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3 Co- and Terpolymers of Tetrafluoroethylene and Non-fluorine-containing Alkenes

3 Co- and Terpolymers of Tetrafluoroethylene and Non-fluorine-containing Alkenes

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250



Chapter 9

NB-F-OH



TBA



TFE

F2

C



F2

C



H2

C



H

C



OC(CH 3)3



O

OCH2C(CF3)2OH



Figure 9.23



F2C



CF2



Reaction scheme for the synthesis of poly(TFE-ter-NB-F-OH-ter-TBA).

Reproduced from ref. 211.



F



F



F



F



+

Radical Initiator

F

F3C



y



x



CF3

OH



F

F3C



CF3

OH



Figure 9.24



Polymerization scheme for the TFE–norbornene-based materials.

Reproduced with permission from ref. 212 and 213.



compositions are given in Table 9.11. Some of these materials have also been

used to make photoresist materials. An example is the use of a 2-heptanone

solution of the methoxymethyl ether-protected poly(TFE-co-TCN-di-F-OH)

and triphenylsulfonium nonaflate. Other photoresist materials have been

prepared in a similar way by using the methoxymethyl ether-protected

poly(TFE-co-NB-di-F-OH) and methoxymethyl ether-protected poly(TFE-terNB-F-OH-ter-NB-di-F-OH).214

Two important studies215,216 involved a series of co- and terpolymers of

TFE with different monomers such as cyclopentene (CP), cyclooctene (COC),

2,3-dihydrofuran (DHF), 3,3-dimethylcyclopropene (DMCP), dicyclopentene

(DCP), tert-butyl a-fluoroacrylate (TFBA), 2-cyclopentene-1-tert-butyl acetate

(CPBA) and HOC(CF3)2-functionalized cyclopentene (FCP). The monomers

are shown in Figure 9.26.

All of the polymerizations were carried out in HCFC-141B as solvent with

TCP [bis(4-tert-butylcyclohexyl) peroxydicarbonate] as the initiator. A full

list of the final compositions of the polymers and their experimentally

determined absorption coefficients are given in Table 9.12. The poly(TFEco-DMCP) and poly(TFE-co-DCP) copolymers were not tested for their

absorption coefficients, but they are included in the table in order to account

for the materials being prepared.215



OCH 2C(CF 3)2OH

H



NB-di-F-OH (B)



O



NB-F-OH (A)



O

O



OCH 2C(CF 3)2OH



O



H



HADA (F)

H



MADA (G)



H



CH 2OCH 2C(CF 3)2OH



CF2



OH

OH



TCN-di-F-OH (C)

CH 2OCH 2C(CF 3)2OH



H



CF2



O



TCN-(F2)(F2) (E)



OH

O



2HeTA (J)

CO2C(CH 3)3



O



PinAc (I)

O



CH 3



TCN-(CO2-t-Bu)(CO2-t-Bu) (D)

CO2C(CH 3)3



O

O



t-BuAc (H)



Figure 9.25



CH 3



H 3C



OH

H 3C



Monomers used in the preparation of co-, ter-, quad- and pentapolymers of TFE.

Adapted with permission from A. E. Feiring, M. K. Crawford, W. B. Farnham, J. Feldman, R. H. French, C. P. Junk, K. W.

Leffew, V. A. Petrov, W. Qiu, F. L. Schadt III, H. V. Tran and F. C. Zumsteg, Macromolecules, 2006, 39, 3252. Copyright (2016)

American Chemical Society.207,214



Research and Non-major Commercial Co- and Terpolymers of Tetrafluoroethylene



OCH 2C(CF 3)2OH



251



252



Chapter 9

O

O

O



DHF



CP



CPBA



DMCP



COC

CF3



O



OH

O



Figure 9.26

Table 9.11



CF3



TFBA



DCP



FCP



F



Monomers co- and terpolymerized with TFE.215,216

List of copolymers made and their compositions (each row in the table

denotes a different example in the patent).207,214,a,b



Copolymer



Compositionc



Poly(TFE-co-C)

Poly(TFE-co-B)

Poly(TFE-ter-A-ter-B)

Poly(TFE-ter-A-ter-B)

Poly(TFE-ter-B-ter-G)

Poly(TFE-quad-B-quad-I-quad-F)

Poly(TFE-quad-E-quad-B-quad-H)

Poly(TFE-quad-E-quad-B-quad-D)

Poly(TFE-penta-E-penta-B-penta-H-penta-J)

Poly(TFE-quad-B-quad-J-quad-F)



EA: C ¼ 39.57; H ¼ 3.07;

MP: 54–46

MP: 55–34–11

MP: 55–26–18

MP: 23–33–45

EA: C ¼ 46.72; H ¼ 4.66;

MP: 32–26–10–32

MP: 48–24–10–18

EA: C ¼ 45.61; H ¼ 4.02;

EA: C ¼ 46.42; H ¼ 4.78;



F ¼ 44.74



F ¼ 30.69

F ¼ 37.09

F ¼ 31.61



a



A ¼ NB-F-OH, B ¼ NB-di-F-OH, C ¼ TCN-di-F-OH, D ¼ TCN-(CO2-t-Bu)(CO2-t-Bu), E ¼ TCN-(F2)(F2),

F ¼ HADA, G ¼ MADA, H ¼ t-BuAc, I ¼ PinAc and J ¼ 2HEtA.

