JPH01228987A - N-glycidylimide compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R<1> is 4-30C bifunctional organic group containing carbon-carbon double bond). EXAMPLE:N-Glycidyl-5-norbornene-2,3-dicarboximide. USE:A raw material for producing coating compound, adhesives, composite materials and improving agents for polymers. PREPARATION:1mol of a dicarboxylic acid imide (e.g., 5-norbornene-2,3- dicarboximide) shown by formula II is reacted with preferably >=2mol of an epihalohydrin (e.g., epichlorohydrin) in the presence of an onium salt catalyst such as benzyltriethylammonium chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a specific N-glycidyl imide compound and a method for producing the same. More specifically, the present invention relates to specific N-glycidyl imide compounds useful as paints, adhesives, composite materials, polymer modifiers, etc., or as raw materials for producing these, and methods for producing the same.

[Prior Art/Problems to be Solved by the Invention] Epoxy resins have characteristics such as good mechanical properties, adhesive properties, and easy moldability, and are therefore used in large quantities as matrix resins for various composite materials. However, depending on the application, the heat resistance may be insufficient, and the development of highly heat-resistant epoxy resins is desired.

[Means for Solving the Problems] The present inventors have conducted intensive research on N-glycidylation of dicarboxylic acid imides in order to obtain glycidyl compounds having an imide skeleton for the purpose of synthesizing heat-resistant epoxy resins. The present inventors have discovered an N-glycidyl imide compound that can provide a highly heat-resistant epoxy resin or can be used as a highly heat-resistant epoxy resin, and a method for producing the same, and have completed the present invention.

That is, the present invention provides an N-glycidyl imide compound represented by -maximum (I): (wherein R1 represents a divalent organic group having from 4 to 30 carbon atoms and having at least one carbon-carbon double bond) and one dose M: A dicarboxylic acid imide represented by S (in the formula, R1 is the same as above) and epihalohydrin are reacted, -maximum (I)
The present invention relates to a method for producing an N-glycidyl imide compound represented by:

[Function and Examples] The N-glycidyl imide compounds of the present invention have -maximum (I)
: (wherein R1 represents a divalent organic group having 4 to 30 carbon atoms and having at least one carbon-carbon double bond).

- In the compound represented by maximum (1), the carbon-carbon double bond portion of R1 functions to impart reactivity to the compound and improve the heat resistance and strength of the cured product, and the imide ring portion contributes to improving heat resistance, and the epoxy group portion imparts reactivity to the compound and functions to improve the heat resistance and strength of the cured product.

R1 in the general formula (1) is a group having at least one carbon-carbon double bond, preferably 1 to 2 carbon-carbon double bonds, and the double bond of R1 is used when the compound represented by the general formula m is polymerized. Since it becomes a site involved in polymerization, at least one is required. In addition, if the number of carbon atoms in R1 is less than 4,
Industrially, raw materials are difficult to use, and if the molecular weight exceeds 30, the molecular weight becomes large relative to the imide ring moiety, impairing heat resistance, which is not preferred.

Representative examples of the compound represented by the general formula (1) having R1 include, for example, the general formula (■); (wherein R2,
R3, R4, It5 represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydrogen atom or a halogen atom), a compound represented by the general formula (IID).

(In the formula, R3 and R4 are the same as above, R6 has 1 to 5 carbon atoms.
(representing an alkylene group of
- 3 alkyl group or hydrogen atom).

Specific examples of R2, R3, R4 and R5 in general formulas (It) to N include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
5ec-butyl group, tert-butyl group, pentyl group,
Examples include alkyl groups such as isopentyl group and neopentyl group; alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, and isopropoxy group; hydrogen atom or halogen atoms such as fluorine atom, chlorine atom, and bromine atom. Among these, hydrogen atoms, methyl groups, methoxy groups, and chlorine atoms are preferred from the viewpoints of easy availability of raw materials, high heat resistance of cured products, and high strength.

Specific examples of R6 in the general formula (II) include methylene group, ethylene group, ethylidene group, propylidene group,
Examples include alkylene groups such as isopropylidene group, methylethylene group, and trimethylene group. Among these, methylene group is preferred from the viewpoint of easy availability of raw materials.

Specific examples of R7 and R8 in general formula N include alkyl groups such as methyl, ethyl, and propyl groups, or hydrogen atoms. Among these, hydrogen atoms and methyl groups are preferred from the viewpoint of easy availability of raw materials.

In particular, a compound in which 1-3, R4, R7 and R8 in the general formula N are all hydrogen atoms is preferred because it is easily available as a raw material.

The N-glycidyl imide compound represented by the above general formula m is a crystalline solid or liquid compound, and can be used as it is or after polymerization as an epoxy resin with good heat resistance.

