Chuong 1 Phan Ung Trung Hop

7/30/2019 Chuong 1 Phan Ung Trung Hop

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1

Ho hc polime


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Chng 2: Trng hp gc

nh ngha: Trng hp l phn ng cng hp lintip nhiu phn t nh (monome) to thnhphn t ln (polime).

Phn ng trng hp khng gii phng cc snphmph phn tnh, cc mt xch cs l ccng thnhphnvi monome ban u.

Phng trnh tng qut:


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Phn loi phn ng trng hp

Da vo bn cht ca cc trung tm hot ng tac th chia phn ng trng hp ra thnh 2 loi:

- Phn ng trng hp gc

- Phn ng trng hp ion

Trong thc tphn ng trng hp gcphbinhn,phnng ny csdngtnghp ccpolime thng thngnh: cao su, si,chtdo,


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iu kin phn ng trng hp gc

Cc monome tham gia phn ng phi c lin kt i

Cc monome c cu to vng


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1. Gc t do1.1. nh ngha

Gc t do l nhng nguyn t hay nhm nguynt hoc mt phn ca phn t c cha in tcha ghp i

Gc t do c to thnh do s phn ct ng lyca cc phn t


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1.2. Hot tnh ca gc t do

Gc t do c hot tnh cng mnh th mc nnh in t cng cao.

Hot tnh ca cc gc c th sp xp nh sau:

Ti sao ta c th sp xp nh trn?


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1.3. Cc phn ng ca gc t do


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2. Cch phn ng trng hp gc2.1. Giai on khi mo2.1.1.Khi mo nhit


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2.1.2. Khi mo quang ho

u im c th tin hnh nhit thp C tnh chn lc cao Tnh chn lc ph thuc vo bc sng nh

sng tc ng


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2.1.3. Khi mo bc x Khi chng ta dng cc tiabcx, , .. Hoc cc dng

int c nnglnglnchiutrctip vo monome ths to thnh cc gc t do hotngkhi mo cho qutrnh trng hp.

Nhcim l khi tng dung mi, gct do tng nn dxyraphnngngtmch


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2.1.4. Khi mo bng ho cht y l phng php khi mo phbin trong

nghin cu v snxut polime. Ccphnng nythng s dng cc hp cht khng bn nhpeoxyt (-O-O-), cc hpcht azo (-N=N-) cc lin

kt ny d phn hu khi gpnhit khng caolm


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V d phn ng trng hp stiren


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2.2. Giai on pht trin mch

Giai on ny xy ra mtlot ccphnngcnghpgiagcang pht trinvi monome tothnh cc gclnhn


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2.3. Giai on ngt mch Sngtmch l qu trnh bo ho intcagc

t do v cagcangln. Cchphnngnhsau:


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3. Cc yu t nh hng n qu trnh trng hp3.1. Nng cht khi mo

Tc trng hp Vp t l thun vi nng cht khi mo trng hp trung bnh t l nghch vi nng cht khi mo


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3.2. nh hng ca nhit


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3.3. nh hng ca p sut

Nhn xt:


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4. Qu trnh trng hp chuyn ho


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5. S chuyn mch v nh hng ca n

Ngoi 3 giai on chnh nh trn cn xy ra nhiutrng hp chuyn mch nh hng ti tc

phn ng trung bnh


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Phn ng chuyn mch c th xy ra vi ccthnh phn c trong h phn ng nh: monome

(M) , polime (Pm) , dung mi (S), cht khi mo (I)


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Phn loi tc nhn A1. A l cht chuyn mchNu gc t do A. C hot tnh tng ng vi gc R.th A.c th tham

gia phn ng


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2. A l cht lm chm

Cht lm chm thng dng nh: CCl4,C2H2Cl4, cc mercaptan, axit triglycolic

Cht lm chm c ng dng rng ri trongcng nghip tnghp cao su iuchnhkhilng mch polime. Hm lng cht iu khincsdngkhong 2-6% so vi monome.


