CA1215497A - Process for preparing tetrafluoroethylene/fluoro(alkyl vinyl ether) copolymer - Google Patents

Process for preparing tetrafluoroethylene/fluoro(alkyl vinyl ether) copolymer

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Publication number
CA1215497A
CA1215497A CA000427076A CA427076A CA1215497A CA 1215497 A CA1215497 A CA 1215497A CA 000427076 A CA000427076 A CA 000427076A CA 427076 A CA427076 A CA 427076A CA 1215497 A CA1215497 A CA 1215497A
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Prior art keywords
vinyl ether
copolymer
process according
reaction
fluoro
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CA000427076A
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French (fr)
Inventor
Shinichi Nakagawa
Kohzoh Asano
Mitsugu Omori
Toshihiko Amano
Tsuneo Nakagawa
Sadaatsu Yamaguchi
Kiyohiko Ihara
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Daikin Industries Ltd
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Daikin Kogyo Co Ltd
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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18Monomers containing fluorine
    • C08F214/26Tetrafluoroethene
    • C08F214/262Tetrafluoroethene with fluorinated vinyl ethers

Abstract

Abstract:
The invention provides a process for preparing a tetrafluoroethylene/fluoro(alkyl vinyl ether) copoly-mer comprising polymerizing tetrafluoroethylene and a fluoro(alkyl vinyl ether) in an aqueous suspension system which comprises a mixed medium of water and a fluorohydro-carbon or a chlorofluorohydrocarbon in a volume ratio of from 1 : 1 to 10 : 1 at a temperature of from 0 to 25°C in the presence of a polymerization initiator of the formula:
[C1(CF2)n-COO?2 (I) wherein n is an integer of 1 to 10. The copolymer obtained by the process has a small number of unstable terminal groups and excellent durability under flexing.

Description

~l2~5~9'7 Process for preparing tetrafluoroethYlene/
fluoro~alkyl vinyl ether~ coeolymer This invention relates to a process for preparing a tetrafluoroethylene (hereinafter referred to as "TFE")/
fluoro(alkyl vinyl ether) (hereinafter referred to as ~FAVEn) copolymer. More particularly, it relates to a process for preparing a TF~/FAVE copolymer by aqueous suspension polymerization of TFE and FAVE in the pres-ence of a certain specific polymerization initiator.
Solution and emulsion polymerizations have been used for the preparation of TFE/FAVE copolymers. For example, the solution polymerization of TFE and FAVE in 1,1,2-trichloro-1,2j2-trifluoroethane is described in Japanese Patent Publication No. 2223/1973. In Japanese Patent Publication No. 41942/1973, it is proposed to carry out the solution polymerization of TFE and FAVE in perfluoro-solvents, certain specific chlorofluoroalkanes or certainspecific chlorofluorohydroalkanes in the presence of a hydrogen-containing chain transfer agent in order to mini~
mize the formation of unstable terminal groups or the tendency of the produced copolymer to expand, and further to improve its toughness.
In solution polymerizatîon, as the pol~merization proceeds, the viscosity of the solution increases so that agitation of the polymerization system becomes harder, the ~ ~1 5 ~b3 7 produced copolymer is not dispersed well, and control of the heat of polymerization and homogeneous heating of the polymeriz~tion system become difficult. There-fore, solution polymerization has the drawbacks that the production efficiency is extremely low since the weight ratio of the produced copolym~r to the solvent should be less than 0.2, and that it is uneconomical to use the expensive solvent in large amounts. In addition, when the weight ratio of the produced copolymer to the solvent 13 is large, the component distribution in the molecule of the copolymer becomes unhomogeneous and the physical properties, for example, toughness of the copolymer, are adversely affected.
