JPS60364B2 - Method for producing polyadducts containing imide groups - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing polyadducts containing imide groups.

Bis- and tris-maleimides are known to be used as raw materials for the production of polyadducts and polymers.

For example, French Patent No. 1555564 states that N, N
It is described that '-bis-maleimide is polyadded with primary diamines and that this preadduct is cured by thermal polymerization. However, the succinimide group-containing polymers thus obtained are unsatisfactory for many uses. That is, the polymer has a relatively low heating strain point. The bending strength and impact strength of polyaddition products of this type are also often insufficient. Furthermore, the corresponding manufacturing method also has drawbacks. US Pat. No. 3,741,942 describes polyadducts of bisumareimide and organic dithiols.

It is notable that the examples are limited to polymers produced by polyaddition of aliphatic dithiols and maleimides. All of these known polyadducts and their preparation methods have serious drawbacks characteristic of sulfur-containing polymers. In particular, there is a strong odor due to dithiols and their toxic effects. Similar disadvantages during combustion and decomposition at high temperatures of this sulfur-containing vehicle adduct often prevent it from being used as a structural material, in particular in the building sector, in automobile and airplane construction. Another disadvantage of this car additive is that its softening point is 110-170 oo.
It is not more expensive. The object of the present invention is to avoid the disadvantages of conventionally known polyadducts using maleimide as a substrate,
The object of the present invention is to produce polycondensation products containing imide groups using bis- and/or trismaleimides as substrates, which can be produced without using substances harmful to health and without unpleasant odors. .

The present invention contains an imide group and has the following formulas 1 and .': and (wherein R represents a hydrogen atom or a methyl group, The process relates to the production of polyadducts of repeating structural units represented by , the following formula Da: day.

-X-〇day (roa) (wherein,
) (in which B has the meaning as described above), optionally in the presence of a basic compound as a catalyst, at a temperature of 50°C to 280°C. It is characterized by

Basic catalysts suitable for the invention are in particular tertiary, secondary or primary amines or amines with several different types of amino groups (e.g. tertiary-secondary hybrid amines). be.

These amine catalysts may be monoamines or polyamines. When using primary and secondary amines, monoamines are preferred. Particularly preferred catalysts are tertiary, secondary or mixed tertiary-secondary amines. Examples of this type of amine catalyst include the following materials:
Diethylamine, triptylamine, triethylamine, triamylamine, benzylamine, N-methylpyrrolidine, 7-tramethyldiaminodiphenylmethane, quinoline, N,N-diisobutylaminoacetonitrile, N
, N-dibutylaminoacetonitrile, imidazole,
Benzimidazole and its congeners. The catalyst should be present in the reaction mixture in a concentration of 0.2 to 1% by weight, preferably 0.5 to 5% by weight, based on the total amount of starting components reacted.

In the operation of the present invention, the following proportions of polyhydric phenols and primary polyamines are used per equivalent of bis- and/or trisimide.

That is, the sum of polyhydric phenol and primary polyamine is 0.
These are used in such a way that the polyhydric phenol to polyamine equivalent ratio is from 0.5:1 to 4:1. The equivalent ratio of polyamine to polyhydric phenol is 1
:1 to 4:1 is desirable. The polyaddition according to the invention is based, in whole or in part, on a new bond between bis- and trisimides and polyhydric phenols according to the following chemical formula (11P), which for the sake of simplicity uses bifunctional reactants and bis-maleyl. using niimide.

The polyaddition reaction is further based on the bonding of imide and polyamine according to the following chemical formula (1-A).

For simplicity, this formula also uses a bifunctional reactant and a peace-maleimide. The two types of bonds first give rise to molecular chains, and then the chemical formulas (1-A) and (
The chain components generated by 11P) are added into the molecular chain alternately, in a statistical distribution, or separately, ie cumulatively, each in the form of block polymers.

During the course of the reaction according to the invention, cross-linking also takes place, mainly due to homopolymerization of the bis- and trisimide double bonds used.

