JPS5912909A - Preparation of fluoroalkyl methacrylate copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having improved resistance to thermal decomposition and adhesive property, by copolymerizing a specific methacrylic acid ester containing fluorine with a monomer copolymerizable therewith and a vinyl monomer capable of forming a hydrophilic homopolymer in a specific proportion. CONSTITUTION:(A) 70-99.95pts.wt. 2,2,2-trifluoroethyl methacrylate is copolymerized with (B) 0-30pts.wt. monomer copolymerizable with the component (A), e.g. methyl methacrylate, and (C) 0.05-30pts.wt. vinyl monomer capable of forming a hydrophilic homopolymer, e.g. (meth)acrylic acid, glycidyl methacrylate or (meth)acrylamide, to give the aimed copolymer. USE:A sheath material for light transmitting core materials, e.g. polymethyl methacrylate rsin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a copolymer having excellent heat decomposition resistance and adhesiveness. More specifically, the present invention comprises methacrylic acid, 2. ．． 2-Fluoroethyl 70~qct, q
S heavy part and vinyl monomer θ~30 parts copolymerized with this and other vinyl monomers 003~JOI (mFAk copolymerized in the presence of copolymerization) forming a hydrophilic homopolymer. The present invention relates to a method for producing a copolymer having excellent heat decomposition resistance and adhesion to a polymethyl methacrylate plate by polymerization.

In addition to being used as heat-resistant, corrosion-resistant materials and high-performance secondary coatings, fluorine-containing composites have been used as materials with various functionalities. Due to its characteristic surface properties, optical properties, radiation sensitivity, electrical properties, and medical material properties, it is functionally applied in various fields.

Among fluorine-containing polymers, fluorotetraalkyl methacrylate electrolyte polymers are special because they maintain a low refractive index of light and are also excellent in water repellency, oil repellency, radiation sensitivity, hygroscopicity, and dimensional stability. It is positioned as a unique resin.

Fluorine-containing adhesives are used as optical transmitter resins by taking advantage of these characteristics, particularly their low refractive index for light. Specifically, it is used as a sheath material for a core material of an optical transmission body such as gelystyrene, polymethyl methacrylate, or gelicarbonate resin.

In addition, fluorine-containing binders are also used as molding materials, but because fluorine-containing binders are expensive, the technology for manufacturing and molding them is not well established compared to general-purpose resins. Not yet.

When a mixture of a fluorine-containing main body combination and a general-purpose resin is thermoformed at high temperature, so-called jetting, silvering, etc. occur, and the quality of the processed product is poor. When mixed and melt-molded, the quality and appearance of the molded product will be poor.

Furthermore, when conventional fluorine-containing polymers are thermoformed, a foaming phenomenon occurs along with the generation of silver, and this is because fluorine-containing polymers generally have poor decomposition resistance. Currently, polymers have been forced to be processed at low temperatures, resulting in problems in shapeability.

Furthermore, a normal fluorine-containing polymer is formed into a film, and T
- After that, when laminating with a general-purpose resin plate, the adhesion strength between the two is low and easily peels off because the fluorine-containing adhesive has water and oil repellency.

The inventors of the present invention conducted extensive research to eliminate the above drawbacks and found that methacrylic acid co, 2,2-trifluoro p-ethyl 70~qqq! When copolymerized with M< Co. W6, a vinyl monomer o-, iodine, which forms a hydrophilic homopolymer, and other vinyl monomers OO3-30, radical decomposition occurs. It has been found that a copolymer can be obtained in which thermal decomposition due to polymerization is suppressed and also has excellent adhesion to general-purpose resins.

Thermal decomposition based on radical depolymerization Comparatively, fluoroalkyl has a large G-Komi qi negativity, so
The double bond density is sparse, resulting in a molecular structure that is not susceptible to radical depolymerization, and the depolymerization activation free energy is low, so it is easily decomposed. In order to prevent this, it is possible to copolymerize something with a somewhat high depolymerization activation free energy, such as an acrylic ester, with a fluorine-containing methacrylic ester, but this alone will not solve the problem, as there is also the problem of copolymerizability. This is not a practical solution. However, Metak1JAJ1. ．． 2. ．． 2. When a vinyl monomer is copolymerized to form a J-trifluoroethyl hydrophilic ζ homopolymer, the water and oil repellency of the fluoropolymer decreases, and the layering properties with polymethyl methacrylate improve. It has also been found that such hydrophilic monomers improve the above-mentioned thermal decomposition resistance.

