JP3477892B2 - Fluorine-containing polymer composition, crosslinked product thereof, and use - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoropolymer composition, its crosslinked product and its use. The fluorine-containing polymer composition of the present invention has chemical resistance such as electric insulation derived from a polyfunctional compound and solvent resistance due to its highly crosslinked structure, heat resistance and the like, as well as chemical resistance inherent to the fluoropolymer. It has solvent, oil resistance, acid resistance, alkali resistance and chemical resistance, weather resistance, etc., and the crosslink density can be adjusted arbitrarily, and the elastic modulus, hardness,
It also has physical properties that allow you to freely control tensile strength and tensile elongation.

[0002]

Generally, homopolymers of polyfunctional compounds, such as triallyl isocyanurate (TAIC) homopolymers having three allyl groups in the isocyanuric ring, are
Like other resins with an isocyanuric ring as the skeleton, heat resistance,
It is a resin with excellent electrical properties, and it is desired to use it as a molding material that can be easily processed for electrical insulation applications (see Science and Industry 56, (7) 254-262 (1982); 5).
7 (8) 302-308 (1983)). However, T
The high molecular weight polymer of AIC is a resin that is extremely hard and brittle, and does not melt even if the temperature rises above its melting point, resulting in poor moldability (see US Pat. No. 3,576,576).
789; Lecture Collection 26, 3
1-72 (1969)). Therefore, TAIC is more often used as a cross-linking agent than as a monomer for molding materials because of its heat-resistant structure.

In addition, TAIC during crosslinking of elastomers
Although the development of low-polymerization prepolymers has been extensively pursued because of the problem of mixing the polymer with the elastomer (see:
JP-A-53-77294; JP-A-2-2747
No. 09), the use as a high molecular weight polymer has not yet been found due to the above problems.
(See: Science and Industry 56, (7) 254-262 (198
2); 57 (8) 302-308 (1983)).

As a copolymer of a polyfunctional compound, a polyallyl compound is copolymerized with polyester at a high content (1 to 50% by weight) for the purpose of improving the mechanical properties of a polyester molded product, Although it has been reported that the solvent resistance, heat resistance, and high-temperature mechanical strength are improved (see JP-A-53-117047), this is also mainly based on the modification of polyester.

On the other hand, an elastomeric or non-elastomeric fluoropolymer is known as a material excellent in heat resistance, chemical resistance, electrical properties, mechanical properties, weather resistance, etc., and has heat resistance, corrosion resistance lining, coating, electric wire. Destruction,
It is used in a wide range of applications such as packing. Fluoropolymers are often crosslinked to take advantage of their properties. The cross-linking mainly used for modifying the elastomer is usually polyamine cross-linking, peroxide cross-linking, polyol cross-linking, etc., and is selected according to the purpose of use. Further, radiation crosslinking is also known, and it is considered that radicals are generated in the polymer chain and a crosslinking reaction is caused by the bonding of radicals. Furthermore, cross-linking is effective in enhancing the mechanical properties, chemical resistance, creep resistance, etc. of the fluoropolymer, and therefore, easy and easy cross-linking brings great benefits.

Further, regarding modification by cross-linking, in thermoplastics, by cross-linking of an allyl compound,
There is a report example that the thermal characteristics and the high temperature mechanical strength can be improved (see: West German Published Patent No. 2336625).
No .; United States Patent No. 3947525).

[0007]

The fluorine-containing polymer is
Although it is handled as a heat-resistant resin, so-called engineering plastic resin (polyimide resin, polyamide-imide resin, etc.),
Actually, there are some problems in creep resistance at high temperature and mechanical strength (tensile rupture strength, tensile elastic modulus, viscoelastic modulus, etc.). For example, deterioration of mechanical properties such as flowing out at a temperature equal to or higher than the crystal melting point, and those of radiation cross-linking include coloring due to breaking of the polymer main chain, reduction of high temperature elongation and strength. Further, depending on the polymer composition, it is the actual situation that the chemical resistance is not sufficient, and further improvement is required.

