JPH0753787B2 - Method for producing propargyl etherified cresol novolac resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel propargyl etherified cresol novolac resin.

<Prior Art> Conventionally, an allyl etherified cresol novolac resin is known as a thermosetting etherified cresol novolac resin, and is useful as a material for various electric / electronic parts and a structural material requiring heat resistance. (JP-A-59-36
121, JP-A-61-95012).

<Problems to be Solved by the Invention> However, the known allyl etherified cresol novolac resin is difficult to cure by itself or does not cure, so it is necessary to mix it with an N, N′-bismaleimide compound and cure it. Yes The process becomes complicated and disadvantageous.

<Means for Solving the Problem> From the above facts, the present inventors have earnestly studied the etherified cresol novolac resin containing a functional group that can be cured alone, and as a result, the following propargyl etherified cresol novolac resin was found to be obtained. The inventors have found that the above objects are satisfied and completed the present invention.

That is, the present invention is characterized by reacting a cresol novolak resin or a co-condensed novolak resin of cresol and other phenols with a propargyl halide in the presence of a base, Relates to a method for producing a propargyl etherified cresol novolac resin having a unit represented by:

The propargyl etherified cresol novolak resin of the present invention can be synthesized by subjecting cresol novolak or a co-condensation novolak resin of cresol and other phenols to a propargyl halide in the presence of a base for dehalogenation hydrogenation reaction.

The cresol novolac resin used in the present invention means cresol (o, m, p-each isomer) and aldehydes such as formaldehyde, furfural and acrolein by condensation reaction in a known method in the presence of an acid or alkali catalyst. The resin obtained is usually a resin having an average number of nuclei of 3 to 15, and a novolak resin formed from o-cresol and formaldehyde is particularly preferable. Further, instead of the cresol novolac resin, a co-condensed novolac resin of cresol and other phenols containing other phenols to the extent that the effect of the present invention is not impaired (usually 50 mol% or less based on total phenol), for example, It is also possible to use a co-condensed novolak resin with a monovalent phenol such as phenol, ethylphenol, isopropylphenol, butylphenol, octylphenol and xylenol, and a divalent phenol such as resorcinol, hydroquinone and catechol.

Examples of the propargyl halide used in the present invention include propargyl chloride, propargyl bromide, propargyl iodide and the like.

The amount of propargyl halide used is 0.1 to 2 mol, preferably 0.1 to 1.5 mol, per equivalent of phenolic hydroxyl group of the novolac resin. Here, when the amount of propargyl halide is less than 0.1 mol, the propargyl ether conversion effect of the resin obtained is decreased, while when it exceeds 2 mol, the amount of propargyl halide not directly involved in the reaction is increased, which is industrially disadvantageous. And the halogen content increases due to side reactions.

Examples of the base used in the present invention include alkali hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium silicate, sodium aluminate, potassium carbonate and sodium carbonate. Typical examples thereof include alkali metal salts of ## STR1 ## or alkali metal alcoholates such as sodium methylate and sodium ethylate, and tertiary amines such as trimethylamine, triethylamine, dimethylaniline and pyridine.

As the reaction solvent, in addition to dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, water and the like, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatics such as benzene, toluene and xylene, methanol, ethanol and isopropyl alcohol. , Alcohols such as butanol, diethyl ether,
An ether solvent such as tetrahydrofuran or dioxane may be used, and the reaction may be performed without a solvent particularly when the viscosity of the reaction system is low. If the reaction is carried out in an atmosphere of an inert gas such as nitrogen, a resin having a good hue can be obtained.

The propargyl etherification reaction of the present invention is usually 10 to 120.
C., preferably 20-80.degree. C. When the temperature is lower than 10.degree. C., it takes a long time to complete the reaction, and when it is higher than 120.degree. Further, when the polymerization of the propargyl group occurs during the reaction or in the post-treatment stage and it is difficult to obtain the desired product, it is possible to add various polymerization inhibitors, and as a specific example, 2,6-di-tert-butyl-
4-methylphenol, methylhydroquinone, p-te
Phenolic compounds such as rt-butylcatechol, phenothiazine compounds such as phenothiazine, benzophenothiazine, acetamidophenothiazine, quinone compounds such as p-benzoquinone and naphthoquinone, N-nitrosodiphenylamine, N-nitrosodimethylamine and the like N-
Nitrosamine compounds and the like are common, but are not limited to these.

The propargyl etherified novolak resin thus obtained can be heat-cured alone. However,
It can also be mixed with an N, N'-bismaleimide compound or the like and thermally cured.