The above-mentioned cross-linking is particularly effective when the number of double bond equivalents is larger than the sum of amino equivalents and hydroxyl equivalents. The formation of cross-linked products is particularly evident when trifunctional or higher functional starting materials are used. The polyaddition that occurs when carrying out the method of the present invention is
Considering the related literature, the bond according to the above chemical formula (1-P) was particularly surprising.

For example, attention should be drawn to US Pat. No. 3,678,015, which concerns a method for preparing polyimide prepolymers.

According to the invention, maleic anhydride and p, p'
-Methylene dianiline in a molar ratio of 2:1 from 80 to 200
Dissolve and react at a temperature of qo. The solvent used is a mixture of a hydrocarbon and a liquid phenol (for example cresol), the cresol being used in large excess.
It cannot be inferred from the patent specification that the formation of the prepolymer is in any way hindered by the presence of phenol. It is clear that cresol takes little part in the reaction process. German Published Application No. 2,114,076 discloses that organic diamines are mixed with maleic anhydride, e.g.
A method is described for producing polyimide by reaction in the presence of an acidic catalyst in a molar ratio of:

It is emphasized that even with this method, good results are obtained when cresol is used as solvent. Again, it is not implied that the cresol participates in any way in the reaction of maleic anhydride with the amine. In particular, German Application No. 1962845 relating to a process for producing polyimidoamines by reaction of maleic anhydride, maleic acid, maleic esters or maleic acid amides with diprimary amines also mentions that phenols (especially cresols) are Listed as suitable solvents.

In this publication, too, these phenols are not understood as reactants, but simply as inert solvents. Finally, in this connection, the aforementioned US Pat. No. 3,741,942 is once again cited.

That is, the procedure described in that example also operates with a large excess of cresol. Even there, there is no mention of cresol being involved in the reaction. Even if tri-n-butylamine is used as a catalyst, the reaction process does not change. Considering such state of the art, it was completely unexpected that polyaddition would occur when the technical idea of the present invention regarding the reactants bis- and trismaleimides and polyhydric phenols was applied.

However, polyaddition according to the chemical formula (11P) unexpectedly occurs. With the course of the reaction according to formula (1-A), the polyaddition results in polymers with surprisingly good thermal stability and at the same time good mechanical properties. Many of the bis- and trisimides that can be used according to the invention are well described in the literature.

These can be prepared by reacting the corresponding diamines with unsaturated dicarboxylic acid anhydrides by the methods described in US Pat. No. 3,010,290 and British Patent No. 1,137,592. Particularly suitable bis-maleimides include compounds represented by the following formula m: (wherein A represents a solid divalent organic residue having 2 to 3 carbon atoms).

The radical A of the formula rainbow is preferably of the formula W: where RI represents one of the groups -CH2-, SO2-, -SO-, -S- and -○-, and n is 0 or 1).

Specific examples of known imides suitable for the process of the invention include the following substances: N,N'-ethylene-bis-maleimide N,N'-hexamethylene-bis-maleimide N,N'- m-phenylene-bis-maleimide N,N'-p-phenylene-bis-maleimide N,N'-4,4'-diphenylmethane-bis-maleimide N,N'-4,4'-3 , 3'-dichlorodiphenylmethane-bis-maleimide N, N'-4,
4'-diphenyl ether bis-maleimide N,
NJ-4,4'-diphenylsulfone-bis-maleimide N,N'-4,4'-dichlorohexylmethane-bis-maleimide N,N'-Q,Q'-4,4'-dimethylenecyclohexane -bis-maleimide N,
N'-m-xylylene-bis-maleimide N,N'
-p-xylylene-bisumaleimide N,N'-4
,4'-diphenylcyclohexane-bis-maleimide N,N'-m-phenylene-bis-citraconimide N,N'-4,4'-diphenylmethane-bis-citraconimide N,N'-4,4'-2,2'-diphenylpro/zine-bis-maleimideN,N'-y,y
'-1,3-dipropylene-5,5-dimethyl-hydasotoin-bis-maleimideN,N'-4,4'-diphenylmethane-bis-dimethylmaleimide N,N
'-4,4'-2,2'-diphenylpropane-bis-dimethylmaleimide N,N'-hexamethylene-bis-dimethylmaleimide N,N'-4,4'-diphenyl ether-bis-dimethylmaleimide N,N
'-4,4'-Diphenylsulfone-bis-dimethylmaleimide However, it is also possible to use novel pis- and tris-imides having the following formula:

