JPH06248029A - Vulcanizable fluorine-containing elastic copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer, comprising a fluorine-containing alkyl vinyl ether, an epoxy group-containing vinyl ether and an ethylenically unsaturated monomer in a specific proportion, vulcanizable without using a vulcanizing agent and useful as a medical tube, etc. CONSTITUTION:This elastic copolymer is obtained by copolymerizing (A) 0.1-20mol% fluorine-containing alkyl vinyl ether of the formula CF2=CF-O- Rf-(CH2)nOH [Rf is 1-20C and 0-30 ether bond-(un)containing bivalent polyfluoroalkylene; (n) is 1 or 2] (e.g. the formula CF2=CF-O-CF2CH2OH) with (B) 0.05-40mol% epoxy group-containing vinyl ether of the formula CX2=CX<1>-Y [X and X<1> are H, F or Cl; Y is epoxy-containing and fluorine-(un)containing monovalent group] (e.g. a compound of the formula) and (C) 40-99.85mol% one or more other monomers copolymerizable with the components (A) and (B) (preferably a fluorine-containing ethylenically unsaturated monomer, e.g. vinylidene fluoride) in the presence of a radical initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing elastic copolymer which can be automatically vulcanized.

[0002]

2. Description of the Related Art Fluorine rubber is used in a wide range of fields including automobile parts since it is a material excellent in heat resistance, oil resistance, weather resistance and the like. These are all diamines and polyhydroxy compounds. It is vulcanized and molded using a vulcanizing agent such as organic peroxide. However, the vulcanizates obtained by these vulcanization methods, since the vulcanizing agent and vulcanization accelerator used are not suitable for medical applications, food applications, etc.,
It was not always suitable for those applications.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and by introducing vulcanizable groups which react with each other into one molecule, the vulcanizable group can be added without a crosslinking agent. A vulcanizable elastic fluorine-containing copolymer is provided.

[0004]

That is, the present invention is
(A) CF ₂ ═CF—O—R _f — (CH ₂ ) _n OH (where R _f has 1 to 20 carbon atoms and has 0 to 3 oxygen atoms and contains or does not contain an ether bond. A fluoroalkylene group, where n is 1 or 2, and 0.1 to 20 mol% of a fluorine-containing alkyl vinyl ether (hereinafter, also simply referred to as component (A)) represented by (B) CX ₂ = CX ¹ −
Y (where X and X ¹ are the same or different atoms selected from hydrogen, fluorine and chlorine; Y is a monovalent group containing an epoxy group and containing or not containing a fluorine). Epoxy group-containing vinyl ether (hereinafter also simply referred to as component (B)) 0.05 to 40 mol%
And (C) at least one other ethylenically unsaturated monomer copolymerizable with the fluorine-containing alkyl vinyl ether (A) and the epoxy group-containing vinyl ether (B) (hereinafter, also simply referred to as component (C)) 40 It is a vulcanizable elastic fluorine-containing copolymer composed of about 99.85 mol%.

In the fluorine-containing elastic copolymer of the present invention,
The hydroxyl group in the component (A) reacts with the epoxy group in the component (B) to obtain a vulcanized product without using a vulcanizing agent or a vulcanization accelerator.

In the fluorine-containing elastic copolymer of the present invention,
The copolymerization ratio of the component (A) is in the range of 0.1 to 20 mol%, preferably 0.5 to 5 mol% from the viewpoint of vulcanizability, copolymerizability, physical properties of the obtained rubber and the like. Further, the copolymerization ratio of the component (B) is 0.05 to 40 mol%, preferably 0.1 to 40 mol% from the viewpoint of vulcanizability, copolymerizability, physical properties of the obtained rubber and the like.
It is in the range of 30 mol%. The copolymerization ratio of the component (C) is 40 to 99.85 mol%, preferably 65 to 9
It is in the range of 9.6 mol%.

