11/18/2014

Tnh cht c trng ca cc

sn phm ny?

Plastics
Additives Market
(Functions, Product Types,
Applications, Geography) Global Industry Analysis,
Size, Growth Trends, Share,
Opportunities and Forecast
2012 - 2020

Phu gia polymer

Published Date:- Apr-2014

Pages
108

Cc y t nh hng gia cng va s dng nha

Nguyn liu
Tnh cht VL
Cu to HH

Gia cng
iu kin
gia cng

SP/s dng

Nhit
Vn tc chy
p sut
Thi gian

nh sng
m
Oxy

T/c sp
VSV

Mi trng
s dng

11/18/2014

Cc vn thng xy ra khi gia cng va s dng nha

Nha nhit do
(kt tinh, v nh hnh)
Nha nhit rn

Nguyn liu
Tnh cht VL
Cu to HH

Sn lng nha nhit

do hng nm > 120
triu tn

Gia cng
iu kin
gia cng

> 95% th tch o k th

s dng dc nu
khng c phu gia (PG)

SP/s dng

Sn lng v tiu th ph gia trong

cng ngh nha nhit do

Nhit
Vn tc chy
p sut
Thi gian

nh sng
m
Oxy

T/c sp
VSV

Mi trng
s dng

Phn loi polymer

Nha nhiet deo

Cao su, chat an hoi

Nha nhiet ran

Polymer co the chuyen

trang thai ran sang
trang thai mem deo bi
s gia tang nhiet o va
qua trnh nay thuan
nghch, co the lap i lap
lai nhieu lan nen co the
tai sinh (ngoai tr PTFE,
polytetraflouroethylene)

Polymer mach thang ma lc

lien ket th cap rat yeu, vat
lieu dang chat long rat
nht. e s dung ta phai
tao cac lien ket ngang gia
cac mach phan t e tao
thanh mang li khong gian
ba chieu. ac trng cua cao
su la chung co kha nang dan
dai cao co the en 1.000%
(cao su t nhien lu hoa).
Tuy nhien, do tao lien ket
ngang nen chung khong the
tai sinh c.

Mat o noi ngang day

ac, cao hn t 10 en
1.000 lan so vi cao su.
Do cau truc khong gian
ba chieu, tnh chat nha
nhiet ran rat cao so vi
nha nhiet deo, nhat la
kha nang chu nhiet.
Nha nhiet ran khong
chay, khong tai sinh
c.

11/18/2014

Cu trc polymer

Trng thi vt l ca polymer

Polymer nhit do phan loai theo cau tao co hai dang

Cu truc ket tinh

Cau truc vo nh hnh

Khi cac mach phan t polymer khong the
sap xep theo mot trat t nao th ta co cau
truc vo nh hnh. V du nh nha
PMMA, PC, PS, PVC, SAN, ABS,

Polymer ket tinh la nhng polymer co

cau truc sap xep eu an trong khong
gian ba chieu theo dang bo hoac xep
gap. V du nh nha PE, PP, PET,
POM, PA, Teflon,

ket tinh do keo dan

Trng thi thy tinh

trang thai mem

cao, polymer co kha
nang bien dang thuan
nghch di tac dung
cua ngoai lc khong
ang ke. Trang thai
mem cao c xem
nh mot trang thai vat
ly AC TRNG cua
polymer va ch ton tai
vat lieu polymer.

trang thai mem cao cua polymer, cac

mat xch trong phan t co o linh ong ln
nen de dang thay oi hnh dang sap xep.
Khi lam lanh polymer nhanh, do thi gian
hoi phuc cua cac mat xch tang len nhieu
lan nen thay oi hnh thai sap xep cua
mach polymer va qua trnh ket tinh cua
polymer gap kho khan. Trong mot pham vi
nhiet o nao ay polymer b cng lai ma
khong tao thanh mang li tinh the th goi
la polymer chuyen thuy tinh.

ieu kien co bien

dang mem cao la
mach phan t polymer
phai co o mem

hai pha
ket tinh dang xep gap

Trng thi mm cao

vo nh hnh

nh hng t/c VL n gia cng VL

ng cong c nhit

deo nhat nh va
van toc bien dang
ln.

Trng thi chy nht

Chay la qua trnh chuyen
dch khong thuan nghch gia
cac phan t cua mot chat tng
ng vi nhau di tac dung cua
ngoai lc.

Polymer co kha nang ket tinh th nhiet

o chuyen thuy tinh luon luon nho hn
nhiet o ket tinh.
Qua trnh chuyen thuy tinh khong phai
la qua trnh chuyen pha, tren va di nhiet
o chuyen thuy tinh th polymer eu
trang thai pha vo nh hnh.

Cht do v nh hnh

Nhiet o trung bnh trong

pham vi phat trien qua trnh mem
cao la nhiet o chuyen thuy tinh
(Tg). Tai iem nhiet o thuy tinh hoa
polymer thay oi ot ngot cac tnh
chat nh: tnh chat c, quang,
ien,

Nhiet o trung bnh trong pham vi phat trien qua trnh chay thc la
nhiet o chay (Tf). Trong thc te ngi ta da vao gia tr nay e xac nh
che o gia cong.
Nhiet o trung bnh trong pham vi phat trien qua trnh phan huy goi la
nhiet o phan huy (Td). Khi gia cong cung can phai lu y en gia tr nay va
khoang cach gia Tf vi Td e ieu chnh phu hp vi cong nghe.

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Cc vn thng xy ra khi gia cng va s dng nha

Phn hy nhit/quang

Nguyn liu

Phn hy oxy ha

Tnh cht VL

nhit/quang

Cu to HH

Polyolefins (PE, PP)

tinh khit d bi oxi
ha

Gia cng
iu kin
gia cng

PVC tinh khit d b

phn hy khi p dn
hoc c khun

SP/s dng

Vn tc chy
p sut
Thi gian

nh sng
m

Phn hy nhit

L qu trnh phn hy polyme xy ra di tc ng ca

nhit cao trong mi trng khng c oxi.

Xy ra theo c ch dy chuyn gc t do gm 3 giai on:

Khi mo

Oxy

Pht trin mch

VSV

Ngt mch phn ng

T/c sp
Mi trng
s dng

Nhit

16

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Mechanism of thermal oxidation

of polymers
1) Chain initiation

Khi mo
Di tc ng nhit, mch polyme c th
b ct t ngu nhin,

2) Chain propagation

b t ti cc lin kt yu nht trong mch i phn t

3) Chain branching

(nguyn t cacbon bc 3, 4, C-H, C-Cl, C-O, C-C, C-N)

4) Chain termination

Nguyn t hydro b t tch khi mch phn t polyme

-CH2-CHR-CH2-CHR- -CH2-CHR + CH2-CHR-

.
.
-CH -CHR-CH -CHR- -CH -CR-CH -CHR- + H

-CH2-CHR-CH2-CHR- -CH2-CHR-CH-CHR- + H

Antioxidants:
primary (chain-breaking) interfere with the chain propagation step
secondary (preventive) destroy hydroperoxide groups

18

Nu polyme ln phn d ca cht khi mo, kim loi, oxit

ca kim loi chuyn tip trong q/t tng hp polyme Gc
t do ca polyme c to thnh d dng

R + R RH + -CH=CHR-

-CH2-CH-CH2-CH2-

+ -CH2-CH-CH2-CH2-

-CH2-CH2-CH2-CH2-

+ -CH2-CH=CH-CH2-

KT QU: polyme b
gim khi lng phn t trung bnh
Pht trin mch

thay i cu trc
q/t gii trng hp (to thnh monome: polyme cha
nguyn t cacbon bc 4)
19

20

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2 Phn hy oxy ha nhit

L qu trnh phn hy polyme xy ra di tc ng ng

cacbon bc 3 hoc c cc nhm hot ng nh nhm

thi ca oxi v nhit cao, thng xy ra theo c ch dy

phenyl (PS) d b oxy ha to thnh peoxit hn

chuyn gc t do.

polyme cha cacbon bc 2

Khi mo

kh nng ct t nguyn t hydro khi hp cht c

RH + O2 R + HOO
RH + O2 + HR 2R + H2O2

Polyme c cha nguyn t hidro linh ng ngt

ng/t bc 1, bc 2, bc 3 theo t l 1:3:33

Trong q/t trng hp polyme c xy ra p/ truyn mch

tn ti mt lng nh cc nhnh xut hin nguyn t
cacbon bc 3 v bc 4.
21

22

Polyme khng no b phn hy nhanh hn nhiu so

vi polyme no, oxi tn cng LK khng no d dng hn
y nhanh giai on khi mo phn hy oxi ha
tng tc to thnh gc t do

23

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Pht trin mch

P/ pht trin mch phn hy oxi ha nhit PVC:

Nhm hydropeoxit b phn hy thnh cc nhm alkoxi

v hydroxyl:

26

25

P/ oxi ha nhit ca cht ha do c s dng

trong PVC:

Tt mch
R + R RR
R + R RH + -CH=CH-R
R + RO ROR
R + ROO ROOR
RO + RO ROOR
RO + ROO ROOR + 1/2O2
ROO + ROO ROOR + O2

27
28

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Bc sng m

Phn hy quang polyme

0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45 0,50

L qu trnh phn hy polyme di tc ng ca nh

T ngoi
chn khng

T ngoi

sng v cc yu t mi trng khc

0,60 0,70 0,80

Kh kin

1,0

0,90

1,5

2,0

Hng ngoi gn

3,0

4,0

Hng ngoi

Nng lng in t

Cc p/ oxy ha xy ra khi polyme b chiu sng ng

vai tr quan trng trong q/t lo ha polyme v nh
hng quyt nh ti tui th sd/thi hn sd.

Nng lng ph lin kt

-(C=O)-(C=O)-, beta-xeton

Nng lng dao ng

0,43

dao ng ha tr C-H 3,45

-N=N-, in t azo 0,35

dao ng ha tr O-H, N-H 2,95

0,205 in t este, -(C=O)-O

Cc polyme vi cu trc no s hp th nh sng

0,2 nng lng ph v lin kt i, -CH2=CH2-

vng sng ngn (<200 nm) v t ngoi chn khng

0,145 nng lng ph v lin kt ba, -CHCH0,28 nng lng ph v lin kt cacbon-hydro, CH3-H

gy ra ph hy lin kt ha hc v lin quan n vic

0,53 nng lng ph v lin kt peroxit, HO-OH

ng dng polyme trong khng gian.

0,33 nng lng ph v lin kt cacbon-cacbon, CH3-CH3

Khi chiu nh sng vo hp cht, in t c kch

thch, phn t b ph v lin kt to gc t do

Nng lng phn ly lin kt ca mt s lkhh

Lin kt
C-H

R-X R + X
Polyme hp thu mnh nh sng vng t ngoi
(bc sng 200-400nm), nng lng nh sng t
ngoi ln lm t cc lin kt trong polyme (lin

30

Nng lng
phn ly (kcal/mol)
85-99

C-H (allyl)

77

C-C

83

C-N

82

C-Cl

78

C-O

93

O-O

66

kt cacbon-cacbon, cacbon-nit, cacbon-hydro,..)

31

32

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Cu trc hp cht (m hnh)

Nng lng phn ly lin kt

(kcal/mol)

Polyme tng ng

Km bn

Nng lng phn ly lin kt

(kcal/mol)

Polyme tng ng

Polyete

78

HDPE, Nylon

61,5

ABS, PC/ABS,
HIPS,

82

63

PS, HIPS, ABS,

ASA, SAN/EPDM,

92

PVC, CPE, CPVC

94

HDPE

PP, LLDPE

103

AN, ABS,
PC/ABS,

73
77
85

Cu trc hp cht (m hnh)

PVC, CPE, CPVC

PVC, CPE, CPVC

33

34

C ch

Cu trc hp cht (m hnh)

Nng lng phn ly lin kt

(kcal/mol)

-O-(C=O)-C-, cacbonat
-(C=O)-NH-, amit

-(C=O)-O-, este

Polyme tng ng

nhm c kh nng hp th bc x t ngoi nh cc

lin kt i, nhm cabonyl (nhm mang mu) tn ti

PC
Bn vi nh sng
Khng bn khi thy
phn

Q/trnh khi mo ph thuc vo s c mt ca cc

trong polyme, cc nhm th gn vi cc nguyn t

Nylon

cacbon ca nhm mang mu (-SH, -NH2, -OH,).

PMMA, Acrylic,
polyeste, PET

Cc nhm mang mu c th l cc cht xc tc trng

hp cn st li, cc bt mu hoc cc cht ph gia
trong phn t cha lin kt i hp th bc x t

35

ngoi lm t cc lk trong polyme to gc t do

36

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Cc ion v cc mui kim loi cng c th xc tc khi

mo phn hy quang

cha lin kt i v gc mi

-CH2-CH2-CH2-CH2-

-CH2-CH-CH2-CH2- + H

-CH2-CH2-CH2-CH3

Cc gc i phn t b phn hy thnh phn t c

-CH2-CH2-CH-CH2-

-CH2-CH2-CH2- + CH3

-CH2-CH=CH2 + CH2-

Cc gc i phn t kt hp to thnh cu trc khu

Cc gc t do linh ng ly mt nguyn t hydro ca

i phn t polyme v tch ra khi mi trng p/

mch

-CH2-CH-CH2-CH2-

dng sn phm d bay hi

-CH2-CH2-CH-CH2-

-CH2-CH2-CH2-CH2- + H -CH2-CH2-CH-CH2- + H2

-CH2-CH-CH2-CH2-CH2-CH2-CH-CH2-

Qu trnh phn hy t mch v khu mch lun xy

-CH2-CH2-CH2-CH2- + CH3 -CH2-CH2-CH-CH

2- + CH4

ra ng thi vi t l tc khc nhau

37

38

Qu trnh phn hy t mch d xy ra vi cc

polyme

cha

cc

nguyn

bc

nh

polyizobutylen, PMMA,
Vi nhng polyme c cha nhm cacbonyl nh
hng r rt ti s hp th nh sng v mch
polyme c th b t to thnh cc gc t do v kh
CO

R1-C(O)-R2 R1-C=O + R2 R1 + CO + R2
39

10

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Phn hy oxi ha quang polyme

L phn ng phn hy polyme di tc ng ca

nh sng trong mi trng c oxi
Xy ra theo c ch gc, bao gm 3 giai on: khi
mo, pht trin, v ngt mch.
h
Polyme RH gc i phn t polyme oxi
gc peoxit

ROO.

i phn t polyme

hydropeoxit ROOH

R. + mch polyme c cha nhm

km bn

phn hy

R. +

HO .
42

Sn phm ca qu trnh oxy ha quang polyme cha

S t mch ca q/t phn hy oxi ha quang ca cc

cc nhm c oxi (nhm cacbonyl, cacboxyl, peoxit,

polyme PE, PP, PVC, thng chim u th v to

hydropeoxit, hydroxyl,), cc lin kt i, cc hp

thnh cc sp cha cc nhm cacbonyl, cacboxyl,

cht c khi lng phn t thp nh axeton,

hydroxyl,

axetaldehyt, nc, cc kh CO, CO2,

Cc polyme khng no rt nhy cm vi tc ng ca

Phn hy oxi quang ha polyme dn n gim tnh

cht c, tnh cht nhit, tnh cht in, bin i cu
trc, mu sc, v gim thi gian s dng

Nguyn t hydro () d dng b tch ra gc i

phn t oxi
gc peoxit

Vic gim khi lng v t mch i phn t ca

polyme to iu kin cho nm mc, cc vi sinh vt
tip tc tn cng gy phn hy sinh hc

nh sng t ngoi.

43

-CH2-CH=CH-CH2-

-CH2-CH=CH-CH-

-CH2-CH=CH-CH-

OO

44

11

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Gc peoxit p/ vi lin kt i trong polyme hp cht

epoxy hoc nhn mt nguyn t hidro ca polyme
hydropeoxit

Polyme cha hydropeoxit b phn hy to thnh gc

alcoxi v gc hydroxyl
p/ truyn mch, ngt mch

to sp cha cc nhm cacbonyl/xeton v hydroxyl

-CH=CH-

-CH2-CH=CH-CH-

OO

RH

-CH2-CH-CH-CH2O

-CH2-CH=CH-CH- + R

-CH2-CH=CH-CH- + OH

-CH2-CH=CH-CHOOH

RH

-CH2-CH=CH-CH-

OOH

OH

-CH2-CH=CH-C(O)- + H2O

45

P/ truyn mch, ngt mch ca gc alcoxi polyisopren

CH3
CH3
-CH=CH-C-CH2O

Cc loi phn ng t mch phn t polyme

Qu trnh t mch

xy ra nhiu v tr khc nhau

-CH=CH-C-CH2RH

46

Ngun nng lng,

xc tc
Tia t ngoi ngn
Tia X, chm in t

V tr xy ra
Nhm CH hoc nhm
CH2 tt c cc
polyme

Tia bc x, nhit, c
hc

+ R

OH

CH3-C(O)-CH2- + CH=CH-CH=CH-C(O)-CH2- + CH3

-CH=CH-C(O)-CH3 + CH247

Tia t ngoi

Cc nhm xeton, amit,

uretan, este

Tia t ngoi

Cc nhm xeton, este

nh sng, nhit

Bt k phn polyme b
oxi ha no

48

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Cc loi phn ng t mch phn t polyme

Qu trnh t mch

Nha nhit do
(kt tinh, v nh hnh)
Nha nhit rn

Ngun nng lng,

xc tc

V tr xy ra

Thy phn (xt baz)

Amit, uretan, imit, ure

este

Thy phn (xt axit)

Nhit

Amit, uretan,
siloxan, axetal

Phn hy nhit
Phn hy oxy ha nhit

este,

Nguyn liu
Tnh cht VL
Cu to HH

Gia cng
iu kin
gia cng

Polyolefin

SP/s dng

Nhit
Vn tc chy
p sut
Thi gian

nh sng
m
Oxy

T/c sp
VSV

Mi trng
s dng

49

1. PH GIA
Nha nhit do
(kt tinh, v nh hnh)
Nha nhit rn
Phn hy nhit/quang

Nguyn liu
Tnh cht VL
Cu to HH

Phn hy oxy ha

Gia cng

nhit/quang

iu kin
gia cng

SP/s dng

Nhit

Phu gia l nhng hp cht c b sung t c tnh cht nh

mong mun trong qu trnh ch bin hoc trong sn phm.

Vn tc chy
p sut
Thi gian

PG c s dng nhm

Gim s phn hy trong ch bin va bo v nha khi s dng

Gip qu trnh gia cng d dng

Oxy

Ci tin hoc bin tnh cc tnh cht vt ly, ha hc, c ly

VSV

Gim gia thnh

nh sng
m

T/c sp

Phu gia

Mi trng
s dng

13

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PG c th
tn ti trng thi rn, lng, bn rn.

monomers, oligomer, polymers

thnh phn chnh trong sn phm cui hoc thnh phn

ci thin mt tnh cht, a tnh cht

phu gip tng cng mt tnh cht c trng (

bn)
cht

hu

(VD

alkyl

phenols,

hydroxybenzophenones), v c (e.g. oxides, salts,

fillers), hp cht c kim - organometallic (e.g.
metallocarboxylates, Ni complexes, Zn accelerators).

VD
PG a chc nng:
Dimethyl methyl phosphonate (DMMP) dng trong nha
epoxies a ng rn (cross-linked epoxies), c vai tro
- cht khng do (antiplasticiser)
- tr gia cng (processing aid)
- chng chy (flame retardant)

La chn PG

Tiu th ph gia USA nm 1999

Vic la chn PG phu hp vi CNCB nha ty thuc

vo
Thnh phn ha hc ca polymer
Qu trnh gia cng
Yu cu sn phm
C ch phn hy ca polymer di tc ng ca
nhit , nh sng, lc ct ko, m trong qu trnh
ch bin va khi s dng
C-H, C-Cl trong polymer pht trin mch nh polyolefins, PS,
PVC b phn hy di nhiu tc nhn ca mi trng
cn c bo v khi tc ng ca oxi ha, nh sng,
phn hy nhit

14

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La chn PG

PG cng c b sung tng thm nh cht mi

C ch phn hy ca polymer di tc ng ca nhit ,

hoc ci thin mt s nh cht nh kha nng chng

nh sng, lc ct ko, m trong qu trnh ch bin va khi

chy, chng nhim in, tng nh va p, tng kha

s dng

nng tng hp khi trn polymers (blend)

C-H, C-Cl trong polymer pht trin mch nh polyolefins, PS,

PVC b phn hy di nhiu tc nhn ca mi trng
cn c bo v khi tc ng ca oxi ha, nh sng, phn
hy nhit

Thng nhiu hn 1 PG c dng cn hiu ro

Polymer ha bc bn i vi oxy, nh sng nhng chng

thng d b thy phn gim cp khi c s hin din ca
m. Nhit cao trong qu trnh ch bin hoc khi c s hin
din ca nhng cht xc tc cn st li tng tc phn
ng thy phn

Phn loi

tng tc gia cc PG ti u cng thc

Mt s PG khc
PG ha do-Plasticizers

Cht bi trn va tho khun - Lubricants and Mold-Release Agents

PG chng chy-Flame Retardants

Cht n gia cng (Reinforcing Fillers), tc nhn gia cng

PG bn mi trng-Impact Modifiers

Cht mu va cht lm sng - Colorants and Brightening Agents

PG bo v

PG chng oxi ha-Antioxidants

Tc nhn to bt vt ly va ha hc - Chemical and Physical Blowing

PG bin tnh

PG khng khun-Antimicrobials

Chc nng

PG tr gia cng
PG khc

PG bn nhit, nh sng-Stabilizers
PG to lin kt coupling agents
PG to/pha bt coupling agents
Chng nhim in, mu

(Reinforcing Agents), tc nhn to lin kt (Coupling Agents)

Agents

PG chng lo ha - Antiaging Additives (Antidegradents)

Tc nhn chng nhim in - Antistatic Agents

Chng oxi ha va kh kim loi - Antioxidants

and Metal Ion

Deactivating Agents

PG khng cc tc nhn sinh hc - Biocides Against Biological

Degradation of Plastics

15

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PG bi trn, tho khun

Nguyn liu

PG ha do

Tnh cht VL

PG chng oxi ha

Cu to HH

Gia cng

PG bn nhit
PG bn mi trng

iu kin
gia cng

PG bn nh sng
PG chng nhim in
PG chng chy
PG gia cng
PG to lin kt

PG khng
khun

SP/s dng

Yu cu khi s dng ph gia

Nhit

S dng ng, theo mc ch ci

Vn tc chy
p sut

thin tnh cht ca polyme

Thi gian

S dng vi lng nh nht

nh sng

Kim sot cc p/ ph khi dng ph gia

m
Oxy

T/c sp

S dng ph gia nhiu chc nng

VSV

Mi trng
s dng

Khng c hi

PG to bt

Qu trnh gia cng nhit cao

n
nh
S dng cc cht ph gia: n nh nhit, cht chng
chng
oxi ha, cht n nh quang, cht hp th tia t ngoi,
phn
hy
cht kh hydropeoxit,
polyme

Qu trnh s dng vi s c mt ca bc x t ngoi,

oxi, ozon, m, vi sinh vt, cc tc ng khc ca
mi trng,

Phn hy nhit, phn hy oxy ha nhit.

Phn
hy
Polyme

Phn hy do ozon, do tc ng c hc, do vi sinh vt

3. PG n nh chng phn hy
Polyme

Phn hy quang, phn hy oxy ha quang.

Gim tnh cht, bn, kh nng s dng, kh nng
gia cng, v thi hn s dng ca vt liu.
63

64

16

11/18/2014

Ph gia c a trc tip vo polyme trong q/t trng

hp monome, q/t bin tnh v ch to s/p polyme trn
cc thit b gia cng trng thi nng chy nh my n,
my trn, my cn, my p phun,

Yu cu i vi ph gia
C kh nng trn ln, tng hp tt vi polyme v cc
cht ph gia khc
Kh cc tp cht xc tc phn hy polyme nh cc gc

Ph gia c ha tan trong dung mi d bay hi v trn

ion v oxit kim loi, cht khi mo trng hp cn st li

vi polyme, hoc khuch tn vo si v mng polyme

Khng b khuch tn ln b mt v khng b ra tri khi

b mt

TiO2 c s dng lm cht nhy quang kh ph bin

Khng c hoc t c tnh

khi a vo cc lp ph polyme
65

66

c ch qu trnh phn hy oxi ha polyme cc giai

Nu tp cht tan tt trong dung mi polyme ch trng

trong dung mi tch tp cht ra khi polyme

on p/
1. c ch q/t oxi ha giai on khi mo p/:
a. Kh cc tp cht xc tc khi mo p/

b. Gim nng oxi trong polyme

Cc cht khi mo trng hp gc, cht xc tc trng hp,

Oxy d xm nhp vo vng v nh hnh ca polyme

cc ion kim loi chuyn tip, d thc y phn hy oxi

ha polyme

tham gia trc tip q/t oxi ha polyme

Cn x l, bin tnh, gia cng v ch to cc s/p polyme

Cn loi b bng cch ha tan polyme trong dung mi

trong mi trng chn khng hoc ym kh trn cc thit

b gia cng nha nhit do (my n- phun-p c ht

thch hp tp cht khng tan s tch ra

67

chn khng hoc thi kh tr

68

17

11/18/2014

Gim nng oxi trong polyme bng vic a vo

polyme cc cht hp th oxi nh sulphit hc bisulphit

2. c ch q/t oxi ha giai on pht trin mch

p/:
Cht c ch q/t oxi ha c kh nng kt hp vi cc gc
.

R-S-R + 1/2O2 R-S-R

O

t do R , RO , ROO

Cht chng oxi ha (cht nhn gc t do cht cho ng/t

R-S-R + 1/2O2 R-S-S-R

hydro n cc gc t do)

Cht chng oxi ha (AH) phi c kh nng p/ cao, gc t

Phng php ny t t hiu qu cao do trong q/t gia

cng v s dng, polyme thng xuyn tip xc vi oxi
khng kh

do ca cht chng oxi ha phi kh bn

Hiu qu chng oxi ha ca cht chng oxi ha ph thuc
vo:
Bn cht ca cht chng oxi ha

69

70

Tng s nhm hydroxyl (nhiu ng/t hydro) hiu qu c

Kh nng tan hay khuch tn vo polyme

ch chng oxi ha polyme tng

Khi lng phn t v bn gc ca n

bn gc ph thuc vo bn cht nhm th gn

2a. C ch
Cht chng oxi ha (AH) tc dng vi oxi, gc t do, v

vi vng thm
Cc nhm nhn in t (NO2, COOH, Cl, Br,) tng

hydropeoxit
AH + O2 RH + A

kh nng p/ ca gc
Cc nhm cho in t (CH3, OCH3, t-C4H9,) lm
gim kh nng p/
S lng nhm hydroxyl trong ph/t c nh hng n
hiu qu chng oxi ha

AH + R
AH + RO

A. + RH

A. + ROH

A. + ROOH

AH + ROO
71

72

18

11/18/2014

AH + ROOH A + RO + H2O

Cc hydropeoxit tn ti trong polyme v to thnh khi

Gc t do ca cht chng oxi ha tc dng vi cc gc t

polyme b phn hy oxi ha l tc nhn thc y q/t phn

do ca polyme v tc dng vi nhau to thnh s/p bn

hy polyme tip theo cn phi kh v bo m khng

A +R

RA

A + RO
.

A + ROO
.

A +A

hoc rt t gc t do to thnh

ROA

ROOA

AA
73

Irganox 1010
74

19

11/18/2014

R2S + ROOH ROH + R2SO

(ROCOCH2CH2)2S + 3ROOH 2ROCOCH2=CH2 + SO2 + H2O

R2SO + ROOH ROH + R2SO2

+ 3ROH
Hp cht hu c thic cha lu hunh l cht kh nhm

kh nhm hydropeoxit m khng to thnh

gc t do

hydropeoxit rt hiu qu
(C4H9)2Sn(SR)2 + ROOH (C4H9)2Sn(OR)(OH) + R-SSR-

s/p ca q/t kh l h/c sulphoxit c hot tnh kh

hydropeoxit mnh hn nhiu so vi sulphit ban
u
Tr v mt ha hc, khng nh hng ti q/t
oxi ha polyme
77

78

Qu trnh kh nhm hydropeoxit ca gc peoxit v gc

alcoxi ca este photphit:
P(OR)3 + ROOH ROH + O=P(OR)3
.

RO. + O=P(OR)3

R. + O=P(OR)3

R-O. + ROP(OR)2

P(OR)3 + ROO

P(OR)3 + RO
P(OR)3 + RO

80

20

11/18/2014

Kh cc nhm km bn v kh kim loi xc tc

phn hy polyme

-CHCl-CH=CH- + P(OR3)
-CH(OP(OR)2)-CH=CH- + HCl

Cc nhm km bn s kch thch v xc tc phn hy

polyme, c bit i vi cc polyme phn cc nh PVC, PA
Hp cht diketon, este photphit c kh nng n nh mu
PVC nh kh nng th ng ha ng/t clo km bn trong
i phn t PVC

Cc hp cht cha lu hunh cho hiu qu kh tt lin

quan ti tc dng kh lin kt i trong gia cng v s
dng cc s/p PVC
-CH=CH- + RSH -CH2-CH(SR)-
-CH2-CH=CH2+ROCOCH2SHROCOCH2SCH2CH2CH2-

-CHCl-CH=CH- + RCOCH2COR
-CH(RCOCHCOR)-CH=CH- + HCl
81

Hiu qu ca cc cht n nh PVC c th hin bi hm

lng v tc tch HCl khi PVC, gim hm lng lin
kt i, hm lng nhm cacbonylallyl, nhm hydropeoxit
S dng oxit kim loi chuyn tip c kh nng c ch phn
hy nhit PVC (c ch tch HCl, gim tc tch HCl ln
nht, gim tng lng HCl tch ra theo thi gian phn hy

82

nh hng ca cc oxit KL chuyn tip n q/t tch HCl sau

3h phn hy nhit PVC (210oC)
Oxit KL
chuyn tip

Vmax x 105
(mol/l/pht)

Ct x 103
(mol/g.l)

TiO2
V2O5
Cr2O3
-

1,5
1,0
2,0
21,5

1,86
1,10
2,15
19,34

nhit PVC
83

84

21

11/18/2014

n nh quang polyme

Tng bn nh sng

Tng bn oxi ha quang

S dng cht n nh quang:

Cht hp thu tia t ngoi

Cht c kh nng c ch cc q/t phn hy quang polyme

S dng mng che chn, ngn cch cc tia bc x

Cht c kh nng phn x tia t ngoi

Cht c kh nng lm mt/tt hot tnh cc trng thi kch

thch ca polyme khi b bc x t ngoi

85

Khi lng phn t ti u ca cht n nh quang khong

400 600

86

Cht hp th tia t ngoi bo v polyme l cht c kh

nng hp th nng lng ln ca cc tia t ngoi v
truyn nng lng di dng pht quang v ln quang

Khi lng phn t qu ln hoc qu nh s lm gim

vi bc sng di hn v ta nhit v hi cho polyme

Hot ng ca cht hp th tia t ngoi (A)

hiu qu n nh, chng oxi ha quang ca chng

A + h A*

Khi lng phn t qu ln gim s linh ng v kh

nng phn tn vo polyme

A* A + h (pht quang)
A* c th khng pht quang m truyn di dng ta nhit
C th q/t xy ra va ta nhit, va pht quang tn s nh sng

Khi lng phn t qu nh gim bn nhit

nh hn
87

88

22

11/18/2014

Cht hp th tia t ngoi c th lm tt trng thi kch thch

ca polyme theo c ch truyn nng lng nh sau:
Truyn nng lng gia cc phn t: q/t xy ra gia i
phn t polyme b kch thch (cht cho) v cht n nh
quang (cht nhn) hoc gia cht nhy quang (cht cho)
v i phn t polyme b kch thch (cht nhn)
Truyn nng lng ni phn t: nhm mang mu trong
i phn t polyme b kch thch (cht cho) v cc on
khc trong i phn t polyme (cht nhn)

89

Mt s dn xut benzophenon c s/d rt hiu qu do

Cht hp th tia t ngoi tiu biu:

Cc hp cht trong phn t c nhm hydroxyl v tr octo so
vi nhm mang mu gn vo vng thm (d to thnh lk

trong phn t c cha nhm o-hydroxyphenylketon:

h

-h

hydro ni phn t ca vng 6 cnh)

CH
O
H
R

O
91

92

23

11/18/2014

Cc dn xut o-hydroxyphenylsulphoxit:

Cht n nh quang cha amin:

CH3
H2
C C x
C

Cc cht hp th tia t ngoi cha nit ang c s dng

CH3
H2
C C y

kh hiu qu hin nay: hydroxyphenyl benzotriazol,

xyanoacrylat, hydroxyphenyl triazin,

N
H
93

94

24

11/18/2014

C ch hot ng: nhm 2,2,6,6-tetrametyl-4-piperidin b

oxi ha do p/ vi hydropeoxit to thnh gc t do nitroxyl
(NO)

O
N

Cc cht n nh tiu biu ca polyme

Loi cht n
nh
n nh
nhit

Gc t do nitroxyl

(NO)

phn ng vi gc t do ca polyme

amin alkoxi (NOR)

Amin alkoxi (NOR) phn ng vi gc t do peoxit (ROO)
gc t do nitroxyl mi

Tc dng

V d

n nh nhit cho polyme Cacboxylat kim loi (stearat,

(s dng cho PVC trong laurat, adipat ca Ba, Ca, Pb,
qu trnh gia cng nhit Zn,), dibasic, tribasic ch,
cao)

Chng oxy
ha

c ch q/t oxi ha

Phenol
Cht n nh quang
cha amin

Cht hp
th tia t
ngoi

Hp th tia t ngoi

Dihydroxybenzophenon
Benzotriazol

97

98

Loi cht n nh

Tc dng

V d

Nng cao bn thi tit ca

Cht lm mt/lm

P/ vi trng thi kch

thch ca polyme v
chuyn polyme sang
thng thi khng hot
ng

Mecaptan, Quinin
Cht n nh quang
cha amin

polyme

Cht kh
hydropeoxit

Kh nhm hydropeoxit

Tiobisphenol
Dilauryltiodipropionat
Dialkylsulphit
Trialkylphotphit

Cht n/Cht h
tr kt tinh

Gim linh ng
Gim kh nng khuch
tn ca cc phn polyme
b tn cng

tt hot tnh cc
trng thi kch
thch

1. Cc yu t nh hng n bn thi tit ca polyme

Thi tit l trng thi ca kh quyn mt khu vc hay mt

a im vo mt thi im c th, c c trng bi cc
tr s v nhit , m, lng ma, nng lng bc x

Photphat bisphenol
vng
Dibenzyliden sorbitol
Dicacboxylat

mt tri, gi, thi tit c tnh cht khng n nh, thay

i bt thng
99

100

25

11/18/2014

Kh hu: trng thi ca kh quyn mt ni no c c

trng bi tr s trung bnh nhiu nm v nhit , m,
lng ma, lng nc bc hi, nng lng bc x mt

1.1. Bc x t ngoi:
L nguyn nhn u tin gy phn hy cc polyme khi s
dng chng ngoi tri
3 loi phm vi bc sng nh sng t ngoi

tri,. c tnh cht n nh

S suy gim tnh cht v bn ca polyme khi s dng
ngoi tri lun chu tc ng ca cc yu t thi tit khc

UV-A: 315-400 nm (95%)

UV-B: 280-315 nm (5%) ch yu gy phn hy quang v
oxi ha quang i vi polyme

nhau
Yu t thi tit ch yu: bc x t ngoi, nhit , m,

UV-C: 100-280 nm (khng n c b mt tri t do

ozon, oxi phn t, hi nc trong bu kh quyn hp th

oxi v ozon, vi sinh vt

hon ton.
101

Ph thuc vo cu to, cu trc ca polyme m mi polyme

102

bn thi tit v bc sng nh sng lm t mch phn

c bc sng nh sng ch yu lm t mch v bn

t polyme
Loi polyme

thi tit tng ng.

bn thi tit ca polyme c tnh ton theo thi gian
th nghim m polyme b gim 50% bn ko t, dn
di khi t hay bn va p
Bc x t ngoi c th gy ra hin tng phn ha b mt
polyme, phai mu, mt mu, chuyn sang mu vng, vng
nu, mu nu,, suy gim cc tnh cht c l ca polyme

103

Bc sng nh
sng lm t
mch (nm)

bn thi tit
(nm)

Yu cu mt s sn
phm

Polyetylen

< 180

0,5 1,0

ng (HDPE) ~ 50 nm

Polypropylen

< 180

0,2

Polyoxymetylen

< 210

0,3

Polyvinylclorua

~220

0,5

Polyamit

~240

34

Polystyren

~270

0,1(chuyn mu
vng)

Polycacbonat

~280

0,5

Poly(phenylen oxit)

~280

<0,5

Polyuretan

~280

Poly(etylen terephtalat)

~280

ng ~ 50 nm
Ca ~ 15 nm

104

26

11/18/2014

1.2. Nhit :

1.3. m:

Nhit khng kh thp lm polyme tr nn gin, tng

Vic s dng polyme ngoi tri, m (hi m, hi nc, nc

modul n hi, gim dn di khi t, v gim bn va

ma, sng, tuyt,..) c th b polyme hp th .

Mt s polyme c kh nng ht m mnh nh polyeste,

p polyme.
Nhit khng kh cao gy suy gim tnh cht c l do tng

polyamit, polycacbonat, polyuretan,

m s gy ra phn ng thy phn, lm t cc lin kt trong

tc phn hy polyme ni chung.

Nhit khng kh cao cn c kh nng thc y cc qu
trnh phn hy polyme do cc yu t khc nh phn hy oxi
ha nhit, phn hy oxi ha quang, thy phn, phn hy do

iu kin khng c nh sng chiu lm gim tnh cht c

l v tnh cht b mt ca polyme
m cng c th phn ng vi cc cht ph gia trong polyme
nh bt mu gy hin tng phn ha, ma gy ra tri cc

vi sinh vt,...
105

Nu c tc ng ng thi ca m v bc x nh sng t
ngoi, qu trnh thy phn polyme xy ra phc tp hn vi
tc ln hn rt nhiu.

cht ph gia ra khi polyme

106

1.4. Oxi v Ozon:

Hu ht polyme phn ng chm vi tc ng ca oxi.
Nu ng thi c tc ng ca bc x t ngoi hoc nhit
khng kh cao, oxi d dng tn cng vo mch polyme,

Phn ng thy phn lm t mch polyme cng vi s to

thnh cc nhm mang mu hp th mnh bc x nh sng
t ngoi, y nhanh qu trnh oxi ha quang polyme

c bit cc polyme cha lin kt i trong phn t.

Qu trnh phn hy polyme bi oxi v ozon lm gim cc
tnh cht c l, bn nhit, bn dung mi, kh nng
nng s dng,

107

108

27

11/18/2014

1.5. Vi sinh vt:

Bi bn, khng kh bm vo mu nm mc pht trin

Polyme (ph gia ha do, cht bi trn, cht n nh, cht

chng oxi ha,) b phn hy bi vi sinh vt trong iu kin

polyme b

kh hu nng m
Yu t thc y qu trnh pht trin ca VSV
m khng kh - quan trng nht (nc chim khong
90% khi lng c th nm mc, cc phn ng sinh ha

mt mu
thay i hnh thc b mt
gim cc tnh cht

khng th thc hin c nu khng c nc)

s khuch tn PG ln b mt vt liu
mu polyme to khng ng u, khng bng phng
to kh nng ht m

Qu trnh phn hy polyme bi vi sinh vt lm vt liu

tng gin

109

110

Polymer SH: cellulose, tinh bt, polypeptide,

cellophane d b VSV tn cng
Polymer tng hp bn vi cc tc nhn SH
PMMA, PAN, CA, phenolic resin, PE, PVC cng, PIB, silicone
rubber: hon ton tr vi VSV

Polymer phn hy SH: polymer b phn hy thnh

cc thnh phn hu c bi tc ng ca VSV nh
nm mc, vi khun
Polyamide, PVC do, PCL, PVAI, cellulose nitrate, natural
rubber, polycaprolactone: nhay vi nm mc (fungi)
Nha nhit do thng c phn hy bi tc ng ca
nm mc u tin phn hy chnh Cc h vi sinh vt
khc pht trin p tcphn hy

Polymer nhy vi tc nhn SH khi a b phn hy bi

UV ct ko to thnh phn t thp, dng bt
tng b mt p xc d bi phn hy SH
Tnh bn ca polymer tng hp/tc nhn SH vn
mi trng c quan tm nghin cu
Khuynh hng dng polymer PHSH

Cu trc c cha C, N, cc thnh phn thn thin vi hot

ng VSV
k Mi trng

28

11/18/2014

VSV thng gy bnh, mi va lm h hng vt

liu PG chng vi sinh cn thit
VSV tc dng ln chu yu l cht ha do, cht
nhu ha cn st li va cht n trong nha
B mt tm PVC ha do vi dibutyl sebacate tr
nn gin do tc ng mycelia
Trong cc cht ha do, acid bo nh oleate,
cinioleate, stearate, laurate nhy vi VSV nht

C ch hot ng
C ch hot ng nh cc cht dit nm, mc.
Cc ph gia ny phi m bo: an ton, khng c
vi con ngi v mi trng.

Hai c ch hot ng c bn:

Khng ch s ti to va pht trin ca VSV

Tiu dit nm mc gim s lng VSV

Hot nh cht chng vi sinh nh hng

Nng cht khng sinh

pH, nhit
Loi polymer
nhy vi h vi sinh c th

Hot nh ca khng sinh

Biocides are preservatives used to stop their
proliferation
Cht khng sinh hot ng thng qua s chen
ngang vi qu trnh trao i cht
Tc nhn hot ng b mt nh HC mamonium
bt 4, lm v t bo. Hu ht cht khng sinh c
tc dng c ch hot ng ca enzyme
B sung = cch trn
Dng mi nht l ht pellet

29

11/18/2014

2. Nng cao bn thi tit ca polyme

Examples of commercially available biocides

2.1. S dng cc cht ph gia

Cht chng oxi ha
Cht n nh quang
Cht hp th tia t ngoi

Preservatives for use in PVC

Cht c kh nng lm tt, lm mt hot tnh cc trng thi

kch thch ca polyme
Cht che chn tia bc xa
Cht kh, phn hy hydropeoxit
118

2.2. Bin tnh polyme

ng trng ngng monome vi cc cht chng oxi ha

Thay i cu trc v bin tnh polyme, bin i ha hc cc

nhm km bn, cc nhm hot ng trong mch polyme
(hidro ha cc lin kt i,)
Phi hp v trn ln polyme c kh nng n nh quang v
bn thi tit vi mt polyme km n nh quang v km bn

2.3. S dng mng sn v vecni

Gii php kh hiu qu nng cao bn thi tit
To mng mng trn b mt polyme che chn tc ng
ca bc x t ngoi, phn x nh sng mt tri, ngn nga

thi tit
Khu mch polyme ang c s dng kh ph bin

tc ng ca cc yu t mi trng khc
Cc lp ph thng c s dng: polyvinylidenflorua

tng cng bn thi tit v cc tnh cht polyme

ng trng hp monome vi cc cht hp th tia t ngoi
(vinyl-, allyl salixylat,)

(hydroquinon, axit dicacboxylic,)

119

(PVDF), polyvinylflorua (PVF), PU,TiO2 chng kh nng bm

bi bn v t lm sch

120

30

11/18/2014

1. PG ha do

p.85
121

31

11/18/2014

H
n CH2

[ CH2

CH
Cl

H C C H

HCl

C]

Cl

Cl

H H
C C
n
H Cl

L mt loi nha cng c ho do bi ph gia ho do

(diisooctyl phtalat, tritolyl photphat, du epoxy ho,)
PVC c kh nng khng thm nc v chng chy

PVC c ng dng trong nhiu lnh vc: thay th cc vt liu xy

dng truyn thng

ng dng lm a nhc, ng nc, trn nha, khung ca nha, o

Phn hy ca PVC
120-140 oC: PVC bt u phn hy HCl

i ma, mn che trong bung tm, bc nm, bc dy cp,..

Di tc ng ca nhit v nh sng, PVC phn hu cho ra kh HCl

gy nh hng n mi trng xung quanh
H H
C C
H Cl

C C
H H

HCl

Cht ha do s dng nhiu trong cng ngh PVC (80%)(cng,

mm). Khng th gia cng nu khng c ph gia.
127

32

11/18/2014

Phu gia ha do

Ph gia ha do (plasticizer)

Dng lng, bn rn & rn

Cn tng hp vi polymer va cc thnh phn khc
khng tng hp kho gia cng
Nhim v

Nguyn tc hot ng
Cht ha do (CHD) thng c khi lng phn t thp.
To lin kt yu vi mch polymer tng khong cch gia cc

Lm hn hp linh ng, mm do, d gia cng m rng

phm vi tnh cht, ci thin tnh do nhit thp

Ci thin nh cht: linh ng, nht, phn tn PG khc

(cht n, pigment, du bi trn, cht tho khun)
Ester ca phthalate, adipate, benzoate, melliates, diphthalate
Nhc im: d di chuyn ra ngoi, cn thn khi p xc vi
thc phm
ng dng: to mng mng, film, ng, o ma, mn

mch gim tng tc gia cc mch tng linh ng ca i

phn t vt liu mm do.
Polymer tinh th, CHD ch tc ng ln vng v nh hnh.

L thuyt bi trn

L thuyt ha do

Cc i phn t chuyn ng tng i vi nhau s

Thuyt bi trn
Thuyt gel
Thuyt th ch t do

hin din ca cht ha do s bi trn cc mt phng trt

ni

131

33

11/18/2014

L thuyt gel
nha c cu trc dng t ong vi cc im tng tc gn

L thuyt th tch t do

nhau. Khi chu tc dng ca ngoi lc rt kh xy ra cc di

chuyn bn trong cu trc
S hin din cht ha do s b gy cc lk v che chn
cc v tr lin kt trong cu trc bng cch solvat ha cc
im lin kt, khi polyme trng v hn, cc lin kt gia
cc mch hon ton ph v gim cng ca cu trc

polyme
Tng s lng hoc chiu di ca mch nhnh (ha do

gel
Cht ha do c nh hng n kh nng trng ca gel
v h tr cho q/t di chuyn cc p/t polyme lm tng s
mm do ca polyme

Khng Cht ha do

Tng th tch t do lm tng s vn ng ca phn t

ni)
Tng s vn ng ca cc dy bng cch gim cn tr
khng gian v gim tng tc gia cc ph/t (ha do ni)

vi Cht ha do

a vo polyme mt hp cht thch hp c trong lng

phn t nh hn nhng to ra c cc hiu qu trn (ha
do ngoi)

C ch ha do
Ha do gia cc cu trc
Th ch tng = th ch phn phn t polymer + khong trng gia cac chuoi.
Trng thi thy tinh: s chuyn ng chui b ng cng + th ch t do c
nh kch thc, phn b khng thay i khng khng gian mch
chuyn ng
Ti Tg, phn t nhn u nng lng khong trng gin n phn t bt u
dao ng
Trn Tg: cc phn th ch gin n tng khong trng cho cc phn t chuyn
ng mch linh ng gd mm cao,

cht ha do c i lc KHNG CAO vi polyme CHD

khuch tn vo polyme v phn b gia cc cu trc cu
trc xa nhau hn v linh ng hn Tg gim

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Ha do bn trong cu trc

Mt s chc nng vt l ca cht ha do

cht ha do c i lc cao vi polyme Phn t CHD

phn tn vo bn trong cc b tng linh ng ca

Gim nhit gia cng, gim dnh khun, tng tnh nhn,
ci thin tnh cht chy (i vi sn)

mch phn t polyme

(1): ha do bn trong b

Lm mm nha, gim modun, gim bn ko, tng

Tg gim lin tc khi tng

hm lng cht ha do
(2): ha do gia cc cu
trc Tg gim n mt gi

gin di, tng bn rch, tng do, tng bn va

p, tng khong nhit s dng, ci thin s trt hoc
gim ma st, ci thin ngoi quan b mt, bng, gim

tr xc nh
nhit thy tinh ha

nh hng ca CHD n nhit thy tinh ha Tg v

nhit chy Tf
gim Tg l thc o hiu

nh hng ca cht ha do n tnh cht c l

hm lng CHD thm vo thp (<8%) CHD xen vo gia
cc cu trc tng linh ng ca cc cu trc , tng s nh
hng tng h ca mch bn ca polyme tng

ng ha do i vi cc loi
polyme cng.
Tng hm lng CHD
Tg, Tf , nu tng qu
nhiu hm lng cht ha
do Tf gim mnh thu

thm CHD vo vi hm lng ln CHD chui vo bn trong

cc cu trc lm cho mch tr nn qu mm bn ca
polyme gim
tng hp gii hn: Hm lng ti a cht ha do m ti
chng vn cn th hin hiu qu kh nng ha do. Khi tng

hp phm vi nhit s

vt mc gii hn ny, hh s tr nn d th v cht ha do

dng

khng cn tc dng

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Gin c nhit ca polyme c i phn t cng

1. Khng CHD; 2-4: hm

lng CHD tng. 5: dung
dch polymer trong CHD.
|a: trng thi thy tinh. b:
tt. mm cao. c: tt chy nht
Polyme c i phn t rt
cng, trng thi mm cao
hon ton khng c hoc
th hin rt yu.
CHD ch c tc dng lm gim Tg - lng ho do cng nhiu th Tg
cng gim mnh; xut hin hoc m rng khong nhit mm cao
ca polyme ( ng 1,2,3)
Do tng tc mnh gia cc phn t CHD v cc nhm nguyn t
trong i phn t
Tip tc tng CHD, mm do k tng thmng cong c nhit
tng t polymer mch mm do (4,5)

trng thi mm
cao bin mt
tng ng vi s
chuyn bin t
polyme do ho
sang dung dch
polyme trong
cht ho do

polyme c cc phn t mm do

Polyme c cc phn t mm do a cht ho do tng linh ng

ca cc n v ng hc gim Tg v nhit chy nht (Tf), ng thi lm
cc nhit ny gn li vi nhau.
V vy vng trng thi mm cao ca polyme chuyn sang vng c nhit
thp hn, ng thi khong nhit mm cao nh li v moun n hi
gim xung.
Khi lng CHD ln, trng thi mm cao bin mt (ng 4)

Effect of (0) tricre syl phosphate, (X) 2Effect of tricresyl phosphate on the brittletough temperature (Tb) of plasticized PVC
(WI = weight fraction of the plasticizer)

ethylhexyl phosphate and (.) Mesamol on

the glass transition temperature (Tg ) of
plasticized PVC

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Action of a polar aromatic

plasticizer on PVC chains.

