JPS5923325B2 - Resin composition that exhibits elastomeric properties through polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition that exhibits elastomeric properties through polymerization.

The most common resin curing system is a system in which a highly polymerizable unsaturated bond is placed at the end or inside a prepolymer and crosslinked and cured through a polymerization reaction.

For this reason, various unsaturated bond-introducing agents are known. Examples include β-hydroxyethyl methacrylate, β-hydroxyethyl acrylate, β-hydroxypropyl methacrylate, and glycidyl methacrylate. It is often used alone as a reactive monomer, and various prepolymers synthesized using these are commercially available.For example, Japanese Patent Publication No. 47-16195, Japanese Patent Publication No. 48-10394, Japanese Patent Publication No. 48 −
No. 41708, No. 48-43657, etc. all use β-hydroxyethyl methacrylate compounds, but these are in great demand as prepolymers used for multiple purposes. However, Most of the unsaturated bond-introducing agents listed here are methacrylic acid or acrylic acid derivatives, and all of these unsaturated bond-introducing agents or prepolymers synthesized using them have different characteristics due to the properties of the methacrylic and acrylic groups themselves. In other words, methacrylic groups and acrylic groups are highly polymerizable and therefore unstable, and are often susceptible to undesirable polymerization due to heat or impurities.For this reason, the presence of polymerization inhibitors in these systems is necessary. is essential, and when using these as unsaturated bond-introducing agents, it is unavoidable that the reaction conditions are subject to restrictions such as high temperatures cannot be used.The present invention utilizes maleic as an unsaturated bond-introducing agent. By using acid esters or fumaric acid ester derivatives, it is an object of the present invention to improve the above problems and provide a resin composition that has useful properties that have not been available in the past.

The present invention provides (a) a monoalkyl ester of maleic acid or a monoalkyl ester of fumaric acid and
An alkylhydroxyalkyl ester of maleic acid or an alkylhydroxyalkyl ester of fumaric acid (1) obtained by reacting approximately equimolar amounts of a compound having oxirane oxygen, and an organic polyisocyanate in a polyether polyol with a molecular weight of 300 to 3,000. A reaction product obtained by reacting a polyether polyol derivative () having isocyanate groups obtained by reacting an organic polyisocyanate such that the isocyanate groups are in excess of the hydroxyl groups of the polyether polyol, (b)
Vinyl polymerizable monomer copolymerizable with (a) and (c
) The present invention relates to a resin composition containing a radical generator and exhibiting elastomeric properties through polymerization.

The reaction product of the present invention itself has very high thermal polymerization stability, and therefore also has excellent storage stability.

When subjected to a crosslinking reaction, a vinyl polymerizable monomer copolymerizable with the reaction product and a radical generator are allowed to coexist, and a cured product can be easily obtained by a conventionally known polymerization initiation method. Furthermore, a reaction product obtained using an alkylhydroxyalkyl ester of maleic acid or an alkylhydroxyalkyl ester of fumaric acid as an unsaturated bond-introducing agent in the present invention, a vinyl polymerizable monomer copolymerizable with this reaction product, and A cured product obtained from a composition containing a radical generator has approximately the same mechanical strength as, for example, one synthesized using β-hydroxyethyl methacrylate, and may have even better impact resilience. Found out. In conventional methods, for example, attempts have been made to provide impact resilience by integrating the backbone polymer with the block polymer, but the reality is that it has not been possible to obtain a satisfactory result. In the present invention, it is possible to change the physical properties of the cured product by variously changing the alkyl group in the monoalkyl ester of maleic acid or the monoalkyl ester of fumaric acid. The alkyl group in the monoalkyl ester of maleic acid or the monoalkyl ester of fumaric acid used here is not particularly limited, but it is preferable that the alkyl group has 4 to 15 carbon atoms. , or ~
* is because the system may become complicated if a low-boiling alcohol is produced by the transesterification reaction.

Suitable examples include n-butyl, i-butyl, t-butyl, pentyl, neopentyl, cyclohexyl, tricyclo[5.2.1.02"6j
Examples include -3-decenyl group. Compounds having one oxirane oxygen in the molecule used in the present invention include ethylene oxide, propylene oxide, 1.2
-butylene oxide, 2,3-butylene oxide,
Epichlorohydrin, phenyl glycidyl ether, butyl glycidyl ether, etc. are used.

These compounds having one oxirane oxygen are reacted with a monoalkyl ester of maleic acid or a monoalkyl ester of fumaric acid in approximately equimolar amounts to form an alkylhydroxyalkyl ester. An excess of the compound having one oxirane oxygen may be added, and after the reaction, the remaining compound having the oxirane oxygen may be distilled out of the system. If necessary, a solvent such as toluene or xylene may be used.
・O Also, if necessary, quaternary ammonium salts and amines may be used as catalysts.There are no particular restrictions on the reaction temperature and reaction time.(・Polyether polyol has a molecular weight of 3
00 to 3000 is used, but this is 3
If it is less than 00, the obtained cured product will not have excellent rubber elasticity, and if it exceeds 3,000, it will have poor mechanical strength. As the polyether polyol, one or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin polyoxypropylene adducts, trimethylolpropane polyoxypropylene adducts, etc. can be used (although polytetramethylene glycol alone is used) Alternatively, those used together with other polyether polyols have a desirable effect on imparting impact resilience to the cured product.

Examples of organic polyisocyanates used in the present invention include tolylene dicaricyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and urethane prepolymers containing isocyanate groups, which may be used without a catalyst or in the presence of a catalyst. Subjected to reaction.

Catalysts used include pyridine, triethylamine,
Examples include dibutyltin dilaurate, zinc acetate, and chromium acetate. The above polyether polyol is reacted with an organic polyisocyanate in such a way that the isocyanate groups of the organic polyisocyanate are in excess with respect to the hydroxyl groups of the polyether polyol, and this is caused by a reaction with an alkylhydroxyalkyl ester of maleic acid or a fumaric acid. This is to make it reactive with the alkylhydroxyalkyl ester of the acid.

The reaction between the polyether polyol and the organic polyisocyanate may be performed by reacting the polyether polyol and the organic polyisocyanate all at once, or by reacting a part of the organic polyisocyanate with the polyether polyol to elongate the chain. , and may be further reacted with an organic polyisocyanate. It is preferable that the reaction between the noalkylhydroxyalkyl ester (1) and the polyether polyol derivative () is carried out in such a manner that the proportions of hydroxyl groups and isocyanate groups are approximately equal. There is no problem even if the hydroxyl group is in excess of the isocyanate group (・o If necessary, a catalyst such as pyridine, dibutyltin dilaurate, zinc acetate, etc. is used (・). In the reaction, a vinyl polymerizable monomer such as styrene, Solvents such as benzene, ethyl acetate, etc. are used as necessary, but if a solvent other than the vinyl polymerizable monomer is used, it must be removed after 5 reactions. There is no particular restriction on the vinyl polymerizable monomer that can be copolymerized with the reaction product (a) in the present invention, such as styrene, acrylic ester, methacrylic ester, vinyl acetate, vinyltoluene, divinylbenzene, etc. There are no particular restrictions for use.

The vinyl polymerizable monomer is preferably used in excess of the number of double bonds contained in the reaction product (a). Examples of the radical generator in the present invention include polymerization initiators such as benzyl peroxide, methyl ethyl ketone peroxide, and azobisisobutyronitrile, benzophenone,
Photosensitizers such as 4,4'-dimethylaminobenzophenone and benzoin alkyl ether are used.

Radical generators are used in commonly used amounts. The resin composition exhibiting elastomeric properties in the present invention may further contain dyes, pigments, fillers, reinforcing materials, and the like.

Examples of the present invention will be described.

Example 1. Synthesis of alkylhydroxyalkyl ester of maleic acid or alkylhydroxyalkyl ester of fumaric acid 1-(1) 344v of mono-i-butyl maleic acid was placed in a reaction flask, and 2507m of epichlorohydrin and 400η of benzyltrimethyl chloride were added thereto at 100°C under a nitrogen stream.
The mixture was reacted at 120° C. for 8 hours, and excess epichlorohydrin was distilled off under reduced pressure to obtain alkyl hydroxyalkyl maleate ((1)-n).

During the reaction, 15% of fumaric acid ester was produced due to isomerization reaction. Below, this is also written down as the fumarization rate as necessary. Similarly, using fumaric acid mono-1-butyl ester 3447 (fumarization rate of 98% or more), epichlorohydrin 2507, and benzyltrimethylammonium chloride 400 mg, a product (1)-F rich in fumaric acid ester (acid value 0. 4 Fumarization rate 98.5%
) was obtained.

Maleic acid monoalkyl ester consisting of tricyclo[5.2.1.02゜6]-3-decenyl group (synchropentanenyl group 248t1 epichlorohydrin 105
Using f, reaction was carried out under the same conditions as in Example 1-(1) to obtain product (2)-M.

(Fumaralization rate 25% or more). This product was also reacted with fumaric acid monoalkyl ester under the same conditions to produce the product (
2)-F (fumarization rate of 90% or more) was obtained. 2. Synthesis of reaction product (a) 2-{1) Takenate L-2710 (molecular weight 20001, Takeda Pharmaceutical Co., Ltd.), which is an isocyanate group-containing urethane prepolymer
manufactured by L-2710, hereinafter abbreviated as L-2710.

)200P (1.0 equivalent) (1)-F54r(2
．． 3.05 equivalent) was reacted for 6 hours at 70°C under a nitrogen stream, and the resulting product was diluted with styrene to produce a reaction product with a resin content of 70%. Curing example 2 of reaction product -(1)~2
- Add 1 part by weight of benzoin isopropyl ether to 100 parts by weight of each reaction product (a) obtained in (3) to form a thick film with a thickness of 2 mm, and after degassing, use an IKW high-pressure mercury lamp. Curing was carried out by irradiating ultraviolet light for 7 minutes at a distance of 15 degrees.

Table 2 shows the mechanical properties of the cured product. was used as the evaluation standard.

On the other hand, a similar cured product was obtained by adding 0.5 part by weight of benzoyl peroxide to each 100 parts by weight of reaction product (a) and curing by heating at 100°C for 3 hours.

Claims (1)

[Claims] 1 (a) An alkylhydroxyalkyl ester of maleic acid or a monoalkyl ester of fumaric acid obtained by reacting a monoalkyl ester of maleic acid or a monoalkyl ester of fumaric acid and a compound having one oxirane oxygen in the molecule in approximately equimolar amounts. An isocyanate group obtained by reacting an alkylhydroxyalkyl ester (I) with a polyether polyol having a molecular weight of 300 to 3000 and an organic polyisocyanate in such a manner that the isocyanate groups of the organic polyisocyanate are in excess of the hydroxyl groups of the polyether polyol. A reaction product obtained by reacting the polyether polyol derivative (II) having (b) (
A vinyl polymer monomer copolymerizable with a) and (c)
A resin composition containing a radical generator and exhibiting elastomeric properties through polymerization.