As the component (A), there are chemical formula 1, chemical formula 2, chemical formula 3,
The compounds of Chemical formula 4, Chemical formula 5, and Chemical formula 6 can be exemplified, and as the component (B), the compounds of Chemical formula 7, Chemical formula 8, Chemical formula 9, and Chemical formula 10 can be exemplified.

[0008]

Embedded image CF ₂ ═CF—O—CF ₂ CH ₂ OH

Embedded image CF ₂ ═CF—O—CF ₂ CF ₂ CH ₂ OH

Embedded image CF ₂ ═CF—O—CF ₂ CF ₂ CF ₂ CH ₂ OH

Embedded image CF ₂ ═CF—O—CF ₂ CF ₂ CF ₂ CF ₂
CH ₂ OH

Embedded image CF ₂ ═CF—O—CF ₂ CF (CF ₃ ) OC
F ₂ CF ₂ CF ₂ CH ₂ OH

Embedded image _{CF 2 = CF-O- (CF} 2 CF (CF 3)
O) ₂ (CF ₂ ) ₃ CH ₂ OH

[0009]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

Examples of the component (C) include the following compounds. Vinylidene fluoride, hexafluoropropene,
1,1,1,2,3-pentafluoropropene, 3,
3,3-trifluoropropene, tetrafluoroethylene, trifluoroethylene, 1,2-difluoroethylene, dichlorodifluoroethylene, chlorotrifluoroethylene, hexafluorobutene, ethylene, propylene, 1-butene, fluorinated alkyl vinyl ethers, Fluorinated vinyl ethers.

The fluorine-containing elastic copolymer of the present invention is a component (A) -component (B) -vinylidene fluoride-hexafluoropropene copolymer, in view of heat resistance and oil resistance.
Component (A) -Component (B) -vinylidene fluoride-hexafluoropropene-tetrafluoroethylene copolymer,
(A) component- (B) component-tetrafluoroethylene-propylene copolymer, (A) component- (B) component-vinylidene fluoride-tetrafluoroethylene-propylene copolymer, (A) component- (B) Component-vinylidene fluoride copolymer, component (A) -component (B) -vinylidene fluoride-perfluoroalkyl vinyl ether copolymer, component (A) -component (B) -vinylidene fluoride-tetrafluoroethylene-per A fluoroalkyl vinyl ether copolymer or the like is preferably used.

As described above, a vulcanized product can be obtained by simply mixing the components (A) and (B) without using a vulcanizing agent and heating them. You may mix an acidic or basic substance as.

The fluorine-containing elastic copolymer of the present invention is obtained by copolymerizing each monomer in the presence of a radical initiator by a known polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization or solution polymerization. Manufactured. The monomer charging system may be a batch system or a system in which additional charging is continuously carried out so that the molar ratio of the monomers in the reaction system is kept constant.

The polymerization temperature, which is determined by the decomposition rate of the radical initiator, is usually selected from the range of 0 to 150 ° C. The polymerization pressure is determined by the polymerization temperature and the polymerization method, but is usually selected from the range of 0 to 50 kg / cm ² G. The molecular weight can be adjusted by adjusting the relationship between the copolymerization rate and the amount of the initiator, but it can be easily performed by adding a chain transfer agent.

The fluorine-containing elastic copolymer of the present invention may be mixed with conventionally known reinforcing fillers, extenders, pigments, internal release agents, plasticizers and the like used for fluororubber. To mix these vulcanization accelerators, fillers, etc., a mixing device such as a two-roll mill or kneader that is usually used for mixing rubber is used.

Vulcanization and molding of the fluorine-containing elastic copolymer of the present invention can be carried out in the same manner as in ordinary fluorine rubber.
That is, press molding, injection molding, extrusion molding, calender molding, dip molding by dissolving in a solvent or the like, coating, etc. can be performed.

The vulcanization temperature and time vary depending on the thickness and shape of the molded product, but are generally in the range of 120 ° C to 400 ° C for several seconds to 5 hours. In addition, in order to stabilize the properties of the vulcanizate, the temperature is adjusted to 0.5 at 150 ° C to 300 ° C in an oven.
Secondary vulcanization may be performed for about 48 hours.