On the other hand, polyfunctional compounds, especially homopolymers of triallyl isocyanurate (TAIC) are heat resistant,
Although it is a resin having excellent electrical properties, most of the applications of TAIC are cross-linking agents for monomers and prepolymers because of the drawbacks described above. Therefore, it is desired to develop a molding material that can be easily processed as an electric insulating material that takes advantage of the excellent heat resistance and electric characteristics inherent in TAIC.

[0009]

The present invention comprises (a) a polyfunctional compound, (b) a fluorine-containing polymer containing iodine and / or bromine and a blend thereof, and (c) a radical generating source, Further, there is provided a fluoropolymer composition characterized in that the component (a) is 18 to 99% by weight of the total amount of the component (a) and the component (b).

The polyfunctional compound (a) is effective in principle as long as it is reactive with peroxy radicals and polymer radicals, and the kind is not particularly limited. The functional group of the polyfunctional compound (a) is, for example,
Examples thereof include vinyl group, allyl group, acrylic ester group, methacrylic ester group, and sulfur. The number of functional groups is at least 2 and is not particularly limited. Preferred examples of the polyfunctional compound (a) include triallyl isocyanurate (TAIC), triallyl cyanurate, triallyl formal, triallyl trimellitate, N, N ′.
-M-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, 3,3,4,4,5,5,6,6-octafluoro-1,7-octadiene, 4,4,5 , 5-Tetrafluoro-1,5-hexadiene, 4,4,5,5,6,6,7,7
-Octafluoro-1,9-decadiene, 5,5,6,6,
6-pentafluoro-1-iodo-1,3-butene, 1,
3-dichloro-1,1,1,6,6,6-hexafluoro-
2,5-bistrifluoromethyl-2,4-hexadiene,
Unsaturated compounds such as 1,4,7-perfluorooctatriene are mentioned. The lower limit of the amount of the polyfunctional compound (a) used is usually 17% by weight, preferably 20% by weight, more preferably 23% by weight, particularly preferably 26% by weight of the total amount of the components (a) and (b). May be%. The upper limit of the amount of the polyfunctional compound (a) used may be usually 99% by weight, preferably 90% by weight, more preferably 70% by weight, particularly preferably 50% by weight. In the range of 17 to 99, especially 23 to 99% by weight of the polyfunctional compound (a), the cured product obtained by using the composition shows the maximum tensile breaking strength and breaking elongation.

Polyfunctional compound (a) (eg TAIC)
When partially or wholly fluorinated is used, the mixed and dispersed state in the fluoropolymer (b) is further improved, and the content of the polyfunctional compound (a) is increased. You can Further, in order to add a higher content of the component (a), a small amount of a polyfunctional compound was added to the end of the component (b) to improve the compatibility between the component (a) and the component (b). It is better to use one. The polymer synthesizing method and the physical properties of the crosslinked film are shown in Examples 5 and 6.

Further, as another method, in order to add the polyfunctional compound (a) in a higher content, a compatibilizing agent composed of various organic solvents, fluorine-based organic solvents, hydrocarbon-based rubbers, fluorine-based rubbers, etc. Can be achieved by blending Further, when a polyfunctional compound whose homopolymer is inherently brittle is used as the component (a) and a crosslinked product having a high content of the component (a) is molded, brittleness is likely to appear in the molded product after crosslinking. Become. Therefore, as the component (b), it is more effective to improve the brittleness by blend-crosslinking using a polymer such as an elastomer that absorbs impact.

The fluoropolymer (b) contains an iodine atom and / or a bromine atom chemically bonded to the polymer. In the fluoropolymer (b), the content of iodine atom is 0.001 to 10% by weight, preferably 0.01 to
It is 5.0% by weight, and the content of bromine atoms is 0.05 to 15
% By weight, preferably 0.05 to 7.5% by weight. The amount of the fluoropolymer (b) used is 1 to 83% by weight, preferably 10 to 8% by weight based on the total amount of the component (a) and the component (b).
It is 0% by weight, more preferably 30 to 77% by weight, and particularly preferably 50 to 74% by weight. The molecular weight of the fluoropolymer (b) is usually 1000 to 10,000,000,
For example, it may be 1000 to 1,000,000. It is preferable that iodine and / or bromine are present at at least one end of the molecule of the fluoropolymer (b), more preferably at both ends. Usually, the amount of component (a) used is
It is known that about 16% by weight of the total amount of the components (a) and (b) is used as the upper limit value (for example, Japanese Patent Publication No. 60-52173). In general, it has been considered that it is not common sense to use the component (a) above the upper limit value.

The fluorine-containing polymer (b) is, for example, a radical source and a formula: RfXm [wherein Rf is a saturated or unsaturated fluorohydrocarbon group or a chlorofluorohydrocarbon group, and X is iodine or bromine]. And m is the number of Rf bond and is 1 or more, preferably an integer of 1-2. ] It can manufacture by polymerizing the fluoro olefin which may or may not contain iodine or bromine in the presence of the iodide compound or bromide compound shown by these.

The fluorine-containing polymer (b) can also be, for example,
Fluorine-containing homopolymer consisting of homopolymerization of iodine- and / or bromine-bonded fluoroolefin, and copolymer consisting of the fluoroolefin and at least one other fluoroolefin and / or α-olefin copolymerizable therewith Is. In addition, the component (a)
It is more effective to use a copolymer obtained by copolymerizing these comonomers in the form of block or graft in order to improve the compatibility with and to facilitate blending.

The iodide compounds and bromide compounds may be monoiodide compounds, monobromide compounds, diiodide compounds, dibromide compounds and the like. Specific examples of the iodide compound and bromide compound include monoiodoperfluoromethane,
2-iodo-1-hydroperfluoroethane, 2-iodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,3-diiodoperfluoropropane,
2-chloro-1,3-diiodoperfluoropropane,
2,4-dichloro-1,5-diiodoperfluoropentane, 4-iodoperfluorobutene-1, monobromoperfluoromethane, 2-bromo-1-hydroperfluoroethane, 2-bromoperfluoropropane, 1 , 4
-Dibromoperfluorobutane, 1,3-dibromoperfluoropropane, 1,3-dibromo-2-chloroperfluoropropane, 1,5-dibromo-2,4-dichloroperfluoropentane, 4-bromoperfluorobutene- 1 etc. can be illustrated.

Examples of fluoroolefins include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, pentafluoropropene, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether). , Perfluoro (propyl vinyl ether) and the like. Examples of the α-olefin include ethylene, propylene, methyl acrylate, methyl methacrylate, styrene and the like. Examples of the fluoroolefin bonded with iodine and / or bromine include CF ₂ ═CFI, CF ₂ ═CFCF ₂ I,
CF ₂ = CFCF ₂ CF ₂ I, CH ₂ = CHCF ₂ CF ₂ I,
CF ₂ = CFBr, CF ₂ = CFCF ₂ CF ₂ Br, CH ₂ =
CHCF ₂ CF ₂ Br and the like are exemplified.

The method for producing the fluoropolymer (b) is described, for example, in JP-B-63-41928 and JP-B-61-31.
No. 725, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 1-57125, Japanese Patent Publication No. 1-16844,
It is described in detail in Japanese Examined Patent Publication No. 5-405. As the fluorine-containing polymer (b), it is possible to add the polyfunctional compound (a) at a higher content by using iodine, bromine, or any other polymer having more crosslinking sites.

The radical source (c) is, for example,
Examples thereof include organic peroxide compounds and azobis compounds. The amount of the radical source (c) used is the amount of the component (a)
And 100 parts by weight of the component (b) in total, usually 0.0
The amount is 01 to 10 parts by weight, preferably 0.01 to 5 parts by weight. If necessary, radiation (γ rays, electron rays, α rays, β rays, X rays
High-energy electromagnetic waves such as rays) and ultraviolet rays may also be used.

As the organic peroxide compound, a compound which easily generates a radical in the presence of heat or a redox system is generally preferable, for example, 1,1-bis (t-butylperoxy) -3,5,5. -Trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide,
Di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
2,5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane , T-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, perfluorodimethyl peroxide, perfluorodi-t-butylperoxide, perfluoro-t-butylhydroperoxide and the like. Preferred are dialkyl type compounds. Generally, the type and amount used are selected based on the amount of active —O—O—, decomposition temperature and the like.

Examples of the azobis compound include azobisisobutyronitrile, 2,2-azobis- (2,4-dimethylvaleronitrile) and azobismethylbutyronitrile. The composition of the present invention is an additive used as a compounding agent in the crosslinking of a usual fluorine-containing elastomer, for example, an acid acceptor, an antioxidant, carbon black, a processing aid, a plasticizer, a pigment and glass fiber. The filler and the like can be used according to the purpose.

As a means for mixing and dispersing each component, an appropriate method is adopted depending on the viscoelasticity and form of the material. For example, in the case of a solid state, an ordinary open roll or a powder mixer is used, and in the case of a liquid state. A usual mixer is used as appropriate.
Of course, it is also possible to dissolve or disperse solid components in a solvent and disperse and mix them. In the present invention, a particularly preferred method for preparing the composition is a method in which solid components are dissolved or dispersed in a solvent, dispersed and mixed, and then the solvent is removed under vacuum. In the case where the component (b) is a block or graft copolymer containing a segment having a high compatibility with the component (a), it is easy to mix and contributes to improvement of transparency and mechanical properties.

As a cross-linking method, for example, in the case of forming a cross-linked sheet, the composition is charged into a pre-heated mold for heat compression molding and pre-heated. The residual heat is 10 of organic peroxide.
Perform until the sample melts near the time half-life temperature,
After that, it is melt-molded into a sheet. The sheet is then heat compression molded at a temperature at which the half-life time of the organic peroxide is several minutes, for a time 5 to 7 times the half-life time. A crosslinked sheet is produced by this series of steps. Also, if necessary,
After molding, the residual organic peroxide in the sheet is decomposed and removed by an oven heat treatment at a high temperature.

The polymer composition of the present invention has oil resistance, chemical resistance, solvent resistance, acid resistance, alkali resistance, weather resistance, heat resistance, electric insulation, and high elasticity, high strength, and improved brittleness due to a crosslinked structure. It is effectively used when required. The polymer composition of the present invention is used as a cross-linked product, for example, a general molding material composition, a resin modifier composition, a coating composition,
Used as an adhesive composition, a sealant, a crosslinking agent composition (uncrosslinked composition), these are an electrical insulator and a protective film, a heat resistant resin, a solvent resistant, an oil resistant, an acid resistant, an alkali resistant and a chemical resistant resin, It can be used as composite fiber and sheet (composite with glass fiber and engineering plastic resin), weather resistant sheet and parts. The polymer composition of the present invention can also be used as an alternative to general-purpose engineering plastic resins. Further, in the composition of the present invention, glass, mica, other inorganic oxides and heat-resistant resins other than the fluorine-containing polymer of component (b) (polyimide, polyamideimide, polyethersulfone, polyphenylene sulfite, polybutylene phthalate, etc.)
It is also possible to mix and disperse and crosslink and use.

The crosslinked product obtained by using the composition of the present invention can be used as tubes, packings, O-rings, fibers, sheets, etc., and is particularly preferable as a sealing material for engines or compressors and IC substrates. The molding material composition is
It is melt-molded for applications such as insulator parts, tubes, packing, and O-rings. Flowability at high temperatures is suppressed. In order to increase the heat resistance such as increasing the continuous use temperature and the solvent resistance, a polyfunctional compound may be added at a high content.

The coating composition is used as a coating having weather resistance, heat resistance and water / oil repellency for buildings or household cooking appliances. The adhesive composition is used for adhesion between multi-layer films, adhesion between a fluoropolymer and a hydrocarbon polymer, and the like. The sealant is used as one having water / oil repellency and weather resistance by taking advantage of the characteristics of the fluoropolymer. The crosslinking agent composition (uncrosslinked composition) and the resin modifier composition are used for the purpose of improving the mechanical strength of the resin.

As the electric insulator and the protective film, a sheet,
It is used after being melt-molded into tubes. The heat-resistant resin is used as a fiber or a film that can be used without causing flow even at a use temperature above the crystalline melting point of the fluoropolymer. As a solvent resistant, oil resistant, acid resistant, alkali resistant and chemical resistant resin, it is used in a state in which its durability is further improved due to its highly crosslinked structure. As the composite fiber and the sheet, a composite with glass fiber or engineering plastic resin can be mainly used to provide a reinforcing effect of mechanical strength.

The weather resistant sheet and parts are used after being heat-treated by being heat-treated after molding. The heat treatment after molding is usually performed at a temperature above the molding temperature and below the decomposition temperature of the molded product for a few minutes to a few days, but it depends on the type. Further, the temperature may be raised stepwise. Further, for all of these applications, by increasing the content of the polyfunctional compound (a), the hardness, strength, elasticity, etc. of the material can be adjusted to a higher level.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the examples, unless otherwise indicated,% is% by weight and parts are parts by weight.

In the examples, the performance was evaluated by the following test methods. Test method: (1) Tensile test Using ASTM No. 5 dumbbell, pulling speed 100 mm /
The tensile breaking strength (TCnsile Strcngth: TS) and tensile breaking elongation (Elongation: EL) were measured at min. The measuring device is Tensilon UCT-500 (Orientee Corporation
Manufactured). (2) Dynamic viscoelastic modulus measurement test Dynamic viscoelastic modulus (E ′) and Tan δ were measured using a dynamic viscoelastic modulus measuring device RSA-2 (manufactured by Rheometrics).

(3) Gel Fraction (GF) Measurement A sample piece obtained by punching the crosslinked film into a dumbbell shape was used.
After carrying out reflux extraction with a mixed solvent of N, N′-dimethylformamide and acetone (volume ratio 7: 3) at 110 ° C. for 72 hours in the flask, the solvent was replaced with acetone and further refluxed at 90 ° C. for 2 hours. The gel content was vacuum dried at 70 ° C. for 16 hours, and then the dry weight was weighed. From the weight change before and after extraction, the gel fraction was calculated from the following formula. Gel fraction (%) = (weight after extraction / weight before extraction) × 100

Example 1 Compositions The compositions of samples (X1) to (X3) are shown below. Fluorine polymer having iodine terminal [Sample (X
1)] and a fluoropolymer having no iodine atom [Samples (X2) and (X3)] were used. Samples _{(X1) I- (CH 2 CF} 2) m- (CF 2 CF 2) n-I copolymer [vinylidene at both ends with iodine fluoride / tetrafluoroethylene copolymers, VdF / TFE = 8
0/20 (mol%), iodine content: 0.49%, melting point: about 120 ° C, number average molecular weight = 52300 (GPC polystyrene conversion)]: 76.3% TAIC (triallyl isocyanurate, manufactured by Nippon Kasei) :
22.9% Perhexin 2.5B (Made by NOF Corporation): 0.8%

Sample (X2) vinylidene fluoride / tetrafluoroethylene copolymer (VdF / TFE = 80/20 (mol%), number average molecular weight = 55500): 76.3% TAIC: 22.9% Perhexin 2.5B: 0.8% sample (X3) vinylidene fluoride / tetrafluoroethylene copolymer (VdF / TFE = 80/20 (mol%), number average molecular weight = 55500): 100% TAIC: 0% Perhexin 2.5B: 0% composition The sample was heat-pressed and molded at 150 ° C. for 10 minutes, and then a crosslinked film (thickness: 1.0 mm) was molded by secondary vulcanization at 180 ° C. for 20 minutes. Table 1 shows the measurement results of mechanical properties of this film at room temperature and 150 ° C.

[0034]

[Table 1] Sample No. (X1) (X2) (X3) Tensile breaking strength [Kgf / cm ² ] 600 400 530 Room temperature tensile breaking elongation (%) 100 90 480 Room temperature viscoelasticity [dyne / cm ² ] 9.0E9 1.0E10 8.0E9 room temperature tensile strength at break [Kgf / cm ^2] 90 10 fluidized 0.99 ° C. unmeasurable tensile strength elongation (%) due to a 125 40 flow was for 0.99 ° C. unmeasurable viscoelasticity ^{[dyne / cm 2] 1.05E8 2.0E7} 150 for the flow ℃ Cannot be measured

Example 2 I- (CH ₂ CF ₂ ) m- (CF ₂ CF ₂ ) n-I copolymer [VdF / TFE = 80/20 (mol%), iodine content = 0.15%, number average) Molecular weight = 172000 (in terms of polystyrene)], TAIC, and Perhexin 2.5B blend compositions were prepared by changing the amount of TAIC blended. The mechanical properties of the film at 150 ° C. were measured. The results are shown in Table 2. The amount of Perhexin 2.5B was 1 part based on 100 parts of the total amount of the polymer and TAIC in all cases.