In the above formula, A' and A'' represent an aromatic group optionally substituted or interrupted by an oxygen atom, an alkylene group or a sulfonyl group, Z represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom. or represents a methyl group,
m represents the number 1 or 0, and n' represents the number 2 or 3.

The novel bis- and trisimides represented by the formula are dicarboxylic acid monoamides represented by the following general formula: where one of R' and R'' represents a hydrogen atom and the other represents a methyl group. by closing the compound at a temperature below 9000 °C in the presence of a catalyst (Na and K salts) and simultaneously eliminating n' moles of water, and subsequently precipitating the reaction product in water or in an aqueous alcohol solution. It is obtained by isolating a compound expressed in formula blood.

The dicarboxylic acid monoamide compound used in this case is produced by a known method. This is discussed in U.S. Patent No.
No. 444,536 and British Patent No. 102,705y are cited. Examples of novel maleimides of this type suitable for the process of the invention are: 4,4'
-N,N'- of diamino triphenyl phosphate
Bismaleimide, N,N'-bisumaleimide of 4,4'-diaminotriphenyl thiophosphate, N,N',N''-trisumaleimide of tris-(4-aminophenyl)-phosphate, and tris -(4-aminophenyl)-thiophosphate N,N
′,N″-tris-maleimide.

According to the invention, mixtures of any two or more of the bis- and trisimides can be used.

Polyhydric phenols (optionally mixtures of different phenols) suitable as starting materials for the present invention include mononuclear phenols such as hydroquinone, oxyhydroquinone, pyrogallol, phloroglucin, pyrocatechol and resorcin, as well as polynuclear phenols.

Polynuclear phenols of this type are, for example, of the following formula V: (wherein R'
and n is as defined above).

In particular, mention may be made of pisphenol A. Compounds corresponding to the above formula V include bis(p-hydroxyphenyl)-methane, bis(p-hydroxyphenyl)
-sulfone, bis-(p-hydroxyphenyl)-sulfoxide, bis-(p-hydroxyphenyl)-sulfide, bis-(p-hydroxyphenyl)-ether and 4,4'-dihydroxydiphenyl.
In principle, a portion of the hydrogen atom in the nucleus is C. Polynuclear phenols substituted with gen atoms can also be used. For example, tetrafrom bisphenol A may be mentioned.
Other polynuclear polyphenols suitable for the method of the invention are compounds containing fused rings.

For example, there is 1,4-dihydroxynaphthalene. All the polyphenols mentioned above which are suitable as starting materials for the process according to the invention are conventionally known to the person skilled in the art, and therefore a detailed description of their preparation is omitted here.

A particularly preferred embodiment of the invention is the use of novolak as the polyhydric phenol.

As is well known, novolak is a non-self-curing and meltable, ethyl alcohol-soluble or aromatic soluble phenolic resin, which is prepared by combining phenol and formaldehyde with an acid (tartaric acid, oxalic acid, hydrochloric acid,
It is produced when heating in the presence of dilute sulfuric acid, acid salts). For more information about Novolac, see for example “UI1m
anns Encyclopadder chnSc
henChem et al.'' (1962) pages 458 and 459. In the present invention, aromatic or araliphatic di- or tri-primary amines having 2 to 4 N carbon atoms in the molecule are used. It is preferable to use

Particularly preferred is the compound represented by the following formula: (where RI and n are as defined above). 1st French patent
In principle, all the polyamines already listed in No. 555,564 can also be used.

