JPS584027B2 - Method for producing polyacrylate or polymethacrylate having a cyanuric ring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of novel polyacrylates or polymethacrylates.

Conventionally, various methods for producing polyacrylates or polymethacrylates have been reported, but there have been few reports regarding polyacrylates or polymethacrylates having a cyanuric ring.

The present inventors investigated the synthesis of easily polymerizable compounds having a cyanuric ring, and completed the present invention.

The present invention is a method for producing polyacrylate or polymethacrylate having a cyanuric ring, which is characterized by reacting an acrylic ester or methacrylic ester having a hydroxyl group with cyanuric chloride in the presence of a hydrochloric acid acceptor.

The hydroxyl group-containing acrylic ester or methacrylic ester used in the present invention is represented by the following structural formula.

(However, here R1 is H or CH3, and R2 has 2 to 2 carbon atoms.
4 alkylene group.

Specific compounds (same hereinafter) include 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropylacrylate or methacrylate, 3-hydroxyglobyl acrylate or methacrylate, 4-hydroxybutyl acrylate or methacrylate, and the like.

The reaction of the present invention is shown by the following formula.

The charging ratio in the present invention can be varied depending on the number of hydroxyl groups contained in the hydroxyl group-containing acrylic ester or methacrylic ester and the optionally used monovalent hydroxy compound, but usually 1 mol of cyanuric chloride is used. It is preferable that the acrylic ester or methacrylic ester is added at a ratio of about 3 to 5 equivalents of hydroxyl groups.

In the present invention, a monovalent hydroxyl compound can be simultaneously reacted and bonded to the cyanuric ring in order to modify the polymerizability or cured physical properties of the produced polyacrylate or polymethacrylate.

Examples of such compounds include allyl alcohol,
Methallyl alcohol, cinnamyl alcohol, sidecanol (Hitachi Chemical brand name), methanol, ethanol, t
-butanol, 2-chloroethanol, 2-bromoethanol, 4, 4, 4, 2-tetrachlorobutanol, 2
・3-dibromopropanol, phenol, xylenol, pentachlorophenol, tribromophenol,
Examples include dibromophenol.

Such compounds are used to lower the crosslinking density of the cured product, but they are also used to act as a polymerization accelerator to increase curability, or to increase flame retardancy. is also effective.

The present invention includes conventional equivalents of hydrochloric acid acceptors such as trimethylamine, triethylamine, triptylamine, aniline, dimethylaniline, dimethylpenzylamine, ammonia, pyridine, vicolin, collidine, quinoline, lutidine, triethylenetetramine, urothrobin, 1.
5-diazabicyclo[3.4.0]nene-5, and others such as soda carbonate, caustic soda, and sodium alcoholate are used.

As a solvent for the reaction, benzene, toluene, xylene,
Ethyl acetate, ethyl ether, diisopropyl ether, acetone, acetonitrile, n-hexane, cyclohexane, THF, DMF, chloroform, carbon tetrachloride,
Preferably, inert solvents such as methylchloroform, trichloroethylene, perchloroethylene, chlorobenzene are used.

The process according to the invention is preferably carried out at temperatures below 100°C, especially from 0 to 60°C.

The reaction is very fast, and the usual method is to gradually add an acrylic ester or methacrylic ester having a hydroxyl group and a hydrochloric acid acceptor to a cyanuric chloride solution or suspension.

Finally, the reaction temperature may be raised to reflux temperature to complete the reaction.

When the reaction is completed, hydrochloride precipitates, which is filtered off or removed by washing with water, and the oil phase is distilled under reduced pressure to remove the reaction solvent, and the polyacrylate having cyanuric rings is obtained as a clear liquid. Alternatively, polymethacrylate can be obtained in good yield.

The present invention is preferably carried out in the presence of a polymerization inhibitor, such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, copper salt, copper powder, p-phenylenediamine, catechol, and the like.

The polyacrylate or polymethacrylate having a cyanuric ring obtained in the present invention can be used in adhesives, anaerobic fixing agents, thermosetting paints, photocurable coatings, photocurable resins, printing resins, molded products, laminated materials, electronic materials, etc. Used for line curing resins, etc.

The present invention will be specifically explained below with reference to Examples.

Note that parts are parts by weight.

Example 1 36.9 parts of cyanuric chloride and 10 parts of chloroform in a flask
0 parts of 2-hydroxyethyl methacrylate 8
A mixture of 4.5 parts of triethylamine, 65.7 parts of triethylamine, and 0.12 parts of phenothiazine was added dropwise, and the mixture was reacted with stirring at 5 to 10°C.

After the dropwise addition, the reaction mixture was reacted at 65 to 70°C for 2 hours, and then the reaction mixture was cooled and washed three times with 200 parts of water each time to remove triethylamine hydrochloride.

For the oil phase, chloroform was distilled under reduced pressure at 50°C to obtain 91 parts of pale yellow polyacrylate.

The yield was 97%, d23=1.080, η30=39C
．． P,, n = 1.4900, bromine number [amount of bromine added (g) per 100 g of sample, same hereinafter] = 98.6 (theoretical value = 103.1).

In addition, the infrared absorption spectrum of this object was taken17
Absorption characteristic of methacrylate groups was observed at 20, 1645, 1165, and 810 cm.

A film obtained by curing this material with ultraviolet rays had a Shore hardness of D-82.

Example 2 18.5 parts of cyanuric chloride and 10 parts of chloroform in a flask
A mixture of 46.4 parts of 2-hydroxyethyl acrylate, 40.4 parts of triethylamine, and 0.05 parts of phenothiazine was slowly added dropwise and reacted with stirring at 0 to 5°C.

After reacting at 50 to 60° C. for 2 hours, the mixture was cooled and washed twice with 100 cc of water, and then chloroform was distilled under reduced pressure to obtain 32 g of pale yellow polyacrylate.

The yield was 74%, η30=38C. P. , bromine number -10
It was 9.1 (theoretical value=113.2).

In addition, the infrared absorption spectrum of this object was taken17
25, 1640, 1620, 1200, 810 cm-1
showed an absorption characteristic of acrylate groups.

A product to which 0.5% of penzophenone was added was easily cured by irradiation with ultraviolet rays in the air.

Claims (1)

[Scope of Claims] 1. A polyacrylate having a cyanuric ring, which is obtained by reacting an acrylic ester or methacrylic ester having a hydroxyl group represented by the following structural formula A with cyanuric chloride in the presence of a hydrochloric acid acceptor. Or a method for producing polymethacrylate. (However, here R1 is H or CH3, and R2 has 2 to 2 carbon atoms.
4 alkylene group).