[0036]

[Table 2] TAIC content (%) 0 9.1 20 23.1 28.6 Tensile breaking strength [Kgf / cm ² ] 20 45 120 130 125 Tensile breaking elongation (%) 320 260 370 330 260 Viscoelastic modulus [dyne / cm ² ] 2.6E7 4.0E7 9.0E7 1.0E8 1.8E8

Example 3 I- (CH ₂ CF ₂ ) m- (CF ₂ CF ₂ ) n-I copolymer [vinylidene fluoride / tetrafluoroethylene copolymer having iodine at both ends, VdF / TFE = 8]
0/20 (mol%), iodine content: 0.25%, number average molecular weight = 103000 (GPC polystyrene conversion)], T
In the blend of AIC and Perhexin 2.5B, T
Films were prepared by changing the amount of AIC compounded. The gel fraction of the film was measured in order to examine the effect of improving the chemical resistance by crosslinking. The results are shown in Table 3. The amount of Perhexin 2.5B is the total amount of polymer and TAIC 1
It was 2.0 parts with respect to 00 parts. Further, the gel fraction was measured using a DMF / acetone mixed solvent.

[0038]

[Table 3] TAIC content (%) 1.0 3.8 9.1
18 25 75 Gel fraction (%) 84 94 96 98 99 99

Example 4 In this example, the mechanical strengths of crosslinked films obtained from crosslinked compositions (Y1 and Y2) with various polyfunctional monomers were compared. A film was prepared from the samples shown below, and the mechanical strength of the film was measured. The results are shown in Table 4. As the fluoropolymer, I- (CH ₂ C
F ₂ ) m- (CF ₂ CF ₂ ) n-I copolymer [vinylidene fluoride / tetrafluoroethylene copolymer having iodine at both ends, VdF / TFE = 80/20 (mol%), iodine content: 0.49% , Number average molecular weight = 5230
0 (in terms of polystyrene of GPC)] was used. Samples _{(Y1) I- (CH 2 CF} 2) m- (CF 2 CF 2) n-I copolymer:
83% TAIC: 17% Perhexin 2.5B: 1.0 part (polymer and TAI
C of the total amount 100 parts) samples _{(Y2) I- (CH 2 CF} 2) m- (CF 2 CF 2) n-I copolymer:
83% TRIAM-705 (triallyl trimellitate, manufactured by Wako Pure Chemical Industries, Ltd.): 17% Perhexin 2.5B: 1.0 part (polymer and TAI)
(For 100 copies of C)

[0040]

[Table 4](Y1) (Y2) Tensile breaking strength [Kgf / cm²] 540 530room temperature Tensile breaking elongation (%) 182 180 room temperature Tensile breaking strength [Kgf / cm²] 80 70150 ° C Tensile elongation at break (%) 175 125150 ° C

Example 5 In a 500 cc round bottom flask, 250 g of iodine-terminated fluoropolymer dispersion [solid content 45.4
g, I- (CH ₂ CF ₂ ) m- (CF ₂ CF ₂ ) n-I copolymer (vinylidene fluoride having iodine at both ends /
Tetrafluoroethylene copolymer, VdF / TFE =
80/20 (mol%), iodine content = 0.73%, number average molecular weight = 34600)], and TAIC 1.95 g were charged and sufficiently stirred. Thereafter, 17.7 mg of ammonium persulfate was added, and emulsion polymerization was carried out at 80 ° C. for 1.5 hours while stirring at 250 rpm under a nitrogen stream, and TAI was added.
A polymer having C bonded to both ends was synthesized. After the polymerization, the polymer is purified by putting the freeze-coagulated solid content in 1 liter of pure water, stirring and dispersing at high speed, and then filtering with a glass filter three times, and the same work twice with methanol. After that, it was dried in vacuum at 100 ° C. for 24 hours. Elemental analysis and IR of purified polymer
The measurement confirmed the presence of TAIC in the polymer particles. By elemental analysis, the TAIC content was 2.9%.

