nc, mc ht m <0,01%
bn c hc
+Trng lng phn t nm trong khong 80.000 200.000
+T trng thp d=0,9 0,92 ( d
VLDPE
=0,09 0,91)
+ bn ko t :
k
(KG/cm
2
) = 300 350

n
(KG/cm
2
) = 600 700

u
(KG/cm
2
) = 900 1200 cao hn PE
+ gin di : % = 300-800% (cao hn PE)
+ bn nhit (theo Vica)
o
C =105 110
+tg (10
6
hex, t
o
=25
o
C) : 0,0002 0,0003
+Nhit gin gy thp hn PE: (-5
o
C) (-15
o
C)
+ cng Brinel: 6 6,5 kg/cm2
+Tnh bm dnh km
+Ch s chy t 2 60 gr/10pht
3. ng dng: Hon ton ging PE
Loi thng thng sn xut cc loi vt dng thng thng. Loi trng hp khi:
sn xut cc vt dng cht lng cao, chi tit cng nghip, cc loI van, v hp acqui,
Loi tnh nng c l cao: dng sn xut cc vt dng cht lng cao.
Loi c bit: chuyn dng cho chi tit sn phm cng nghip, chi tit nha trong xe
my, t, in t, hp thc phm, my git,
Loi trong: nhiu pha v nh hnhdng cho bao b y t, bao b thc phm, xylanh
tim, CD, VCD, sn phm loI c bit trong cho thc phm , khng mi, c bng b
mt cao.


































CHNG III: SN XUT POLYSTYREN (PS)
I/ Nguyn liu
-Nguyn liu sn xut PS l Styren c cng thc phn t C
8
H
8
v cng thc cu to
CH=CH
2



-Cc tnh cht vt l ca Styren: Styren l mt cht lng trong sut, khng mu n
hi vng c mi hc, khc x nh sng mnh.
- Khi lng ring 25
o
C : d= 0,9045 (g/cm
3
)
- nht (25
o
C) = 0,7 cp
- Nhit si: t
s
= 145,2
o
C
- Nhit nng chy: t
nc
= -30,63
o
C
- Nht bng chy: t
bc
= 34
o
C
- Nhit ho hi: 86,9 (kcal/mol)
- Nhit trng hp: 16,5 (kcal/mol)
- Gii hn chy n trong khng kh (%V): 1,1 6,1
- co th tch khi trng hp: 17%
Styren tan trong cc dung mi khng phn cc hay phn cc yu: xtn, CS
2
, este,
hydrocacbon mch h, vng no hp cht thm v dn xut halogel. Styren t tan trong
nc v trong cc glycol khc.
Styren c, gy kch thch nim mc mt, mi, phi, gy ng c thn kinh. Vi
nng 0,2 mg/ lit c th lm h da, nim mc mt v c hng.
-Tnh cht ho hc ca Styren:
+ Cng hydr:
CH=CH
2
CH-CH
3

H
2
, Ni
25
o
C, 3at
+ Cng halogen:
C
6
H
5
-CH=CH
2
+ Br
2
C
6
H
5
-CHBr-CH
2
Br
+ Cng HA ( HOH, HX, H
2
SO
4
...)
C
6
H
5
-CH=CH
2
+ HA C
6
H
5
-CH-CH
3

A
+ Phn ng oxy ho:
C
6
H
5
-CH=CH
2
+ O
2
C
6
H
5
-COOH + CO
2
+ H
2
O
Styren rt d trng hp v c ni i v vng thm, trong qu trnh bo qun nn
hn ch cho tip xc vi nh sng, oxy, nhit . Thng thng khi bo qun ta cho 0,5
1,5 % khi lng hydroquinon vo lm cht c ch trng hp.
-iu ch Styren: Styren c th thu c t hai ngun:
+ T sn phm Cracking v chng ct du m, kh ho than cc.
+ Bng con ng tng hp:

C
2
H
6
+ C
2
H
4
C
6
H
5
-CH
2
-CH
3


C
6
H
5
-CH
2
-CH
3
C
6
H
5
-CH=CH
2
+ H
2


II/ L thuyt trng hp Styren
Trong sn xut Styren ch trng hp theo c ch trng hp gc v thu c
polymer c cu to ch yu l lin kt u - ui v dng v nh hnh. Trong nghin
cu ngi ta c s dng trng hp ion to PS tinh th hu ht dng izotactic, mt phn
dng syndiotactic, rt t dng atactic.
Styren d trng hp khi, trng hp dung dch, trng hp nh tng v trng hp
huyn ph. Mi phng php u c nhng u, nhc im ca n.
1/ Trng hp khi
Trng hp Styren thnh khi c th tin hnh khi un nng c cht khi u hoc
khng c cht khi u.
Cht khi u thng l cc peroxit hu c. Benzoyl peroxit l cht khi u rt
ph bin nhng khng thch hp khi trng hp styren v n lm vng sn phm.
Tc trng hp tng theo nhit nhit di 50
o
C vn tc trng hp rt
chm (c khi n hng nm), 150
o
C phn ng kt thc trong vi gi. Nhng khi chuyn
ha c khong 90% th phn ng chm li v khi c 9899% th phn ng hu nh
khng xy ra na. iu c ngha l polymer c trng lng phn t cao khng thu
c vi hiu xut cao. Nu cn li nhiu monome th nhit chy mn ca PS s gim
xung, vt phm tr nn c do monome chuyn ln b mt v bc hi t t i khi lm
vng sn phm.
thu c polymer c trng lng phn t trung bnh cao tng i v cha
monome cn li t nht ta dng ch trng hp hai giai on:
+ Giai on u: to ra xirop (PS c trng lng phn t thp tan trong monome)
vi hiu sut 3040%.
+ Giai on hai: vo khun ( c th tch nh 510 lt) sau trng hp tip tc
cho n khi kt thc. Tho sn phm ra khi khun em p, nghin, sng hay to ht.
2/ Trng hp dung dch
So vi trng hp khi th phn ng trng hp trong dung dch xy ra vi vn tc
b ( iu kin khng c cht khi u) v polymer to ra c trng lng phn t thp
hn. Gi tr trng lng phn t trung bnh ca PS ph thuc vo iu kin trng hp v
90-95
o
C
AlCl
3
dehydro ha
ZnO, 500
o
C
loi dung mi. Qua th nghim thy benzen, xiclohexan, toluen trng hp tt hn cc
dung mi khc.
iu ch polymer trong dung dch thun li lm sn, cn vi mc ch khc th
thm cht lm lng kt ta polymer.
3. Trng hp nh tng
Nh tng gm c: monome, nc, cht nh ha, cht khi u v cht iu chnh
sc cng b mt.
C ch trng hp nh tng: cht nh ha khi tan trong nc to thnh cc Mixen
hnh cu m cc u khng a nc ca phn t nh ha s hng vo trong v cc
u a nc hng ra ngoi. Cc phn t cht khi u tan trong nc to thnh cc gc
t do nh phn a nc ca cht nh ha i vo Mixen v tip xc vi cc phn t
monome xy ra cc phn ng trng hp.
+ Nc l mi trng phn tn cng l cht ti nhit iu chnh nhit phn ng
ta ra.
+ Cht nh ha: gi monome v polymer mi trng thi phn tn trong pha
nc. Cht nh ha thng dng l cc loi x phng nh: lat kali, natri, starat hay cc
sunfoaxit ca ru cao bo, x phng nha thng, nkan
Nu gim nng cht nh ha th vn tc phn ng gim, nhng thi gian trng
hp v trng lng phn t trung bnh polymer tng. V vy mun iu chnh trng lng
phn t trung bnh polymer trc ht nn thay i nng cht khi u ch ng thay
i lng cht nh ha. V cht nh ha ch thay i M ca PS mt t nhng li tng thi
gian trng hp ln rt nhiu.
+ Cht kch ng: l cc peroxit v hydroperoxit tan trong nc ( H
2
O
2
, pesulfat
amn v kali..) vi hm lng 0,11% trng lng monome.
Khi thnm cht xc tin ( cc mui kim loi c tnh axit: ion Ag
+
) lm phn hy
cht kch ng vo hn hp phn ng th thi gian trng hp gim.
Nu dng h thng oxi ha-kh: cht oxy ha ( cht kch ng ) v cht kh (
mui kim loi c ha tr thay i) th vn tc ca qu trnh trng hp c th tng v gim
nhit phn ng xung.
+ Cht iu chnh: thng dng ru hay cc cht lm gim sc cng b mt ca
h thng tc l c kh nng lm tng khuch tn ca nh tng.
4/ Trng hp huyn ph
Huyn ph gm: monome, nc, cht kch ng, cht n nh v cht hot ng b
mt. y cht kch ng peroxit hu c khng tan trong nc m tan trong monome.
+ Nc dng tch monome ra thnh tng ht ring ng thi cng l mi
trng trao i nhit.
+ Cht n nh l cc polymer hu c tan trong nc nh ru polyvinilic, metyl
xenluylochng phi hon ton khng tan trong monome. Vai tr ca n l lm tng
nht ca nc v do ngn cn cc ht polymer dnh vo nhau.
III/ Sn xut Polystyren (PS)
1/ Trng hp khi:
+ Phng php gin on
Qu trnh gm hai giai on
- Giai on 1: trng hp s b Styren p sut thng sau to chn khng 200-270
mmHg v un nng. Khi hiu sut phn ng t khong 30-40% tin hnh lm lnh n
70-80
o
C v rt vo khun c dung tch t 5-10 lt.
- Giai on 2: trng hp xirp trong khun nh nh un nng. Sau tho sn phm
ra ri em i p, nghin, sng v ng bao.
Cc yu t nh hng n qu trnh trng hp khi:
Nhit trng hp
(
o
C)
Vn tc ban u (%
trong 1 gi)
nht (Cp)
(d
2
10% trong Toluen)
MP

60 0,089 3.000 2.250.000
80 0,462 650 880.000
100 2,15 200 420.000
140 28,4 30 130.000
160 -- 14 83.000

50
o
C phn trm chuyn ho rt b, thi gian trng hp rt lu.
150
o
C trng hp ch trong vi gi,
MP
=100.000.
+ Phng php lin tc
Hnh v ( xem sch )
-Styren t thng lng (1) t chy lin tc vo ni phn ng (3). Trn ng chy
c b tr thit b lc (2) tch b cc tp cht c hc. Nhit phn ng duy tr ni (3)
t 75-80
o
C, vn tc cnh khuy khong 50-60 vng/pht. Khi hiu sut phn ng t t
18-20% ta cho xirp chy vo thp trng hp c chiu cao 7.000 mm, ng knh 650
mm. Thit b (4) chia lm 4 khu vc, khu vc I ch c v bc ngoi un nng, cc khu
vc khc c thm ng xon rut g bn trong un nng. Hi bay ra khi thit b phn
ng (4) c ngng t thit b lm lnh (5). Sn phm PS nng chy t khu vc VI i
vo phn hnh nn ca thp c nhit 235
o
C sau nh trc vt y lin tc ra thnh
bng hay thi, ri em i lm ngui v thc hin qu trnh p, nghin, sng, ng bao.
-Ch nhit trong thp phn ng (4):
STT
Nhit phn ng (
o
C)
Ch 1 Ch 2 Ch 3
I 100-110 100-110 100-110
II 100-110 120 145
III 150 145 165
IV 150 190 220
V 180 200 230
VI 180 215 235
2/ Trng hp dung dch
- Phng php gin on c 3 giai on: trng hp trong ni phn ng, tch
polymer khi dung dch, p nh polymer.
- Phng php lin tc: cho Styren v dung mi t thng lng theo t l nht nh
vo thp trng hp (gm nhiu thp ni tip nhau). Dung dch PS nht t cui thp trng
hp chuyn vo thit b un nng nhit lm vic khong 225
o
C tch dung mi v
mt phn monome khng phn ng. Sau PS dng nng chy cho qua my n trc
vt to dng cho sn phm v lm ngui bng nc.
3/ Trng hp nh tng
Nguyn liu I II III
Styren 100 100 100
H
2
O 250 175 200
X phng du thu du (du ve) 3 0,4-1,2 -
K
2
S
2
O
8
0,25 0,3 -
H
2
O
2
(d
2
30%/H
2
O) - - 2,5
u tin cho nc v x phng du ve vo thit b phn ng tin hnh khuy trn.
Sau cho styren v cht khi u vo, duy tr vn tc cnh khuy khong 120-160
vng/pht. un nng hn hp ln 65-70
o
C lc ny cht khi u bt u phn ly v to ra
cc gc t do, phn ng xy ra theo c ch trng hp gc, phn ng to nhit nn nhit
ca hn hp t tng ln 85-90
o
C. Gi nhit ny cho n khi hm lng monome d
trong hn hp phn ng nh hn hoc bng 1%. Khng nn tng nhit ln na v khi
cc ht PS va to ra s chy mm v dnh li vi nhau.
Sau tin hnh ph nh tng ri em i lng, lc, ly tm tch polymer ht b
v dung dch cht nh ho, cht khi u cn d...Monome t do c th c tch bng
cch sc hi nc qu nhit vo hn hp polystyren nc thc hin qu trnh li cun
hi nc.
Vic ph nh tng c th thc hin bng nhiu cch khc nhau chng hn nh:
- Dng nhit ph h nh tng
- Dng c hc: khuy mnh vi vn tc khuy 3.000-6.000 vng/pht.
- Dng in trng
- Dng cht in ly: mui n, NH
4
Cl, ZnCl
2
, CH
3
COOH...
Sn phm to ra em ra nhiu ln bng H
2
O lm sch ht cc cht nh ho cn
li trn b mt cho n khi trung tnh. Cui cng em i sy kh n m nh hn 0,5
% v sng phn loi, ng bao.
4/ Trng hp huyn ph
Cho nc, monome v cht khi u t t vo thit b phn ng ng thi m
cnh khuy chy vi vn tc 80-120 vng/pht. Cho tip dung dch PVA vo. Ban u
nng nhit ln 75-80
o
C trong vng 1,5h sau tng nhit ln 88-90
o
C trong vng
2h. Tng thi gian phn ng khong 4-5h, hiu sut t 95-98%.
Hn hp huyn ph gm: ht PS, mi trng em ly tm v ra bng nc m
45-50
o
C sau em i sy kh nhit 65-75
o
C trong chn khng n m nh hn
0,2-0,5%.
IV/ Cu to, tnh cht, ng dng ca PS
1/ Cu to
Qua nhiu phng php nghin cu khc nhau, c bit l phng php nhit phn
PS th thy rng PS c cu to u ni ui
CH
2
CH CH
2
CH CH
2
CH

PS nhit phn ng khng cao th t to nhnh v nhnh b.
2/ Tnh cht
PS l cht do trong sut , cng chc, khng mi, khng v, khi chy c nhiu
khi, gi thnh r, d gia cng bng phng php p v c di p sut, chu ho cht v
nc cao...
V c nguyn t H C bc 3 linh ng nn H ny d tham gia phn ng oxi ho v
th PS nhanh b lo ho trong khng kh khi c nh sng trc tip. Vng bezen c th
tham gia phn ng sunfo ha, nitro ho,...dng sn xut nha trao i ion nh cationit
axit mnh.
PS khng phn cc do bn vi cc ho cht phn cc v phn cc mnh.
PS c trng lng phn t thp rt gin v c bn khi ko cng b. dn di
tng i ca PS tng vt sau 80
o
C v tr nn mm do nh cao su v dnh.
-Khi lng ring d=1,05-1,1 g/cm
3

-Ch s chy MI: 1-8 g/10pht
- bn ko t: 400-450 kg/cm
2
Tnh cht PS huyn ph Dung dch Khi Nh tng
Gii hn bn un [KG/cm
2
] 816 875 800 900
bn va p [KG/cm/cm
2
] 14,7 15 15 180
bn nhit (Mactanh) [
o
C] 80 80 80 80
thm in mi (in th
xuyn thng) (10
6
hex)
2,6 2,6 2,6 2,6
tg (10
6
hex) 0,0004 0,0006 0,0004 0,0008
3/ ng dng
-PS c lm vt liu cch in (iu kin khng ti hoc ti trng b v tnh)
-Lm cc sn phm khc dng trong dn dng v cng nghip, phi bin tnh bng
cch ho do hoc ng trng hp vi cc monome khc.
-PS xp dng lm v ng my khi vn chuyn, cch m v nhit thp trong xy
dng



