In particular, polyamines suitable for the process of the invention include: 1,2,4-triaminobenzene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 2,4,6-triamino 1,3,5
-trimethylbenzene, 1,3,7-triaminonaphthalene, 2,4,4'-triaminodiphenyl, 3,4,
6-triaminopyridine, 2,4,4'-triaminophenyl ether, 2,4,4'-triaminodiphenylmethane, 2,4,4'-triaminodiphenyl sulfone, 2,4,4' triami/penzophenone, 2,4,
4-triamino-3-methyl-diphenylmethane, N,
N,N-toIJ-(4-aminophenyl)-amine, tri-(4-aminophenyl)-methane, tri-(4-aminophenyl)-phosphate), tri-(4-aminophenyl)-phosphite, tri(4-aminophenyl)-thiophosph ate, 3,5,4'-triaminobenzanilide, melamine, 3,5,3',5-tetraaminobenzophenone, 1,2,4,5-tetraaminobenzene, 2,3,6,7 -tetraaminonaphthalene, 3
, 3'-diaminobenzidine, 3,3,4,4'-tetraminophenyl ether, 3,3,4,4'-tetraminodiphenylmethane, 3,3,4,4-tetraminodiphenyl sulfone , 3,5-bis(3,4'-diaminophenyl)-pyridine, 4,4'-diaminodicyclohexylmethane, 1,4-diamino-cyclohexane, m-phenylenediamine, p-phenylenediamine "4,4' -diaminodiphenyl-methane, pis-(
4-aminophenyl)-2,2-pro/dine, 4,4'
-diaminodiphenyl enal, 4,4-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, m-xylylene diamine, p-xylylene diamine, ethylenediamine, hexamethylene diamine, pisu(y-aminopropyl)-5, 5-dimethyl-hydantoin and 4,4'-diaminotriphenyl phosphate. The amines suitable for the method of the present invention and their preparation methods are well known, so detailed description thereof will be omitted.

For the sake of completeness, polyamines obtained by reaction of primary aromatic amines with aldehydes or ketones are also suitable as starting materials. In this regard, reference is made to French Patent Nos. 1,430,977 and 1,481,932. According to the invention, mixtures of several polyamines can also be used. In the reaction according to the invention, the equivalent ratio of polyhydric phenol to polyamine is from 1:1 to 4.
:1 is desirable.

The reaction according to the invention is preferably carried out in the melt or partly in the melt and partly in the solid phase.

However, it is also possible to carry out the reaction in solution. When carrying out the method of the present invention in a melt, 150 to 250 pm C.
Particularly preferred is a temperature of .

In solutions, on the other hand, lower temperatures, for example from 50 to 150 qo or from 50 to 220 oo, can also be applied. Suitable solvents include, for example, the following substances: aromatics such as xylene and toluene; halogen hydrocarbons such as trichloroethylene, tetrachloroethane, tetrachloroethylene, chlorobenzene; ethers such as dioxane, tetrahydrofuran, Dibutyl ether; dimethylformamide, tetramethylurea, dimethyl sulfoxide and N-methylpyrrolidone.

In many cases, it is appropriate to accelerate the reaction with a basic catalyst, especially when relatively unreactive substance mixtures are used or when polyadditions are carried out in solution at low temperatures.

The products resulting from the reaction, which contain secondary or tertiary amino groups, also act as catalysts during the course of the reaction.

In general, when carrying out the process of the invention, one starts from a reaction mixture which, in addition to the bis- or trisimide, simultaneously contains a polyhydric phenol and a primary polyamine.

However, another method involves first reacting a specific imide in whole or in part with a specific phenol in the presence of a catalyst;
The remaining reaction is then reacted with the primary polyamine and, if appropriate, with the remaining phenol.

The reverse method of operation is also possible.

A specific imide is first reacted in whole or in part with a specific primary polyamine. This is followed by a reaction with the specific polyhydric phenol and, if appropriate, the remaining primary polyamine. In these two last discussed methods, for practical purposes, a prepolymer is first produced.

However, the prepolymers can also be prepared and further processed in the manner described below. After all the starting materials have been mixed and, if appropriate, subsequently ground, the powder is first heated for a certain period of time, preferably to 140 to 17,000 °C. This results in a partially soluble product which can still be thermally deformed. , optionally ground to a powder that can be processed again, and finally hardened during subsequent finishing processing.Preparation can also be carried out by heating the solution or suspension of the starting materials. The production according to the invention of polyadducts having groups generally includes molded bodies, planar structures, laminates,
This is done while molding the adhesive and foam.

In this case, it is possible to add to the curable composition the additives customary in the art of thermosetting plastics, such as fillers, plasticizers, pigments, dyes, mold release agents and flame retardants. As a filler, glass fiber, mica, quartz powder, kaolin, colloidal silicon dioxide, or metal powder can be used, and as a template agent, various waxes, zinc stearate, calcium stearate, etc. can be used. . The products which can be produced by the process of the invention are molded in a very simple manner by the casting method using a casting mold.

However, the above-mentioned products are shaped by a hot compression method using a press.

Often at pressures of 1 to 200 KP/c flow for short periods of time
It is sufficient to heat to a temperature of 0 to 25,000 °C and to completely harden the molded body thus obtained outside the press. The method of the invention involves first preparing a prepolymer, suspending or dissolving it in a suitable solvent, and then producing a porous planar structure, such as a woven fabric, a fiber mat or a fiber fleece, in particular a glass fiber mat or a glass fiber woven fabric. The substrate is impregnated with the above solution or suspension, the solvent is removed by a drying process, and finally the substrate thus obtained is dried in a press preferably at a rate of 5 to 200 KP/
It can also be carried out by heating to 170 to 250 qo under low pressure.

It is also possible to precure the laminate in a press and to postcure the product thus obtained in an oven until optimum use properties are achieved. The process according to the invention and the polyadducts which can be produced thereby can be used in particular in the fields of surface protection, electrical engineering, lamination, foam production and architecture.

The manufacture of the foam will be specifically described below.

To produce foam, a blowing agent is added to the mixture which is solid at room temperature but decomposes at relatively high temperatures.

Sulfonyl hydrazides, such as benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide or 4,4
Materials such as '-oxydibenzenesulfonic acid hydrazide, and also azodicarboxylic acid amide or Q-Q'-azoisobutyric acid nitrile can be used. As blowing agent it is preferred to use azodicarboxylic acid amide. The density of the novel foam is determined in large part by the weight ratio of reaction mixture to blowing agent. Foaming agent 0.5-7%
It is preferable to use In order to obtain a homogeneous porous structure, surface-active substances can also be added in amounts of 0.1 to 1%, based on the total weight of the reaction mixture.

The reactants must be ground as finely as possible and mixed homogeneously before foaming.

For example, the starting material is dissolved or suspended in a low-boiling soot, such as a fluorocarbon, and a homogeneous mixture is created, after which the soot is again thoroughly removed. This method is particularly advantageous when the reactants have low melting points and are likely to stick during grinding. To produce a cured foam molding, the mixture according to the invention or the prepolymer prepared therefrom is filled together with a blowing agent and a surface-active substance into suitable molds, which can be closed if necessary.

Foaming, molding and curing: 80~22000, especially 160~
It is carried out in a 20,000 liter furnace. If the formed foamed body is dimensionally stable at the applied temperature, it can be removed from the mold. If necessary, it can be postcured at the same temperature or at a higher temperature, thereby achieving advantageous use properties. The new foams can be advantageously used where a foam with high thermal stability, high heating strain point and good dielectric properties and high adhesion even at relatively high temperatures is required.

Furthermore, the new foams can be used where the processing of previously known thermally stable foams was accompanied by considerable difficulties in shaping and processing. The present invention also provides a bis- and/or trisimide containing, per molecule, at least two groups represented by the following general formula 1: (wherein R represents a hydrogen atom or a methyl group); polyhydric phenol, c
The present invention relates to a storage-stable thermosetting mixture characterized in that it contains a primary polyamine of the formula ob and d optionally a basic compound as a catalyst.

This curable mixture is preferably a powder mixture.

This mixture is very advantageously obtained by grinding or post-milling the solid components together using intensive grinding equipment (for example a Pall mill). This powder mixture can in many cases be used as such, but it contains relatively large particles which are particularly suitable for tabletting, granulating or similar processes, for example by hot pressing, in a known manner. Materials can also be manufactured. Preparation of the starting materials for the process according to the invention 1 Preparation of Novolac F In a sulfonation flask equipped with a thermometer, an internal thermometer and a reflux condenser, 940 g (10 mol) of phenol was added to 900 g.
Heat to 0.

To the melt, 780 g of 30% formaldehyde (7.8
25 moles of oxalic acid (0.25 moles) dissolved in
1/ Add to the bottle for the life of the fly. After 8 hours of condensation at the same temperature, the pressure was reduced (starting with 76 mHg and 17 mHg).
lower to ) The temperature is raised to distill off the generated reaction water and unreacted fer/fer via a descending condenser. The internal temperature of 160° C. finally reached is maintained until no volatile constituents are present anymore and the oxalic acid used has completely decomposed. Novolak 862 is obtained which hardens at low temperatures.

Appearance: Yellow, clear. Novolak has a softening point of 108°C and a
It has an average molecular weight of 0.00. B. Preparation of trisimide of the formula W a. Into a reaction vessel equipped with a thermometer and a thermometer, 294 mol of maleic anhydride (30 mol) dissolved in 800 ml of dioxane are first charged.

Add dioxane 2 to this solution at 10 to 20 oo for 4 to 5 hours.
．． A solution of tris-(4-aminophenyl)-phosphate 371 (1 mol) dissolved in the solution is added dropwise. After the addition is complete, stir the mixture further for 11 hours,
and then the reaction product is heated, washed with chlorophor,
and dry. A yellowish substance 6699 is obtained with a melting point of 127-13000. According to the analytical data, this substance has the following structural formula: b. In a reaction vessel equipped with a thermometer and a thermometer, 85% of sodium acetate and 1.1% of acetic anhydride are first charged, and then using an oil bath, Flooded to 60qC.

Add tris-maleamic acid 9 prepared in a) to this solution.
54 was added little by little for 30 minutes until the reaction temperature reached 90q.
Do not exceed o. After the addition was complete, the mixture was cooled to room temperature, followed by 2 hours of isopropanol and 0.7 hours of water.
The mixture is added dropwise to obtain a partially crystallized reaction product. The precipitated material is filtered off, washed acid-free with isopropanol and water, and dried. 532 substances with a melting point of 173.5-1770 were obtained, which according to the analytical data is a tris-
Tris-maleimide of (4-aminophenyl)-phosphate: Example 1 N,N'-p,p'-diphenylmethane-pis-maleimide 57.3 times (0.16
4.6 moles of pisphenol AI (0.064 moles) and 12.7 moles of 4,4'-diaminodiphenylmethane (0.064 moles) were mixed well, and 1
Melts at 80°C and about 5 sides Hg, dimensions 150 x 150
Pour the mixture into a 4-sided mold, heat to 19,000 for 1 hour, and post-cure at 22,000 for 4 hours.

The measured properties are summarized in Table 2. EXAMPLES 2-11 This example was carried out identically to Example 1, except that some different reaction components were used and the proportions of the components were varied.

Table 1 shows the reaction components and their usage amounts. Examples 12 and 13 (comparative examples) In these examples the technical details described in French Patent No. 1555564 were followed (again using the casting method).