A fluoropolymer having a TAIC monomer and an iodine terminal which is not converted to the terminal TAIC (Example 5)
Compatibility with the above-mentioned raw material polymer) and the above-mentioned fluorine polymer having a terminal TAIC and having an iodine terminal (final polymer of Example 5). As a method, during the examiner,
The same weight of the polymer and the TAIC monomer was added, the temperature was raised to 190 ° C., which is higher than the melting point (120 ° C.) of the polymer, in an oil bath, and the transparency and the melt viscosity during melting were visually confirmed. As a result, as compared with the former, the latter polymer was clearly confirmed to have increased transparency and melt viscosity during melting. From this fact, the TAI was changed to the terminal TAIC.
It was confirmed that the compatibility between C and the fluoropolymer was improved.

Example 6 In FIG. 1, a fluorine polymer having a terminal TAIC-modified iodine terminal (final polymer of Example 5), a fluorine polymer having an iodine terminal [I- (CH ₂ in the sample (X1) of Example 1) CF ₂ ) m- (CF ₂ CF ₂ ) n-I Copolymer], TAIC, and Perhexin 2.5B as a peroxide, TAIC content and viscoelasticity of a film obtained by cross-linking and molding the compositions of Samples 1 to 4 below. The relationship between the modulus (E ′) and tan δ is shown. From Figure 1, TAI
With increasing C content, the viscoelastic modulus at high temperature tended to become higher.

Sample 1 (A1, A2 in FIG. 1) TAIC charging amount: 47.5% Polymer used: Iodine-terminated fluoropolymer [I- (CH ₂ CF ₂ ) m in sample (X1) of Example 1]
-(CF ₂ CF ₂ ) n-I copolymer] / terminal TAIC-modified iodine-terminated fluoropolymer (final polymer of Example 5) = 1/1 (weight ratio) Peroxide: 1 part (total amount of polymer and TAIC) To 100 copies)

Sample 2 (B1, B2 in FIG. 1) TAIC charging amount: 43.4% Polymer used: Iodine-terminated fluoropolymer [I- (CH ₂ CF ₂ ) m in sample (X1) of Example 1]
-(CF ₂ CF ₂ ) n-I copolymer] / terminal TAIC-modified iodine-terminated fluoropolymer (final polymer of Example 5) = 1/1 (weight ratio) Peroxide: 1 part (total amount of polymer and TAIC) To 100 copies)

Sample 3 (C1 and C2 in FIG. 1) TAIC charging amount: 28.6% Polymer used: Iodine-terminated fluoropolymer [I- (CH ₂ CF ₂ ) m in sample (X1) of Example 1]
_{- (CF 2 CF 2) n} -I copolymer] peroxide: 1 part (per 100 parts of total amount of polymer and TAIC)

Sample 4 (D1, D2 in FIG. 1) TAIC charging amount: 23.1% Polymer used: Iodine-terminated fluoropolymer [I- (CH ₂ CF ₂ ) m in sample (X1) of Example 1]
_{- (CF 2 CF 2) n} -I copolymer] peroxide: 1 part (per 100 parts of total amount of polymer and TAIC)

Example 7 Fluorine polymer having an iodine terminal which is not TAIC-terminated (I- (C in the sample (X1) of Example 1)
H ₂ CF ₂ ) m- (CF ₂ CF ₂ ) n-I copolymer) and the TAIC-terminated iodine-terminated fluoropolymer synthesized in Example 5 (final polymer of Example 5) with the following compositions, respectively. Crosslinking molding was performed using TAIC and perhexin 2.5B as a peroxide to obtain a crosslinked film with a high content of TAIC, its viscoelastic modulus, and tan δ.
Was measured. The result is shown in FIG. As is clear from FIG. 2, the elastic modulus at high temperature was higher in the crosslinked film molded using the fluorine polymer having a terminal TAIC and having an iodine terminal. In addition, the film made from the polymer having the terminal TAIC was better in transparency of the film than the film made from the polymer having no terminal TAIC.

Sample 2 (B1 and B2 in FIG. 2) TAIC charging amount: 43.4% Polymer used: Iodine-terminated fluoropolymer [I- (CH ₂ CF ₂ ) m in sample (X1) of Example 1]
-(CF ₂ CF ₂ ) n-I copolymer] / terminal TAIC-modified iodine-terminated fluoropolymer (final polymer of Example 5) = 1/1 (weight ratio) Peroxide: 1 part (total amount of polymer and TAIC) To 100 copies)

Sample 5 (E1 and E2 in FIG. 2) TAIC charging amount: 43.4% Polymer used: Iodine-terminated fluoropolymer [I- (CH ₂ CF ₂ ) m in sample (X1) of Example 1]
_{- (CF 2 CF 2) n} -I copolymer] peroxide: 1 part (per 100 parts of total amount of polymer and TAIC)

[0051]

EFFECTS OF THE INVENTION According to the present invention, a cured product having excellent chemical resistance and weather resistance as well as high tensile strength and tensile elongation can be obtained. In the present invention, compared with the conventional polyfunctional compound in an amount used, due to its highly crosslinked structure, problems such as flow and creep resistance above the crystalline melting point of the polymer are improved, and tensile strength of the cured product is improved. It shows an unexpected improvement that mechanical properties at high temperature such as breaking strength and viscoelastic modulus are high. Further, in the present invention, T
Brittleness, which is a drawback of homopolymers of polyfunctional compounds such as AIC, is improved by reinforcement with a fluoropolymer, and moldability is improved by molding the composition in advance and then crosslinking.

[Brief description of drawings]

FIG. 1 shows the relationship between TAIC content, viscoelastic modulus (E ′) and tan δ in a crosslinked film.

FIG. 2 shows the relationship between the polymer used and the viscoelastic modulus (E ′) and tan δ of the crosslinked film.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09K 3/10 C09K 3/10 M (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 3/24 C08L 27 / 12-27/20

Claims (17)

(57) [Claims] 1. A compound comprising (a) a polyfunctional compound, (b) a fluorine-containing polymer containing iodine and / or bromine and a blend thereof, and (c) a radical generating source, and the component (a) is a component (a). A fluorine-containing polymer composition, which is 18 to 99% by weight of the total amount of a) and component (b). 2. The component (b) is 0.001 of the component (b).
A composition according to claim 1 containing from 10 to 10% by weight iodine or from 0.05 to 15% by weight bromine. 3. The composition according to claim 1, wherein the component (b) is 1 to 82 % by weight of the total amount of the component (a) and the component (b). 4. The component (c) is the component (a) and the component (b).
The composition according to claim 1, which is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight in total. 5. The component (a) is the component (a) and the component (b).
20-90% by weight, preferably 23-70% by weight, of the total amount of the composition according to claim 1. 6. A crosslinked body obtained by crosslinking the polymer composition according to claim 1. 7. A molding material composition comprising the polymer composition according to claim 1. 8. A resin modifier composition comprising the polymer composition according to claim 1. 9. A cross-linking agent composition comprising the polymer composition according to claim 1. 10. A coating composition comprising the polymer composition according to claim 1. 11. An adhesive composition comprising the polymer composition according to claim 1. 12. A sealant comprising the polymer composition according to claim 1. 13. A crosslinked product obtained by crosslinking the polymer composition according to claim 1 with an inorganic compound or a heat-resistant resin other than the fluorine-containing polymer of component (b) mixed and dispersed. 14. The crosslinked product according to claim 6, which is an electrical insulator. 15. The crosslinked product according to claim 6, which is a heat resistant sheet, a heat resistant film, or a heat resistant tube. 16. The crosslinked product according to claim 6, which is a sealing material for an engine or a compressor. 17. The crosslinked product according to claim 6, which is an IC substrate.