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3. A l cht c ch

Cht c ch c a vo lm dng hn qutrnh trng hp hoc hn ch ng k qu trnhphn ng.


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6. Cu trc khng gian ca mch polimetrong trng hp gc


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7. Trng hp ion

Phn ng c th xy ra theo 2 c ch l:cation v anion.

Phn ng khng s dng cht sinh gc m

dng cc cht xc tc c kh nng sinh ion, vth phn ng ny cn gi l phn ng trnghp xc tc

Phn ng c tc cao, nhit phn ngthp mt vi trng hp xy ra nhit -50n -130oC


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7.1. Trng hp cationPhn ng xy ra theo 3 giai ona. Giai on kch thch s dng cc cht xc tc Fridel-Craft

nh AlCl3, SnCl4, BF3, TiCl4,... V dung mi l cc chtd cho H+nh: nc, ru, axit,

SnCl4 + HO2 H [SnCl4OH]

+ -

H [SnCl4OH]

-CH

2CH

OOC-CH3

CH

2

H C

OOC-CH3

H [SnCl4OH]

-+

+ +


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b. Giai on pht trin mch

..c. Giai on ngt mch

CH

2

H C

OOC-CH3

H [SnCl4OH]

-CH

2CH

OOC-CH3

CH

2

CH3

CH

OOC-CH3

C

OOC-CH3

H [SnCl4OH]

-+

+ +

CH

2

CH3

CH

OOC-CH3

C

OOC-CH3

H [SnCl4OH]

-

CH3

CH

OOC-CH3

CH

CH

OOC-CH3

H O2

SnCl4

CH3 C

H

OOC-CH3

CH2

C

H

OOC-CH3

OH

SnCl4+

+

+

+


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7.2. Cc yu tnh hng n trng hp cation

a. nh hng ca cht xc tc b. nh hng ca cht xc tc v cht ng xc tc

c. nh hng ca bn cht monome

d. nh hng ca phn cc ca mi trng e. nh hng ca nhit


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7.2 Trng hp anion Phn ng trng hp cc hp cht khng no lin

quan n s hnh thnh cacbanion do tng tcgia monome vi anion ca cht xc tc

Cc monome thng cha cc nhm ht e lm

phn cc lin kti vbn ho cacbanion CH2=CH-CN, CH2=CH-NO2, CH2=CH-C2H5

Cht xc tc thng dng l nhng cht cho

electron nh: baz, kim loi kim, hydrua,amitdua ca kim loikim,hpchtckim.


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Cch1. Giai on kch thch:

2. Giai on pht trin mch:

3. Giai on tt mch

An + CH2

CH

X

CH

2

CH

X

An --

+ CH2 C

H

X

CH

2

CH

X

An CH

2

CH

X

-

CH2

CHX

An

-

+ CH2 CH

X

CH

2

CH

X

An CH

2

CH

X

-

CH

2

CH

X

An-

n [ ]n

++C

H2

CH

X

An CH

2

CH

X

-[ ]

nH C

H2

CH

X

An CH

2

C

H2

X

[ ]n


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Quy trnh tng hp polime

Nhp nguyn liu v ho cht cn thit Gia nhit n nhit phn ng Tin hnh tng hp Loi b phn d Lm ngui phn ng Xut liu


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8. Cc phng php tin hnh trng hp8.1. Trng hp khi


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8.2. Trng hp dung dch

Monome tan c trong dung mi Thu polime bng phng php kt ta hoc

chng ct li

Trnh c cc nhc im ca trng hpkhi

Trong qu trnh trng hp c th xy ra phn

ng chuyn mch vi dung mi Khi lng trung bnh thp


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8.4. Trng hp nh tng

8.5. Trng hp huyn ph

8.6. Trng hp pha kh


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Chuong 1 Phan Ung Trung Hop