The usage percentages are summarized in Table 1 and the test results are summarized in Table 2. The reaction mixture was cured as follows: 1. at 140°C. Morning time, 1. at 160qC. Song time, 180 pieces 0
At 1. 1 at period time and 20,000. $hour. Discussion of Examples and Test Results (Examples 1 to 13) From Tables 1 and 2 it can be seen that the polyadducts prepared by the process of the invention (Examples 1 to 11) are in all cases the same as those of French Patent No. 1555564 (Example 12). It can be seen that it has a much higher heating distortion point than the polyadduct produced by 13) and 13).

In many cases, the products produced by the process of the invention are markedly superior in flexural strength and impact strength. In these cases, the superiority of the heating distortion point is particularly pronounced. Table *VSM = Swiss Society of Mechanical Engineers standard **ISO/R = International Standards Organization standard/recommended example 14
Preparation of the adduct 7 parts by weight of bisumarein-diimide diphenylmethane are heated to 15,000 ℃ in a beaker.

1 part by weight of 4,4'-diaminodiphenylmethane is admixed in the melt and the solution is maintained at the same temperature until its viscosity increases to such an extent that a resinous, brittle product forms after cooling; Pour onto a flat plate and cool quickly. The resulting solid adduct with a softening point (Kofler method) of 72°C was ground. Production of compression molded material 8 parts by weight of the above adduct, 2 parts by weight of phenol novolak (hydroxyl equivalent 9.5/k9), 0.08 part by weight of imidazole, 2 parts by weight of chamotte kaolin, 0.2 parts by weight of gas carbon black. and 0.1 part by weight of montan wax were weighed into a laboratory ball mill and ground for 1 press.

The resulting finely powdered product is granulated and tableted.

A tablet preheated to 7000°C was molded by a transfer method in a hot compression mold at 170°C.

Pressing time was 10 minutes. Bending strength (VSM771
03) 9.3k9/Yanagi 3, impact strength (VSM7710
3) 4.5 skin kg/c flow, heating distortion point (ISO/R7
5) 195oo (240 after curing for 1 time at 20000)
°C) and electrical volume resistivity of 5×1 and 50·arc were measured. Examples 15-20 This example operates as follows: a specific polymaleimide is melted with a specific phenol and a specific primary polyamine at 180 oo and about 5 skin Hg, and the resulting mixture is Pour into the mold described in 1.

Then heat to i9000 for 1 hour and 220oo for 4 hours. Table 3 summarizes the starting materials and their amounts for each example, and Table 4 summarizes the test results.

Table 3 Table 4 Example 21 1 mol of N,N'-4,4'-diphenylmethane-bis-maleimide, bis-phenol AO. A mixture of 4 mol and 0.4 mol of diaminodiphenylmethane is mixed with 1% by weight of silicone foam stabilizer (Si3193) and 4% by weight of azodicarbosamide.

The conditions of the conemase process are as follows: 25 minutes/12
0ko○.

The mixture thus obtained is ground in a ball mill.

In this way, a powder with an extremely uniform appearance is obtained. A foam with a uniform pore structure is obtained by maintaining the following foaming conditions: A I time / 1600 C + 4 min / 18000 Density 0.3 min / Mass B I time / 16000 + 4 min / 18
000 density 0.25 evening/lump C I hour/16000 14
Powder / 18000 density 0.15 evening / swimming D I time / 16
000 14 powder/18000 density 0.1 evening/ground.

Claims (1)

[Claims] 1 Contains an imide group and has the following formulas I and I': ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a hydrogen atom or a methyl X represents a polyhydric phenol group, and B represents a primary polyamine group) In the production of a polyadduct having a repeating structural unit represented by the following formula II: ▲ mathematical formula, chemical formula, There are tables etc. ▼ (In the formula, R has the meaning as described above) A bis- and/or trisamide containing a group represented by the following formula I
Ia: HO-X-OH (IIa) (In the formula, X has the meaning as described above) and the following formula IIb: H_2N-B-NH
_2 React with a primary polyamine represented by (IIb) (wherein B has the meaning as described above) at a temperature of 50 to 280°C, optionally in the presence of a basic compound as a catalyst. A method for producing the polyadduct, characterized in that: