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第 6 章 离子聚合 PowerPoint PPT Presentation


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第 6 章 离子聚合. 6 . 2 阴离子聚合. 反应通式:. :阴离子活性种;. : 反离子,一般为金属离子( Metallic Ion )。单体插入离子对引发聚合。. 与阳离子聚合不同,阴离子聚合中,活性中心可以是 自由离子、离子对,甚至是处于缔合状态的阴离子。. 阴离子聚合应用比阳离子多,应用广泛。由于具有活性无終止的特点,可以制备嵌段共聚物。. 1.阴离子聚合单体. 阴离子聚合的单体可以粗分 烯类 和 杂环 阴离子聚合单体必须含有能使链增长活性中心稳定化的 吸电子基团。 带吸电子取代基的烯类单体原则上容易阴离子聚合. 带吸电子取代基的烯类单体

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第 6 章 离子聚合

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6

6


6

6.2

Metallic Ion


6

1.


6


6

-


6


6

p-

p-


6

A

B


6

C

D

a-


6

2.


6

-

1


6

-

THF

-

-


6

  • NaNH2KNH2

2


6

KNa

K Na Li Mg Al

0.8 0.9 1.0 1.2~1.3 1.5

KC NaC LiC MgC AlC


6

Mg

RMgX

Mg-C


6

3

R3PR3NROHH2O


6

3.


6


6

aABCD

CD

b

BCD

cCD

dd


6

4.

  • H+


6

100%


6

1956THF

Living Polymerization

100%

Living Polymer

100%

  • THF100


6

  • Stoichiometric


6

  • CO2


6


6

5.

  • 104107

    kp

    [M] 103 ~ 102 mol / L

    [M] 109 ~ 107 mol / L

    [M] > [M] 104 ~ 107


6

(1)

:

Rp = kp [M] [M]

kp

[M]

[M] = [ C]

27


6

Rp = kp [C] [M]

kp

[C]

ln[M0]/[M]=kp[C]t

M0

[C]


6

(2)


6

=/n=[M-]/n

[C]

n

n = 2

n = 1

100


6

StTHF= 1. 06 ~ 1. 12


6

1

2/

3

4


6

6.

(1)


6

P-C+ P-


6

P-C+ P-

kp

K

Rp = kp [M] [M]


6


6

kp[M-]1/2

K


6

(2)

102103


6

3

820 kJ/mol


6

7 .

GPC


6

StBStBSt

M1M2


6

6.3


6

1.


6

(1)-


6

-


6

820kJ / mol

-


6

p-

(2)


6

-

(3)


6

1

2

Lewis

2.


6

(1)

H2SO4H3PO4HClO4 CF3COOHCCl3COOH

H

  • H


6

  • XHCl

  • HSO4 H2PO4

  • HClO4CF3COOHCCl3COOH


2 lewis

Lewis

BF3 , AlCl3,SnCl4 , TiCl4, PCl5, ZnCl2

Lewis

(2)Lewis

Lewis


6

H2OROHHXRCOOH

RXRCOX(RCO)2O

BF3

-


6

  • ,

    BF3 > AlCl3 > TiCl4 > SnCl4

    BF3

    50 1. 5 1


6

Rp

,

  • Rp


6

(3)

I2


6


6

3 .

(1)

LewisCRH


6

:

Ei = 8.4~21 kJ/molEi = 105150 kJ/mol


6

(2)


6

  • 3--1-:


6

(3)


6


6


6


6

4 .

SnCl4

,


6

[c]

[RH]

[M]


6

Rp


6


6


6

5.

  • ,

(1)


6

(2)

  • Cl

I2SnCl4-H2OHClO41,2 -250.0030.421.70 L/mol.s


6

(3)


6

6.4

Rp

Lewis


6


6

f

[M]Rp

RpXn

CS2SO2CO2

(THF)


6

50 80

70 100

Rp [I] 1/2

Rp [C]


6

DPPH

CO2


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