JPS63101422A - Production of polycyanic ester polymer - Google Patents

Abstract

PURPOSE:To produce the title uniform polymer of excellent properties in an excellent catalytic performance, by adding a small amount of a diorganotin oxide to a polycyanic ester compound and heating the mixture. CONSTITUTION:A polycyanic ester compound (A) [e.g., 2,2-bis(4-cyanatophenyl) propane] is mixed with a small amount of a diorganotin oxide (B) (e.g., dibutyltin oxide or dioctyltin oxide), and the mixture is heated to produce a polycyanic ester polymer or its cured product. The amount of catalyst B added is preferably 0.005-1.0pt.wt. per 100pts.wt. component A. A polycyanic ester polymer which is more uniform and has good physical properties can be obtained since catalyst B can exhibit both a catalysis at least equivalent to that of a well-known excellent catalyst and excellent solubility. Especially, di-n-octyltin oxide is one excellent in safety and capable of being used also in food materials.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to producing a high molecular weight polyfunctional cyanate ester resin by heating a polyfunctional cyanate ester compound, or further producing a polyfunctional cyanate ester resin. Cured, molded product,
This invention relates to a method for manufacturing coating films, castings, laminates, sheets, etc.

[Conventional methods and their problems]

The polyfunctional cyanate ester compound is polymerized and cured by heating, and is also subject to West German patent Nα1190184 (196
5,04,01), Lewis acid, phosphoric acid, hydrochloric acid, sodium hydroxide, tributylphosphine, trimethylamine, Phospholin-Δ'-1-oxo-1-
Methods using catalysts such as phey 1, and
A method is known in which a metal chelate such as acetylacetone metal salt is blended and heated as in No. 9-16800.

Without a catalyst, the curing reaction takes time, and in the West German patented method, the physical properties such as electrical properties of the cured product are inferior. or,
In Tokkosho's method, the solubility of the catalyst in the resin was poor, and it was necessary to use special solvents.

[Means for solving problems]

The present invention has excellent solubility in polyfunctional cyanate esters,
As a result of extensive research into a method that can significantly accelerate and control the curing polymerization reaction with a small amount, the present invention was completed.

That is, the present invention is a method for producing a polyfunctional cyanate ester polymer or a cured product thereof, which comprises blending a small amount of diorganotin oxide into a polyfunctional cyanate ester compound and heating the mixture. The diorganotin oxide used is selected from di-n-butyl oxide or di-n-octyl tin oxide.

The present invention will be explained below.

The polyfunctional cyanate ester compound of the present invention has the general formula (
1): R(OCN)m---(1) (m in the formula is an integer of 2 or more and usually 5 or less, R is an aromatic organic group, and the cyanato group is It is a compound represented by (bonded to an aromatic ring). To give a concrete example, 1.3
- or 1.4-diallylbenzene, 1.3.5-) lycyanatobenzene, 1.3-, 1.4-, 1.6-,
'1.8-, 2.6- or 2.7-dicyanatonaphthalene, 1.3.6-tricyanatonaphthalene, 4.4°-
Dicyanatobiphenyl, bis(4-cyanatophenyl)
Methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-cyclo-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 O
Cyanic acid ester (USP-
4026913), cyanic acid esters obtained by the reaction of novolacs with cyanogen halides (USP-40
22755, USP-3448079). In addition to these, Tokuko Sho 41-1928, Sho 43-184
68, 44-4791, 45-11712, 4
6-41112, 47-26853, Japanese Unexamined Patent Publication No. 51-6
3149, USP-3553244, 3755402,
Cyanic acid esters described in 3740348, 3595900, 3694410 and 4116946 can also be used.

In addition, the above-mentioned polyfunctional cyanate ester generally has a sym-) formed by trimerization of the cyanide group in the above-mentioned polyfunctional cyanate ester compound. It can also be used in the form of a prepolymer.

The above-mentioned polyfunctional cyanate ester can be used as a composition containing thermosetting monomers, prepolymers, and resin components used as necessary, and can also be used as a composition containing other fibrous reinforcing materials. , fillers, dyes, pigments,
Naturally, a mixture of various known additives such as thickeners, lubricants, coupling agents, and flame retardants can also be used.

Examples of thermosetting monomers or prepolymers include polyfunctional (meth)acrylates and alkyl (meth)acrylates.
Poly(meth)acrylates such as acrylate and epoxy(meth)acrylate; polyallyl compounds such as diallyl phthalate, divinylbenzene, diallylbenzene, and trialkenyl isocyanate and their brevolimers; dicyclopentadiene and its prepolymers; phenolic resin: epoxy Known resins such as resin are exemplified. In addition, as a resin component, polyvinyl acetal resin such as polyvinyl formal, polyvinyl acetal, polyvinyl butyral; phenoxy resin; 011
or C00II group; silicone resin; alkyd resin; thermoplastic polyurethane resin;
Non-crosslinked (non-vulcanized) rubbers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber; polyethylene, polypropylene,
Polybutene, poly-4-methylpentene-1, polyvinyl chloride, vinylidene chloride resin, polystyrene, polyvinyltoluene, polyvinylphenol, As resin, ABS
Resin, MBS resin, poly-4-fluoroethylene, fluoroethylene-propylene copolymer, 4-fluoroethylene-
Vinyl compound polymers such as 6-fluorinated ethylene copolymer and vinylidene fluoride; resins such as polycarbonate, polyester carbonate, polyphenylene ether, polysulfone, polyester, polyether sulfone, polyamide, polyaimide, polyester imide, polyphenylene sulfide, etc. In addition, low molecular weight polymers (prepolymers) having a molecular weight of 10,000 or less, usually 1,000 to several thousand, which are low polymers of these thermoplastic resins, can be mentioned.