Adapted with permission from A. E. Feiring, M. K. Crawford, W. B. Farnham, J. Feldman,

R. H. French, C. P. Junk, K. W. Leffew, V. A. Petrov, W. Qiu, F. L. Schadt III, H. V. Tran and

F. C. Zumsteg, Macromolecules, 2006, 39, 3252. Copyright (2016) American Chemical Society.

c

EA, elemental analysis (%); MP, molar percentage (mol%).

b



Table 9.12



Final compositions of co- and terpolymers reported.215,216,a



Copolymer



Composition/mol% of

the respective monomer



Absorption coefficient

(at 157 nm)/mmÀ1



Poly(TFE-co-CP)

Poly(TFE-co-DHF)

Poly(TFE-co-COC)

Poly(TFE-co-DMCP)

Poly(TFE-co-DCP)

Poly(TFE-ter-DHF-ter-TFBA)

Poly(TFE-ter-CP-ter-TFBA)

Poly(TFE-ter-CP-ter-TFBA)

Poly(TFE-ter-CP-ter-TFBA)

Poly(TFE-co-CPBA)

Poly(TFE-co-FCP)



50–50

50–50

52–48

61–39

51–49

23–33–44

15–40–45

26–34–40

7–52–41

50–50

50–50



0.9

1.0

1.1





3.5

3.6

3.7

4.1

3.2

0.7



a



CP ¼ cyclopentene, COC ¼ cyclooctene, DHF ¼ 2,3-dihydrofuran, DMCP ¼ 3,3-dimethylcyclopropene, DCP ¼ dicyclopentene, TFBA ¼ tert-butyl a-fluoroacrylate, CPBA ¼ 2-cyclopentene-1tert-butyl acetate and FCP ¼ HOC(CF3)2-functionalized cyclopentene.



Research and Non-major Commercial Co- and Terpolymers of Tetrafluoroethylene



253



9.7 Future Work and Conclusions

This chapter contains important information regarding non-commercial coand terpolymers of TFE that have been studied mostly in the past 20 years. It

is clear that the variety of these materials is of equal magnitude to those that

have been commercialized on a large scale, but further work remains to be

done in exploring different monomers, adding other functional groups to

the polymers and using other post-polymerization processes to enhance

the physical and/or chemical properties of the materials. From co- and

terpolymers of TFE including vinyl ethers (as discussed in Section 9.2) to

those of cyclic monomers and TFE-based photoresist materials (as shown

in Section 9.6), it is clear that the applications of these polymers are vast,

regardless of the comonomer used.



Table 9.13



Reactivity ratios for copolymers of TFE.a,b



Copolymer



r1(TFE)



r2



Ref.



Poly(TFE-co-NBVE)

Poly(TFE-co-VAc)

Poly[TFE-co-IB]

Poly(TFE-co-VF)



0.005

À0.009

0.005

0.06

0.05

3.73

0.28

0.39c

1.03d

2.47

1.57

0.18

0.80

0.75

1.0

0.82

0.12

0.21

0.37

0.58

15.9

11.5

1.14

5.0

3.0

10.02

10.81



0.0015

0.95

0.021

0.30

0.27

0.23

0.32

3.37c

0.87d

0.41

0.45

0.20

1.10

1.04

1.0

0.24

5.0

2.3

5.4

0.09

0.059

0.17

0.46

0.10

0.15

0.31

0.23



42

109, 111

119

123

124

130

123

131c

131d

159

159

161

123

168

169

168

171

172

164

164

173

173

123

179

180

189

189



Poly(TFE-co-VDF)



Poly(TFE-co-FA1)

Poly(TFE-co-FA3)

Poly(TFE-co-FAc)

Poly(TFE-co-CTFE)

Poly(TFE-co-BTFE)

Poly(TFE-co-CH2¼CHCF3)

Poly(TFE-co-CH2¼CHC3F7)

Poly(TFE-co-CH2¼CFCF3)

Poly[TFE-co-CH2¼C(CF3)2]

Poly(TFE-co-trans-CHF¼CHCF3)

Poly(TFE-co-cis-CHF¼CHCF3)

Poly(TFE-co-CF2¼CHF)

Poly(TFE-co-MTFP)

Poly(TFE-co-PPOTESF)

a



NBVE ¼ n-butyl vinyl ether, VAc ¼ CH2¼CHCO2CH3, IB ¼ CH2¼C(CH3)2, VF ¼ CH2¼CHF,

VDF ¼ CH2CF2, FA1 ¼ CF2¼CFCH2OH, FA3 ¼ CF2¼CFC3H6OH, FAc ¼ 4,5,5-trifluoro-4-penten-1acetate, CTFE ¼ chlorotrifluoroethylene, BTFE ¼ bromotrifluoroethylene, TrFE ¼ CF2¼CHF,

MTFP ¼ CF2¼CFCO2CH3, PPOTESF ¼ CF2¼CFCF2OCF2CF2SO2F.

b

Adapted from Elsevier Books, B. Ameduri and B. Boutevin, Well-Architectured Fluoropolymers:

Synthesis, Properties and Applications, 187–230, Copyright 2004, with permission from Elsevier.12

c

In the absence of CO2.

d

In the presence of CO2.



254



Chapter 9



Furthermore, one of the most important properties (especially for industrial or production purposes) is the reactivity ratio of TFE to that of any

of the monomers discussed or excluded in this chapter. Since reports of

reactivity ratios do not appear in the literature very often (perhaps because

of confidentiality), that leaves an open opportunity for researchers to investigate them. The available data for reactivity ratios of the polymers reported in this review are summarize in Table 9.13; a few additional data for

the reactivity ratios of commercial TFE-based copolymers can be found

elsewhere.12



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