Vinyl monomers copolymerized with co-, co-, and trifluoroethyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and n-propyl methacrylate.
-butyl methacrylate, tert-butyl methacrylate, lauryl methacrylate, nonyl methacrylate, methyl acrylate, butyl acrylate, coethylhexyl acrylate, styrene, α-methylstyrene, etc., but methacrylate is preferred from the QJ point of copolymer properties etc. Examples of vinyl monomers that form hydrophilic solo polymers include the following.

Ethylenic mono- or dicarboxylic acid [i-mers include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, 3-methylglutaconic acid, muconic acid, dihydromuconic acid, 1 methylene malonic acid, Examples include citraconic acid, mesaconic acid, methylene glutaconic acid, etc., but effective monomers include methacrylic acid,
Acrylic acid is used, and methacrylic acid is particularly preferred since it improves the thermal decomposition resistance of the resulting copolymer.

Examples of the ethylenically unsaturated epoxy monopolymer include glycidyl methacrylate, methyl glycidyl itacrylate, allyl glycidyl ether, etc. Glycidyl methacrylate and methyl glycidyl methacrylate are effective for improving the adhesion of the copolymer. .

Ethylenically unsaturated carboxylic acid amide, N-alkylcarboxylic acid amide, N-methy, 0-carpone peramide and their alkyl ether monomers include acrylamide, methacrylamide, N-methylacrylamide,
N-diethylacrylamide, maleic acid, fumaric acid,
Monoamides, diamides or esteramides of itaconic acid or other ethylenically unsaturated dicarboxylic acids, N-methylolacrylamide, N-methylolmethacrylamide, N-no 1-1'l-/? as long as it is hydrophilic. Ethers of compounds such as methyl ether, ethyl ether, 3
-oxabutyl ether, 3,6-dioxahebutyl ether, J+A+9-)lioxadecyl ether, etc. are mentioned as monomers that improve the adhesion.

Also, N-methylolacrylamide, N-methylolmethacrylamide or N-methylolmaleimide triethylene oxide addition products, N-vinylamides such as N
-vinylacetamide and N-vinylpyrrolidone are also mentioned as hydrophilic monomers.

Ethylenically unsaturated polycarboxylic acids include ester condensates obtained by combining hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate with succinic anhydride, heptatalic anhydride, maleic anhydride or trimellitic anhydride. Examples include monomers that are metal objects.

As the polymerization catalyst, ordinary radical polymerization catalysts can be used, specifically, di-tart-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, tart-butyl peroxide), tart-butyl peroxide, tart-butyl peroxide, tart-butyl peroxide,
-Butyl perbenzoate, methyl isobutyl ketone peroxide, lauroyl peroxide, cyclohexyl peroxide, J,! -Jimesenluko, S-Gtar
Organic peroxides such as t-butylperoxyhexane, tert-butylperoctanoate, tert-butylperisobutyrate, tart-butylperoxyisopropyl carbonate, methylco, 2'-azobisisobutyrate, /- 7'-azobiscyclohexanecarbonitrile, cophenylazo-J, <4-dimethyldermethoxyvaleronitrile, -monocarpomoylazobisisobutyronitrile 1.2. ．． 2'-azobis(,2
,? -dimethylvaleronitrile), co-, -'-azobisisobutyronitrile and the like.

As the chain transfer agent, an alkyl mercaptan, which is usually used as a polymerization degree articulating agent, is used.

As the polymerization method, any of emulsion, suspension, bulk or solution polymerization can be used, but bulk polymerization is preferred in order to obtain a polymer with sieve purity.

The copolymer of the present invention is advantageously used as a sheath material for optical fibers.

l) Evaluation of heat decomposition resistance A fluorine-containing methacrylate polymer was prepared by a bulk polymerization method,
Crush it with a crusher and JISZ-11KO/standard/
A Metsu I Kusu Separated into 3 pieces and 2k
It was shaped into a pellet using an m-bent extruder (manufactured by Osaka Seiki Co., Ltd.). This pellet piece was subjected to a heat resistance test.