The diorganotin oxide of the present invention is R'R25nO (
In the formula, R1 and R2 are hydrocarbon groups),
Normally, it is a white powdery solid, and di-lobyl tin oxide and di-n-octyl tin oxide are particularly suitable.

The amount of diorganotin oxide blended in the polyfunctional cyanate ester compound of the present invention is a small amount, that is, an amount within a range effective as a catalyst, preferably 0.001 parts by weight per 100 parts by weight of the polyfunctional cyanate ester compound. -5.0 parts by weight, particularly from 0.005 to 1 part by weight.

The method of mixing the white solid diorganic acid oxide with the polyfunctional cyanate ester compound of the present invention is not particularly limited as long as it can be uniformly dispersed; however, the method of simply mixing and dispersing; A method in which the ester compound is heated and melted at a temperature of 60°C or higher; A method in which the ester compound is dissolved and mixed and then dissolved in a solvent; oot ~ 1.0 parts by weight A method of combining the molten pool and then adding it thereto and melt-mixing; After melting and mixing,
Method of dissolving in a solvent; 0.00% organic acid in epoxy resin
Method of mixing 0.001 to 1.0 parts by weight of organic acid to epoxy resin and mixing 1 to 1.0 parts by weight of diorganotin oxide to a polyfunctional cyanate ester compound or its solution; A method in which diorganotin oxide is dissolved and mixed with a polyfunctional cyanate ester compound or its solution; 0.001 to 1.0 parts by weight of an organic acid is mixed in a solvent, Examples include a method in which diorganotin oxide is dissolved and mixed in a polyfunctional cyanate ester compound or a solution thereof.

In the present invention, in addition to the diorganotin oxide described above, other polyfunctional cyanate ester compounds and known catalysts can be used in combination as necessary. Such catalysts include organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, and di-tert-butyl perphthalate; 2-methylimidazole, 2-ethyl- 4
- Imidazoles such as methylimidazole; tertiary amines such as triethylamine and N-methylpiperidine;
Phenols such as phenol and cresol; Organometallic salts such as zinc naphthenate, lead stearate, lead naphthenate, zinc octylate, tin oleate, tin octylate, dibutyltin malate, manganese naphthenate, cobalt tephthenate; acetylacetone iron, copper acetylacetone,
Metal chelate compounds such as cobalt acetylacetone;
Examples include acid anhydrides such as trimellitic anhydride and phthalic anhydride.

〔Example〕

The present invention will be explained below with reference to Examples. Note that parts and percentages in Examples and the like are based on weight.

Example 1 2.2-Bis(4-cyanatophenyl)propane (purity 97%) was melted at a temperature of 80°C, and 0.0% of di-n-butyltin oxide or di-n-octyltin oxide was added to it.
1% was added, mixed for 5 minutes to uniformly dissolve, and then cooled to room temperature.

Using this mixture, gel time was measured on a heating plate at 170°C, and this mixture was cast and heated at 170°C for 24 hours.
Table 1 shows the results of measuring the glass transition temperature of the samples that were heat-cured at 180° C. for 3 hours and then at 240° C. for 12 hours.

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

Comparative Example 1 In Example 1, an attempt was made to dissolve and mix 0.1% iron acetylacetonate instead of dialkyltin oxide, but it did not dissolve completely and some undissolved content precipitated. However, the gelation time of this mixture measured in the same manner was 50 seconds.

Example 2 After melting 100 parts of 2.2-bis(4-cyanatophenyl)propane (purity 99.8%) at a temperature of 80°C, 0.15 parts of para-toluenesulfonic acid was added and mixed to form a transparent and uniform resin. It was made into a liquid. Add 0.05 part of di-0-butyl oxide or di-octyl tin oxide to this,
After mixing for a minute to uniformly dissolve the mixture, the mixture was cooled to room temperature.

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

Further, a similar mixture was dissolved in methyl ethyl ketone (=MBK>) to obtain a transparent solution with a concentration of 50%, and the gel time at 190° C. was measured using this solution.

The results are shown in Table 2.

For comparison, 2,2-bis(4-cyanatophenyl)propane (purity 99.8%) alone and 2,2-bis(4-cyanatophenyl)propane (purity 99.8%) were also used.
The results were similarly measured for a transparent and uniform resin liquid obtained by adding and mixing 0.15 parts of para-toluenesulfonic acid to 100 parts of 4-cyanatophenyl)propane.

Example 3 Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy G@, trade name: Epicoat 828, epoxy resin)
fi 184-194) For 100R, cuff: +
-/LzO, 1 part was heated and mixed at 60°C to obtain a homogeneous mixture.

To this epoxy resin mixture, further 0.5 part of di-n-butyltin oxide or di-n-octyltin oxide,
Mixed at 60°C.

2 parts of the above epoxy resin mixture and acetone were mixed with 100 parts of 1.4-dicyanatobenzene (purity 90%) to form a uniform solution with a concentration of 50%.

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

[Operation and effects of the invention]

As described above, according to the method for producing a polyfunctional cyanate ester polymer or a cured product thereof using diorganotin oxide as a catalyst of the present invention, the polyfunctional cyanate ester polymer or its cured product has a catalytic ability equivalent to or higher than that of known excellent catalysts, and has a high solubility. Because it has excellent properties, it is possible to obtain products that are more uniform and have good physical properties, and in particular, di-n-octyltin oxide is also excellent in safety, as it can be used as a food material. be.

Claims (1)

[Scope of Claims] 1. A method for producing a polyfunctional cyanate ester polymer or a cured product thereof, which comprises blending a small amount of diorganotin oxide with a polyfunctional cyanate ester compound and heating the mixture. 2. The manufacturing method according to claim 1, wherein the diorganotin oxide is selected from dibutyltin oxide or dioctyltin oxide.