For example, since the N-glycidyl imide compound has a glycidyl group and at least one carbon-carbon bond, it can be polymerized alone or in combination with other epoxy compounds, vinyl monomers, etc. Reaction using conventional epoxy curing agents such as anhydrides, aromatic or aliphatic amines, heterocyclic amines, polyamides, polyphenolic compounds, etc., by conventional thermal polymerization on the carbon-carbon double bond side, etc. It can be cured by polymerization or the like.

The cured product obtained by the above method has high heat resistance, for example, as shown in Example 1, a cured product made of N-glycidyl-5-norpornel-2,3-dicarboximide and methylnadic anhydride. The softening temperature of is 250°
Indicates C or higher.

Such N-glycidyl imide compounds of the present invention can be used alone or in combination with other materials to be used in paints, adhesives, CFRP,
It is useful as a composite material such as GPRP, a polymer modification material, etc.

Next, a method for producing an N-glycidyl imide compound will be explained.

The N-glycidyl imide compound of the present invention is produced by reacting a dicarboxylic acid imide represented by M: υ (in the formula, R1 is the same as above) with epihalohydrin (hereinafter, this reaction The reaction is also called N-glycidylation reaction).

The dicarboxylic acid imide represented by M has the general formula (VD) produced by, for example, a Diels-Alder reaction between maleic anhydride and a diene compound.

It is easily produced by imidizing a dicarboxylic acid anhydride represented by υ (wherein R1 is the same as above) using an ammonia source such as ammonia, urea, or ammonium carbonate.

Specific examples of the diene compounds include chain diene compounds such as butadiene, isoprene, and 1,3-pentadiene; cyclopentadiene, methylcyclopentadiene, 3,3-dimethylcyclopentadiene, and 1,3-
Examples include, but are not limited to, cyclic diene compounds such as cyclohexadiene; and compounds in which some or all of the hydrogen atoms of these diene compounds are substituted with halogen atoms or alkoxy groups.

Examples of the shrimp halohydrin to be reacted with the dicarboxylic acid imide include epichlorohydrin, shrimp bromohydrin, shrimp iodohydrin, and the like.

The amount of epihalohydrin used is preferably 1 mol or more, more preferably 2 mol or more, per 1 mol of the dicarboxylic acid imide. If the amount of epihalohydrin used is less than 1 mole per mole of the dicarboxylic acid imide, unreacted dicarboxylic acid imide will remain.

In addition, epihalohydrin can be used in large excess to suppress side reactions and can also be used as a reaction solvent;
It is preferable to use about 10 moles.

Furthermore, since the N-glycidylation reaction of dicarboxylic acid imide with epihalohydrin does not proceed easily in the absence of a catalyst, it is preferable to use a suitable onium salt catalyst.

Specific examples of the onium salt catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, and quaternary phosphonium salts such as triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride. , quaternary arsonium salts, etc. These onium salt catalysts may be used alone or in combination of 2'Ff or more.

The amount of onium salt catalyst used is 0 relative to dicarboxylic acid imide.
．． 01 to 100 mol% is preferable, and 0.05 to 10 mol% is more preferable.

If the amount of onium salt catalyst used is less than 0.01 mol% based on the dicarboxylic acid imide, the reaction will take a long time, and if it exceeds 100 mol%, the yield of the target compound tends to decrease. There is.

The N-glycidylation reaction is carried out by adding an onium salt catalyst, a solvent, etc. to the dicarboxylic acid imide and epihalohydrin as necessary, at normal pressure, at 50 to 120°C, more preferably at 80 to 110°C, for 30 minutes to 20 hours. The reaction is preferably carried out for 1 to 8 hours.

The solvents used if necessary include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as 1,4-dioxane and tetrahydrofuran; trichloroethane and tetrachloroethane; Examples include inert solvents such as halogenated hydrocarbons such as . The amount of solvent used in the melon is preferably about 3 to 30 times the weight of the dicarboxylic acid imide.

After the reaction is completed, the resulting reaction mixture is washed with water, and unreacted epihalohydrin and solvent are distilled off to obtain the N-glycidyl imide compound represented by general formula (1).

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited only to these Examples.

Example 1 24.3 g (0.15 mol) of 5-norbornene-2,3-dicarboximide synthesized by reacting 5-norbornene-2,3-dicarboxylic anhydride with urea, 138.8 g (1 mol) of epichlorohydrin , 5 mol) and benzyltriethylammonium chloride 0.34 g
While stirring a mixture of (0,0015 mol) lO
Raised to OoC? After heating, stirring was continued for 3 hours.

After stopping the stirring, the mixture was washed with 1 OOm+ of water, and unreacted epichlorohydrin was distilled off at room temperature under reduced pressure. The resulting residual aroma was then recrystallized from methyl isobutyl ketone to obtain white crystals IG, 96 F: (yield 51.9%).
).

Melting point determined by DSC (heating rate 10°C/min) is 112
°C, and the tetraethylammonium bromide/perchloric acid method (solvent: tetraethylammonium ethane/phenol-5
The epoxy equivalent calculated from 0750) is 242 (calculated value 2
19).

The IR spectrum (Nujol method, hereinafter the same) and l) I-NMR spectrum of the obtained white crystals are shown in FIGS. 1 and 3. For reference, the raw material 5-norbornene
IR spectrum of 2,3-dicarboximide and I
The H-NMR spectra are shown in FIGS. 2 and 4.

From the results of IH-NMR spectrum analysis and IR spectrum analysis, N-glycidyl-5-norbornene-2,3
- It was confirmed that dicarboximide was changed.

Next, 1.00 g of the obtained white crystals and 894 g of methyl pear anhydride were mixed together, poured into a mold, placed in an oven, and heated at 150°C for 10.5 hours + 20.
0°C 10.5 hours + 250°C 75 hours + 250°C
It was heat cured for 73 hours. The Vicat softening point of the obtained cured product was 250°C or higher.

Example 2 5-norbornene-2,3-dicarboximide and epichlorohydrin were reacted in the same manner as in Example 1, and then purified as follows.

After the reaction was completed, most of the solvent (unreacted epichlorohydrin) was distilled off, and 20 g of chloroform was added to dissolve the contents. After washing this solution twice with 20 ml of water, the solvent was distilled off under reduced pressure in a room with 1 H1. The resulting residue was washed with 10ml of hexane, and placed in a Tenkater.
Drying at room temperature yielded white crystals. Yield: 4.19g
The crude yield was 96% and the melting point was 84-86°C.

The yield calculated from the purity determined by liquid chromatography was 8396. The epoxy equivalent of this product was determined by the tetraethylammonium bromide persalt hydroxide method (solvent: tetraethyloethane/phenol-1/l).
It was 98.

[Effects of the Invention] According to the production method of the present invention, it is possible to obtain N-glycidyl imide compounds that can be used as highly heat-resistant epoxy resins or are raw materials for producing highly heat-resistant epoxy resins; It is useful as a component of adhesive paints, shielding agents, gold materials, polymer modifiers, etc.

[Brief explanation of the drawing]

FIGS. 1 and 2 show the N− obtained in Example 1, respectively.
Glycidyl imide compound and raw material 5-norbornene-
3 and 4 are charts showing the IR spectra of 2,3-dicarboximide, respectively, of the N-glycidyl imide compound obtained in Example 1 and the raw material 5-norbornene-2,3-dicarboximide. 'H-NMR
It is a chart showing a spectrum. 1. Indication of the case Patent Application No. 55705 filed in 1988 2. Name of the invention N-glycidyl imide compound and its manufacturing method 3. Relationship with the case Patent applicant address Nakanoshima 3, Kita-ku, Osaka Chome 2-4 Name
(094) Kanebuchi Chemical Industry Co., Ltd. Representative Masato Niino 4 Agent 540 5 Subject of amendment (1) Column 6 “Detailed explanation of the invention” of the specification Contents of amendment (1) Specification page 17, line 4 r250"c/3 hours"
280℃/3 hours”. that's all

Claims (1)

[Claims] 1 General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 has at least one carbon-carbon double bond and has a carbon number of 4 to 30 An N-glycidyl imide compound represented by (representing a divalent organic group). 2 A compound represented by general formula (I) is a compound represented by general formula (II)
): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^2, R^3, R^4, R^5 have a carbon number of 1 to
5. The compound according to claim 1, which is a compound represented by an alkyl group having 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydrogen atom, or a halogen atom. 3 A compound represented by general formula (I) is a compound represented by general formula (II)
I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^3 and R^4 are the same as above, R^6 represents an alkylene group having 1 to 5 carbon atoms) The compound according to claim 1, which is a compound. 4 A compound represented by the general formula (I) is a compound represented by the general formula (IV)
): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R^3, R^4 are the same as above, R^7, R^8
represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom)
The compound according to claim 1, which is a compound represented by: 5 R^3, R^4, R^7 and R in general formula (IV)
5. The compound according to claim 4, wherein all ^8 are hydrogen atoms. 6 General formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R^1 is the same as above) A dicarboxylic acid imide and epihalohydrin are reacted to form the general formula (
A method for producing an N-glycidyl imide compound represented by I). 7. The method of claim 6, wherein an onium salt catalyst selected from quaternary ammonium salts, quaternary phosphonium salts and quaternary arsonium salts is used.