JPH01311111A - Novel heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant resin useful as a blending resin for improving the heat-resistance and thermal stability of the base resin by copolymerizing a specific N-substituted norbornenedicarboximide compound and vinyl monomer copolymerizable with said compound. CONSTITUTION:The objective heat-resistant resin can be produced by copolymerizing (A) preferably 10-90mol of an N-substituted norbornenedicarboximide compound of formula (R is H, 1-18C alkyl, etc.) (e.g., 5-norbornene-2,3-dicarboximide) and (B) preferably 90-10mol% of a vinyl monomer copolymerizable with the component A (preferably styrene, etc.) in the presence of (C) a radical initiator (preferably benzoyl peroxide, etc.). The copolymerization is carried out preferably at 30-200 deg.C for 1-24hr.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel heat-resistant resin comprising an N-substituted norbornene dicarboximide compound and a vinyl monomer.

<Prior Art> Studies on polymers of N-substituted norbornenedicarboximides are described, for example, by N.G., Gaylord et al.; J.
, Macromol, Sci, , A19(4) , 5
37-558 (I983) or Aa+, Chem,
Soc, Symp., 212, 449-457 (I
Studies on homopolymers of N-phenyl-5-norbornene-2゜3-dicarboximide have been reported as shown in U.S. Patent No. 45607).
As shown in No. 42, N-phenyl-5-norbornene-
Although there are examples where 2,3-dicarboximide was used,
There has been no research or disclosure regarding copolymers of dicarboximide and vinyl monomers.

<Problems to be Solved by the Invention> An object of the present invention is to provide a novel heat-resistant resin obtained by copolymerizing an N-1-substituted norbornene dicarboximide compound and a vinyl monomer.

Means for Solving the Problems> The present inventors have completed the present invention as a result of intensive studies on a novel copolymer of an N-substituted norbornene dilupokidiimide compound.

That is, according to the present invention, -formation (I) (wherein R is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched alkyl group, or a cycloalkyl group).

Represents an aryl group or an aralkyl group. ) A heat-resistant resin is provided which is obtained by copolymerizing the N-M-converted norbornenedicarboximide compound represented by the above formula and a vinyl monomer copolymerizable with the same.

The present invention will be explained in more detail below.

In the present invention, an N-substituted norbornenedicarboximide compound represented by the general formula (I) is used. In the formula, R is a hydrogen atom, having 1 to 18 carbon atoms.
represents a straight-chain alkyl group, branched alkyl group, cycloalkyl group, aryl group or aralkyl group. Number of carbons is 1
If it is 9 or more, it becomes difficult to manufacture and cannot be used. As the compound (I) used in the present invention, for example,
5-norbornene-2,3-dicarboximide, N-
Methyl-5-norbornene-2,3-dicarboximide, N-ethyl-5-norbornene-2,3-dicarboximide, N-n-propyl-5-norbornene-2
, 3-dicarboximide, N-isopropyl-5-norbornene-2,3-dicarboximide, N-n-butyl-5-norbornene-2,3-dicarboximide, N-inbutyl-5-norbornene-2 ,3-dicarboximide, N-(3-methylpropyl)-5-norbornene-2,3-dicarboximide, N-n-hexyl-5-norbornene-2,3-dicarboximide, N,n -Octyl-5-norbornene-2,3-dicarboximide, N-n-dodecyl-5-norbornene-2,3-dicarboximide, N-n-octadecyl-5-norbornene-2,3-dicarboximide , N
-cyclohexyl-5-norbornene-2,3-dicarboximide, N-(2-methylcyclohexyl)-5
Examples include -norbornene-2,3-dicarboximide, N-phenyl-5-norbornene-2,3-dicarboximide, and N-benzyl-5-norbornene-2,3-dicarboximide. These compounds (I)
can usually be synthesized by Diels-Alder reaction between cyclopentadiene and N-1 substituted maleimide.

In the present invention, a vinyl monomer copolymerizable with compound (I) is used. Examples of such vinyl monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, Methacrylic acid-n-
Butyl, phenyl methacrylate, benzyl methacrylate, ethylene glycol methacrylate, diethylene glycol methacrylate, acrolein, acrylonitrile, acrylamide, N,N'-dimethylacrylamide, styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, P- methylstyrene, 2,
Examples include 6-dimethylstyrene, 0-chlorostyrene, P-chlorostyrene, 2゜4.6-trichlorostyrene, vinyl acetate, vinyl propionate, vinyl chloroacetate, ethylene, propylene, isobutylene, 1,3-butadiene, etc. These can also be used in combination of two or more types. Particularly preferred among these vinyl monomers are styrene, methyl methacrylate and vinyl acetate.

The blending ratio of compound (I) and vinyl monomer is not particularly critical, but it is preferably 99 to 1 mol of vinyl monomer per 1 mol to 99 mol of compound (I), preferably compound (I). I) 90 to 1 vinyl monomer per 10 to 90 moles
It is desirable to mix 0 mol.

The novel copolymer of the present invention can be obtained by copolymerizing an N-substituted norbornenedicarboximide compound and a vinyl monomer copolymerizable with the same in the presence of a radical polymerization initiator. Examples of the radical initiator include known ones such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, and azoisobutyronitrile. . The copolymerization reaction can be carried out by known radical polymerization methods such as suspension polymerization, solution polymerization, and bulk polymerization. The copolymerization reaction is usually preferably carried out at a temperature in the range of 30 to 200°C for 1 to 24 hours.

<Effects of the Invention> According to the present invention, a novel copolymer consisting of a hitherto unknown N-substituted norbornenedicarboximide compound and a vinyl monomer can be obtained.

Moreover, by blending the obtained novel copolymer with various general-purpose resins, it is possible to improve not only heat resistance but also thermal stability measured by softening point and the like.

<Example> The present invention will be specifically explained below using reference examples, working examples, and comparative examples, but the present invention is not limited to the present invention.

(On the board <Preparation of N-cyclohexyl-5-norbornene-2゜3-dicarboximide> 20 mQ (0.3 mol) of cyclopentadiene was added dropwise with stirring, and the mixture was reacted for 2 hours at room temperature.
) Recrystallization was performed from the solution to obtain 20.1 g of the target product (yield 82.1%, melting point 157-160°C).

Preparation of N-phenyl-5-lanebornene-2,3-dicarboximide> Reference example except that 17.3 g (0.1 mol) of N-phenylmaleimide was used instead of N-cyclohexylmaleimide. 1
Similarly, N-phenyl-5-norbornene-2,3
- Crystals of dicarboximide (hereinafter abbreviated as PhN) were obtained.

The yield is 20. og (yield 83.6%, melting point 142-1
44°C).

(isolated (manufactured by !li of N-benzyl-5-norbornene-2,3-dicarboximide) Reference except that N-cyclohexylmaleimide was replaced with 18.7g (0.1 mol) of N-benzylmaleimide Example 1
Similarly, N-benzyl-5-norbornene-2,3
- Crystals of dicarboximide (hereinafter abbreviated as BzN) were obtained.

Yield: 21.8g (yield: 86.1%, melting point: 81-83
℃).

Reference example 1 for the Pyrex glass polymer tube! 0.220 g of N-cyclohexyl-5-norbornene-2゜3-dicarboximide (hereinafter abbreviated as CHN),
1.771 g of styrene and 0.020 g of supercharged benzoyl
Weigh out g, immerse it in refrigerant, and then apply vacuum insufflation (0,0・I
Torr) Ll, dry nitrogen gas was introduced. After repeating the usual liquid-same conditions and sealing the tube, a polymerization reaction was carried out. The polymerization temperature was 70"C and the polymerization time was 16 hours. After polymerization.

The polymer was poured into excess methanol to precipitate it, and the resulting copolymer was separated in a furnace, thoroughly washed with methanol, and dried under vacuum.

The polymerization yield was 87.0%, the elemental analysis content of the obtained copolymer was 0.41%, and the number average molecular weight Mn was determined by gel permeation chromatography to be 1.66 x 1041.The weight average molecular weight was manufactured by CoRONA. A value of 14.41×10′ was obtained using a 114-type vapor pressure molecular weight measuring device.

N- prepared in Reference Examples 1 to 3 with the structure shown in Table 1
51-substituted norbornenedicarboximide compound CHN,
PhN, BzN, styrene, and an initiator were weighed out, and a polymerization reaction was carried out in the same manner as in Example 1. Table 2 shows the properties of the obtained copolymer. In addition, as Comparative Example 1, polystyrene was manufactured according to Example 1. Table 2 shows the results.
Shown below.

(Hereinafter, blank spaces) A polymerization reaction was carried out in the same manner as in Examples 1 to 5, using methyl methacrylate in place of the styrene used in Examples 1 to 5. The charging composition is shown in Table 3, and the polymerization reaction results are shown in Table 4.

In addition, as Comparative Example 2, polymethyl methacrylate was produced according to Examples 1 to 5. The results are shown in Table 4.

(Hereinafter, blank spaces) Summary 9-11 Polymerization reactions were carried out in the same manner as in Examples 1 to 5, using vinyl acetate instead of the styrene used in Examples 1 to 5. The charging composition is shown in Table 5, and the polymerization reaction results are shown in Table 6. In addition, as Comparative Example 3, polyvinyl acetate was manufactured according to Examples 1 to 5. The results are shown in Table 6.

(Margin below)

Claims (1)

[Claims] General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched alkyl group, a cycloalkyl group) A heat-resistant resin obtained by copolymerizing an N-substituted norbornenedicarboximide compound represented by the following formula, and a vinyl monomer copolymerizable with the N-substituted norbornene dicarboximide compound.