Action of a polar aliphatic

plasticizer on PVC chains

Cht ha do mch thng c hiu qu ha do cao hn vng

thm
t cng knh.
Phn phn cc c th bi che chn gim lin kt lin phn
t

Cc c trng ca CHD theo cu trc ha hc

Phthalic Acid Esters: Di(2-ethylhexyl) phthalate hoc

CHD mch thng c cc so vi CHD c vng

thm
kho trn vi polymers d b tch khi polymer
Hiu qu ha do cao hn CHD c cu trc vng thm
Vng nhit ha do rng hn hiu qu ha do
nhit thp
i vi PVC, thm tc dng gim mu

Dioctyl

phtalate (DOP) and diisooctyl phthalate (DIOP) c s dng

rng ri gia cng PVC va copolymer ca PVC vi vinyl acetate
or propene

Cn i gia tnh ha do va cc tnh

cht khc
C i lc cao vi polymer
C kha nng solvate cao
Duy tr c linh ng cho sn
phm tt nhit thp
bay hi thp va tnh khng nc tt

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Butyl octyl phthalate (BOP), butyl decyl phthalate (BDP), and

butyl benzyl phthalate (BBP) c trn ln t c tnh
do c trng nh mong mun va bin tnh trong qu trnh
ch bin PVC blends. Cc cht ha do ny c tnh solvat tt

Phosphoric Acid Esters: trioctyl phosphate (TOP), diphenyl 2ethylhexyl phosphate, and tri(2-ethylhexyl) phosphate are used as
flame retardants as well as plasticizers. They have a low volatility
resist oil extraction well.

va c dng iu chnh nht va thi gian chy cho sn

Polyfunctional Fatty Acid Esters: Dioctyl sebacate (DOS),

phm c phm cht cao.

dibutyl sebacate (DBS), diisobutyl adipate (DIBA), monoisopropyl

citrate, stearyl citrate, triethyl citrate (TEC),... DOS c dng

Dibutyl phthalate (DBP) c s dng chu yu cho verni va

nhiu nht do hiu qu ha do cao, bay hi thp, va khng

keo dn gc cellulose. Tuy nhin, chng KHNG tin dng

nc dung dch.

ha do PVC v kha nng bay hi cao, nhng chng vn

DBS, DIBA, and monoisopropyl, stearyl, and triethyl citrates

c s dng trong hn hp cht ha do lm tng kha

c nghi s dng trong thnh phn nha dng trong bao

nng solvate.

b thc phm

CHD cao phn t: oligomers hoc polymers Mw~ 600 to 8000:

poly(ethylene glycol), polyesters, and polyepoxides.
Poly(ethylene glycol) dng ha do proteins, gelatin.
Dioctyl sebacate (DOS)

Polyesters: hiu qu khng tch CHD dng trch ly bng

du, nc, cht hot ng b mt. ng dng: PVC c bit
PVC-based blends and in nitrocellulose varnishes

triethyl citrates

Antiplasticization
B sung mt lng nho cht ha do (<15% khi lng) c th
to ra hiu ng gin, d gy v cho nha and some of their
mechanical properties such as impact resistance, ductility, and

diisobutyl adipate (DIBA)

so on, may be reduced

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Nng lng solvate ca CHD cao the greater the fragility

effect and the more extended is the effect to higher
concentrations of plasticizer

Tn tht cht ha do
Do bay hi
B trch ly bng dung mi, nc, du khi tip xc vi nha

Volatility of some plasticizers in plasticized PVC

Tensile strength of PVC as a function of plasticizer concentration.

Critical concentration for DOS = A; DOP = B; TCP = C

PG bi trn va tho khun

2. PG bi trn va tho khun

Lubricants and Mold-Release Agents
Thuc loi PG tr gia cng
Nha nhit do thng c gia cng nhit cao.
nht chy k t yu cu gia cng b sung cht bi
trn (lubricant)
B sung cht bi trn lng thp tc gia cng
hoc ci thin tnh cht b mt

S dng hiu qu trong cng ngh c, p, nn sn

xut

PVC,

ABS

(acrylonitrile-butadiene-styrene

terpolymer), PS, PMMA, CA (cellulose acetate), PTFE

Some examples of lubricants: stearic acid and its Ca, Li,
Ba, AI, Pb, etc ., salts, natural waxes, microcrystalline
paraffins, mineral and vegetable oils
Lng s dng PG bi trn trong nha A: PVC,
58.6% by weight. B: Polyolefins , 14.5% by weight.
C: PS and its copolymers, 20.9% by weight. D:
Other polymers, 6% by weight

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Chc nng
Ngn cn khuynh hng bm dnh trn b mt kim loi
bi trn ngoi (external lubrication). Cht bi trn
thng khng tan trong polymer
Ci thin nh chy t do ca polymer bi trn ni
(internal lubrication), cht bi trn ha tan tt vi
polymer

PPA cho PVC

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PPA: polymer processing aids

La chon cht bi trn

Tng tc gia cht bi trn va PG khc (cht n, cht n

Phn loi CBT theo chc nng

nh)
Cht bi trn nn c tan t vi polymer c hiu qu bi

Bi trn ngoi: phn t CBT c tan trong polymer

trn & c s gn kt vi phn t polymer chng k b tch ra

thp d b tch khi khi polymer phn lp gia

khi nha

polymer va b mt kim loi ca thit b gia cng

Thng l hydrocarbon mch di va c nhm c cc

Cn la chn CBT c nhit nng chy phu hp i vi qui

Bi trn ni: phn t CBT c i lc cao vi phn t

trnh gia cng. VD CBT n hn hp PVC 165 oC c Tm ~

polymer lm gim nht polymer trng thi

100-120 oC

chy

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Tnh cht c s cho cht bi trn

Xa phng kim loi nh stearates i lc yu vi tt

Action of various lubricants

ca

polymers bi trn ngoi.

Acid bo mch di, ru, amides i lc cao vi polymer c
cc (PVC, polyamide) bi trn ni; i lc yu vi
polymer khng cc (polyolefins) bi trn ngoi
Dialkyl Ester mch di: i lc trung bnh vi hu ht polymer
bi trn ni & bi trn ngoi cn bng tnh nht
Sp paraffin khi lng phn t cao: bi trn ngoi cho
polymer phn cc (i lc thp); bi trn ni cho polyolefins (i
lc cao)

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