JPS6050369B2 - Method for producing cured product of odorless or low odor resin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, the present invention relates to a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, the present invention relates to a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, a method for producing a cured product of an odorless or low-odor resinous substance, and more specifically, a method for producing a cured product of an odorless or low-odor resinous substance. The present invention relates to a method for producing a cured product of an odorless or low-odor resinous material obtained by

Regarding aromatic hydrocarbon formaldehyde resin, 1
Already in the latter half of the 9th century, research was conducted by A. J. Baeyer et al. by reacting aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, duurene, naphthalene, and acenaphthene with formaldehyde in the presence of a strong acid catalyst. The following products were obtained (A, J,
Baeyer, Ber, Volume 5, Page 1098 (18
7 Law), Volume 6, p. 223 (187 Law) and Volume 7, 1
(See page 190 (187 poems)), and during World War II, R.
Wegler discovered new knowledge in the condensation reaction of aromatic hydrocarbons and formaldehyde, and the basis thereof was established (R. Wegler, Anho, Chem.
A/60, No. 4, p. 88 (1948)).

In Japan, after the war, Minoru Imoto, Qingun Huang, and others conducted extensive research on aromatic hydrocarbon formaldehyde resins and laid the groundwork for their development, so aromatic hydrocarbon formaldehyde resins such as xylene formaldehyde resins were industrially produced. ing.

As is well known, aromatic hydrocarbon formaldehyde resins are generally viscous liquids and have excellent adhesion, water resistance, moisture resistance, acid resistance, alkali resistance, and electrical insulation. Utilizing the reactivity of ether bonds and acetal bonds, phenols,
Electrical insulating materials and the like have been obtained by condensation reactions with amines, etc., but they have drawbacks such as the hydrodynamic reaction during the condensation reaction and the need for high temperatures to complete the reaction.

In addition, many low-molecular-weight polymers such as prepolymers are odorous, and when they are cured they emit an even more intense odor, which is not good for the health of workers and local residents, and a solution to this problem is needed. Ta.

An object of the present invention is to provide a method for producing a cured product of an odorless or low-odor resinous material that can be radically polymerized at low temperatures.

In order to achieve the above object, the present inventors have conducted various studies and found that a resinous material obtained by the reaction of an aromatic hydrocarbon formaldehyde resin with acrylic acid, methacrylic acid, or an alkyl ester thereof at low temperature. They discovered that it is capable of radical polymerization and is odorless to low odor, leading to the completion of the present invention.

The present invention relates to a method for producing a cured product by curing an odorless or low-odor resinous material obtained by reacting an aromatic hydrocarbon formaldehyde resin with acrylic acid, methacrylic acid, or an alkyl ester thereof.

The aromatic hydrocarbon formaldehyde resin used as a raw material component in the present invention is obtained by a condensation reaction between an aromatic hydrocarbon and formaldehyde, and representative examples include xylene formaldehyde resin, toluene formaldehyde resin, mesitylene formaldehyde resin,
Examples include duurene formaldehyde resin and naphthalene formaldehyde resin.

Acrylic acid, methacrylic acid, or an alkyl ester thereof is reacted with the aromatic hydrocarbon formaldehyde resin.

The reaction of the above-mentioned aromatic hydrocarbon formaldehyde resin with acrylic acid, methacrylic acid, or an alkyl ester thereof is carried out under heating using an esterification catalyst, a transesterification catalyst, a polymerization inhibitor, etc., if necessary.

During the reaction, acrylic. By changing the reaction conditions such as changing the amount of acid, methacrylic acid or alkyl ester thereof, any acryloylmethyl group or methacryloylmethyl group can be introduced.Also, by changing the molecular weight of the aromatic hydrocarbon formaldehyde resin, By varying the viscosity of the crosslinkable compound that is the product, it is possible to arbitrarily adjust the viscosity of the crosslinkable compound that is the product.In this way, the viscosity of the aromatic hydrocarbon formaldehyde resin and acrylic acid that are the raw material components,
The amount of methacrylic acid or alkyl ester thereof used,
By appropriately varying reaction conditions such as reaction temperature and reaction time, it is possible to obtain various resinous substances suitable for end uses. The obtained resinous material was confirmed by its infrared absorption spectrum to have an ester bond derived from the reaction between the aromatic hydrocarbon formaldehyde resin and acrylic acid, methacrylic acid, or an alkyl ester thereof.

This substance has the feature of being odorless to low odor. In addition, it can undergo radical polymerization at low temperatures, forms a cured product by itself, and the obtained cured product has excellent electrical insulation properties. Furthermore, resinous materials can also be used as crosslinking agents for unsaturated polyester resins and the like. When producing the cured product of the present invention, the above resinous substance includes a curing agent, a curing accelerator,
It can contain crosslinking monomers, polymerization inhibitors, fillers, etc.

As curing agents, acyl peroxides such as benzoyl peroxide and acetyl peroxide; hydroperoxides such as tert-butyl peroxide and kyumene hydroperoxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Dialkyl peroxides such as ly-butyl peroxide and dicumyl peroxide; oxyperoxides such as tertiary-butyl perbenzoate and tertiary-butyl peroxyacetate can be used.

The amount used is generally from 0.5 to 0.5 based on the resin composition.
5% by weight, preferably in the range 1-3% by weight. As a curing accelerator, commonly used metal salts of naphthenic acid or octenoic acid (for example, cobalt, manganese, iron, lead, nickel, tin, zinc salts, etc.) can be used, and the amount added depends on the resin composition. 0-2. There is a range of call volume %. As the crosslinking monomer, styrene, various high-boiling acrylic acids or methacrylic esters, and high-boiling allyl ethers or allyl esters are used as required.

As the polymerization inhibitor, quinones such as hydroquinone, paratertiary butylcatechol, pyrogallol, and other commonly used substances can be used. The amount added is in the range of 0 to 0.5% by weight based on the resin composition.
As fillers, silica, talc, calcium carbonate, asbestos, glass fiber, wood flour, coloring agents, etc. added to unsaturated polyester resins are used as necessary. The present invention will be further explained below using reference examples and examples, but the present invention is not limited to these examples.

Reference Example 1 Production of resin-like material In a 3E four-necked flask equipped with a stirrer, a thermometer, and a bulb condenser, 800 q1 methacrylic acid 250 Then, 1 g of tert-butylcatechol and 3 g of p-toluenesulfonic acid were added, and the mixture was reacted at 100° C. for 8 hours.

The reaction product was dissolved in 1e of benzene, washed with 500 TILt of about 10% by weight aqueous sodium carbonate solution, and then washed with distilled water. After dehydrating the organic phase over anhydrous sodium sulfate, benzene was distilled off to obtain a resinous material (A) 720
I got g. This substance (4) was almost odorless and had a viscosity of 1.2 poise (25°C). When we measured the infrared absorption spectrum of this material prisoner, it was 1720cm-
Strong absorption based on the carbonyl group of methacrylic acid ester was observed in No. 1. Also, by the pyridine dibromide sulfate method,
It was also revealed that there were 0.5 equivalents of unsaturated bonds per 100y of this material. Reference Example 2 Production of resinous substance (B) In a 3E four-bottle flask equipped with a stirrer, a thermometer, and a bulb condenser, 8OO g of Nicanol LLL and 1 gram of methacrylic acid were added.
60qNt-butylcatechol 1q. ．． p-Toluenesulfonic acid 2y was added and reacted at 100°C for 8 hours.

After the reaction is completed, the acid component is removed using an ion exchange resin.
700 y of resinous material (B) was obtained. This substance (B) is almost odorless, and its viscosity is 1.6 poise (at 25°C).
It was hot. When the infrared absorption spectrum of this substance (B) was measured, strong absorption based on the carbonyl group of the methacrylic ester was observed at 1720cTn-1. or,
It was also revealed by the dibromide sulfuric acid pyridine method that there were 0.5 equivalents of unsaturated bonds per 1009 of this substance (B). Reference Example 3 Production of resinous substance (C) The reaction was carried out under the same conditions as Reference Example 1, except that Nicanol LLL was changed to Nicanol LL (xylene formaldehyde resin, average molecular weight 350-380E, manufactured by Ryogas Kagaku Co., Ltd.). , an almost odorless resinous substance (C) 760y was obtained.

As a result of measuring the infrared absorption spectrum of this substance (C), strong absorption based on the carbonyl group of methacrylic ester was observed at 1720c7n-1. Reference Example 4 Production of resinous substance (D) Nicanol LLL was converted into Nicanol HH (xylene formaldehyde resin, molecular weight 500-600, manufactured by Mitsubishi Gas Chemical Co., Ltd.
The reaction was carried out under the same conditions as in Reference Example 1, except that the reaction mixture was changed to (manufactured by Co., Ltd.), and 750q of an almost odorless resinous substance (D) was obtained.

When the infrared absorption spectrum of this substance (D) was measured, a strong absorption based on the carbonyl group of the methacrylic ester was observed at 1720 cm<-1 >. Reference Example 5 Production of resinous substance (E) The reaction was carried out under the same conditions as in Reference Example 1, except that methyl methacrylate 200y was used instead of methacrylic acid, and an almost odorless resinous substance (E) 730f was obtained. Ta.

When the infrared absorption spectrum of this substance (E) was measured, it was 1720C! Strong absorption based on the carbonyl group of methacrylic acid ester was observed in TL-1. Reference Example 6 Production of resinous substance (F) The reaction was carried out under the same conditions as Reference Example 2 except that methacrylic acid was replaced with acrylic acid and the reaction flask was shielded from light, resulting in an almost odorless resinous substance (F) 730y. I got it.

PT-
28 (cobalt naphthenate solution, manufactured by Hitachi Chemical Co., Ltd.) at 0.5% by weight, and 1.5% by weight of CT-3 (tert-butyl perbenzoate, manufactured by Hitachi Chemical Co., Ltd.). When % of the amount was added, gelatinization occurred at approximately 2 powders.

After a further 1 hour at 100°C, a resinous material (4
When the electrical properties of the cured products of ) to (F) were measured, all showed the values shown in Table 1, and it became clear that the electrical insulation properties, especially the boiling insulation resistance, were high.

Claims (1)

[Claims] 1. Production of a cured product characterized by curing an odorless or low-odor resinous substance obtained by reacting an aromatic hydrocarbon formaldehyde resin with an acrylic acid/methacrylic acid or an alkyl ester thereof. Method. 2. The method for producing a cured product according to claim 1, wherein the aromatic hydrocarbon formaldehyde resin is a xylene formaldehyde resin.