JPH0819231B2 - Method for producing polyfunctional cyanate ester polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is directed to the production of a high-molecular-weight polyfunctional cyanate ester resin by heating a polyfunctional cyanate ester compound, or a further polyfunctional cyanate ester resin. The present invention relates to a method for producing a molded product, a coating film, a cast product, a laminated plate, a sheet, etc. by curing.

[Conventional method and its problems]

The polyfunctional cyanate ester compound is polymerized by heating,
Hardened and, as in West German Patent No. 1190184 (1965.04.01), Lewis acid, phosphoric acid, hydrochloric acid, sodium hydroxide, tributylphosphine, trimethylamine, Phospholin-
A method using a catalyst such as Δ ³ -1-oxo-1-pheyl,
Also known is a method in which a metal chelate such as an acetylacetone metal salt is blended and heated as in JP-B-49-16800.

Without a catalyst, the curing reaction takes a long time, and the physical properties such as electrical properties of the cured product are inferior by the method of West German Patent.
Also, in the method of Japanese Patent Publication No. Sho, the solubility of the catalyst in the resin is not good, and it is necessary to adopt a method of using a special solvent.

[Means for solving problems]

The present invention has completed the present invention as a result of extensive studies on a method which has excellent solubility in a polyfunctional cyanate ester, promotes a remarkable curing polymerization reaction with a small amount, and can control the curing polymerization reaction.

That is, in the present invention, 0.001 to 5.0 parts by weight of a diorganotin oxide selected from dibutyltin oxide or dioctyltin oxide is mixed with 100 parts by weight of a polyfunctional cyanate compound represented by the following general formula (1). Then, the polyfunctional cyanate ester polymer is produced by heating.

General formula (1): R (OCN) _m (1) (wherein m is an integer of 2 or more and 5 or less, R is an aromatic organic group, and the cyanato group is the organic group. The present invention will be described below.

Specific examples of the polyfunctional cyanate compound represented by the above general formula (1) of the present invention include 1,3- or 1,4-
Dicyanatobenzene, 1,3,5-tricyanatobenzene,
1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanato Biphenyl, bis (4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane,
2,2-bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, Bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and terminal OH group-containing polycarbonate oligomer and halogen Examples thereof include cyanate ester (USP-4026913) obtained by reaction with cyanide and cyanate ester (USP-4022755, USP-3448079) obtained by reaction between novolac and cyanogen halide. In addition to these, Japanese Examined Patent Publications 41-1928, 43-18468, 44-479
1, the same 45-11712, the same 46-41112, the same 47-26853, JP-A-51
-63149, USP-3553244, 3755402, 3740348, 3595900,
Cyanate esters described in 3694410 and 4116946 can also be used.

The above-mentioned polyfunctional cyanate ester is generally a prepolymer having a sym-triazine ring formed by trimerization of the cyan group in the polyfunctional cyanate compound and an unreacted cyanato group. It can be used even in the state of.

The above-mentioned polyfunctional cyanate ester includes a thermosetting monomer or prepolymer which is optionally used,
It can also be used as a composition containing a resin component, and other known various additives such as other fibrous reinforcing materials, fillers, dyes, pigments, thickeners, lubricants, coupling agents, flame retardants, etc. Naturally, it can be used as a mixture of kinds.

Here, as the thermosetting monomer or prepolymer, poly (meth) acrylates such as polyfunctional (meth) acrylate, alkyl (meth) acrylate, and epoxy (meth) acrylate; diallyl phthalate,
Examples thereof include polyallyl compounds such as divinylbenzene, diallylbenzene, and trialkenyl isocyanurate, and prepolymers thereof; dicyclopentadiene and prepolymers thereof; phenol resins; known resins such as epoxy resins. Further, as the resin component, polyvinyl acetal resin such as polyvinyl formal, polyvinyl acetal, polyvinyl butyral; phenoxy resin; O
Acrylic resin having H group or COOH group; silicone resin; alkyd resin; thermoplastic polyurethane resin; polybutadiene, butadiene-acrylonitrile copolymer,
Non-crosslinked (non-vulcanized) rubbers such as polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, and natural rubber; polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, polyvinyl chloride, chloride Vinylidene resin, polystyrene, polyvinyltoluene, polyvinylphenol, AS resin, ABS resin, MBS
Vinyl compound polymers such as resin, poly-4-fluoroethylene, fluoroethylene-propylene copolymer, 4-fluoroethylene-6-fluoroethylene copolymer, vinylidene fluoride; polycarbonate, polyester carbonate, Resins such as polyphenylene ether, polysulfone, polyester, polyether sulfone, polyamide, polyadimide, polyester imide, and polyphenylene sulfide, and low molecular weight polymers of these thermoplastic resins have a molecular weight of 10,000 or less, usually 1,000 to several thousand. A low molecular weight polymer (prepolymer) may be mentioned.

The diorganotin oxide of the present invention is R ¹ R ² SnO (R in the formula
¹ and R ² are compounds represented by hydrocarbon groups), which are white powdery solids in the normal state, and specifically, di-n-butyltin oxide and di-n-octyltin oxide.

The compounding amount of the diorganotin oxide of the present invention with respect to the polyfunctional cyanate ester compound is a small amount, that is, an amount within a range effective as a catalyst, and preferably 0.001 to 5.0 with respect to 100 parts by weight of the polyfunctional cyanate ester compound. Parts by weight, especially
It is appropriately selected from the range of 0.005 to 1 part by weight.