CHNG IV: CHT DO TRN C S CC POLYMER
CA RU VINYLIC V CC DN XUT
A- SN XUT PVAx
I/ Nguyn liu
Nguyn liu chnh sn xut polyvinyaxetat l vinyaxetat
Tnh cht: l mt cht lng trong sut, khng mi, t tan trong nc, tan trong dung
mi hu c, c:
+ Nhit si t
s
= 73
o
C
+ Nhit ng bng t= -84
o
C
+ Nhit bc la t
l
= -5 -8
o
C
+ Khi lng ring 20
o
C
20
= 0,934 (g/ml)
+ nht 20
o
C = 0,432 Cp
+ n nhit bc hi: 7,8 ( Kcal/mol)
+ ho tan trong nc 20
o
C : 2,5 %
+ Cng thc cu to:

CH
2
CH
OCO CH
3

Tnh khng no: do trong mch c ni i nn VA c kh nng tham gia cc phn
ng cng, ng vng, oxi ho. C lin kt este nn tham gia phn ng thu phn vi
nc, ancol
CH
2
CH
OCO CH
3
C
4
H
9
OH
CH
3
C OH
O
CH
2
CH
O C
4
H
9
+
+

* iu ch: C hai phng php
+ Sn xut VA trong pha lng theo phng php gin on hoc lin tc.
Cho axetylen (C
2
H
2
) qua hn hp CH
3
COOH m c v anhydrit axetic c cha
sunfat thu ngn hoc phtphat thu ngn. Phn ng xy ra nhit 75-80
o
C, kt thc
phn ng C
2
H
2
tha c tch ra v mt lng nh VA c a i x l.
Vi phng php gin on cui qu trnh ta lm chm vn tc hp th C
2
H
2

gim lng VA b tht thot v i xc tc mi.
Cn i vi phng php lin tc th lin tc cho C
2
H
2
, CH
3
COOH v cht xc tc
mi vo thp phn ng ng thi lin tc tho xc tc phn ng ra.
Sn xut VA theo phng php pha kh th ngi ta tin hnh theo phng php
lin tc. Cht xc tc thng dng l axetat km (CH
3
COO)
2
Zn hoc (CH
3
COO)
2
Cd
c ph ln b mt than hot tnh sau sy kh. Nhit phn ng 170
o
C 240
o
C.
Lc u nhit phn ng 170
o
C nhng sau do hot tnh ca xc tc gim nn tng
vn tc phn ng th nhit phi nng ln 210
o
C 220
o
C. hiu sut phn ng cao th
dng t l C
2
H
2
: CH
3
COOH = 9 : 1 khi hiu sut t c l 80 85%.

C H CH CH
3
C OH
O
CH
2
CH
OCO CH
3
+

+ Phng php mi sn xut VA l phn gii diaxetat-etyl theo phng trnh phn ng
cho hiu sut cao
C H
3
CHO
C H
3
CO
O
CO
C H
3
C H
3
CH (OCO CH
3
)
2
CH
2
CH
OCO CH
3
CH
3
COOH
+
+

II/ L thuyt trng hp VA
Vinylaxetat d b trng hp di tc dng ca nh sng, nhit , cht kch ng
v cht xc tc.
Nhit to ra do trng hp kh ln
+ VA : 21,3 Kcal/mol
+ MMA :13 - 13,6 Kcal/mol
+ Styren : 16 17,5 Kcal/mol
+ Etylen : 25 26 Kcal/mol
V vy khi trng hp VA cn mt nng lng kch ng kh ln, gy kh khn cho
qu trnh iu chnh.
Cc monome c cha nguyn t C bc 3 c khuynh hng to ra polymer nhnh
ln do phn ng chuyn mch.
+ Chuyn mch qua monome

CH
2
CH
OCO CH
3
RH CH
2
C

OCO CH
3
R

+ +
xt, t
O

Hoc

CH
2
CH
OCO CH
3
RH CH
2
CH
OCO C

H
H
R

+ +
xt, t
O

: gc polymer ang pht trin. Nu trng hp tip tc th sinh ra nhnh.
Xc tc
Xc tc,t
o
Xc tc,t
o
R

R

CH
2
C

OCO CH
3
CH
2
C
OCO
R
CH
3
(a)
R

CH
2
CH
OCO C

H
H
CH
2
CH
OCO
R
CH
2
(b)
+
xt, t
O
+
xt, t
O

C ch to nhnh theo kiu (a) nhiu hn (b)
+ Chuyn mch cho phn t polymer khng hot ng
R
.
+ R
,
H RH + R
,.

Mun lm gim s nhnh trong polymer hoc ta cho ngng phn ng trng hp
mc chuyn ho thp. Hoc cho tin hnh phn ng trong dung mi hoc cho thm cht
iu chnh (mecaptan, aldehyt...) c nguyn t H linh ng.
S chuyn mch t polymer ang pht trin sang dung mi c m t nh sau:
R
.
+ HA RH + A
.
(km hot ng)
III/ Sn xut PVAx
C 4 phng php trng hp VA: trng hp khi, trng hp dung dch, trng hp
huyn ph v trng hp nh tng. Trong phng php trng hp khi t c s
dng v to thnh khi PVAx gy kh khn cho cc cng on x l tip theo (Tg =
28
o
C). Trng hp huyn ph cng t c s dng, phng php c s dng ph bin
nht l trng hp nh tng.
1/ Trng hp dung dch
Sn phm thu c dng lm sn, vecni, keo dn, sn xut PVA
Thnh phn hn hp phn ng
+ Monome 100 PKL
+ Dung mi 70 100 PKL
+ Cht khi u [ (C
6
H
5
COO)
2
] 0,2 0,5 %
+ Cht iu chnh ( C
2
H
5
CHO ) 0,01 0,1 %
iu kin tin hnh phn ng
+ Dung mi ho tan c monome v
+ Nhit phn ng ban u 75 80
o
C sau tng ln 85
o
C, hiu sut phn ng
t 98%
+ Thi gian phn ng 4 6h
Khi c mt ca dung mi th s phn tn nhit c ng u hn. Nhng nng
monome trong trng hp dung dch nh hn nng monome trong trng hp khi nn
vn tc phn ng khng cao v trng lng phn t b hn so vi trng hp khi v c s
chuyn mch, ngt mch vi dung mi.
Vinylaxetat tan tt trong cc dung mi etylaxetat, axeton, benzen, toluen, ru
tuyt i. Bn cht v nng dung mi khc nhau th dn n hiu sut v trng lng
phn t ca polymer cng khc nhau c th.
Nguyn
liu
Axeton Toluen Ru tuyt
i
Etylaxetat Benzen
Hiu sut
to P
o
(%)
68,5 28 22,6 89,3 55
nht
(Cp)
3 2,9 5,6 8,2 18,2
Ta thy ru tuyt i, benzen v toluen lm chm qu trnh trng hp VA, tc
phn ng ln nht l tin hnh trng hp trong dung mi etylaxetat v axeton. Cn trong
dung mi benzen th polymer thu c c trng lng phn t cao nht, nu dng toluen
th trng lng phn t rt thp mc d nhng tnh cht ca hai dung mi gn ging
nhau.
Trong k thut dung mi thng dng trng hp VA l etylaxetat, axeton v
benzen. Ru etanol v metanol ch dng khi sn xut polymer tip tc x l thnh
PVR v polyvinylaxetal.
2/ Trng hp nh tng
C 2 loi nh tng : nh tng mn
ht
= 0,05 0,5 m
nh tng th
ht
= 0,5 10 m
Thnh phn nh tng mn:
+ VA : 100 PKL
+ H
2
O : 100 120 PKL
+ Cht nh ho C
17
H
33
COOK: 0,1 0,5 ( dung dch 10 15%)
+ Cht khi u H
2
O
2
: 0,5 1,5%
+ Cht iu chnh C
2
H
5
CHO : 0,01 0,1%
Chun b:
+ Ho tan cht nh ha trong nc
+ Ho tan cht khi u trong t nc
+ Ho tan dung dch cht iu chnh vo nc
Cc bc tin hnh trng hp:
+ Cho ht dung dch nc v cht khi u vo thit b phn ng, cho cht nh ho
vo khuy u.
+ Cho t t monome vo khuy u
+ un nng n nhit 65 70
o
C gi trong khong 1h, do phn ng to nhit
nn nhit t nng ln 90
o
C, tip tc duy tr nhit ny trong khong 1,5 2h. Cho
cht iu chnh vo gn cui qu trnh, kt thc phn ng hiu sut chuyn ho t 98%
+ Lm lnh hn hp phn ng n 40
o
C, thm cc cht khc nu cn thit.
+ Hm lng cht kh trong nh tng khong 50%
3/ Trng hp huyn ph
Thnh phn nguyn liu:
+ VA: 100 PKL
+ H
2
O: 100 PKL
+ (C
6
H
5
COO)
2
: 0,5 1 PKL
+ Cht n nh huyn ph : 0,1 0,2 PKL ( dung dch PVA c 8 20 % nhm
axetat)
S dy chuyn cng ngh
Hnh v: (xem sch)
Cc bc tin hnh
+ Chun b nguyn liu:
-Ho tan cht khi u vo monome
-Ho tan PVA trong H
2
O
-Trn hn hp dung dch cht khi u vo ht monome cn li
+ Tin hnh phn ng
u tin cho ht phn nc vo thit b phn ng (6), cho dung dch PVA ho
tan trong nc vo ng thi tin hnh khuy trn. Ri cho t t hn hp VA v cht
khi u vo thit b phn ng. Thit b phn ng c v bc bn ngoi gia nhit cho
hn hp phn ng. Dng hi nc bo ho nng nhit ln khong 70 80
o
C ng
thi khuy u lin tc to c cc git lng monome c dung dch PVA bao bc
xung quanh. PVA c nht tng i ln nn ngn cng khng cho cc git monome
dnh li vi nhau. Khi un nng phn ng xy ra v to nhit nn nhit ca hn hp t
tng ln 80 90
o
C, khi ta ng van hi nc li v m van nc lnh gi nhit
ny trong vng 45 60 pht. Tip tc nng nhit ln n 90 95
o
C trong thi gian 30
35 pht. Tng thi gian phn ng ny mt khong 2h.
Trong qu trnh phn ng hi monome v nc bay ra c cho vo thit b ngng
t lm lnh bng nc (7) ri cho hi lu tr li thit b phn ng. Hiu sut chuyn ho
ca qu trnh khong 98 99%. Khng kh nn hoc N
2
(nu dng khng kh nn th phi
lc) c tc dng ngn khng cho khng kh bn ngoi vo trong thit b phn ng, ng
thi khng cho hn hp bn trong thit b phn ng b trn. Khi cho kh nn vo th phi
ng tt c cc van khc li. Hn hp phn to ra trong thit b (6) c chuyn sang thit
b cha (9), ti y hn hp c duy tr nhit 50
o
C gim nht, v trnh sa
lng th thit b phi c cnh khuy hot ng lin tc. Sau hn hp c chuyn sang
my ly tm (10), y dung dch nc thi em i x l cn cc ht polymer c
chuyn sang xe gong (11) v theo h thng nng (12) i vo thit b sy (13). Ti thit b
sy (13) nhit sy c duy tr 65 70
o
C trong iu kin chn khng vi thi gian
khong 15-20 pht ( y ch c tc dng lm kh nc ch khng sy kh trit , cc
ht polymer to ra c th ht m tr li). Sau khi sy xong a vo my sng phn loi
ht th em i nghin nh ri trn li vi sn phm ht nh.
IV/ Cu to, tnh cht v ng dng ca PVAx
1/ Cu to
Ngi ta dng phn ng x phng ha PVAx to thnh PVA nghin cu cu
trc ca PVAx. Cc monome VA kt hp vi nhau to thnh polymer PVAx theo nguyn
tc u ni ui.
Cc phng php nghin cu:
+ Khi oxi ho PVA bng HNO
3
ta thy c to ra acid oxalic:
CH
2
OCO
CH
CH
3
CH
2
OCO
CH
CH
3
CH
2
OH
CH CH
2
CH
OH
HOOC COOH

+ Xt ph hp th th thy PVA c vch hp th ging 2,4-pentadiol
CH
3
CH CH
2
CH CH
3
OH OH

+ Phn tch Rnghen ta thy PVA c cu trc -glycol.
+ Dng phn ng oxi ho PVA bng HIO
4
chng minh PVA c cha nhm -
glycol hay -glycol. Nu PVA c cha nhm -glycol tc l mch phn t PVA c cu
trc u ni u khi PVA d b oxi ho bng HIO
4
. Nu ta un nng PVA vi HIO
4

th thy nht gim nhng khng ng k, chng t lc u c phn ng t mch xy
ra nhng sau nht khng gim c ngha phn ng khng xy ra na.
Phn ng t mch PVA nh sau:

CH
2
OH
CH CH
2
CH
OH
CH CH
2
CH CH
2
CH
OH OH
OH
HIO
4
CHO CH
2
OH
CH CH
2
CH
2
CH CH CH
2
CH
OH
OH
O H
2
+
+

Phn ng t mch xy ra mt s v tr u ni u, ui ni ui nhng v
tr ny rt t nn nht gim t.
PVAx l mt polymer v nh hnh, nu mc ko cng ln (nh hng) cng
khng kt tinh v bn cht ca n khng nh hng c do nhiu nhnh v nhnh ln.
Polymer phn cc trung bnh yu = 2,3.10
-18
debay, do vy tan tt trong cc dung
mi phn cc tng ng.
2/ Tnh cht
a/ Tnh cht nhit:
+ PVAx c Tg = 28
o
C khi trng lng phn t trung bnh ln hn 30.000, nu
trng lng phn t trung bnh thp 15.000 th Tg = 17
o
C
+ PVAx c th chy lnh( mu PVAx chu tc dng ca ti trng no y nhit
thng khng un nng, mu cng b bin dng chy)
+ Khi un nng 170
o
C tr ln th PVAx b phn gii to CH
3
COOH

CH
2
OCO
CH
CH
3
CH
2
OCO
CH
CH
3
CH CH CH
2
CH
CH
3
COOH
OCO CH
3
+

Do lm cho polymer b vng, c th to polymer mng li khng gian khng
nng chy, khng ho tan trong bt k dung mi no. Kh nng to mng li khng gian
l do m lin kt i trong mch.
b/ Tnh cht ho hc
+ PVAx bn oxi ho, lo ho, nh sng
+ PVAx tan trong cc dung mi: xton, este, dn xut ca HC, HC thm.
+ PVAx phn cc trung bnh nn khng tan trong xng, du ho, HC bo mch
thng no, cc cht c phn cc ln: glycol, glyxerin.
+ PVAx b trng trong nc v c th bn vi cc mui.
+ PVAx b thu phn to PVA trong mi trng kim hoc axt
+ Trn ln tt vi cc polymer: nitro xenlulo, cc dn xut khc ca xenlulo, cao
su clo ho, mt s polyeste, nha epoxy, phenolformaldehyt nhng khng trn ln vi cc
nha alkyd, ure-formaldehyt v melamin-formaldehyt.

c/ Tnh cht c hc
Ph thuc vo trng lng phn t trung bnh v phng php sn xut
+ Khi lng ring d= 1,18 1,19 g/cm
3

+ Gii hn bn ko (KG/cm
3
): -10
o
C 600
10
o
C 400
20
o
C 350
30
o
C 150 180
+ bn nhit (Vica,
o
C): 37
+ ht nc (24h, t
o
=20
o
C): 3%
+ thm in mi (60 hex): 6,1
+ tg (60 hex): 0,025
3/ ng dng
+ sn xut PVA
+ Lm sn, vecni, keo dn thng thng trn vi polymer khc
170
O
C
+ Dng PVAx nh tng dng trong xy dng tng Mac ca va ximng v
ximng btng, tng chng thm
+ Dng PVAx nh tng dng lm sn trong trang tr ni tht