Alternatively, emulsion polymerization of TFE and FAVE
is described in, for example, Japanese Patent Publication No. 20788/1973. Emulsion polymerization should be carried out at a compartively high temperature and the resulting copolymer often has unstable terminal groups. Furtherr it is troublesome to remove the required emulsifier from the reaction mixture.
In the course of study of the aqueous suspenion polymerization of TFE and FAVE, it has been revealed that when di(perfluoroacyl)peroxides [which are employed in the Examples of U.S. Patents Nos. 3,528,954 and 3,642,742] are used as the polymerization initiators, they are hydrolyzed by the water present in the polymerization system and their initiation efficiency is greatly reduced so that the poly-merization rate is lowered. Further, the formation of unstable terminal groups increases, and thus, volatiles are generated in larger amounts when the copolymer is heated.
As the resul~ of the further study, it has now been found that aqueous suspension polymerization of TFE and FAVE can be carried out effectively by the use of certain specific polymerization initiators, and the drawbacks of the conventional process can be largely overcome.
According to the present invention, there is provided 1,~15~9'7 a process for preparing a TFE/FAVE copolymer comprising polymerizing TFE and FAVE in an aqueous suspension system which comprises a mixed medium of water and a fluorohydro-carbon or a chlorofluorohydrocarbon in a volume ratio of from 1 : 1 to 10 : 1 at a temperature oE from 0 to 25C in the presence of a polymerization initiator of the formula:
[Cl(CF2)n-COO ~2 (I) wherein n is an integer of 1 to lOo In the process of the invention, TFE and FAVE are polymerized in an aqueou5 suspension polymerization system.
Therefore, the viscosity of the polymerization system does not increase appreciably, so that the produced copolymer is well dispersed in the system and the-system can be easily stirred. The heat of polymerization is easily eliminated and the polymerization medium can be uniformly heated. The weight ratio of the produced copolymer to the solvent may be 0.4 or more, and the amount of the solvent to be used can be lowered. Further, the produced copolymer is easily recovered from the reaction mixture.
In addition, the polymerization initiator (I) used in the process of the invention is hardly hydrolyzed and can retain a high initiation efficiency. The produced copolymer has few unstable terminal groups, such as carbonyl fluoride groups, and generates only a small volume of volatiles when heated~ ~his means that the copolymer has less tendency to foam during molding than conventional TFE/FAVE copolymers.
Since the initiator to be used according to the invention has a high activity in the temperature range between 0C and 25C, polymerization can be carried out at a comparatively low temperature, and the formation of unstable terminal groups tends to be reduced.
Generally, FAVE to be copolymerized with TFE in the process of the invention may be rep~esented by the formula:
CF2=CF-(O-cF2lc~)a~~(cF2)bcF2 (II) l~LS4~'7 wherein X is hydrogen or fluorine, a is 0 or an integer of 1 to 4, and b is 0 or an integer of 1 to 7. Specific examples of the compound (II) are perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether), CF2=CF-O--CF2CF--O--CF2CF3, (~F2=CF--O-CF2fF--O--(CF2)2CF3, CF2=CF-0-CF2CF-n-(CF2)3CF3, CF2-CF (O-~F2CF)2-0-CF2CF3, CF2=CF-(O-cF2~F)2-o (CF2)2c 3' CF2=CF-(O-CF2CF)2-0-(CF2)3~F3.

The weight ratio of TFE to FAVE is usually from 1 : 1 to 10 : 1.
The polymerization is usually carried out in a mixture of water and an organic solvent at a volume ratio of from 1 : 1 to 10 : 1, preferably from 1.5 1 to 5 : 1. When water is used in an amount less than the lower limit, the viscosity of the polymerization system rises and the stirring of the system becomes difficult, which result in difficult control of the polymerization temperature and unhomogeneous heating of the medium. Thus~ the produc-tivity of the copolymer per unit volume of the medium tends to decrease. When water is used an amount more than the upper limit, the amount o~ the produced polymer per unit volume of the polymerization system is reduced, which is not economical.
Examples of the organic solvent are halogenated hydrocarbons and fluorohydrocarbons and chlorofluoro-hydrocarbons are preferable. Specific examples are 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-lrl,2,2-tetrafluoroethane, trichlorofluoromethane, dichlorodifluoromethane, perfluorocyclobutane, etc.
Of the polymerization initiators, the compounds (I) wherein n is an integer of 1 to 4, particularly 2, are preferable.

'7 Since the initiator has a high initiation efficiency at a comparatively low temperature, as described above, the polymeri~ation temperature in the process of the invention may be from 0 to 25C, preferably from 5 to 15C. The reaction pressure may be from 0.5 to 15 Kg/cm~G, preferably from 1 to 10 Kg/cm2G.
In the process of the invention, a chain transfer agent may be added to the polymerization system in order to control the molecular weight of the copolymer.
Specific examples of the chain transfer agent are alcohols (e.g. methanol, ethanol, etc.3, ketones (eg. aceton, etc.), ethers (e.g. dimethyl ether, diethyl ether, etc.), esters (e.g. methyl acetate, ethyl acetate, etc.) and halogenated hydrocarbons (e.g. carbon tetrachloride, chloroform, etc.). Of these, methanol and dimethyl ether are the most preferable.
The thus prepared copolymer may be recovered from the reaction mixture by a per se conventional method, for example, by removing the organic solvent and the unreacted monomers from the reaction mixture and isolating the co-polymer from the mixture of water and the copolymer, for example, by filtration, evaporation~ freeze drying, etc.
The present invention will be hereinafter explained in more detail by the following Examples, wherein parts and percentages are by weight unless otherwise indicated.
The melting point, specific melt viscosity, MIT flex life and volatile index of the copolymer given in each example were measured as follows:
Meltinq point A Perkin-Elmer DSC II ~ type apparatus was used.
The copolymer was heated from room temperature at a rate of 10C/min., and the peak value of the melting curve was regarded as the melting point.
SPecific melt viscosity -A Koka ~ -type flow tester was used. The copolymer was charged to a cylinder of 11.3 mm in ;nner diameter and lZ:~l5'~'7 kept at 380C for 5 minutes. Then, the copolymer was extruded from an orifice of 2.1 mm in inner diameter and 8 mm in length under a piston load of 7 Kg. The specific melt viscosity was calculated by dividing 53,150 by the extrusion rate (g/min.)~
MIT flex lie A standard type MIT fold endurance tester as described in ASTM D-1276-63 T was used. A copolymer film of about 90 mm in length, about 12.5 mm in width and about 0.2 mm in thickness was attached to the chucks of the tester and bent from side to side at an angle of 135 on each side under a load of 1.25 Kg at a rate of about 175 cycle/min.
The bending cycles before the breakage of the film were recorded. The test was repeated twice and the results were averaged. The averaged cycles were defined as the MIT flex life.
Volatile index A piece of copolymer film (10.0 g) was charged to a 45 ml volume glass bottle which was connected to a vacuum line. The bottle was evacuated to a pressue (P0) of
2 mmHg on a manometer. When an equilibrium pressure was attained, the bottle was immersed in a salt bath kept at 380C. The bottle was kept at the same temperature for 40 minutes and then the pressure in the bottle (P40) was measured.
The volatile index was calculated according to the following equation: p p Volatile index = 40 1O x V
wherein V is the total volume (ml) of the bottle and of the vacuum line.
Furthermore, reference is made in the Examples to the accompanying drawings, in which Figs. 1 and 2 are graphs showing the hydrolysis rates of an initiator according to the invention and another initiator.
Example 1 Premineralized and deaerated pure water (260 parts) 5'~

was charged to a glass made autoclave equipped with a stirrer, which could contain 1,000 parts of water. The autoclave was purged thoroughly with pure nitrogen and evacuated. Thereafter, 1,2-dichloro-1,1,2,2-tetrafluoro-ethane (hereinafter referred to as "R-114") (200 parts) and CF2=CFOC3F7 (hereinafter referred to as "FVE"J (10 parts) were injected therein. The autoclave was pressur-ized with TFE to 2.9 Kg/cm2G at 15C under stirring. As soon as [ClCF2CF~CO~ ~2 (hereinafter referred to as "Initiator An) (0.8 part) was injected, the reaction was initiated. During the reaction period, TFE was injected repeatedly to increase the pressure to from 2.4 to 2.9 Kg/cm G. After 23 minutes of the reaction, as a chain transfer agent, methanol (24 parts) was added to control the molecular weight of the copolymer. After the reaction was continued for 144 minutes, unreacted monomers, R-114 and the polymer particles were recovered. The particles were washed with water ~y means of a mixer and dried at 120C for 16 hours to yield the copolymer (81.9 parts~:
M.P. 306C; Speciic melt viscosity 7.6 x 104 poise; MIT
flex life 193,620 cycles.
Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except for charging no water, adding meth-anol (0.08 part) after 28 minutes of the reaction and continuing the initiated reaction for 108 minutes. A
copolymer ~78.3 parts) was thus obtained: M.P. 308C;
Specific melt viscosity 7.7 x 104 poise; MIT flex life 37,870 cycles.
After about 90 minutes of the reaction, the dispers-ibility of the polymer in the reaction medium rapidly decreased and the reaction mixture could not be thoroughly agitated so that it was difficult to control the tempera-ture of the reaction medium. After 108 minutes of the reaction, the temperature of the autoclave interior abruptly rose to 17.5C and the reaction was stopped.

The results of Example 1 and Comparative Example 1 are shown in Table 1.

4~7 g _ __ . ,. __ .Y~ ~ x,~ o r-~ -- L~ Ll ) H a~ r~) _ _ :~:
O- _ .C~ ~ r ~ O r ~ CO r ~0 r~ J~ O O U .IJ~ X ~ 1`
H ~:: 1~1 ~ O U~ I_ I_ P~ O O p,po~ _ Q. _1 .-1 ~a _ .
O O ~r~ ,_1 r ~Q. ~ ~ ___ _ ~ ~ o o ~ C ~r r ~ ~ _ ~ r~ ~ ~1 _ .P~ U ___ ~ ..~
~ ¦ ' ~ ~ ~ ¦ _ L~ 8 W

S~

From the results shown in Table 1, it can be seen that when the produced amounts of the copolymers per unit volume of the solvent R-114 were the same, the viscosity of the reaction mixture in Comparative Example 1 rose higher and control of the reaction temperature was more difficult than in Example 1. Further, the MIT flex life of the copolymer obtained in Comparative Example 1 was inferior to that of the copolymer obtained in Example 1 and its toughness was greatly reduced.
Hydrolysis of initiators 1,1,2-Trichloro-1,2,2-trifluoroethane (hereinafter referred to as "R-113") (270 ml~ (hereinafter referred to as "R-113 system") or a mixture of water (270 ml) and R-113 (270 ml) (hereinafter referred to as "R-113/water mixture system") was charged to a glass made autoclave e~uippea with a stirrer, as a liquid medium and the temperature was adjusted to 15C under stirring. After the temperature was stabilized, Initiator A or [CF3CF2COO-~2 (here-inafter referred to as "Initiator B") (each 15 g) was charged. At predetermined intervals, samples of the solution (each 1 ml) were taken out from the auto~lave interior, and the concentration of the initiator was measured by iodometry. The ratio of the concentration of the initiator at each interval to the initial concen-tration was calculated. The results are depicted in FigsO
1 and 2, wherein ~ represents the results in the R-113 system and ~-~C~-- represents the results in the R-113/water mixture system. Fig. 1 shows the results for Initiator A and Fig. 2 shows those for Initiator B.
As can be understood from the results shown in Figs. 1 and 2, Initiator A showed little difference in concentra-tion change between the R-113 system and in the R-113/
water mixture system, while Initiator B showed a large concentration decrease in the R-113/water mixture system.
Namely, Initiator A is not hydrolyzed with water~ but Initiator B tends to be hydrolyzed with water.

~2~541~7 Example 2 A reaction was carried out in the same manner as in Example 1 except for charging 360 parts of water, adding methanol after 35 minutes of the reaction and continuing the reaction initiated for 198 minutes, to yield a co-polymer (84.7 parts): M.P. 307C; Specific melt viscosity 34 x 104 poise; Volatile index 90.

A reaction was carried out in the same manner as in Example 1 except for charg.ing 360 parts of water~ adding.
methanol (48 parts) after 25 minutes of the reaction and continuing the reaction initiated for 266 minutes, to.
yield a copolymer (83.3 parts): M.P. 307C; Specific melt viscosity 10.4 x 104 poise; Volatile index 97.
Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except for using Initiator B (4.8 parts) in place of Initiator A and continuing the reaction initiated for 387 minutes, to yield a copolymer (82.4 parts~: M.P.
307C; 5peciEic melt viscosity 16.5 x 104 poise; Volatile index 130.
The results of Examples 2 and 3 and Comparative Example 2 are summarized in Table 2.

lS~9~

_ _ _ _ ~r ~`I ~`I N
u~ a~ a~ a~
~ ~ ~ ~ ~ _ ~_ ~ n ~ ~ X o r~ o ~o ~ ~ ~ ~ ~
O- __ ~ ~ ~ ~ ~ r~ i-~ ~ ~r co ~r . o O O o r~
- __ ~ ~ .
o--_ ~ _ a) o oo a~ co ~
,I h o o ~ O ~ X ~ u-) ~ t~ _ _ _ .,./~,~ . .
H ~ '¢ ~q . o ~r O ~
_ _ _ >~ o O o _ _ ~ V~ r~
_ _ __ ~ I_ . ~r ~r ~n O o ~ ~ r~ ~
o o O ~ ~ Q. oo cx~ co -1 h O O O p~ ?
~I ~`J ~`J __ _ U~ . _ _ r~l ~
a~ ~ O O o ~ ~ ~ r~
~ ~ ~D ~ ~D ~ U ~ ~ ~ ~D 0
3 ~ 11 ~ ~1 ~ E3 ~ .-1 ~ t~
_ :~ _ _ _ .~ __ _ ~ ~0 ~
~ ~ ~ V ~ r~ '~
a) ~ ~ a) aJ a~
Nl ~ ~i U~ ~1 . ~x ~ ~

l~lti4~7 From the results as shown in Table 2, it can be seen that the conventional initiators such as Initiator B
used in Comparative Example 2 have drawbacks such that they should be used in larger amounts and require longer reaction times than the initiator used in Examples 2 and 3 according to the invention. It can also be seen that the copolymers obtained in Examples 2 and 3 have smaller volatile indices than that obtained in Comparative Example 2 and generate smaller volumes of volatiles when heated.
Comparative Example 3 A reaction was carried out in the same manner as in Example 1 except for using 0.04 parts of Initiator A to initiate the reaction and adding the same initiator ~each 0.04 part) every 40 minutest adding methanol (8 parts) after 15 minutes of the reaction and continuing the reaction at 40C under a pressure of from 6.0 to 5.5 Kg/cm G for 93 minutes, to yield a copolymer (113.6 parts): M.P. 307~C; Specfic melt viscosity 14 x 104 poise; Volatile index 118.
The results of Examples 2 and 3 and Comparative Example 3 are su~nariæed in Table 3.

5~9'7 ~ ~r ~ u~
~ ~ C~ ~ U~
U~ ~ ~ o a~ ~ . . . __ _ _ _ h X ~I ~ ~ a) . _ _ . ~1 , ~ ~ U~ In O ~ ~ O I_ CO
E~ _1 ~ ___ ~r1 ~
~0^ _ ~ ~ ~ U 1- t- ~`
~0 OD . o O O O
~d c~ ~r :~: ~
. __ __ _ . _ ~ ~
O_~ _ _ ~ô aJ o U~ C~ oo o ~ ~ . . .
.,~ S~ o o o C~ ~ X
~ ~ _ _ _, ~ er O ~r H - O
~ . I ~
~> ~ O O O
E4 ~ ~ ,_, ,_, ~d _ O ~ l_ ~ ~
~ ~ ~1 ~') n o o ~ 0~ co ~1 O O O ~ ~ ~ ~1 O O O ~ ~--~ ~ ~ ~ _ . . _ _ _ _ ~ U~
S~ în ,0~ ~
a~ ~ O O o .,~ ~ co ~D
~D ID ~D ~ O O ~:: ~ U~ a~
d _ 1~ __ O
~ ~ ~ ~ ~ ~
a) a) ~ a) a) a) td C) S~
R_ x ~ R ~ ~ x i~

5~7 As can be seen from the results as shown in Table 3, in the polymerization utilizing the initiator according to the invention, the copolymers polymerized at 15C in Examples 2 and 3 have smaller volatile indices than that polymerized at 40C in Comparative Example 3 Example 4 A reaction was carried out in the same manner as in Example 1 except for using 8.0 parts of Initiator A, adding methanol (40 parts) after 24 minutes of the reaction and continuing the reaction at 5C under a pressure of from 2.0 to 1.5 Kg/cm2G for 170 minutes., to yield a copolymer (83~1 parts): M.P. 309C; Specific melt viscosity 3.6 x 104 poise.
Example 5 A reaction was carried out in the same manner as.in Example 1 except for charging 360 parts of water, adding methanol (48 parts) ater 33 minutes of the reaction and continuing the reaction initiated for 295 minutes, to yield a copolymer (84.7 parts): M.P. 307C; Specific.
melt viscosity 11.8 x 104 poiseO
Example 6 A reaction was carried out in the same manner as in Example 1 except for using 0.4 part of Initiator A, adding methanol after 21 minutes of the reaction and continuing the reaction at 25C under a pressure of from 4Øto 3.5 Kg/cm2G for 114 minutes, to yield a copolymer (82.3 parts): M.P. 307C; Specific melt viscosity 4.2 x 104 poise.
Example 7 A reaction was carried out in the same manner as in Example 1 except for using dimethyl ether in place of methanol, pressurizing th~ system with TFE premixed with 0.2 % of dimethyl ether and continuing the reaction initiated for 165 minutes, to yield a copolymer (81.0 parts): M.P. 307C; Specific melt viscosity 4.2 x 104 poise.

12~1S~7 The results of Example~; 4 to 7 are summarized in Table 4.

_ _ ~
au t~ ~n ~ ln ~r~ E
u~ o ~ o ~ ~ . . .
a. ~ ~ ~ ~r _ E c) Ul n 'n u~
~~ _ O- ~ __ _ _ ~ u~ ~ ~ . ~
r~ ~ a) a) P~ c~~ ,_ 1-.C S~ o ~o ~ ~.C . o o o l o ~ ~ ~ ~ ~,~ ~ :~: ~
~a~ . __ _ _ _ _ ~ _ .
O_ _ _ ~ ~ a) O
ul o co ~r . . . . ~ u~ co ~1 ~ co c o o u ~ X . . .
J~ ~ _ _ _ _ ~ ~ ~ u~ ~r c ~ ~ ~ ~ ~ .~ O a) ~
H _ _ O U~ O
~ Q~
__ , _ > ~ O O O O
~4 ~ ,_1 ~ -1 r-l ~ ~
_ O ~ U~ ~ I_ ~ O
_ _ ~ ~ ~ . . .
S~ ~ ~r ~ ~
~n Ood co c~ o~ oo O O O O
O O O O ~ ~--I a~ ~J ~Jt~ ~ __ _ ~ R.
~ U~ _ . r~l ~
a) ~ O o o o ~ ~ o u~ ~r Ir) J ~ ~~O ~D ~ ~ O ~ ~ r~ G~ ~ ~D
~1~ t~l ) ~ ~ '~5 (1~-ri ~1 ~I ~1 3~ _ _ ~ ~13 _ _ , O
~r In ~ ~_ ~ ~ U~ ~D ~_ Q) ~ aJ G~
~r~ ~1 ~ ~ ~ ~ ~ ~ ~
E~ ~ ~ E~ a) E Ei E E;
~1 QX X X X ~ X X r~

Claims (11)

Claims:
1. A process for preparing a TFE/FAVE copolymer comprising polymerizing tetrafluoroethylene and fluoro(alkyl vinyl ether) in an aqueous suspension system which comprises a mixed medium of water and a fluorohydrocarbon or a chloro-fluorohydrocarbon in a volume ratio of from 1 : 1 to 10 : 1 at a temperature of from 0 to 25°C in the presence of a polymerization initiator of the formula:
[C1(CF2)n-COO?2 (I) wherein n is an integer of 1 to 10.
2. A process according to claim 1, wherein the polymerization initiator is a compound of the formula (I) wherein n is an integer of 1 to 4.
3. A process according to claim 1, wherein the polymerization initiator is a compound of the formula:
[C1CF2CF2COO?2.
4. A process according to claim 1, wherein the fluoro(alkyl vinyl ether) is a compound of the formula:
(II) wherein X is hydrogen or fluorine, a is 0 or an integer of 1 to 4 and b is 0 or an integer of 1 to 7.
5. A process according to claim 4, wherein the fluoro (alkyl vinyl ether) is selected from the group consisting of perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether,
6. A process according to claim 1, wherein the weight ratio of the tetrafluoroethylene and the fluoro(alkyl vinyl ether) is from 1 : 1 to 10 : 1.
7. A process according to claim 1, wherein the volume ratio of the water and the fluorohydrocarbon or chloro-fluorohydrocarbon is from 1.5 : 1 to 5 : 1.
8. A process according to claim 1, wherein the fluorohydrocarbon or the chlorofluorohydrocarbon is selected from the group consisting of 1,1,2-trichloro-1,2,2 trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoro-ethane, trichlorofluoromethane, dichlorodifluoromethane and perfluorocyclobutane.
9. A process according to claim 1, wherein the reaction temperature is from 5 to 15°C.
10. A process according to claim 1, wherein the reaction pressure is from 0.5 to 15 Kg/cm2G.
11. A process according to claim 1, wherein the reaction pressure is from 1 to 10 kg/cm2G.

19.
CA000427076A 1982-04-30 1983-04-29 Process for preparing tetrafluoroethylene/fluoro(alkyl vinyl ether) copolymer Expired CA1215497A (en)

Applications Claiming Priority (2)

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JP73671/1982 1982-04-30
JP57073671A JPS58189210A (en) 1982-04-30 1982-04-30 Production of tetrafluoroethylene/fluorinated alkyl vinyl ether copolymer

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