Examples of the above bismaleimide, N, N'-diphenylmethane bismaleimide, N, N'-phenylene bismaleimide, N, N'-diphenyl ether bismaleimide,
N, N'-diphenylsulfone bismaleimide, N, N'-dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-tolylene bismaleimide,
N, N'-xylylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'-dichloro-diphenylmethane bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'-diphenylmethane bismethyl maleimide , N, N'-diphenyl ether bismethylmaleimide, N, N'-diphenylsulfone bismethylmaleimide (including each isomer), N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-hexamethylenebismethylmaleimide, prepolymers of these N, N'-bismaleimide compounds, prepolymers of these bismaleimide compounds with diamines, and maleimides or methylmaleimides of polycondensates of aniline and formalin Examples thereof include compounds. Also, other known thermosetting resins depending on the purpose,
For example, epoxy resin, alkenyl group-containing resin, unsaturated polyester resin, phenol resin, silicone resin, triazine resin, etc. may be added.

<Effects of the Invention> The propargyl etherified novolak resin of the present invention is a known allyl etherified novolak resin (Japanese Patent Laid-Open No. 619501/1986).
No. 2) is hard to cure or does not cure by itself, but it easily heat-cures by itself to give a cured product having excellent heat resistance. When actually heat-curing according to (see Example 1), it is not particularly necessary to use an N, N′-bismaleimide compound or the like in combination, which is extremely simple in the process. On the other hand, N, N′−
Even when the bismaleimide compound is used in combination with heat curing,
It gives a cured product with excellent heat resistance.

The propargyl etherified cresol novolak thus obtained is particularly suitable for various types of electric
It is useful as a material for electronic parts and a structural material.

In addition, if necessary, a filler, a filler, a reinforcing agent, a pigment, or the like is used in combination in the above composition. For example, silica, calcium carbonate, antimony trioxide, kaolin, titanium dioxide, zinc oxide, mica, barite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, glass fiber, carbon fiber, alumina fiber, asbestos. One kind or two or more kinds of fibers, aramid fibers and the like are used, and are used for molding, lamination, adhesives, composite materials and the like.

Example 1 A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 85.1 parts (0.8 mol equivalent) of o-cresol novolac resin having a softening point of 90 ° C. under a nitrogen atmosphere and 82 parts of dimethyl sulfoxide as a reaction solvent. After charging and completely dissolving the resin, powdery sodium hydroxide 13.6 parts (0.33 mol)
And stir well. 24.6g (0.33mol) of propargyl chloride was added dropwise while maintaining the temperature of the reaction system at 40 ℃
Keep it warm for 6 hours. After that, water and methyl isobutyl ketone are added to separate the oil layer. By washing the oil layer with water and then concentrating it, the viscosity by the ICI cone and plate method becomes 33p (5
41.7 g of pale yellow viscous oily resin (0 ° C.) was obtained.

The infrared absorption spectrum of the obtained resin shows that the absorption due to the phenolic hydroxyl group near 3400 cm ^-1 has almost disappeared.
It found to have the cm ^-1 in absorption and 2120 cm ^-1 acetylenic hydrogen from the characteristic absorption of the acetylene group is observed (see FIG. 1) the structure of the object of the propargyl ether of o- cresol novolak.

When the stroke cure gel time at 180 ° C was measured for the resin obtained above alone, it gelled in 22 minutes. Table 1 shows the results of thermal analysis of molded products obtained by curing this resin alone at various temperatures.

It can be seen that the single cured product of the propargyl etherified o-cresol novolac of the present invention has excellent heat resistance.

Example 2 3.10 parts of propargyl etherified o-cresol novolac obtained in Example 1 and 7.17 parts of N, N '-(4,4'-diphenylmethane) bismaleimide were mixed (equivalent ratio 1: 2),
When the stroke cure gel time was measured at 0 ° C, gelation occurred in 9 minutes. Table 2 shows this resin composition at 200 ° C. and 250
The thermal analysis result of the molded product obtained by curing at ℃ is shown.

It can be seen that the propargyl etherified o-cresol novolak of the present invention has excellent heat resistance and gives a cured product having a low coefficient of thermal expansion when mixed with a bismaleimide compound and cured.

Example 3 O-cresol novolac resin having a softening point of 90 ° C. was replaced with 35.0 parts of an o-cresol novolac resin having a softening point of 80 ° C. (0.3
The same procedure as in Example 1 was carried out except that (molar equivalent) was used to obtain 40.1 parts of a pale yellow viscous oily resin having a viscosity of 20 p (50 ° C.) by the ICI cone plate method.

The infrared absorption spectrum of the obtained resin shows almost the same spectrum as that of the resin of Example 1, and it can be seen that the resin has a target propargyl etherified o-cresol novolak structure.

[Brief description of drawings]

FIG. 1 shows the infrared absorption spectrum of the propargyl etherified o-cresol novolak of Example 1.

Claims (1)

[Claims] 1. A formula characterized by reacting a gresol novolac resin or a co-condensed novolak resin of cresol and other phenols with a propargyl halide in the presence of a base. A method for producing a propargyl etherified cresol novolac resin having a unit represented by: