JPS6310147B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to styrene derivatives, and an object of the present invention is to provide a novel styrene derivative that is addition-polymerizable and capable of providing a three-dimensional networked polymer through simple treatment after polymerization. Many cross-linked polymers have been known in the past, but when cross-linking and curing these polymers, catalysts and curing agents are generally required, and these catalysts must be uniformly mixed with the polymer. Otherwise, a cured product with good physical properties cannot be obtained. Therefore, there is a drawback that the operation is complicated. Furthermore, since condensation polymers produce volatile components during curing, they have the disadvantage that they may cause voids in the molded product. As a result of intensive research to solve the above-mentioned drawbacks of the prior art, the inventors of the present invention discovered that the cyanamide group (-
Focusing on the reactivity and self-reticulating property of NHCN),
The compound obtained by introducing the cyanamide group into a conventionally known styrene derivative can be easily homopolymerized or copolymerized with other addition-polymerizable compounds, and has good physical properties without forming voids simply by heating the polymer. The present invention was completed by discovering that a cured product can be obtained. That is, the present invention is a styrene derivative represented by the following general formula. The styrene derivative of the present invention is obtained by reacting the corresponding aminostyrene with cyanogen halide, and the cyanogen halide used is preferably bromic cyan or chlorocyan. The cyanamidation reaction uses methanol, ethanol, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran,
Alkali metal and alkaline earth metal oxides, hydroxides, carbonates, hydrogen carbonates, organic amines, etc. in dioxane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc., or a mixture of these with water. The reaction is carried out by reacting styrene having a primary amino group with cyanogen halide in the presence of a basic substance at a temperature of 20°C or less, preferably 0 to 10°C. The styrene derivatives of the present invention obtained as described above are preferably o-, m- or p-
cyanamide styrene, the most useful one is m
- or p-cyanamidostyrene. The styrene derivative of the present invention is addition-polymerizable, and can be polymerized alone like conventional addition-polymerizable monomers, or can be copolymerized with other addition-polymerizable monomers or oligomers. You can also do that. The polymerization method itself is the same as a conventionally known method. The polymer obtained in this way can be heated simply by heating, for example, at 80° C., without using any curing agent or catalyst after or simultaneously with the molding of the polymer.
At a temperature of 250° C., it is cross-linked and cured into a three-dimensional network without generating low-molecular compounds, and a molded product having excellent physical properties such as heat resistance can be obtained. Further, in the case of a copolymer with other monomers, a polymer having an arbitrary degree of reticulation can be provided by changing the amount of the styrene derivative of the present invention used. Therefore, when the styrene derivative of the present invention is polymerized and cured alone, it exhibits heat resistance, chemical resistance,
Providing molded products with excellent physical properties such as impact resistance,
Furthermore, by copolymerizing with various other addition-polymerizable monomers in various proportions, the physical properties of polymers made of various monomers can be improved. Furthermore, since cyanamide groups easily react with epoxy groups and amino groups, they can be cured using polyepoxy compounds and polyamino compounds. Next, the present invention will be specifically explained with reference to Examples. In the text, parts or percentages are based on weight. Example 1 71 parts of bromcyane to 100 parts of dimethylformamide
and 100 parts of water, and 16.8 parts of calcium carbonate is dispersed therein under stirring.
Next, it is cooled and p-
40 parts of aminostyrene to 150 parts of dimethylformamide
Add the solution dissolved in the solution dropwise. After the dropwise addition was completed, the reaction was continued for about 2 hours at 10°C or lower, and then excess bromic cyanide was distilled off. The obtained reaction solution is poured into ice water to precipitate the reaction product. Then filtration, washing with water,
It was dried under reduced pressure to obtain p-cyanamid styrene.
The yield was almost 100%. The structure of p-cyanamidostyrene of the obtained product was investigated by elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum, and the following results were obtained. (1) Actual elemental analysis values Theoretical values Carbon 74.1% 75.0% Hydrogen 6.6% 5.6% Nitrogen 19.3% 19.4% (2) Infrared absorption spectrum The reaction product has absorption by cyanamide group at 2220 cm ^-1 and absorption by cyanamide group at 990 cm ^-1 and 890 cm Absorption due to vinyl groups was observed in ^-1 . (3) Nuclear magnetic resonance absorption spectrum

[Table] The assignments and integral ratios were as shown above and agreed with the theoretical values. From the above, the reaction product of Example 1 is p-
It is clearly cyanamide styrene. Example 2 33.3 parts of p-aminostyrene was dissolved in diethyl ether
Add 11.2 parts of sodium hydroxide to a solution of 185 parts.
solution of 185 parts of water and Bromsyan 123
A solution prepared by dissolving 1 part of each in 278 parts of diethyl ether was gradually added dropwise at 5°C. After the completion of the dropwise addition, the reaction was carried out at 5° C. for about 6 hours. After the reaction is complete, 400 parts of diethyl ether is added to extract the reaction product, and the ether layer is separated. Concentrate the obtained ether layer,
Precipitate with carbon tetrachloride. The generated white precipitate was filtered, washed with ether, and dried under reduced pressure to determine the yield.
p-Cyanamide styrene was obtained at 61%. The analysis results of this product were the same as those of Example 1. Reference Example 1 A monomer, a reaction solvent, and a polymerization initiator were charged into a polymerization reactor according to the following recipe. Styrene 10 parts p-cyanamid styrene obtained in Example 1
0.2 parts dioxane 20 parts lauroyl peroxide 0.15 parts Total 30.35 parts The polymerization reaction was carried out at about 80°C for about 6 hours. The produced polymer shows absorption of cyanamide groups in the infrared absorption spectrum, and the coating film, which was cured by applying the polymer solution to an aluminum plate and baking it for 30 minutes at 150°C, was a monopolymer of styrene. It showed superior physical properties such as chemical resistance and water resistance compared to those obtained by combining. Reference Example 2 A polymerization reaction was carried out in the same manner as in Reference Example 1 using 10 parts of n-butyl methacrylate or 10 parts of n-butyl acrylate in place of the styrene in Reference Example 1, and a polymer solution with excellent physical properties was obtained. I was able to get it. Example 3 Cyanamide styrene corresponding to the amino compound was obtained in the same manner as in Example 1 except that p-aminostyrene in Example 1 was replaced with o-aminostyrene and m-aminostyrene.

Claims (1)

[Claims] 1. A styrene derivative represented by the following general formula.