The heat resistance test is 270 (20 minutes in air atmosphere, 60
IJII by gear oven heating for 7.2θ min and 7.2θ min.
The heat loss percentage was determined and used as a guideline for heat decomposition resistance or heat resistance.

2) Evaluation of adhesion A fluorine-containing methacrylate polymer was prepared by a bulk polymerization method,
Crush it with a crusher to JISz-gttoi standard
/Remesh Pass Separate into 3 pieces/1
A film having a thickness of lSOμ was formed by hot pressing at a pressure of 10 (: k min/00 kg/cl).

This film was coated with a polymethyl methacrylate board (manufactured by Sanni Rayon Co., Ltd., Acrylite Co., Ltd., L-≠00/, plate thickness 2).
關）&Kuchitori, 2.30C10 seconds! A laminate was formed by pressure bonding under conditions of 9/cl.

A fluorine-containing polymer film is passed over the contact layer film obtained by such G straining to reach the methacrylic resin plate.
Both vertically and horizontally / 11 of width / am, depth / 1III
100 incisions made with a book razor blade
An m X / ta square was created.

A cellophane tape made by Nichiban was pasted on top of this, and the tape was then momentarily peeled off to evaluate adhesion based on the state of adhesion to the tape surface.

Out of 100 items, 1 peels or does not peel at all.
~ SOke What peels off is Δ, and what peels off further is X
It was evaluated as

Example methacrylic rII in the indicated proportions.

- 0.05 parts of azobisisobutyronitrile and 0.7 F of n-dodecyl mercaptan as polymerization initiators in a hydrophilic medium containing monotrifluoroethyl and methyl methacrylate.
M was mixed and dissolved, and this was charged into an autoclave for bulk polymerization, and the autoclave was sealed by repeating degassing and exchanging 10% of nitrogen.
When soaked for a period of time to polymerize the monosensitive substance, it can be used internally / Okg
/c+I Since the gauge is now 70C, it is 3:01.
! When heated, the polymerization exothermic peak was completed, and the polymerization was completed, yielding a clear copolymer. This copolymer was crushed using a crusher, and the adhesion and heat decomposition resistance were determined by the method described above. The results were as shown in the table.

Note that Experiment 1 A/2~/DA is a comparative example in which no hydrophilic simple substance was used.

When the optical refractive index of the copolymer obtained in Experiment AI was measured, it was 2 g.

Claims (1)

[Claims] l Co-, co-, trifluoroethyl methacrylate 70
Copolymerize a mixture consisting of ~99.989m, ~30 parts by weight of a vinyl monofilament O to be copolymerized with this, and 1 part by weight of a vinyl monofilament OθS capable of forming a hydrophilic homopolymer. A fluoroalkyl methacrylate co-coco
A method for producing a copolymer according to claim 7, wherein the vinyl monomer forming the hydrophilic homopolymer is an ethylenically unsaturated mono- or dicarboxylic acid. A method for producing a co-m polymer according to claim 1, which is acrylic acid or methacrylic acid. Range 1
A method for producing a copolymer as set forth in Claim 1-Hydrophilic homopolymer, wherein the ethylenically unsaturated epoxy monomer is glycidyl methacrylate or methylglycidyl methacrylate. The copolymer according to claim 1, wherein the vinyl monomer forming the is an ethylenically unsaturated carboxylic acid amide, an N-alkylcarboxylic acid amide, an N-methylolcarboxylic acid amide, or an alkyl ether thereof. Production method Ethylenically unsaturated carboxylic acid amide is acrylamide, methacrylamide, N-methylacrylamide, N
- A method for producing a co-m combination according to claim 6, which is diethyl acrylamide, N-methylolacrylamide, or the methyl ether or ethyl ether thereof.g) The vinyl monomer forming the hydrophilic homopolymer is ethylenic. A process 9 for producing a copolymer according to claim 1, which is a monomer obtained from unsaturated polycarboxylic acid or carboxylic acid. Ethylenically unsaturated polycarboxylic acid is a monomer obtained from carboxylic acid. A method for producing a copolymer according to claim S, which is a monomer obtained from ethyl acrylate or hydroxyethyl methacrylate and succinic anhydride, heptatalic anhydride, or trimellitic anhydride.