B- SN XUT POLYVINYLALCOL (PVA)
I/ Sn xut PVA
Phng php c bn sn xut PVA l thu phn (x phng ho ) PVAx nh
kim v axit ( NaOH, HCl, H
2
SO
4l
...) thng thng thu phn trong mi trng kim vi
dung mi l CH
3
OH.
Trng kp dng NaOH lm xc tc th cho PVAx tan trong CH
3
OH khan nc
v sau x l bng mt lng nh (0,2 0,4%) dung dch NaOH trong CH
3
OH khan
nc. Gi hn hp nhit phng, PVA tch ra dng gel, dng phng php gn
tch cht lng gm: CH
3
OH tha, axetat v nati axetat, cn PVA tan trong nc. Rt
dung dch ny vo axeton (lng tha) kt ta PVA dng nguyn liu si trng, sch.
iu chnh lng nc, nng PVAx v lng cht xc tc c th khng ch c mc
thu phn bt k. Sau em ly tm, ra, sy chn khng nhit 80 90
o
C n
m 2 3% ( sy bay hi axeton i, cn ht vn m do PVA tan tt trong nc c th
ht m tr li).
Trng hp dng HCl lm xc tc th nht ca PVA gim, c khi PVA khng
tan trong nc v trong axit long. iu c l do PVA b mt mt s nhm hydroxyl
trong qu trnh thu phn hoc trong thi gian sy. Rt kh kh vt axit c bit l axit
H
2
SO
4
ra khi PVA, v th axit cn li c th xc tin qu trnh kh hydro

CH
2
CH CH
2
CH
O C CH
3
O
O
C CH
3
O
CH
2
CH CH
2
CH
OH OH
CH
3
COONa CH
3
COOCH
3
+ +

II/ Cu to v tnh cht ca PVA
1/ Cu to
Dng polyvinylfocmiat th PVA to ra dng syndiotactic

CH=CH + HCOOH CH
2
=CH-OOC-H polyvinylformiat
Dng polyvinylbenzoat to PVA dng izotactic
Dng PVAx to hn hp 3 loi: izotactic, syndiotactic v atactic, trong atactic
chim ch yu nn PVAx l mt polymer v nh hnh.
V c nhm OH phn cc v c lin kt H gia cc mch phn t nn Tg cao, Tg =
85
o
C v th gy kh khn cho qu trnh gia cng.
2/ Tnh cht:
CH
3
OH, NaOH
t
o
=30 - 40
o
C
Xc tc, t
o
C kh nng to ete, phn ng vi cc aldehyt to polyvinylaxetal

CH
2
CH CH
2
CH
OH OH
CH
2
O CH
2
CH CH
2
CH
O
CH
2
O
+

polyvinylformal (form-va)

CH
2
CH CH
2
CH
OH OH
C
3
H
7
CHO
CH
2
CH CH
2
CH
O
CH
O
C
3
H
7
+

but-va
Hai phn ng ny c ngha quan trng
Khi un nng nhit cao (>200 250) th tch nc, to ni i. PVA tan
trong H
2
O ph thuc vo nhit v phn trm nhm CH
3
COO- c trong PVA
+ Nu %CH
3
COO- < 5 th khng tan trong nc lnh m ch tan trong nc nng
(65 70
o
C) dung dch t nng ti a 10 12 %.
+ Nu %CH
3
COO- = 20 th ho tan trong nc, khi un n nhit 30 35
o
C ri
lm lnh th P
o
s lng xung.
+ Nu %CH
3
COO- = 50 th khng tan trong nc lnh v nng m ch trng
nhng tan trong hn hp ru v nc ( thng dng CH
3
OH )
+ Ngoi nc PVA cn c th tan trong glycol thng, glyxerin, phenol, ure ( khi
un nng )
Dung dch PVA bm dnh tt trng thi kh v khng b thi ra bi vi sinh vt
nn dng lm keo dn giy, phong b.
III/ ng dng
Nu PVA cha 15 20% nhm CH
3
COO- th dng lm keo dn. Dung dch PVA
cho thm mt lng nh formalin dng lm keo dn giy, vi, da.
bn c hc ca PVA nh hn polyamid-6, polyamid 6-6, axetat xenlulo, phenol
formaldehyt, ure formaldehyt...
Si PVA x l bng dung dch CH
2
O c dng lm si cu, li nh c. Ngm
si PVA c x l bng CH
2
O trong nc bin trong vng 95 thng th bn thay i
khng ng k.
Si PVA x l ho hc bng CH
2
O kt hp vi si Visco dit vi may mc, mt
s ni gi l si vinylong



CHNG V: CHT DO I T CC DN XUT CA AXIT ACRYLIC
V AXIT METAACRYLIC
Axit polyacrylic v polymetaacrylic ng trng hp vi divinyl benzen ( 10 15%
khi lng ) dng lm nha trao i ion loi cationit

*
CH
2 n
CH CH
2
CH
COOH
CH CH
2

Polyacylat v polymetyl-metaacrylat, polyacrylonitril, polybutylmetaacrylat l cc
loi nha thng thng.
Polyacrylonitril c Tg > nhit phn hu do phi dng dng ng trng hp
ch khng dng dng n trng hp, n khng tan trong bt c dung mi no.
I/ Nguyn liu chnh
1/ Axit acrylic ( CH
2
=CH-COOH ) l axit hu c khng no, n gin nht, c kh nng
trng hp v ng trng hp. C nhiu phng php sn xut axit acrylic.
+ Phng php tng hp Reppe iu ch trc tip t C
2
H
2
, CO, H
2
O ( CO c
iu ch t ttracacbonyl niken ho tan trong HCl )
CH CH O H
2
Cl H Ni(CO)
4
CH
2
CH COOH NiCl
2
CH
2 +
+
1/2 +
1/4 +
1/4 +
1/4

+ Phng php c in: oxi ha acrolin bng khng kh trong mi trng
CH
3
COOH m c 20 40
o
C c oxit bc hoc oxit vanadi
+ Nhng tin nht l:

C H
2
CH
2
O
HCN CH
2
CH
2
CN
OH
+

etylenxianhydril

CH
2
CH
2
CN
OH
O H
2
H
2
SO
4
CH
2
CH COOH (NH
4
)HSO
4 + +
+

Axit acrylic l cht lng khng mu, c mi hc tan trong nc v cc dung mi
hu c theo bt c t l no.
Khi khng c peroxit, trong mi trng N
2
v nhit n 180
o
C vn khng b
trng hp. Ngc li nu c mt lng nh oxi hoc peroxit vo th d to ra P
o
.
2/ Este ca axit acrylic ( CH
2
=CH-COOR )
Trong cc este ca axit acrylic th metyl, etyl, butyl acrylat c dng nhiu nht
Ngi ta tng hp este acrylic t etylenxianhydrin
95
O
C

CH
2
CH
2
CN
OH
ROH H
2
SO
4
CH
2
CH COOR (NH
4
)HSO
4 + +
+

Este tinh khit d b trng hp ngay nhit phng.
3/ Axit metaacrylic
CH
2
C COOH
CH
3

Nhn axeton xianhydrin t axeton v HCN

CH
3
CO CH
3
HCN CH
3
C(CH
3
) CN
OH
+

Kh H
2
O v x phng ha axeton xianhydrin bng H
2
SO
4
.

CH
3
C(CH
3
) CN
OH
CH
2
C COOH
CH
3

Axit metaacrylic l cht lng, khng mu, si 160
o
C.
4/ Este ca axit metaacrylic ( CH
2
=C(CH
3
)-COOR )
Metyl metaacrylat v butyl metaacrylat c dng nhiu nht. Phng php chung
l kh H
2
O, x phng ho v ete ho axeton xianhydrin bng ru tng ng.
CH
3
C(CH
3
) CN
OH
ROH H
2
SO
4
CH
2
C(CH
3
) COOR
(NH
4
)HSO
4 + + +

Tn Nhit si (
o
C) Khi lng ring (g/ml)
CH
2
=CH-COOH 141 1,0487 (20
o
C)
CH
2
=C(CH
3
)-COOH 160 1,015 (20
o
C)
CH
2
=CH-COO-CH
3
80 0,952
CH
2
=CH-COO-C
2
H
5
99,5 100 0,919
CH
2
=C(CH
3
)-COO-CH
3
100,3 0,937
CH
2
=C(CH
3
)-COO-C
2
H
5
117 0,911
* Nhn xt:
Thay H linh ng (1) bng CH
3
- tr thnh (2) th nhit si cao hn do s cn
tr chuyn ng quay ca nhm CH
3
, ng thi khi lng ring ca (2) cng nh hn do
cng knh v mt sp xp khng gian ca mch i phn t. Nhit si thp nht l
metylacrylat v khi lng ring thp nht l etyl metaacrylat. Quy lut trng hp ca
monome ny cng ging nh cc monome ca dn xut vinyl, ch khc v iu kin trng
hp.
* Xt MMA
MMA c nhit trng hp thp ( nh hn Styren ) nn MMA d trng hp. MMA trong
qu trnh bo qun nu tip xc vi nh sng c bc sng ngn, oxi khng kh th n t
trng hp. Do trong qu trnh bo qun cn phi cho thm cc cht c ch (hay hm
trng hp) l cc cht c H linh ng, ph bin nht l hydroquinon. V vy trc khi tin
hnh trng hp th tch lng hydroquinon ny ra khi monome bng dung dch NaOH
nhng hm lng ch nhiu hn mt t so vi hydroquinon v nng xt phi long.

CH
2
C
COOCH
3
CH
3
NaOH CH
2
C
CH
3
COONa
CH
3
OH
+ +

II/ Nguyn tc trng hp
C th trng hp theo mt trong 4 phng php: trng hp khi, trng hp dung
dch, trng hp nh tng , trng hp huyn ph.
1/ Trng hp khi
Thnh phn nguyn liu:
+ MMA: 100 PKL
+ Hn hp cht khi u ( peroxit benzoic:azodiizo butyronitril = 2:1 ): 0,02 1%
S dng hn hp cht khi u gim tc oxi ho ca peroxit benzoic.
Qu trnh phn ng:
+ Chun b nguyn liu: trn cht khi u vi mt t MMA ri sau cho hn
hp ny trn vi lng MMA cn li.
+ Tin hnh gia nhit cho hn hp phn ng, ban u duy tr nht 70 80
o
C,
phn ng to nhit nn s t nmg ln 80 -90
o
C. Khi hiu xut chuyn ho ca hn hp
t 30 40% tin hnh vo cc khun nh c dung tch 5 10 lt v vn gi nhit
80 90
o
C, tip tc trng hp trong l sy vi thi gian 4 6 ngy. Nhit sy trong l
c iu chnh nh sau:
80 - 90
o
C trong 1 2 ngy.
90 95
o
C trong 1 ngy.
95 110
o
C trong 1,5 ngy.
110 120
o
C trong 1 ngy.
co ngt th tch khi trng hp khi l 20,1%
Trong qu trnh sy nng nhit t t trnh hin tng monome bc hi to l
xp v hm lng monome cn li trong sn phm cui cng 0,5 1%. Trng hp khi
c ng dng nhiu nht trong sn xut PMMA.
nng cao hiu xut ng thi gim co ngt ca sn phm ngi ta tin hnh
trng hp MMA theo mt phng php khc: trn MMA vi mt lng xirp ca
PMMA v cht khi u ri tin hnh trng hp theo trnh t cc bc nh trn.
2/ Trng hp dung dch
Bn cht v hm lng dung mi nh hng n trng lng phn t trung bnh
ca Po, vn tc ca phn ng. Dung mi tt nht dng trng hp l benzen do hng s
chuyn mch, ngt mch b nht.
Trong dung mi khng phn cc phn ln polmer c cu to izotactic, trong dung
mi c cc th to ra polymer c cu to syndiotactic.
3/ Trng hp nh tng
Phng php ny rt c hiu qu sn xut nhiu polymer ca ete axit acrylic v
metaacrylic. Dng nhiu nht l latex ca polyetyl v polymetylacrylat ph ln b mt
da, giy... tuy nhin mng nhn t phng php ny km bn hn mng nhn t dung
dch trong cc dung mi hu c.
X phng natri v amn l cc cht nh ho tt nhng khi dng chng th mi
trng kim to ra v monome nhiu hay t cng b x phng ho. V vy nn tin hnh
phn ng trong mi trng trung tnh hoc axit yu. C ch trng hp ging vi trng
hp styren.
4/ Trng hp huyn ph
Phng php ny c dng ph bin gn nh trng hp khi
- T l th tch: H
2
O/MMA = 2/1 n ti a 4/1.
- Cht n nh huyn ph: jelatin, metylxenlulo, PVA (8 -12% nhm axetat t do):
0,05 0,2% so vi monome.
Cht n nh tan tt trong nc, khng tan trong monome, dung dch c nht ln.
Nng cht n nh trong mi trng nc 15 20%.
- Cht khi u: hn hp peroxit benzoic v azodiizobutyronitril vi hm lng:
0,01 1%.
- Cht mu hu c tan trong monome, bn mu, khng c nh hng n qu
trnh phn ng.
Qu trnh tin hnh:
Ban u duy tr nhit 80
o
C sau nng dn nhit ln 90, 95, 98
o
C trong
khong thi gian 2,5 3h. Nhit cui ca qu trnh duy tr 100 110
o
C trong vng 30
pht v kt thc. Tng thi gian phn ng 4,5 5h. Hm lng monome t do cn li
trong hn hp sau phn ng nh hn 1%.
Sau tin hnh ly tm, ra bng nc nhit 65 70
o
C ngay trong thit b ly
tm. Ra bng nc m tch cc cht n nh huyn ph, cht iu chnh... c trit
. em sy nhit 75 80
o
C trong thi gian 30 pht ri tin hnh to ht, ng bao.
III/ Cu to, tnh cht v ng dng ca PMMA
1/ Cu to
Nghin cu cc dn xut ca polyacrylic thy rng cu trc ca chng c th u
ni ui v u ni u. Tt c cc polymer ca ete acrylic v meta acrylic l nhng
sn phm khng mu, trong sut, cng, n hi, chng u l nhng nha nhit do d
gia cng theo nhiu phng php khc nhau.
2/ Tnh cht
a/ Tnh cht ho hc
- PMMA bn vi cc ho cht iu kin thng nh: dung dch nc mui, dung
dch kim long, dung dch axit long...
- PMMA t ht nc, khng tc dng vi ru, cht bo v du khong.
b/ Tnh cht nhit
PMMA c nhit ho thu tinh Tg = 80
o
C










Nhn xt:
(1) : khi gc R c 1C th Tg = 80
o
C, khi tng s nguyn t C th Tg gim n 12C th
Tg bt u tng tr li.
(2) : khi R c 1C th Tg = 0
o
C, khi tng s nguyn t C th Tg gim n 8C th Tg tng
nhanh hn so vi ng (1)
Gii thch:

CH
2
C
COO
CH
3
*
R
n


Khi tng R th n c tc dng che chn nhm phn cc lm Tg gim.
Khi tng R n ln hn 12C th tc dng che chn khng cn na ( ti 12C th hiu ng
che chn t ti hn ) m khi s sinh ra s cn tr khng gian ln lm nh hng n
chuyn ng nhit ca cc mc xch, v th Tg tng tr li. Xt ng (2) c Tg thp hn
v khng c nhm CH
3
- nn mch phn t mm hn so vi (1).
PMMA khi nhit ln hn 180
o
C th bt u b phn hu, khi nhit cao hn
250
o
C th qu trnh phn hu xy ra nhanh hn ( hiu sut phn hu t 75 80%)
c/ Tnh cht quang hc
C O R
Tg(
o
C)
S nguyn t C trong gc R
1
-60
8
12 16
-20
0
80
(1)
(2)
PMMA cho qua 91 -92% tia trong thy, 75% tia t ngoi, cho qua hu ht tia hng
ngoi. PMMA rt trong sut, khi dy tm 6,5 m th trong sut gim 50%.
d/ Tnh cht c hc
Xt polyalkyl metaacrylat
Tnh cht -CH
3
-C
2
H
5
n-C
3
H
7
- n-C
4
H
9
- Izobutyl
d (g/cm
3
) 1,19 1,11 1,06 1,05 1,02

ko
(KG/cm
2
) 630 350 280 70 240
bn va p(KG.cm/cm
2
) 10,5 7,1 6,5 11,5 1,6
Nhit chy mm(
o
C) 125 65 38 30 70




























CHNG VI: CHT DO I T CC POLYMER CA DN XUT
HALOGEN ETYLEN
SN XUT PVC
I/ Nguyn liu
Nguyn liu sn xut PVC l vinylclorua C
2
H
3
Cl

CH
2
CH
Cl

L cht kh khng mu, c mi ete nh, khng tan trong nc nhng tan trong cc
dung mi hu c nh axeton, ru etylic, HC thm, HC mch thng.
PVC c cc thng s vt l nh sau:
+ Nhit si t
s
= -13,9
o
C
+ Nhit nng chy t
nc
= -159
o
C
+ Khi lng ring -12,96
o
C d= 0,9692 g/cm
3

+ nht -20
o
C = 2,81 Cp
+ n nhit ho hi: 85,7 Kcal/kg
+ To hn hp n vi khng kh: 4 21,7% th tch
+ Nng VC cho php trong 1 lt khng kh: 1mg/l
Vinylclorua c th ng trng hp vi nhiu cht khc nhau
* Sn xut vinylclorua
Kh hydro v clo ca diclotan bng dung dch ru kim
CH
2
CH
2
Cl Cl
NaOH CH
2
CH
Cl
NaCl O H
2
+ + +

Phng php ny khng kinh t tn nhiu NaOH, ru v thit b phi ln
+ Clo ho etylen nhit cao

CH
2
CH
2
Cl
2
CH
2
CHCl Cl H
FeCl
3
+ +

Phng php ny cha dng trong cng nghip v cha c phng php ly nhit
phn ng ra.
+ Nhit phn dicloetan

CH
2
CH
2
Cl Cl
CH
2
CHCl Cl H
+

Phng php ny rt kinh t, dy chuyn sn xut n gin nhng xc tc khng
bn, khng ti sinh c v nhit cao to ra sn phm ph nh C
2
H
2
, dien...
+ Hidro v clo ho C
2
H
2


CH CH Cl H CH
2
CHCl
+

(450-600
O
C)
(Al
2
O
3
, C hot tnh)
500-590
o
C
p= 4 - 6atm, t
o
= 200
o
C
Xtc HgCl
2
/cht mang
aluminosilicat
Phng php ny cng c dng ph bin trn th gii: qu trnh thc hin lin
tc trong thit b tip xc loi ng 160 200
o
C. Xc tc l clorua thu ngn ph ln b
mt than hot tnh mt lng 10 - 15%. Kh C
2
H
2
v HCl lm sch, sy kh cho vo thit
b phn ng. Cho cht xc tc vo trong cc ng ca thit b phn ng v khong cch
gia cc ng cho du tun hon nhit 70 130
o
C. Khi nhit t 70
o
C xc tc bt
u lm vic th nhit ca phn ng t n 160
o
C. Hn hp sau phn ng gm:
vinylclorua to ra, dicloetan, axetaldehyt, axetilen, HCl c a qua thit b phun dng
nc v dung dch kim 10% ra kh mc ch l hp th kh HCl. Sau cho vo
thp sy bng KOH rn ri qua thit b lm lnh n 40
o
C ngng t VC v hp cht c
nhit si cao hn. Sau qu trnh ngng t cho qua thp tinh luyn hot ng lin tc
ui sch axetaldehyt, dicloetan v cc sn phm ph khc. Sau VC c tch ra khi
C
2
H
2
ho tan trong thit b chng ct khc.
II/ L thuyt trng hp vinylclorua
Nu khng c oxi v cht khi u ch c nhit th vn tc phn ng b. Khi c
mt cht khi u (C
6
H
5
COO)
2
, cat-19 v cat-29 (dng hn hp 2 cat th iu chnh trng
lng phn t trung bnh v vn tc phn ng c d dng) th tc phn ng ln.
Tp cht nh hng ln n phn ng trng hp: C
2
H
2
, CH
3
OH, C
2
H
5
OH, HCl th
lm chm tc phn ng cn Styren, hidroquinon, rezoxin, anilin, phenol...lm ngng
hn qu trnh.
Khi trng hp VC th rt nhy vi nhit c bit trong dung mi. Trong trng
hp nh tng, huyn ph, dung dch th nhit trng hp 35 55
o
C khi nhit ln hn
75
o
C th % Cl trong sn phm gim xung do kh to HCl ng thi hnh thnh lin kt
i lm cho sn phm c mu.
Nghin cu trng hp VC trong khi c cht kch ng th thy rng trng hp xy
ra theo c ch chui gc bnh thng nhng c nt c bit:
+ Vn tc trng hp tng t lc bt u phn ng n khi hiu sut chuyn ho t
gn 50% th chm li, hin tng gi l hiu ng gel.
+ Vn tc chuyn mch c gi tr ln hn rt nhiu so vi trng hp nhng hp
cht vinyl khc.
nh hng ca dung mi v nhit n mc trng hp v % Clo trong sn phm.
Dung mi Nhit phn ng
(
o
C)
Mc trng hp
(n)
Hm lng clo
trong PVC (%)
CH
3
OH 80 310 55,98
Toluen 85 87 53,3
n-hexan 80 295 55,75
Diocxan 80 100 55,52
Nhn xt: trng hp trong toluen th nhit phn ng cao hn nn trng lng
phn t trung bnh nh. Tt c hm lng clo u b hn theo l thuyt l 56,8% ngha l
c 1 mc xch th c 1 nguyn t clo. Ba dung mi u ch ho tan VC khng ho tan
PVC cn diocxan ho tan t PVC.
Trng hp VC c peroxit benzoic th trng lng phn t trung bnh ca polymer:
+ Thc t khng ph thuc vo nng cht khi u trong gii hn di 2%, nu
nng cao hn th trng lng phn t trung bnh gim nhanh.
+ Trng lng phn t trung bnh khng ph thuc vo mc chuyn ho
monome
+ Trng lng phn t trung bnh gim khi tng nhit trng hp.
III/ Cc phng php trng hp VC
1/ Trng hp VC trong khi
Phng php ny t c s dng v polymer thu c dng khi gy kh khn
cho cng on gia cng sau ny. Qu trnh phn ng kh ly nhit ra lm phn hu
polymer to kh HCl v lm cho polymer c mu.
2/ Trng hp VC trong dung mi
C th dng hai loi dung mi:
- Dung mi khng ho tan polymer ( hay dng ru ): trong trng hp ny sn
phm cui cng ca phn ng l polymer dn dn tch ra dng bt mn.
- Dung mi ho tan c monome v ( hay dng dicloetan, axeton...) sn phm thu
c dng dung dch, mun tch ra th phi tin hnh kt ta hoc chng ct loi b
ht dung mi.
Phng php ny t dng trong thc t do qu trnh trng hp lu v tn nhiu nhiu
dung mi.
3/ Trng hp VC trong nh tng
Cht khi u thng dng l H
2
O
2
, pesulfat kim loi kim. Cht nh ho l cc
loi x phng ncal ( mui natri ca axit izobutyl sulfonaphtalenic ) dng vi lng 0,1
0,5% trng lng nc.
Dng thm mui m gi nguyn pH, thng thng pH = 4 9. Mui m
hay dng l axetat kim loi nng, phtphat, cacbonat kim loi kim...
Vinylclorua trc khi trng hp nn cho qua than hot tnh nhit 70 80
o
C
hoc sc qua dung dch NaOH hay KOH nng 25 60%
4/ Trng hp VC trong huyn ph
Thnh phn nguyn liu
Nguyn liu I II
Vinylclorua 100 100
H
2
O 150 20 100
Cht n nh huyn ph PVA (15% nhm CH
3
-)
dung dch 5% trong nc
Jelatin: 0,5 2%
Cht khi u (peroxit benzoic) 0,04 0,04 0,6%
Ngoi ra c th thm cht ngt mch phn ng AD-3 ( diphenylol propan)

HO C
CH
3
CH
3
OH

Cht n nh nhit AD-5: C
35
H
50
O
3


HO C
17
H
37
CH
2
CH
2
CO
O
C(CH
3
)
3
C(CH
3
)
3

S dy chuyn cng ngh
Hnh v: (xem sch)
u tin phi chun b kn ca thit b phn ng (1) bng cch cho nn N
2
p
sut p= 4 5atm trong thi gian 5 -10 pht sau tho v p sut thng. Chun b dung
dch cht n nh huyn ph, lc (3) vo (2) cha ri vo (1). Cho H
2
O tnh vo
thit b, cho tip dung dch n nh huyn ph v tin hnh khuy trn vi vn tc cnh
khuy 60 80 vng/pht trong thi gian 2 3pht ri ngng khuy. Tip tc cho kh N
2

vo ui ht khng kh trong thit b phn ng ( khng cn p sut cao). Cho t t VC
vo ri cho dung dch cht khi u vo gi p sut 7 8atm ng thi tin hnh khuy
trn trong thi gian 30 pht, khi to ra cc git monome c bao bc bi dung dch
cht n nh huyn ph. Nhit ban u ca phn ng 40 55
o
C thi gian cui c th
nng ln 60
o
C ngt mch.
Ra khi thit b phn ng hn hp qua thng cha (7) lm vic p sut thng,
trc tin cho xt vo o pH ng thi sc hi nc qu nhit vo nhm ui VC t do
v kh khc. Hi nc qu nhit sc vo trong 30 pht, VC khng phn ng b hp th
bi PVC bay ra theo ng hn hp kh ra. Hoc y ht VC v kh khc th sc kh
N
2
vo p sut khng ln. Trong thit b (7) phi tin hnh khuy lin tc PVC
khng b sa lng. Sau khi tch ht VC t do, hn hp PVC c a qua thit b ly
tm. Cht lng tch ra ban u cn nhiu NaOH nn cho vo thng (9), nc m dng
ra nha sau khi ly tm c cho vo thit b (10) ri em i x l. PVC bt mn lng
xung y ca thit b (9), (10) c tch ra v thu hi. Ly tm xong bt PVC c hm m
tng i ln nn cho qua thit b sy (11). Bt PVC c th sy theo nhiu phng php
khc nhau: sy pht bng khng kh nng (thi gian sy 30 45 pht, nhit ca khng
kh nng 95 105
o
C), sy tng sibt PVC sau khi sy c hm m W 0,5%. Cui
cng chuyn sang cng on sng, ng bao.
IV/ Cu to, tnh cht v ng dng PVC
1/ Cu to ca PVC
Trng hp VC theo c ch gc t do l s kt cc phn t theo u ni ui
thnh mch pht trin.

CH
2
CH
Cl
CH
2
CH
Cl
CH
2
CH
Cl

Ngi ta dng nhiu phng php ho hc, Rnghen v quang hc chng
minh cu to ca PVC:
+ Cho tia phng x xuyn vo PVC th xy ra qu trnh kh HCl v to thnh ni
i cch mt trong polymer.
+ Quang ph t ngoi hp th PVC cng tng ng vi quang ph hp th 2,4-
diclobutan hoc nhiu hn l vi quang ph hp th 2,3-diclobutan.
+ Cho KI tc dng vi dung dch PVC th khng thy I
2
t do thot ra ( I
2
t do
thot ra khi KI tc dng vi cc cht m cc nguyn t Cl ni lin vi hai nguyn t C
cnh nhau)
PVC cng c cu to nhnh nhng rt t, t 50 100 mc xch mi c mt nhnh.
PVC l mt polymer phn cc mnh. trng thi khng ko cng PVC hon ton v nh
hnh, ch khi no ko cng tht mnh mi c kh nng nh hng mt phn.
2/ Tnh cht
a/ ha tan: polymer phn t thp vi n=300 500 tng i d tan trong axeton,
kton, este, xiclohexanol...Khi trng lng phn t trung bnh cao th PVC rt kh ho tan
(1 10%) tan trong: dicloetan, clo benzen, diocxan, tetrahidrofuran.
iu kin ngui PVC khng tan trong cc cht ho do nhng nhit cao th
b trng nhiu v c trng hp li tan. Polymer dng nh tng c ho tan km
hn polymer huyn ph, polymer dung dch.
b/ Tnh cht nhit
Nhit chy mm ca PVC cao hn mt t so vi nhit phn hu ca n.
PVC khng bn nhit, ngay 140
o
C bt u phn hu chm v 170
o
C th nhanh hn
khi HCl b tch ra lm bin mu sn phm v mt tnh tan. Mt tnh tan ca PVC l do
to ra lin kt ngang

CH
2
CH
Cl
CH
2
CH
Cl
CH
2
CH
Cl
CH
2
CH
Cl
CH
2
C CH CH
CH
2
CH CH
2
CH
Cl
Cl

-2HCl
Bin mu ca PVC l do to ra lin kt i

CH
2
CH
Cl
CH
2
CH
Cl
CH
2
CH
Cl
CH CH CH CH CH CH

n nh nhit ca PVC ta thm cht n nh vo theo 4 nhm: hp th kh HCl,
cht trung ho HCl, cht ngn chn tc dng ca O
2
v cht hp th tia t ngoi.
c/ bn ho hc
PVC l mt polymer bn ha hc cao lm cc thng cha, ng dn ho cht (axit, kim,
mui...)
d/ Tnh cht c hc
- Tg = 78 80
o
C
- d = 1,38 1,4 (g/cm
3
)
-
k
= 400 600 (KG/cm
2
)
-
u
= 900 1200 (KG/cm
2
)
-
n
= 800 1600 (KG/cm
2
)
- = 10 25%
- bn va p = 70 160 (KG/cm
2
)
- bn nhit (Mactanh) = 65 70
o
C
- Nhit gin = -10
o
C
+ Kh nng trn ln vi cc cht khc
Vi polymer: PVC trn c vi phenolformaldehyt, epoxy...
Vi cht ho do: PVC trn c vi hu ht cht ho do loi este phn t thp nh:
DOP, DBP, tricrezylphotphat...
3/ ng dng
PVC cng ( khng c cht ho do) lm tm, ng dn, vt liu cch in
PVC mm: ng dn mm, bc dy in, mng mng, da gi











-HCl
PHN II
CNG NGH SN XUT MT S POLYMER TRNG NGNG
CHNG VII: SN XUT NHA PHENOL-FORMALDEHYT
I/ Nguyn liu
1/ Cc phenol
a/ Phenol C
6
H
5
OH
Phenol tn ti dng tinh th hnh kim, khng mu v c mi hc c trng.
lu trong khng kh phenol c mu hng, nu c mt ng, st, amoniac th phenol d
bin mu nhanh hn v chuyn sang mu nu nht.
+ d (45
o
C) = 1,0545 g/cm
3

+ t
nc
= 40,9
o
C
+ t
s
= 182,2
o
C
Phenol l cht ht m, nhit thng tan n 27% trong nc to thnh dung
dch ng nht. Phenol rt c, gy bng da v kch thch nim mc. Nng gii hn
cho php trong khng kh l 0,005 mg/l.
* Tnh cht ho hc
Phn ng to mui phenolat
C
6
H
5
OH + NaOH C
6
H
5
ONa + H
2
O
Phn ng th S
E
v nhm OH- l nhm th loi mt nn n nh hng ch yu
vo v tr octo hay para.
Phn ng halogen ho

OH
Br
2
OH
Br
Br
Br
+

* iu ch phenol
Phng php i t than : khi cc ho than thu c nha than , sau chng
nha ny ta c du nh ( hydrocacbon thm ), du trung ( phenol, crezol, xylenol,
naphtalen) v du nng.
Phng php tng hp:
+ Phng php benzosunfonat: cho sunfo ho benzen ri trung ho benzosunfonic
axit bng cch un nng chy n vi kim, phn gii phenolat v chng phenol.
+ Phng php clobenzen: cho clo ha benzen, sau cho clobenzen tc dng vi
dung dch NaOH 10% theo t l 1 :1,25 vi iu kin phn ng nhit 400
o
C.
+ Phng php Rasic: cho benzen tc dng vi HCl v khng kh nhit 200
230
o
C vi xc tc l mui nhm, st hoc ng. Tch clobenzen v thu phn trong mi
trng kim nhit 350
o
C vi xc tc l SiO
2
hay Ca
3
(PO
4
)
2
. Sau ra phenol bng
nc, tin hnh chng ct cui cng thu c phenol.
+ Phng php Cumen: iu ch izopropylbenzen khi c xc tc, sau oxy ho
izopropylbenzen bng oxi khng kh c thm cht nh ho 85
o
C. Tip tc thu phn sn
phm va mi to ra bng dung dch H
2
SO
4
10% thnh phenol v axeton. Sau dng
phng php chng ct tch phenol.
b/ Mt s phenol khc
+ Crezol ( CH
3
C
6
H
4
OH )

OH
CH
3
OH
CH
3
OH
CH
3
o-crezol(35%)
m-crezol(37-49%)
p-crezo(25%)

+ Xilenol (CH
3
)
2
C
6
H
3
OH
c tch ra t phn c nhit si cao nht ca du trung ( 210 25
o
C) c 6 ng phn

OH
CH
3
CH
3
OH
CH
3
CH
3
OH
CH
3
C H
3
OH
CH
3
CH
3
OH
CH
3
CH
3
OH
C H
3
CH
3
1,2,3 Xilenol 1,2,4 Xilenol
1,2,5 Xilenol
1,2,6 Xilenol 1,3,4 Xilenol
1,3,5 Xilenol

+ Rezorsin: C
6
H
4
(OH)
2


OH
OH

Rezorsin c 3 v tr hot ng rt mnh hn phenol
2/ Cc andehyt
a/ Formaldehyt (andehyt formic) CH
2
O

H C H
O

* Tnh cht vt l
iu kin thng formaldehyt l mt cht kh khng mu, c mi hc, gy kch
thch nim mc.
+ d = 0,8153 g/cm
3

+ t
nc
= -92
o
C
+ t
s
= -21
o
C
Formaldehyt dng ch yu dng dung dch nc gi l formalin. Formalin cha
33 40% th tch formaldehyt tng ng vi 33 37% theo khi lng.
* Tnh cht ho hc
Formaldehyt c kh nng t trng hp nhit thp to thnh nha
polyformaldehyt (parafoc) v khi un nng th phn hu cho ra li formaldehyt.

HCHO *
CH
2
O
n
*
CH
2
O
n
HCHO
n
n

Parafoc l polymer v nh hnh c mu trng. V d trng hp nhit thng
nn khi bo qun ta cho vo 7 12% ru metylic.
Formaldehyt d tan trong nc khi trong nc n dng hydrat ho
(metylenglycol)
HCOH + H
2
O HO CH
2
OH
Dng hydrat ho ny d bt c nng no cng to ra polyoxymetylglycol
2 HO CH
2
OH HO CH
2
O CH
2
OH + H
2
O
HO CH
2
O CH
2
OH + n HO CH
2
OH HO-(-CH
2
O-)
n+1
CH
2
OH + H
2
O
* iu ch formaldehyt
Oxy ho ru metylic:
2CH
3
OH + O
2
2 HCHO + H
2
O + 36,8 Kcal/mol

CH
3
OH HCHO + H
2
- 28,8 Kcal/mol
Phng php oxy ho kh metan
CH
4
+ O
2
HCHO + H
2
O (phn ng chnh)
2 CH
4
+ O
2
2CH
3
OH (phn ng ph)
b/ Cc andehyt khc
Furfurol C
5
H
4
O
2


CH CH
C CHO
O
CH

Urtrpin (CH
2
)
6
N
4

II/ L thuyt trng ngng phenol vi formaldehyt
* Phn loi
Vi n= 3 -5
Xt, 400-600
o
C
Tu thuc vo xc tc v t l cu t m chia nha PF ra lm 2 loi: nha novolac
v nha rezolic.
Nha novolac: dng xc tc ion H
+
( cc axit thng dng l HCl, c khi dng
H
2
SO
4
) t l C
6
H
5
OH/CH
2
O = 6/5 hoc 7/6
Nha rezolic xc tc l OH
-
( hay dng NaOH, NH
4
OH, Ba(OH)
2
...). Dng xt lm
xc tc th nha to ra tan trong nc thnh h nh tng. Dng NH
4
OH lm xc tc th
nha to ra khng tan trong nc m tan trong cn. T l C
6
H
5
OH/CH
2
O = 5/6 hoc 6/7.
* Cc yu t nh hng n qu trnh trng ngng
+ Cu to ho hc ca nguyn liu
Cu to khc nhau th nh chc khc nhau dn n kh nng phn ng khc
nhau. Nha nhit rn c iu ch t cc nguyn liu cha phenol c 3 v tr hot ng
nh phenol, m-crezol, 1,3,5-xylenol, v rezorsin. Cn cc andehyt th ch c formaldehyt
v furfurol l to nha nhit rn.
Nha nhit do c th iu ch t nguyn liu cha cc phenol c 2 v tr hot
ng nh octo v para-crezol; 1,2,3 hay 1,3,4-xylenol. Do ch c hai v tr hot ng tc
l nhm metyl khng lm hot ho cc nguyn t hydro bn cnh nhn thm nn khng
c kh nng to nha nhit rn. Cc nhm hydroxyl ca phenol khng tham gia phn ng
a t.
+ T l mol C
6
H
5
OH/CH
2
O
Nu t l mol P:F = 1:1 th ch yu to ra cc octo v para monometylol phenol.
T cc ru phenol ny tip tc a t to thnh nha nhit do.
Nu t l mol P:F = 1:2 hoc cao hn th ch yu to ra cc di v tri metylol
phenol. T cc ru phenol ny tip tc ngng t to thnh nha PF khng nng chy,
khng ho ho tan.
+ pH ca mi trng
pH < 7 th cc ru phenol to thnh khng bn, n nhanh chng ngng t vi
nhau hoc vi phenol to nha nhit do.
pH > 7 th cc ru phenol to thnh rt bn, cc di, tri metylol tip tc trng
ngng vi nhau hoc vi phenol to thnh polymer nhit rn.
* Nguyn tc trng ngng
+ Novolac

OH
CH
2
O
OH
CH
2
OH
+
monometylol phenol
Rt t dimetylol phenol c to:

OH
CH
2
OH
CH
2
OH
dimetylol phenol
V trong mi trng axit nn tc phn ng cu nhm metylol ln. Phn ng
trng ngng to nha c th c vit nh sau:

OH
CH
2
OH
OH OH OH
CH
2
OH OH
CH
2
OH
HOCH
2
OH
CH
2
OH OH
CH
2
H
+
H
+
OH
CH
2
OH
OH
HOCH
2
H
+
OH
CH
2
OH
CH
2
O
+
+
+

cu ni metylen ete
Cu ni metylen ete khi p, gia cng nhit cao th b phn hu to ra CH
2
O.
- CH
2
O CH
2
- - CH
2
- + CH
2
O
Cng thc tng qut ca nha Novolac:

OH
CH
2
OH OH
CH
2
n


+ Rezolic
Xc tc l OH
-
(NaOH, Ba(OH)
2
, NH
4
OH...)
- NaOH l xc tc mnh, lm mu nha ti ( nu sm), tan c trong nc kh
tch lp tc l dng nh tng trong nc.
- Ba(OH)
2
cho nha mu sng hn
- NH
4
OH l xc tc yu, nha c mu sng v phn lp mnh
Phn ng to nha
OH
CH
2
O
OH
CH
2
OH
CH
2
OH
OH-
OH
CH
2
OH
OH
CH
2
OH
CH
2
OH
HOCH
2
+

Trong mi trng OH
-
th cc nhm metylol c vn tc phn ng b.
OH
CH
2
OH
CH
2
OH
OH
CH
2
OH
OH
CH
2
OH
CH
2
OH
HOCH
2
OH-
OH
CH
2
O
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
n

OH
+ +

Nha rezolic c metylol t do v tr para ca phenol nn c kh nng ng rn
nhit thch hp to nhnh mng li khng gian khng nng chy, khng ho tan.
III/ Quy trnh sn xut nha phenol-formaldehyt
1/ Nha Novolac
Thnh phn nguyn liu
C
6
H
5
OH 100 PKL
CH
2
O 26,5 27,5 PKL
HCl (d= 1,19) ln 1: n pH = 1,6 2,3
ln 2: 0,056 PKL
Axit oleic: 1,5 2 PKL
Cho ht formaldehyt ( C%=37%) v phenol vo thit b phn ng ri khuy u,
sau cho axit ln 1 vo trong lc cnh khuy vn hot ng. Mc ch ca vic cho
axit ln 1 l h pH ca formaldehyt v ng thi lm mi trng xc tc. Tin hnh
un nng n nhit 80 85
o
C phn ng to nhit nn nhit ca hn hp t tng ln
95 98
o
C, lc ny hn hp bc u si. Duy tr nhit ny trong khong thi gian 30
pht. Tin hnh cho axit ln hai v gi nhit si t
s
=98
o
C trong thi gian 45 50pht,
cng trong thi gian ny ngi ta ly mu th xc nh d = 1,17 1,2 g/ml. Khi phn
ng kt thc tin hnh sy nha tch loi nc v hm lng phenol t do cn li
trong nha. Sy trong mi trng chn khng p=350 410 mmHg nhng trc khi ht
chn khng phi tin hnh lm lnh hn hp nha xung 75 78
o
C.
Sau khi sy tnh cht ca nha phi m bo cc ch tiu sau:
- Nha c mu vng rm hoc vng hi nu
- Nhit nh git : 95 105
o
C
- nht dung dch 50% trong ru C
2
H
5
OH: 75 160Cp
- Hm lng phenol t do < 9%
Trong qu trnh sy giai on cui dng chng ct bng hi nc qu nhit nhm
mc ch gim hm lng phenol t do trong nha.
Biu tng hp nha











2/ Nha rezolic
Nhit ban u 75 80
o
C un nng trong thi gian 35 45 pht, phn ng to
nhit nn t nng ln 95 98
o
C ( c th ln n 100
o
C ). Gi nhit ny trong khong
thi gian 100 pht v nht t 150 250Cp. Nu nha dng dng nh tng th ch
lng, tch bt nc v em i x dng ( tm ph gia dng si, vi, giy, hoc dng bt,
lm keo dn...). Nu dng dng rn th h thp nhit sn phm xung 70 80
o
C sau
sy chn khng 300 mmHg, sy n khi t c nht 800 1000Cp nha ra
khun v ngui.
Tnh cht ca nha sau khi sy: mu hi nu, hm lng phenol t do khng qu
9%, vn tc ng rn 150
o
C: 75 90 giy/1mm chiu dy sn phm
Nha rezolic thc t c 3 trng thi:
+ Nha rezol l nha cha ng rn n l mt sn phm c phn t thp mch
thng v nhnh
+ Nha rezitol l nha bt u ng rn nhng c mt mng li khng gian
t,c th ho tan hon ton trong mt s dung mi nh:xilohexanol,phenol,dioxan....vi
iu kin nhit ca cc dung dch >100
o
C, lc ny ni ngang b gy
+ Nha rezit l nha ng rn hon ton to thnh polime c mng li dy
c, trng thi khng nng chy, khng ho tan trong bt k dung mi no. Mng li
khng gian to ra do lin kt nhm metylen v lin kt hydro .
c/ Sn xut bt p t nha novolac
Thnh phn nguyn liu:
- Novolac 42,8 PKL
- Ph gia bt g l kim ( g chc, t tp cht, cha nhiu xenlulo, khng cn dng xenlulo
trc tip do sn phm bn thn c mu ti cn xenlulo c mu trng) 43,6 PKL
- Cht ng rn (urotropin) 6,5 PKL
3 5 6
T(
o
C)
Thi gian (h)
20
100
80
1 2 4 7
110
a
c
b
d
e
g
- Cht lm trn, bng (stearat Zn, Ca...) 0,7 PKL
- Cht tr ng rn (CaO, MgO...) 0,9 PKL
- Cht mu (ch l mu sm) 4 4,5 PKL
* Chun b nguyn liu:
Nghin mn nha Novolac
Nghin mn v sng bt g ( 960 l/1cm
2
)
* Tin hnh:
- Trn 1 t nha nghin mn vi urotropin (m nh)
- Trn 1 t nha nghin mn vi cht mu v cc ho cht khc
- Trn nha v ph gia (ph gia c cho vo t t). Sau cho hn hp cht ng rn
v hn hp cht mu chun b trn vo. u tin trn trong my hai trc nm ngang
c cnh khuy hnh ch Z, tip tc trn trn my cn nng 2 trc c t tc nhit <
105
o
C hoc trn trong my trc vt lin tc. Thi gian trn trn my cn 2 3,5 pht/m,
nu trn trong thi gian di s xy ra phn ng ng rn hay b chy ra v dnh vo trc.
Sau lm ngui v p, nghin trn my nghin bi ri sng ng bao.
* Qu trnh p, gia cng sn phm
Nhit p 160 165
o
C ph thuc vo chiu dy sn phm. p sut p 300 350
KG/cm
2
. Khi p c kh NH
3
, N
2
, H
2
O, CH
2
O thot ra nn phi nng chy p ln 1,2 ln
trnh hin tng xut hin l xp do kh thot ra trong qu trnh p. Thi gian p 1,5 2
pht/1mm chiu dy sn phm.
Trong qu trnh ng rn
+ Phenol kt hp vi urotropin to nha novolac trc ri sau to rezol ->
rezitol -> rezit.
+ Nha novolac kt hp vi urotropin to rezol -> rezitol -> rezit
- CH
2
O CH
2
- - CH
2
- + CH
2
O
(CH
2
)
6
N
4
- CH
2
- + 2 N
2
(NH
3
)
+ Nha ng rn c mng li khng gian tng i dy c nn sn phm hi
dn, v vy khi thm ph gia vo th gim c tnh dn ca nha.
+ Khi qu trnh ng rn kt thc th trong cu to ca nha vn cn mt s nhm
CH
2
OH t do hay ti nhn phenol vn cn v tr hot ng.
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
CH
2
OH
CH
2
CH
2
OH
CH
2
OH
OH
CH
2
CH
2
O H
OH
CH
2
OH
CH
2
OH
CH
2

+ CaO ngoi tc dng tr ng rn cn tham gia vo qu trnh phn ng nh:

O
Ca
O

* Tnh cht ca sn phm p:
+ Khi lng ring d = 1,25 1,4 g/cm
3

+ Gii hn bn ko
k
= 400 600 KG/cm
2
+ Gii hn bn nn
n
= 1000 1600 KG/cm
2

+ dn di %= 0,3 0,7%
+ cng Brinel 25 40 KG/mm
+ ht nc tng 0,2 0,6%
+ bn ho hc: bn axit (tr axit c tnh oxi ha mnh), dung dch mui v cc
ho cht, khng bn vi kim (do c OH
-
ca phenol)
IV/ Tnh cht, ng dng ca nha phenol-formaldehyt
* Tnh cht :
Nha rezolic l mt hn hp sn phm phn t thng v nhnh, trng lng phn
t t 400 1000. Nha rezolic c tnh n nh cao, cha t phenol t do, bn ha hc v
cch in cao .
Nha rezolic nhit thng vn mt tnh chy nht, nng chy v ha tan,
ngha l khi bo qun tnh cht ca chng thay i theo chiu hng to thnh polimer
mng li v rezolic chuyn dn sang trng thi rezitol. Hm lng phenol t do cao hoc
thp cn ph thuc vo t l ca cc cu t, c im v lng xc tc, chiu su ngng
t v thi gian sy.
Nha rezolic rn thng cha 812% phenol t do, nha rezolic lng cha 20
hoc cao hn. Lng phenol t do nhiu n s lm gim tc ng rn v tnh cht c
l ca sn phm. Nhng c mt s trng hp cn cha mt t phenol t do trong nha v
n lm cho nha d nng chy hn v to mng sau khi ng rn c n hi hn .
Hm lng oxy trong nha rezolic (khi iu ch dng xc tc NaOH) c mt s
lin kt ete( -CH
2
-O-CH
2
-)v khi un nng nha th thy c CH
2
O ta ra. Trong trng
hp dng xc tc NH
4
OH khng c lin kt ete v un nng nha n 200
o
C th khng
thy CH
2
O to ra.
Nha rezolic c th ha tan hon ton trong nhiu dung mi nh: xilohexanol,
phenol, dioxan, butanol... nhng vi iu kin l nhit si ca dung mi trn 100
O
C
lc th cc ni ngang u b ph hy.
Tc tng nhit nh hng n ha tan ca rezolic .Nu tng nhit
nhanh th lc nha cha kp trng trong dung mi, lng ni ngang tng ln v
ngng hn qu trnh ha tan nha. Nu un nng lu th c th lm rezolic tan hon ton.
Nha rezolic b ng rn (rezit) : trong giai on rezit mng li tham gia to ra
khng nhng ch do lin kt ha hc m cn do lin kt l hc. nhit cao lin kt l
hc b ph hy do xut hin mt t tnh n hi, khi lm lnh tnh n hi mt i.
Trong nhng iu kin xc nh ( nhit cao v un nng lu) nu dng mt
lng phenol tha x l rezit nghin nh th nha ny c th bin thnh nha
novolac trong trng hp ny xy ra hin tng t lin kt ha hc gia cc phn t v
to ra lin kt vi phenol.
*ng dng ca nha rezolic:
Nha rezolic lng (khng c nc) p dng rng ri tm vi, si, dng lm bt
p, dng lm vt liu p tng, keo dn v sn.
+Bt p :
Vt liu p dng bt l hn hp cu t phc tp ch yu t nha novolac v
rezolic .Bt p dng lm dng c k thut v sinh hot, dng lm vt liu cch in, chu
tc dng ca dng in 20kV t
o
=200
o
C.
+Vt liu p tng:
Tectolit l cht do lp, c dng ch to t ca nhng tm vi c tm nha
rezolic, vi dng c th l vi thy tinh, vi dt cho, vi tng hp.
Tnh cht ca Tectolit: C bn nn, va p cao nhng km bn nc, chu xng
du tt nn dng trong cng nghip ch to my.
+ Keo dn v sn:
Nha phenol - formaldehyt c ngha quan trng dng sn xut keo dn v
sn. Keo phenol - formaldehyt c bn mi ni cao, chu m v vi khun nhng c
nhc im l mng dn gin. Nha phenol - formaldehyt l loi nha tng hp dng
sn xut sn. Ngoi nha v ru cn thm 5 10% colophan vo sn.
Sn du cao cp iu ch t nha 100%. Sn du Copan l loi sn c iu ch
t Copan trn vi du lanh nhit cao t 230 280
o
C. Sn t nha rezolic tan tt
trong cn. Ngoi ra nha rezolic cn dng lm cht dobt.

















CHNG VIII: SN XUT NHA URE-FORMALDEHYT
I/ Nguyn liu
1/ Ure CO(NH
2
)
2

d = 1,335 g/cm
3

t
nc
= 132,7
o
C
+ Cu trc tinh th hnh kim di khng mu hoc hnh lng knh trng. Ure ho tan
tt trong nc, trong ru v trong amoniac lng, nhng ho tan t trong este v khng
tan trong cloroform. Ure c c tnh kim yu v khi t nng dung dch nc ca ure
n 80
o
C to ra mui amon ca axit cacbamit NH
3
COOH, khi t cao hn 130
o
C ure b
phn hu thnh CO
2
v NH
3
.
+ iu ch: NH
3
tc dng vi CO
2
to thnh cacbamat amon, sau tch nc t
cacbamat rn hoc dng chy lng bng cch un nng n nhit 135 150
o
C v p
sut 55 60atm trong autoclave
CO
2
+ 2NH
3
NH
2
COONH
4
CO(NH
2
)
2
+ H
2
O
2/ Formaldehyt ( CH
2
O) phn trc
II/ L thuyt trng ngng ure vi formaldehyt v cu to ca nha
1/Qu trnh to ra cc sn phm ban u
Nhiu kin cho rng mono v dimetylol ure l nhng sn phm u tin ca phn
ng ure vi formaldehyt. Ph thuc vo cc iu kin sau:
+ T l xc nh gia ure v formaldehyt
+ Mi trng trung tnh hoc kim yu
+ Nhit phn ng thp
Trong mi trng kim yu pH = 7,5 8 v t l ure : formaldehyt = 1 : 1,6 2 th
ban u to ra monometylol v dimetylol ure.

O
C
NH
2
NH
2
CH
2
O
CO
NH
NH
2
CH
2
OH
+

monometylol ure (tinh th)

O
C
NH
2
NH
2
CH
2
O
CO
NH
NH CH
2
OH
CH
2
OH
+

Dimetylol ure (tinh th)
Monometylol ure c nhit nng chy t
nc
=111 113
o
C, cn dimetylol ure
khong 121 122
o
C, chng tan tt trong nc, trong ru metylic, etylic, khng tan trong
ete.
Trong mi trng axit pH = 1 5 vi t l ure:formaldehyt = 1 : 2 hoc 1 : 1 th to
ra sn phm v nh hnh khng trong sut, khng tan.
t
o
2
t
o

N CH
2
CO
NH
2
N CH
2
CO
N
CH
2

monometylen ure dimetylen ure
2/ Qu trnh to nha v cu to ca nha ure-formaldehyt
T monometylol ure to ra nha mch thng qu trnh xy ra theo tng bc

NH CH
2
OH
CO
NH
2
NH
2
CO
NH
2
CH
2
O H
NH CH
2
OH
CO
NH CH
2
NH CO NH
2
O H
2
NH CH
2
OH
CO
NH CH
2
O CH
2
NH
NH CH
2
OH
CO
O H
2
+ +
+

Tng qut:
H
2
N-CO-NH-CH
2
-[-NH-CO-NH-CH
2
-]
n
-NH-CO-NH-CH
2
OH
T dimetylol ure c th to ra nha mch thng v vng

CH
2
n
N
CH
2
OH
NH CH
2
OH
CO
NH CH
2
OH
O H
2
HOCH
2
NH CO NH
CO NH
CH
2
` CO NH CH
2
OH N
CH
2
OH
+

Hoc:

N CH
2
CO
NH CH
2
N
NH
CO
CH
2
OH
CH
2
N
n

CH
2
N CH
2
N CH
2
CO
NH
CO
CH
2
OH
N CH
2
OH
N CH
2
CO
NH
CO
CH
2
OH
CH
2
N

3/ Qu trnh ng rn
ng rn nha UF ch xy ra trong trng hp nha cha cc nhm metylol t do.
Lng nhm metylol trong nha cng ln nu lng CH
2
O ly dng cho phn ng cng
nhiu. Nhit v xc tc c nh hng n tc ng rn ca nha.
Cht xc tc ng rn nha ure-formaldehyt l cc axit hu c (axit oxalic, axit
leic, axit formic....) axit v c (HCl, H
3
PO
4
...) mt s mui (clorua amn, clorua km...).
III/ Sn xut nha ure-formaldehyt
Hoc
(n+2)
T l ure/formaldehyt = 1/1,6 2, pH = 7,5 8 (dng dung dch xt nng
C%=10% trung ho). Cho axit oxalic hoc axit formic cui qu trnh 0,01 0,02
phn so vi ure
Th t cho vo: cho formaldehyt vo thit b phn ng ri dng dung dch NaOH
10% khmg ch pH=7,5 8 sau cho ure vo tin hnh khuy trn. Nhit ban u
ca phn ng 40 50
o
C, trong giai on ny to dn xut mono nn khng nng nhit
cao, duy tr nhit ny trong vng 30 45pht. Sau tng nhit ln 80 85
o
C
trong thi gian 20 pht v bo m pH khng thay i.
Lm ngui xung 60 65
o
C, cho thm dung dch axit oxalic nng 10 15%
vo nhm mc ch to nha phn t ln hn v xc tc ng rn. Tng thi gian phn
ng 4 5 gi/1m.
* Sn xut bt p ure-formaldehyt
Thnh phn:
+ Nha (dung dch keo trong nc): 45 PKL
+ Sunfit-xenlulo: 55 PKL
+ Cht lm trn: 0,8% so vi nha
+ Cht xc tc ng rn ( cc mui c tnh axit nh ZnCl
2
, NH
4
Cl hoc mui
sunfua axit)
+ Cht mu (mu sng)
Qu trnh phi trn tng t nh qu trnh chun b bt p phenol-formaldehyt
nhng phi ch nhit v thi gian. Tin hnh sy nhit thp v trong mi trng
chn khng. S dng my nghin bi pha ngoi my phi c b phn lm lnh bng nc.
* iu kin p:
p sut p: 250 280 KG/cm
2
Nhit p: 135 145
o
C
Thi gian p: 70 110 giy/1mm chiu dy sn phm
Trong qu trnh ng rn c to ra nc
Nhn xt: Mng li khng gian tha, cn mt lng nh nhm CH
2
OH- v NH
2
t do.
+ Nha bt p ure-formaldehyt
bn nhit cao nhng km bn vi nc c bit l nc nng
Khi lng ring d = 1,35 1,45 g/cm
3


ko
= 350 500 KG/cm
2


nn
= 1200 1500 KG/cm
2

u
= 600 900 KG/cm
2

bn nhit (Martens) 100 120
o
C
ht m ( 25
o
C, thi gian 3 ngy m) 1 1,5%
IV/ Tnh cht v ng dng ca ure-formaldehyt.
Nha ure c ng dng rng ri sn xut vt liu p, cht do lp, cht do
bt, keo dn, mng ph...
- Vt phm t bt p ure formaldehyt dng lm cc dng c in ( chp n,
cng tc, cu dao...), chi tit my in thoi, v my thu thanh, hng tiu dng (chu, cc
o, vn p...). un nng nhanh th vt phm t nha ure formaldehyt chu nhit 100
118
o
C, nu un lu th chu c nhit di 75
o
C.
- Cht do lp dng lm bn, trang hong phng, bung li my bay, tu thu,
toa tu ho, dng c m nhc...
- Cht do bt mipo l loi vt liu nh cch nhit, cch m ch yu i t nha ure
formaldehyt. u im c bn ca mipo l nh, dn nhit khng ln vo khng chy
nu thm photphat amon vo. Mipo c c im rt qu l ht th m thanh mnh, c
bit t tn s trung bnh n cao nn dng n truyn m rt tt khi xy dng nh ht,
rp chiu bng...
- Keo t ure formaldehyt c s dng nhiu trong cng nghip sn xut vn p, c
khi dng lm keo dn snh s, kim loi
- Nha ure formaldehyt khng tan trong ru v du, sau khi ng rn th n
nh trong dung dch km v chu nc khng m bo. Do tnh a nc ca nha nn
mng nha to ra d b m v nt ng thi khng t do cn thit. V vy mun s
dng nha ure formaldehyt lm sn th phi bin tnh nha.


















CHNG IX: SN XUT NHA MELAMIN-FORMALDEHYT
I/ Nguyn liu:
1/ Melamin: (2,4,6 triamino-1,3,5 triasin)
dng tinh th melamin l bt tinh th mu trng, c tnh kim yu nhng mnh
hn ure, tan trong amoniac lng v dung dch NaOH, KOH, tan km trong nc v dung
mi hu c. Melamin c cng thc cu to c biu din nh sau:

N
C C
N
NH
2
N
C
NH
2
N H
2

2/ Formaldehyt: xem phn trc
II/ L thuyt a t melamin vi formaldehyt
Thng thng th t l gia melamin v formaldehyt l: 1/ 2,8 1/3 c dng
lm bt p, cn nu 1/3 1/4 dng lm sn.
iu kin phn ng: phn ng thc hin trong mi trng trung tnh hoc kim
yu pH = 7,5 8 v nhit t 90 98
o
C.
C ch phn ng: tng t nh ure-formaldehyt hay phenol-formaldehyt ban u
to ra cc dn xut metylol melamin sau cc dn xut ny lin kt li vi nhau to
ra sn phm nha melamin-formaldehyt.


t l R

N H
2
R NH
2
NH
2
CH
2
O
OH-,to
N H
2
R NH
2
NH CH
2
OH
NH R NH
2
NH CH
2
OH
HOCH
2
NH R NH
NH CH
2
OH
HOCH
2
CH
2
OH
+
N
u tip tc un nng mnh hn th to ra:
N H
2
R NH CH
2
OH
NH
2
N H
2
R NH
NH CH
2
OH
CH
2
OH
N H
2
R NH CH
2
OH
NH
2
OH-,to
N H
2
R NH CH
2
NH
2
NH R NH
NH CH
2
OH
CH
2
NH R NH
NH CH
2
OH
+ +

N
C C
N N
C
Nhng nhm CH
2
OH t do v NH
2
t do c kh nng tham gia phn ng tip
tc thc hin qu trnh ng rn to thnh mng li khng gian dy c trong mi
trng axit v nhit 130 150
o
C.

NH R NH CH
2
NH
NH R NH
NH CH
2
CH
2
NH R NH
NH
CH
2
CH
2
NH R NH CH
2
NH R NH CH
2
NH R
NH CH
2
OH
NH NH
NH
CH
2

Do melamin c nhiu nhm inh chc hn nn trong nha c nhiu ni ngang. V
vy nha melamin-formaldehyt c chu nc, chu nhit, cng v bng hn so vi
nha ure-formaldehyt.
III/ Sn xut nha melamin-formaldehyt
Cho formaldehyt vo thit b phn ng, iu chnh pH cho n khi pH = 7,5 8.
Sau ta cho melamin vo ng thi tin hnh khuy trn, lc ny ta thu c hn hp
huyn ph ng nht. Tin hnh gia nhit n nhit 75 80
o
C do phn ng ta nhit
nn hn hp s t nng ln 90 98
o
C. Gi nhit ny trong khong thi gian 40 60
pht ta thu c nha nh tng trong nc.
Khi mun tch nc th h nhit xung v nc s tch thnh lp pha trn
hn hp cn li vn l nh tng nhng nht cao hn.
* Qu trnh sn xut bt p tng t nh PF v UF
Tnh cht ca bt p:
+ Khi lng ring d = 1,45 1,55 g/cm
3

+ Gii hn bn ko
k
620 750 KG/cm
2
+ Gii hn bn nn
u
650 KG/cm
2

+ ht m (3 ngy m 25
o
C) = 0,1 0,15%
+ bn nhit (Martens) > 120
o
C
IV/ Tnh cht v ng dng ca nha melamin-formaldehyt
Cng nh nha ure formaldehyt, nha melamin formaldehyt dng sn xut bt
p, cht do tm, keo dn
- Vt liu p c sn xut khng nhng t nha melamin formaldehyt n cn t
nha melamin ure formaldehyt. iu ch nha c n hi cao ta thm vo cc
polymer khc nh: polyamid, phenol formaldehyt, polyvinyl butyral
- Nha tm melamin c bit l nha tm t vi thy tinh v vi thu tinh c gi tr
rt ln v mt k thut v n rt bn. Nha tm melamin t vi xenlulo v giy dng
sn xut vt liu trang hong ( bc tng nh, lm mt bn gh), vt liu xy dng.
- Keo t nha melamin formaldehyt c dng nhiu trong ngnh g. So vi mi
dn t nha ure formaldehyt th mi dn t nha melamin formaldehyt c kh nng chu
nc si trong thi gian di v gi thnh cng t hn keo ure formaldehyt.
- Nha melamin formaldehyt khng bin tnh th khng trn vi cc cu t khc
trong sn c. n c th tan vo trong cc dung mi hu c v trn tt vi cc loi
nha khc th phi bin tnh nha. Khc vi nha ure formaldehyt bin tnh nha ny c
bn nc v bn kh quyn cao, trn tt vi nha polyester, mng sn chu tc dng
ca cc cht n mn, chu nhit v bn mu, tnh cht in mi tt. Sn l sn phm trn
dung dch nha ete ho vi dung dch nha polyester trong du thu du v sau khi sy
120
o
C th mng sn c bn cao v bng
























CHNG X: SN XUT NHA EPOXY
I/Nguyn liu:
1/ Difenylonlpropan (hay 4,4- dioxy aiphenyl propan hay tn thng mi l bisphenol-
A, dian )

HO C
CH
3
CH
3
OH

iu ch:
-Bisphenol-A iu ch bng cch cho phenol tc dng vi axeton trong mi tng axit
mnh nhit 40-50
o
C. Axit thng dng l H
2
SO
4
, HCl. Thi gian phn ng khong
15-20h.
OH CH
3
C CH
3
O
HO C
CH
3
CH
3
OH O H
2
+
+

-Bisphenol-A c T
nc
=155
o
C, cu trc tinh th mu trng c th lm bng da, khng tan
trong nc.
2> Epiclohidrin.
iu ch:
C H
2
CH
Cl O
CH
2

-i t glyxeryl
u tin cho hai kh HCl tc dng vi glixerin nhit 110-115
o
C trong mi
trng axit c c un nng.

CH
2
CH
OH OH
CH
2
OH
Cl H
CH
2
CH
Cl Cl
CH
2
OH
+

Diclohydrin glyxeryl
Sau cho xt c c un nng vo

CH
2
CH
Cl Cl
CH
2
OH
NaOH C H
2
CH
Cl O
CH
2
NaCl O H
2
+
+ +

-i t propylene:
Clo ho propylen p sut 18 kg/cm
2
v nhit 800
o
C to ra clorua allil, sau
cho clohydrin tc dng ln ni i v cui cng dng kim kh HCl ca iclohydrin
to ra piclohydrin.

CH
2
= CH CH
3
+ Cl
2
CH
2
= CH CH
2
Cl + HCl

2
Xt, t
o
CH
3
COOH
t
o
t
o
800
o
C, 18at
CH
2
= CH CH
2
Cl + HOCl

CH
2
CH
OH Cl
CH
2
Cl

CH
2
CH
OH Cl
CH
2
Cl
NaOH C H
2
CH
Cl O
CH
2
NaCl O H
2
+ + +

Epiclohydrin l mt cht lng khng mu, khng tan trong nc nhng tan trong
cc dung mi hu c (C
6
H
6
, xeton,). Nhit si t
s
=118
o
C, d
20
o
C
( g/cm
3
) = 1,175-
1,180.
II/ L thuyt to nha epoxy:
1> Phn ng a t nha epoxy
Nu tha piclohidrin th c th thu c te diglixit dioxi difenyl propan. phn ng xy
ra trong mi trng NaOH:
C H
2
CH
Cl O
CH
2
HO C
CH
3
CH
3
OH
NaOH
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
O
CH
2
NaCl
O H
2
+
+ +

C ch:
+piclohidrin theo nhm epoxy tc dng vi hydro ca dioxydifenyl propan:
C H
2
CH
Cl O
CH
2
HO C
CH
3
CH
3
OH
C H
2
CH
Cl OH
C
CH
3
CH
3
O CH
2
CH
CH
2
Cl
OH
CH
2
O
+

+To ra nhm epoxy mi do t HCl:
C H
2
CH
Cl OH
C
CH
3
CH
3
O CH
2
CH
CH
2
Cl
OH
CH
2
O
NaOH
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
O
CH
2
NaCl
O H
2
+ +

+Cc sn phm ban u tip tc ngng t vi ioxdifenil propan:
2 2
2 2
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
O
CH
2
HO OH C
CH
3
CH
3
NaOH
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
OH
CH
2
O OH C
CH
3
CH
3
+

Cng thc tng qut:
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
OH
n

CH
2
O O C
CH
3
CH
3
CH
2
CH
2
CH
O

Ta thy nha epoxy trng thi khng ng rn l nhng mch polyete di, trong
nhm hydroxyl t do nm cch nhau mt khong cch tng i xa. Hai u mch l
nhm epoxy. Nhm epoxy v hydroxyl c kh nng phn ng vi nhiu cht v ph thuc
vo nh chc ca cc chc m c th thu c hoc nha nhit do bin tnh hoc
nha ng rn khng nng chy v khng tan.
Qu trnh xy ra chu nh hng ca t l cu t:
T l mol E/D T l mol
NaOH/E
M
p
ng lng
epoxy
Nhit mm,
o
C
2 1,1 451 314 43
1,4 1,3 791 592 84
1,25 1,3 1133 862 100
1,2 1,3 1420 1176 112
T l E/D cng thp th KLPT cng cao, ng lng epoxy cng tng, nhit
mm tng. Cho xt t t, 2-3 ln bi v -Cl c th b thu phn trong mi trng kim to
thnh OH lm bin i nguyn liu ban u.
III/ C ch mg rn nha epoxy
1/ ng rn bng amin
-Thng thng ngi ta dng di hoc tri hoc polyamin, khng dng monoamin v s
khng to mng li khng gian.
-Cc cht ng rn thng dng nht l: etylen diamin (ng rn ngui hoc di 60
o
C ),
dietylen diamin, dietylen triamin (ng rn nhit cao ), trietylen triamin c tc dng
gn ging vi polyamin.
-Phn ng ng rn:
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
OH
n

CH
2
O O C
CH
3
CH
3
CH
2
CH
2
CH
O
N H
2
R1" NH
2
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
OH
n

CH
2
O O C
CH
3
CH
3
CH
2
CH
2
NH CH
OH
R1"NH
2
+

NH
2
t do cn li tip tc tn cng vo u epoxy ca mch diepoxy khc lm ko di
mch
-Cc phn ng ph xy ra:
nhit cao nhm OH phn ng vi u NH
2
ca cht ng rn amin.

CH
OH
NH
2
R1
"
NH
2
CH
NH
R1
"
NH
2
O H
2
+ +

Hoc nhit cao nhm OH phn ng vi u epoxy ca mch:
CH
OH
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
OH
CH
2
CH
O
CH
2
O C
CH
3
CH
3
O
+

+u im : cht ng rn ny c th ng rn cc chi tit ln hoc dn gch p tng.
+Nhc im : amin c v kh iu chnh thi gian chun b .
1> ng rn bng axit hai chc: (cht ng rn nng ), ng rn bng anhidric.
-Thng dng l cc anhidric ca axit dicacboxilic, anhidric malic, anhidric phetalic
-Phn ng ng rn vi axit hai chc:
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
OH n

CH
2
O O C
CH
3
CH
3
CH
2
CH
2
CH
O
HOOC R2 COOH
CH
O
C H
2
CH
2
O C
CH
3
CH
3
O CH
2
CH
OH n

CH
2
O O C
CH
3
CH
3
CH
2
CH
2
OOC CH
OH
R2
"
COOH
+

V xy ra phn ng ng rn khc. To ra sn phm ph l nc khc vi loi cht
ng rn amin, nc to ra bay hi li l xp nn cht ng rn axit t dng
-Phn ng ng rn vi anhidric
140-180
o
C
V d: anhidric phtalic
Phn ng tin hnh nhit cao t 180-220
o
C v qua cc giai on sau:
Trc tin:

CH
OH
CO
CO
O
CH
O
CO
COOH
+

Sau :

CH
O
CO
COOH
C H
2
CH
O
CH
O
CO
COO
CH
2
CH
OH
+

2/ ng rn bng nhng cht ng rn khc
-Ngoi hai cht ng rn trn ta cn dng cc hp cht c hai hay nhiu nhm nh chc
d ng rn nha epoxy nh: nha phenol-formaldehyl, polyamine (-NH-CO-) ,
ure(melamin)-formaldehyl.
-ng rn bng hai cht ng rn trn th nha sau ng rn c nhiu vng thm trong
mch, c cng lm tng bn c hc, bn nhit , trong nha c lin kt ete, este lm
cho mch mm, trong nha c nhm OH t do to nn bm dnh tt, trong nha c s lin
kt ngang khng nhiu ( khng qu tha nh UF) lm mch khng qu cng.
Do nha epoxy va bn nhit , bn c hc, bm dnh tt vi hu ht cc vt liu khc.
IV/ Sn xut nha epoxy
1/ Sn xut nha epoxy phn t thp:(M=370-600 vC)
Sn xut to ra c hai loi : ED-5: ti a 500 vC;
ED-6: ti a 600 vC hoc tng t
T l mol: Dian 1
Epi 2
NaOH 2 (dung dch 15% )
u tin nhit thng cho epiclohidrin vo TB phn ng, ri cho dian vo
khuy u vi s vng 300 vng/pht, to huyn ph ng nht. Sau cho 65% lng
NaOH vo, un nng 60-65
o
C, gi trong mt gi. Chop tip 22% lng NaOH vo nng
nhit ln 65-70
o
C gi trong 2 gi . Cui cng cho ht 13% lng NaOH cn li , nng
nhit ln 70-75
o
C gi trong 45 pht.
n y qu trnh iu ch nha epoxy xem nh kt thc. Tin hnh ra nha mc
ch l tch ht mui NaCl v NaOH d (nu c), ra t 3-5 ln bng nc nng 50-60
o
C.
Nu ch ra bng nc nng th nha khng tan trong nc do NaCl v NaOH pha
trong nha khng tan ra ht. C th kt hp ra bng nc nng v toluen. Ra bng
khuy trn cho nha tan trong toluen to ra nht thp. Mui v NaOH d ni ln trn
c ht ra.
C th tch NaCl v NaOH d bng cch sau:
-Chng tch nc (trc khi chng phi cho toluen vo v khuy u nha tan trong
toluen ). Sy nhit cao 75-85
o
C v p sut chn khng ( 600-650mmHg ). Hn hp
ng ph toluen v H
2
O bc ln c lm lnh s phn lp, nc c tch ra v toluen
quay tr li thit b. Khi nc c tch gn ht th mui trong nha bt u kt tinh. Ta
tin hnh lc nha di li lc kch thc l nh.
-Sau tin hnh chng ct toluene p sut chn khng v nhit ( nhit si ca
toluen 112
o
C ) p sut <= 600 mmHg v nhit 75-85
o
C. n khi chng ct ht toluen,
tin hnh lc vi li c kch thc l ln hn v c un nng ( 40-45
o
C)
2/ Sn xut nha epoxy phn t cao ( M=1500-3500 )
iu ch bng cch lm nng chy nha phn t thp vi dian nhit 200
o
C trong 1,5
2 gi, vi cch ny th nha phn t thp phi sch v vy khng to ra sn phm ph
no v khng cn ra nha. Trng lng phn t trung bnh ca polymer to ra ph thuc
vo t l dian.
CH
O
C H
2
CH
2
O
CH O H R OH CH
O
C H
2
CH
2
O
CH
CH
O
C H
2
CH
2
CH O R O CH
O
CH
2
CH
2
O
CH
OH
+ +

3/ Nha polyepoxy
C
H
2
C
H
2
OH OH OH
C H
2
CH
Cl O
CH
2
O
CH
2
CH
O
CH
2
O
CH
2
CH
O
CH
2
CH
2
C
H
2
O
CH
2
CH
O
CH
2
+

V/ Tnh cht v ng dng
1> Tnh cht:
Tnh cht ED-6 ED-5
30%
anhydric
maleic
65%
polyetylen
polyamin
7%
hexametylen
diamin
10%
polyetylen
polyamin
40%
anhydric
maleic

un
[KG/cm
2
] 1000 1000 750 -- --

va p
[KG.cm/cm
2
] 8,65 7,1 7,0 -- --
bn nhit (Martens)
100 100 100 100 100
ht m (7 ngy
m, t
o
phng)
0,04 0,05%

2> ng dng:
-Sn, vecni, keo dn
-Lm vt liu compozit ( vi si vi thu tinh , si cacbon )
-Trn vi nhiu polymer khc lm vt liu p (vi PVC, phenolformaldehyt)























CHNG XI: SN XUT NHA POLYESTE
I/ Phn loi nha:
Cch 1:
+ PE
s
no: l PE
s
iu ch t axit v ru a chc no
+ PE
s
khng no: l PE
s
iu ch t hoc axit hoc ru a chc khng no
Cch 2:
+ PE
s
nhit do: thu c t axit v ru 2 chc
+ PE

nhit rn: thu c t hoc axit hoc ru 3 chc tr ln (thng l ru 3 chc)
II/ Nguyn liu
1/ Cc ru:
Tn Nhit si
(
o
C)
Nhit ng c
(
o
C)
d
20
(g/ml)
Etylen glycol (EG) 197,5 -13 1,1155
Dietylen glycol (DEG) 245,8 -8 1,1184
1,2-propylen glycol (PG) 187,4 -- 1,0381
Glyxeryl 290 17,9 1,2638
Pentaeritric -- 260 --
Ru alylic (C
2
H
3
-CH
2
OH) 96,7 -129 0,845
2/ Cc axit:
Dng axit 2 chc hoc anhydric ca axit 2 chc
- Axit phtalic (izophtalic, metaphtalic, terephtalic)
COOH
COOH
COOH
COOH
COOH
COOH

Nhng ch c anhydricphtalic t axit izophtalic
- Axit maleic anhydric maleic
C C
COOH
H H
HOOC

C
H
CO
O
CO
C
H

ng phn trans gi l axit fumaric
- HOOC-(CH
2
)-COOH n = 2: axit succinic
n = 3: axit glytalic
n = 4: axit adipic
n = 7: axit azelaic
n = 8: axit xebacic
III/ L thuyt to nha polyeste
im c bit ca qu trnh polyeste ho l phn ng cn bng v thun nghch.
Nhng do hng s cn bng khng ln nn phn ng ph thuc nhiu vo iu kin
chuyn dch cn bng v pha to ra polymer
O H R1" OH HOOC R COOH O H R1"
n

OOC R CO
O H
2
O R1"OCO
R
COOH
+
+
2n
xt, to

Mun chuyn dch cn bng v pha phi th tch nc v dng xc tc c tnh ht
nc.
Cc phn ng ph:
+ Ru phn:
O H R1"
n
OOC R CO O R1"OCO R COOH O H R1" OH
O H R1" O R1 "
x
OH
HOOC
*
R CO O R1" OCOR COOH
y
+
+

Phn ng ru phn do tc dng ca ru n este, t mch ti este to mt cu
ni ete v mt axit a chc.
+ Axit phn:
O H R1"
n
OOC R CO O R1"OCO R COOH R1" HOOC COOH
O H R1" OOC R
x

COOH
HOOC
*
R CO O R1" OCOR COOH
y
+
+

Do phn ng thun nghch v c phn ng ph nn trng lng phn t trung bnh
khng cao thng nh hn 30.000
Qu trnh to polyeste xy ra thao tng bc

O H R1" OH HOOC R COOH O H R1" OOC R COOH O H
2
+ +

monoeste
O H R1"OOC R COOH O H R1" OH O H R1"OOC R COO R1 " OH
O H R1"OOC R COOH HOOC R COOH R COO R1"OCO HOOC R COOH
O H
2
+
+
+

Vn tc phn ng v tnh cht ca polyeste ph thuc vo cu to ho hc ca cc
nguyn liu:
+ Nu ru 2 chc v axit 2 chc th to polyeste nhit do
+ Nu ru 3 chc tr ln v axit 2 chc th to polyeste nhit rn
Xt, 98 110
o
C
+ Ru bc 2 v bc 3 kh phn ng hn ru bc 1 (tc l vn tc phn ng b
hn ru bc 1)
+ cng ca polyeste (ca mng sn)
- Theo th t gim dn ca axit
Axit maleic > phtaleic > adipic > xebacis > limonic
- Theo th t gim dn ca ru
Pentaeritric > glyxerin > EG > DEG
+ Cc polyeste mch thng c kt tinh cao do c th ko si
O H CH
2
CH
2
OH
HOOC COOH O H CH
2
CH
2
OOC
n
CO OH
+

PET c cng ln, khng dng ko si m lm v chai nc do nhit
thng th trong sut, cn khi un nng th c mu c.
Nu dng axit metaphtalic th to ra PE
s
c kt tinh thp
+ Nu thay axit fumaric bng axit xebacis mch thng th kt tinh tng. Nu
thay EG bng DEG th kt tinh gim do DEG c lin kt O-
+ Vn tc phn ng v trng lng phn t trung bnh ph thuc vo cu to v
ng lng chc ca nguyn liu ban u.
IV/ Sn xut nha polyeste
Trc y ngi ta dng phng php 1 giai on tc l un nng hn hp nhit
cao. u im l tng thi gian phn ng gim cn nhc im l tn tht nguyn liu
nhiu ( nht l cc anhydric v axit thng hoa). V vy phng php ny t s dng.
Phng php 2 giai on:
+ Giai on u: un nng hn hp nhit thp 98 120
o
C phn ln l to ra
cc monoeste, gi thi gian thch hp
+ Giai on sau: nng nhit ln n 260 280
o
C v gi nhit ny n khi C
A

cn 1 25 th ngng phn ng. Cui cng lm lnh n nhit 150 180
o
C, nu dng
polyeste lng th em ng thng cn nu dng polyeste rn th rt ra bng ti kim loi,
lm ngui, em p, nghin, sng.
C
A
: s mg KOH phn ng trung ho cc axit t do trong polyeste.
gim C
A
th phi un nng v phi dng hi ca hn hp diphenyl mi to
c nhit cao. giai on u c nhit thp th dng hi p sut nh. Hn
hp hi bay ln ch yu l ru, ngoi ra c anhydric hoc axit do ru ko theo v nc.
thit b phn ly: ru, anhydric v nc phn thnh hai lp; nc trn, ru v
anhydric di. Ru v anhydric ngng t cho quay tr li thit b phn ng cn nc
tch ra ngoi.
* Polyeste khng no (PE
s
KN) ch yu i t axit khng no, ru phn ln l ru no 2
chc.
a/ Phn loi
- PE
s
KN loi maleat

O CO C
H
CH COO
O

- PE
s
KN loi acrylat
- PE
s
KN loi thng (EG + AP + AM)
C C
OH OCO CH CH
2

- PE
s
KN loi do: thay mt phn AP bng axit 2 chc mch thng hoc thay mt
phn EG bng glycol mch di (DEG,DPG)
- PE
s
KN bn mi trng: thm cht n nh quang ( nh benzophenol hoc thay mt
phn styren bng MMA)
- PE
s
KN bn ho hc: dng nguyn liu c vng thm (thay mt phn EG bng
bisphenol-A)
- PE
s
KN bn nhit: thay mt phn AP bng dn xut halogen ca axit 2 chc (axit
tetraclophtalic hoc axit tetrabromphtalic)
Cl
Cl
Cl
Cl
COOH
COOH

- PE
s
KN loi thng: EG-AP-EG-AM-EG-AP...
b/ ng dng chnh ca PE
s
KN
Lm vt liu composite
+ Nha nn (cht lin kt)
+ Ph gia ( cc loi si, vi...)
+ Cht ng rn ( styren, MMA) dng 20 30 PKL so vi PE
s
KN
+ Cht khi u (i vi PE
s
KN-styren): MEKP
C H
3
C
C
2
H
5
O O
OH
C
CH
3
C
2
H
5
HOOC
C H
3
C
C
2
H
5
O O
C
CH
3
C
2
H
5
HOOC COOH

Lm vt liu composite c th dng tay, my, chn khng. Khi lm vt liu
composite th cht nn ( hay cht lin kt ) l nha trn vi ph gia. Cht nn gip to
hn hp vi ph gia thnh mi trng lin tc. Khi tc dng lc (nu ch c nha th dn,
nu ch c ph gia th ri rc v th lc phn b khng u) ln mi trng lin tc th lc
phn b u nn kh nng chu lc tt.
Si thu tinh dng lm vt liu composite c x l cht lin kt b mt. Nu
si khng x l th si v nha khng bm dnh tt v si l hp cht v c v nha l
hp cht hu c bm dnh vi nhau km.
Cht lin din: RMX
R: gc hydrocacbon khng no lin kt vi ni i ca nha hoc vi cht ng rn
(styren)
X: halogen hoc ete b thu phn to lin kt OH (lin kt vi si)
M: Si, Cr
S lin kt gia nha nn v ph gia xy ra
+ Giai on 1: thu phn

CH
2
CH
Si Cl Cl
Cl
O H
2
CH
2
CH
Si OH O H
OH
Cl H
C H
2
C CH
3
C
O
CrCl
2
O
OH
CrCl
2
C H
2
C CH
3
C
O
Cr(OH)
2
O
OH
(HO)
2
Cr
O H
2
Cl H
+
3 +
3
+
4
+
4

+ Giai on 2: to lin kt






//////////////////////////////////////////////////// b mt si ///////////////////////////////////////
//////////////////////////////////////////////////// //////////////////////////////////////
Ni i s tham gia trng hp vi hydrocacbon khng no ca nha hoc styrene.
Si c x l bn hn si thng rt nhiu 20 30 ln.








CH
2
CH
Si OH O H
O
H
O
H
M
CH
2
CH
Si OH O H
O
H
O
H
M
CH
2
CH
Si O O
O
M
CH
2
CH
Si O
O
M









////////////////////////////////////////////////////////// /////////////////////////////////////////////////
V/ Tnh cht, ng dng
Tnh cht ca nha polyeste khng no ph thuc vo thnh phn nguyn liu ban
u v iu kin tng hp. trng thi khng ng rn nha c th c nht thp,
trung bnh hoc cao. trng thi ng rn cc polyeste ny l vt liu rn, trong sut
hoc khng trong sut. Vt liu trong sut cho nh sng i qua n 92% khi tip xc vi
nh sng c bc sng ngn th nha s b vng.
Polyeste ng rn bn axit, dung dch mui axit v trung tnh, cc dung mi c
cc, nhng khng bn kim, kton, anilin, CS
2

Nhc im ca polyeste khng no l co ngt ln, chu nhit khng cao, bn
va p khng t
Polyeste khng no c dng ph bin sn xut cht kt dnh ( ph gia cho xi
mng), mng ph, vt liu composite, vt liu p v cht do thy tinh















C H
2
C CH
3
C
O
CrOH
O
OH
HOCr
O
H H
O
M
O
H H
O
M
C H
2
C CH
3
C
O
CrOH
O
OH
HOCr
O
H H
O
M
O
H H
O
M
C H
2
C CH
3
C
O
Cr
O
OH
-OCr
C H
2
C CH
3
C
O
CrO--
O
OH
Cr
O
M
O
O
M
O
M
O
M
to
CHNG XII: SN XUT NHA POLYAMID, POLYURETAN,
POLYCACBONAT, SILICON
I/Nha polyamid
1/ Nguyn liu
a/ Caprolactam
Caprolactam tinh khit si 262,5
o
C hoc 120
o
C (10mmHg) nng chy i nhit
68,5 69
o
C, d ha tan trong nc v trong a s dung mi.
b/ Axit 11-aminoundecanic
Axit 11-aminoundecanic nng chy 188 190
o
C. Phn ng iu ch n t axit
rixinolic nh sau:
CH
3
(CH
2
)
5
CH CH
2
CH CH (CH
2
)
7
COOH CH
3
(CH
2
)
5
CHO CH
2
CH (CH
2
)
8
COOH
CH
2
CH (CH
2
)
8
COOH Br H Br (CH
2
)
10
COOH CH
3
CH (CH
2
)
8
COOH
Br
Br (CH
2
)
10
COOH
NH
3
N H
2
(CH
2
)
10
COOH Br H
+
2
+ +
+ +

c/ Axit adipic
C th iu ch axit ny t cc sn phm ha hc khc nhau: phenol, furfurol,
xiclohexan, axetylen, andehytTng hp axit adipic t phenol tin hnh qua cc giai
on:
OH
H2
OH
OH
HNO
3
HOOC (CH
2
)
4
COOH NO
2
O H
2
+
+ +
3
+

Nhit nng chy ca axit adipic l 151
o
C
d/ Hexametylen diamin
c tng hp t axit adipic, nhit si 14mmHg l 90 92
o
C


HOOC (CH
2
)
4
COOH
NH
3
NC (CH
2
)
4
CN
NC (CH
2
)
4
CN H2
H
2
N (CH
2
)
6
NH
2
+
+
4

2/ L thuyt to thnh nha polyamid
Ph thuc vo nguyn liu ban u m nhm amid trong polyamid c th nh
hng theo cc chiu khc nhau
+ Polyamid c to ra t axit a chc (2) v amin 2 chc:
-4 H
2
O
(300 375
o
C)

CH
2
NH
2
CH
2
NH
2
COOH
COOH
O H
2
N
H
C C H
2
C C H
2
N
H
O
O
+
-2

+ Polyamid c to ra t aminno axit (hoc lactam ca amino axit 5 10% H
2
O)


N H
2
(CH
2
)
5
COOH H NH
n

(CH
2
)
5
CO OH
O H
2
(CH
2
)
4
CO
CH
2
NH
O H
2
H NH
n

(CH
2
)
5
CO OH
n
+
(n-1)
n
+

i vi lactam ch dng nc trong thi gian u v trong qu trnh trng ngng
to ra nc th nc tham gia phn ng thy phn lactam
Mun nhn c polyamid th c th dng cc axit 2 gc nhng vi iu kin s
nhm metylen trong phn t khng c di 4, c ngha dng axit adipic v cc ng
ng cao hn n. Phn ng to polyamid l phn ng thun nghch theo tng bc v to
ra sn phm ph l nc. V vy tng hiu sut to ra polymer th phi tch bt nc.
Nu tha mt trong cc tc nhn phn ng th c kh nng to ra mch polymer m u
mch c cha nhm ca tc nhn tha v do lm ngng phn ng pht trin mch.
HOOC (CH
2
)
4
COOH H
2
N (CH
2
)
6
NH
2
H NH
n

(CH
2
)
6
NHCO (CH
2
)
4
CO NH (CH
2
)
6
NH
2
O H
2
+
+
n (n+1)
2n

3/ Tnh cht, ng dng
Tnh cht ca polyamid ph thuc vo trng lng phn t trung bnh ca
polymer, cu to ca cc monome ban u v s lin kt hydro
Loi nha Nhit nng chy
(
o
C)
Polyamid-6
210 215
Polyamid-7
220 225
Polyamid-9
204 210
Polyamid-11
186 187
Polyamid-6-6
255 264
Polyamid-6-10
215 223
Khi tng s nguyn t C t 6 7 th c kt tinh ln hon mch c s nguyn t
C t 9 11 nn c nhit nng chy cao hn. Polyamid 6-6 gm 6 nguyn t C v 6
nhm amin c nhit nng chy tng do s lin kt H tng.
Polyamid-6
C
NH
CH
2
CH
2
CH
2
CH
2
CH
2
C
NH
CH
2
CH
2
CH
2
CH
2
CH
2
C
O
O
O
C
NH
CH
2
CH
2
CH
2
CH
2
CH
2
C
NH
CH
2
CH
2
CH
2
CH
2
CH
2
C
O
O
O
NH

Polyamid 6-6
CH
2
CH
2
C
NH
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
NH
C
CH
2
CH
2
CH
2
O
O
CH
3
CH
2
CH
2
C
NH
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
NH
C
CH
2
CH
2
CH
2
O
O
CH
3

Polyamid 6-6 c lin kt hydro ln hn polyamid-6 nn nhit nng chy cao
hn. Polyamid c nhit nng chy cao nn c tnh cht c l cao, bn nhit ln, vt
liu c ma st b v th c dng lm vt liu bi trn.
Polyamid
Tnh cht
6 11 6-6
Khi lng ring d (g/cm
3
) 1,14 1,04 1,14

k
[KG/cm
2
] 500 800 500 700 800 1100

u
[KG/cm
2
] 700 1000 -- 1000 1100

n
[KG/cm
2
] -- 600 1100 1000 1200
Modun n hi E ( KG/cm
2
) 5000 1000 2000 16000
II/ Polyuretan
L polymer c to ra t polyizocyanat vi polyol
nOC = N R N = CO + n HO R
1
OH -[-OCNH R NH COO R
1
O -]
n
-
+ Cc cyanat thng dng:
Hexametylen diizocyanat: OCN (-CH
2
-)
6
-NCO
2,4-Toluen diizocyanat:

CH
3
NCO
NCO

+ Cc phn ng ph:
R NCO + H
2
O RNH
2
+ CO
2

R
1
NH
2
+ R NCO R
1
NH CONH R
2R NCO + H
2
O RNH CONH R + CO
2

R NCO + R
1
OH RNHCO CO R
1
R NCO + R
2
COOH RNHCO R
2
+ CO
2
ng dng:
- Nha xp polyuretan
- Vt liu composite
III/ Polycacbonat
iu ch t Dian v fosgen

HO C
CH
3
CH
3
OH COCl
2
H O
n
R O C
O
OH NaCl
+
+
2n
NaOH, to

bn nhit ln do mch c vng v nhm
+ Khi lng ring d = 1,2 g/cm
3

+ Gii hn bn ko
k
= 650 750 KG/cm
2
+ Gii hn bn nn
n
= 790 900 KG/cm
2

+ Gii hn bn un
u
= 800 1200 KG/cm
2

+ bn nhit (Martens): 115 125
o
C
Polycacbonat cng, trong sut, d trn mu, khng c, c th thay th cho
melamin-formaldehyt chu nhit cao, bn ln
IV/ Silicon
Nng lng lin kt gia Si, C vi cc nguyn t khc

Lin kt Nng lng lin kt E(Kcal/mol)
Khong cch gia 2 nguyn t
(A
o
)
Si Si 42,5 1,9
Si C 58 1,93
Si H 75 1,64
Si F 143 1,54
Si Cl 85 2,0
O C
O
Si O 89 --
C - C 58,6 1,54
C H 87,3 1,54
C F 104 1,35 1,42
C Cl 70 1,69 1,77
C O 75 1,43

Si bn ha hc, bn nhit do c nng lng lin kt vi cc nguyn t khc ln hn
C lin kt vi cc nguyn t .
* Phng php iu ch
RSi O
3
C
2
H
5
O H
2
RSi O
2
C
2
H
5
OH C
2
H
5
OH
RSi O
2
C
2
H
5
OH
R(C
2
H
5
O)
2
Si
O Si(OC
2
H
5
)
2
R O H
2
R(C
2
H
5
O)
2
Si
O Si(OC
2
H
5
)
2
R
O H
2
R(C
2
H
5
O)
2
Si
O Si(OC
2
H
5
)R OH C
2
H
5
OH
R(C
2
H
5
O)
2
Si
O Si(OC
2
H
5
)R OH O H Si(OC
2
H
5
)
2
R
R(C
2
H
5
O)
2
Si
O Si(OC
2
H
5
)R O Si(OC
2
H
5
)
2
R
O H
2
+
+
2
+
+
+
+
+

Tip tc phn ng cho n khi to ra polymer
(C
2
H
5
O)
2
Si R
O Si(OC
2
H
5
)R O Si(OC
2
H
5
)
2
R
n


* Tnh cht ca Silicon
+ Khi lng ring d = 1,9 g/cm
3

+ Gii hn bn un
u
> 500 KG/cm
2
+ bn nhit (Martens): > 200
o
C
+ ht m (trong 24 ngy m nhit thng): 0,25g/dm
2