Polymer Synthesis

CHEM 421

• Odian Book
Chapter 5-2
 Polymer Synthesis
CHEM 421

Cationic Polymerization
 Cationic Polymers Polymer Synthesis
CHEM 421

Commercial and Technological Significance

Chemical Name Trade Name Formula
CH3
• Polyisobutylen Vistanex, Oppanol CH2 C
CH3
CH3
• Isobutylene-isoprene copolymer CH2 C
CH3
CH2 C CH CH2
and chlorinated copolymer CH3

~98% ~2%
Butyl Rubber
and Chlorobutyl
CH2 O
•Polyoxymethylene Delrin
CH2 O C C O
Trioxane-epoxide copolymer Celcon R
~2%
 Cationic Polymers Polymer Synthesis
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Commercial and Technological Significance

Chemical Name Trade Name Formula
CH2Cl
•Polyepichlorohydrin Hydrin Rubber
CH2 CH O
Lycra or Spandex
•Poly(THF) or Poly(tetramethylene oxide)
CH2 CH2 CH2 CH2 O

CH2Cl
•Polybischloromethyl Oxetane
CH2 C CH2 O
Penton CH2Cl
Cationic Polymerizations Polymer Synthesis
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C X R = electron releasing group

R'

R, R’= CH3 CH3 Poly(isobutylene)

O CH3 H
CH3 H
C2H5 H
R H

H
 Cationic Polymerization Polymer Synthesis
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…Also cyclics
O
O
O O

CH2Cl O O

Hydrin Rubber
Poly(oxymethylene)
Delrin
 Cationic Polymerization Polymer Synthesis
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1) Priming H
HX
or or X
RX R

HCl AlCl3 H AlCl4

2) Initiation Step

R H2C C R CH2 C
 Cationic Polymerization Polymer Synthesis
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3) Propagation

R CH2 C H2C C R CH2 C CH2 C

4) CM

C H2C C C C H3C C
H
 Initiators Polymer Synthesis
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A) Bronsted Acids

HA H2C C H CH2 C A
ionic

A  can not be too nucleophilic

 HCl is not very good

O CH3 C A

CH3 S OH covalent
O
Methanesulfonic acid
 Initiators Polymer Synthesis
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B) 1)Lewis Acids
SnCl4, AlCl3, TiCl4, BF3

R3Al, R2AlCl, RAlCl2

2) Co initiator
BF3 H2O HOBF3 H

RCl SnCl4 R SnCl5

RCl AlCl2R R AlCl3R

 Auto Ionization Polymer Synthesis
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2 AlBr3 AlBr4 AlHBr2

BF3 H2C C

Bone dry
 Chain Transfer Polymer Synthesis
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More Important in Cationic than in Anionic

1) To Monomer
CH2 CH HSO4 CH2 CH

CH CH CH3 CH HSO4
 Chain Transfer Polymer Synthesis
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2) Ring Alkylation on Solvent

CH2 CH HSO4
CH2 CH
H
CH2 CH

CH3 CH HSO4
 Chain Transfer Polymer Synthesis
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3) Ring Alkylation on Polymer

CH2 CH CH2 CH HSO4
 Chain Transfer Polymer Synthesis
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4) Hydride Abstraction from Polymer

H
CH2 CH HSO4 CH2 C

CH2 CH2 C HSO4

 Poly(isobutylene) Polymer Synthesis
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Low MW (Mn<50,000 g/mol)

Liquids  adhesives
caulking
sealants
motor oils -  important

Tpzn= 0 to – 40 oC w/AlCl3
 Poly(isobutylene) Polymer Synthesis
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High MW (Mn= 50,000-5,000,000)

Elastomeric

Tpzn= –100 oC w/ AlCl3

w/ 1-5 % isoprene (to vulcanize)

Methylchloride as solvent
CH3 CH3
 Slurry
CH2 C CH2 C CH CH2

CH3
Butyl Rubber Advantages Polymer Synthesis
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• Lower Temp Capability

– -50 oC NO TM
– -70 oC = TG
• More Resistant to Ozone
• Very Low Gas Permeability
 inner tire tubes
Temperature Dependence Polymer Synthesis
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_
Xn

1/T
Temperature Dependence Polymer Synthesis
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As T  Termination  and CT 

Break

 change in mode of CT

 [ions] vs [ion pairs]

 Complications Polymer Synthesis
CHEM 421

CH
R A
H2C
H2C CH

CH CH3
CH CH3

CH3
CH3
3-methyl-1-butene

CH3
A
CH2 CH2 C

 As T  , % isomerization  CH3
 Complications Polymer Synthesis
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3-methyl-1-butene
H2C CH

CH CH3
Temp %isomerization
-130 oC 100 %
CH3
-100 oC 70 %

CH3

CH2 CH CH2 CH2 C

CH CH3
CH3

CH3
Isomerization Polymer Synthesis
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H2C CH

CH2

CH CH3

CH3
 Cationic Living Polymer Synthesis

Polymerization CHEM 421

HI/I2
CH H3C CHI
H2C

OEt
OEt -30 OC
n-hexane
H3C CHI I2
H3C CH I3
OEt
OEt

H3C CH

OEt