The method of mixing white solid diorganotin oxide with the polyfunctional cyanate compound of the present invention is not particularly limited as long as it is a method of uniformly dispersing, but a method of simply mixing and dispersing; polyfunctional cyanic acid A method of melting and dissolving an ester compound at a temperature of 60 ° C. or higher; a method of dissolving and mixing, and then dissolving in a solvent; a polyfunctional cyanate ester compound, and an organic acid such as paratoluenesulfonic acid or octylic acid 0.001 to 1.0 Part by weight Melt-mixing and then adding to it and melt-mixing; Method after melt-mixing and dissolving in solvent; 0.001 to 1.0 part by weight of organic acid is mixed with epoxy resin, and diorganotin oxide is dissolved and mixed therewith A method of mixing an organic acid with a polyfunctional cyanate compound or a solution thereof; mixing 0.001 to 1.0 parts by weight of an organic acid with an epoxy resin and a solvent, A method in which a mixture of ganotin oxide dissolved and mixed is mixed with a polyfunctional cyanate compound or a solution thereof; 0.001 to 1.0 part by weight of an organic acid is mixed with a solvent, and a mixture of diorganotin oxide dissolved and mixed with the solvent is polyfunctional. Examples thereof include a method of mixing with a cyanate ester compound or a solution thereof.

In the present invention, a known catalyst can be used in combination with the above-mentioned diorganotin oxide in other polyfunctional cyanate ester compounds, if necessary. Such catalysts include organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-tert-butyl-peroxide, dicumyl peroxide, di-t-butyl perphthalate; 2-methylimidazole, Imidazoles such as ethyl-4-methylimidazole; tertiary amines such as triethylamine and N-methylpiperidine; phenols such as phenol and cresol; zinc naphthenate, lead stearate, lead naphthenate and zinc octylate;
Organic metal salts such as tin oleate, tin octylate, dibutyltin malate, manganese naphthenate, and cobalt tethenate; metal chelate compounds such as iron acetylacetone, copper acetylacetone, cobalt acetylacetone; acids such as trimellitic anhydride and phthalic anhydride Anhydrous etc. are mentioned.

〔Example〕

Hereinafter, the present invention will be described with reference to examples and the like. In the examples and the like, parts and% are based on weight.

Example 1 2,2-bis (4-cyanatophenyl) propane (purity 9
7%) was melted at a temperature of 80 ° C., 0.1% of di-n-butyltin oxide or di-n-octyltin oxide was added thereto, and the mixture was mixed for 5 minutes to dissolve uniformly and then cooled at room temperature.

Using this mixture, measure the gel time on a heating plate at 170 ° C and cast this mixture at 170 ° C for 24 hours at 180 ° C.
Table 1 shows the results of measuring the glass transition temperature of the resin which was cured by heating for 3 hours at 240 ° C. for 12 hours.

For comparison, the results of the same measurement for 2,2-bis (4-cyanatophenyl) propane (purity 97%) are also shown.

Comparative Example 1 In Example 1, 0.1% of acetylacetone iron was dissolved and mixed in place of dialkyltin oxide, but it was not completely dissolved and an undissolved part was partially precipitated. However, the gelation time of this mixture measured in the same manner was 50 seconds.

Example 2 2,2-bis (4-cyanatophenyl) propane (purity 9
(9.8%) was melted at a temperature of 80 ° C., and 0.15 parts of paratoluenesulfonic acid was added and mixed to obtain a transparent and uniform resin liquid. To this, 0.05 part of di-n-butyltin oxide or di-n-octyltin oxide was added, mixed for 5 minutes to dissolve uniformly, and then cooled to room temperature.

Using this mixture, gel time was measured on a heating plate at 190 ° C., and the glass transition temperature of the mixture which was heat-cured in the same manner as in Example 1 was measured.

In addition, a similar mixture was dissolved in methyl ethyl ketone (= MEK) to form a transparent solution with a concentration of 50%.
The gel time at 0 ° C was measured.

 The results are shown in Table 2.

Also, for comparison, 2,2-bis (4-cyanatophenyl) propane (purity 99.8%) alone and 2,2-bis (4-
The same measurement results were shown for a transparent and homogeneous resin liquid prepared by adding 0.15 parts of paratoluenesulfonic acid to 100 parts of cyanatophenyl) propane and mixing them.

Example 3 Bisphenol A type epoxy resin (produced by Yuka Shell Epoxy Co., Ltd., trade name; Epicoat 828, epoxy equivalent 184)
-194) 100 parts of catechol 0.1 part was heated and mixed at 60 ° C to obtain a uniform mixture.

0.5 parts by weight of di-n-butyltin oxide or di-n-octyltin oxide was added to this epoxy resin mixture.
Mixed at 0 ° C.

To 100 parts of 1,4-dicyanatobenzene (purity 90%), 2 parts of the above epoxy resin mixture and acetone were mixed to form a uniform solution having a concentration of 50%.

Table 3 shows the results of measuring the gel times of these solutions at 170 ° C.

[Operations and Effects of the Invention] As described above, according to the method for producing a polyfunctional cyanate ester polymer using the diorganotin oxide of the present invention as a catalyst or a cured product thereof, it is possible to obtain a catalyst equivalent to or better than a known excellent catalyst. Since it has catalytic ability and excellent solubility, a more uniform and good physical property can be obtained, and especially di-n-octyltin oxide can be used as a food material. It is also excellent in safety.

Claims (1)

[Claims] 1. To 100 parts by weight of a polyfunctional cyanate compound represented by the following general formula (1) is added 0.001 to 5.0 parts by weight of diorganotin oxide selected from dibutyltin oxide or dioctyltin oxide. A method for producing a polyfunctional cyanate ester polymer, which comprises heating. Formula (1): R (OCN) _m (where m is an integer of 2 or more and 5 or less, R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. That is).