[0018]

In the present invention, by introducing two different types of groups having vulcanization reactivity into one molecule, vulcanizability is improved without using a vulcanizing agent or vulcanization accelerator. This gives a fluorine-containing elastic copolymer.

[0019]

【Example】

Example 1 Tetrafluorethylene / Propylene / Compound of Chemical Formula 3 / Compound of Chemical Formula 7 = 55/43/1/1 by emulsion polymerization
A fluorine-containing elastic copolymer having a (molar ratio) and an intrinsic viscosity [η] = 0.4 was obtained. This was press-vulcanized at 180 ° C. for 30 minutes, and then secondary-vulcanized in an oven at 200 ° C. for 4 hours. JI
As a result of measuring the physical properties according to SK6301, the hardness was 61, the 100% modulus was 26 kg / cm ² , the tensile strength was 95 kg / cm ² , and the elongation was 370%.

Example 2 By emulsion polymerization, vinylidene fluoride / hexafluoropropene / compound of formula 5 / compound of formula 7 = 75/22 /
1.5 / 1.5 (molar ratio), intrinsic viscosity [η] = 0.55
A fluorine-containing elastic copolymer of was obtained. To 100 parts by weight of this fluorine-containing elastic copolymer, 30 parts by weight of MT-carbon and 5 parts by weight of magnesium oxide were uniformly mixed with a two-roll mill to obtain a fluorine-containing elastic copolymer composition. This was press-vulcanized at 170 ° C. for 10 minutes, and then secondary-vulcanized in an oven at 200 ° C. for 4 hours. As a result of measuring physical properties according to JIS K6301, hardness 72, 100% modulus 72 kg / cm
² , the tensile strength was 155 kg / cm ² , and the elongation was 210%.

Comparative Example 1 In the same manner as in Example 1, tetrafluoroethylene / propylene / Compound 3 compound = 55/43/2 (molar ratio), intrinsic viscosity [η] = 0.46, fluorine-containing elastic copolymer Got united.
Similar tests were conducted on this, but no vulcanized product was obtained.

[0022]

INDUSTRIAL APPLICABILITY The present invention provides a fluorine-containing elastic copolymer which can be vulcanized without using a vulcanizing agent, and the industrial advantage of the present invention is extremely large. Further, since the fluorine-containing elastic copolymer of the present invention does not require a vulcanizing agent or a vulcanization accelerator as described above, it is only suitable for medical tubes and catheters, food tubes, hoses, packings and the like. Instead, the heat resistance and oil resistance that fluororubber has
Because of its excellent chemical resistance, it can be used for automobiles, ships,
Packing, O-rings, etc. in transportation means such as aircraft
It is suitable for use in gaskets, hoses, sealing materials, diaphragms, valves, similar parts in chemical plants, nuclear plants, and general industrial parts.

Claims (2)

[Claims] 1. (A) CF ₂ ═CF—O—R _f — (CH
₂ ) _n OH (Here, R _f is a divalent polyfluoroalkylene group having 1 to 20 carbon atoms and 0 to 3 oxygen atoms, which may or may not contain an ether bond. N is 1 or 2.)
Fluorinated alkyl vinyl ether represented by 0.1 to 20
Mol% and (B) CX ₂ = CX ¹ -Y (where X and X ¹ are hydrogen,
The same or different atoms selected from fluorine and chlorine. Y is a monovalent group containing an epoxy group and containing or not containing fluorine. 0.05 to 40 mol% of an epoxy group-containing vinyl ether represented by the formula (4), and (C) at least one other ethylenic unsaturated copolymerizable with the fluorine-containing alkyl vinyl ether (A) and the epoxy group-containing vinyl ether (B). Monomer 40-99.8
A vulcanizable elastic fluorine-containing copolymer composed of 5 mol%. 2. The vulcanizable fluorinated elastic copolymer according to claim 1, wherein the ethylenically unsaturated monomer (C) is a fluorinated ethylenically unsaturated monomer.