JPS58174361A - Novel aromatic bis-imide and its preparation - Google Patents

Abstract

NEW MATERIAL:An aromatic bis-imide shown by the formula I (A is SO2, or CO; R' and R'' are H, halogen, or lower alkyl; D is group shown by the formula IIor formula III, may be different each other; n' and n'' are 1-4; two or more R' and R'' respectively are the same or different when n' and n'' are >=2). EXAMPLE:Bis[P,P'-(alpha,alpha-dimethyl-P''-N-maleimidobenzyl)phenoxyph enyl]sulfone. USE:Useful as solventless varnish, electrical insulating material, heat-resistant adhesive, coating compound, molding material, vulcanization auxiliary, etc. Useful as an energy saving material in the preparation of various kinds of materials when it is used as the solventless varnish. Having improved heat resistance and workability, usable in a wide industrial range. PROCESS:An aromatic bis-amide acid shown by the formula IV is reacted with a dehydrating agent in the presence of absence of a solvent in the presence of a catalyst, and, if necessary, a tertiary amine, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic bis-imide having excellent heat resistance and workability, and a method for producing the same.

Maleimide resins, represented by N, N'-(melane-p-phenylene) bismaleimide, are known as resins with excellent heat resistance, and are polymerized with polymaleimide resin amine, which is a homopolymer of bismaleimide. It is widely used as a maleimide-polyamine resin in impregnated varnishes, laminates, molding materials, etc. These maleimide resins generally have sufficiently satisfactory performance in terms of heat resistance, but the melting point of the resin before curing is high, so they are used in the form of a solution, and moreover, they are usually used in the production of impregnated varnishes and laminates. General-purpose organic solvents that are commonly used are poorly understood, but include high-boiling point, hygroscopic, and highly polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. It has the disadvantageous property of being soluble only in The use of impregnating varnishes prepared by dissolving such maleimide resins in polar solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide is difficult because these solvents are expensive and are difficult to penetrate through the skin. It is highly toxic and undesirable in terms of the working environment, health and safety, and also in view of the demands of the era of pollution-free living. Additionally, solvents tend to remain in prepregs made from varnishes prepared using these bath agents, which is a major factor in reducing the performance of the intended laminate.

As a result of intensive research to improve these shortcomings, American inventors discovered an aromatic bis-imide that has excellent solubility in general-purpose organic solvents and a low melting point that can be used in a solvent-free form. The invention has been completed.

The compound of the present invention has the general formula (1) (wherein A represents -8O7- or -00-, n' and R'' are the same or different from each other, a hydrogen atom, and I' is an integer of 1 to 4. When n' and n'' are 2 or more, two or more n' and π' may be the same or different. These compounds have significantly higher solubility in low-boiling solvents such as acetone, methyl ethyl ketone, and tetrahydrofuran, and lower melting points than conventional aromatic bismaleimides. Therefore, it has high utility value as a solvent-free varnish (it does not require a large amount of energy when producing various materials, and is a preferred energy-saving material. It also has excellent thermal properties and compatibility with resins, and the cured product is Due to its good dimensional stability and moisture resistance, it has a wide range of industrial uses, such as electrical insulation materials, heat-resistant adhesives, paints, molding materials, and vulcanization aids.

For example, one of the compounds of the present invention, bis[p, p'
The melting point, thermal decomposition temperature and solubility in organic solvents of -(α,α-dimethyluv/-N-maleimidobenzyl)phenoxyphenyl]sulfone are as follows.

Structural formula % Formula % Temperature of 5φ weight loss measured with thermobalance 450°G Organic bath agent Solubility (at room temperature ℃・) 1.4-
Dioxa7 50″Tetrahydrofuran
50 ″Acetone 50 ″Methyl ethyl ketone 50 ″Next, the production method of the present invention is based on the general formula (II) (R') (wherein A represents -502- or -C〇-, and R' and I (L / is the same or different from each other, hydrogen atom,
Represents a halogen atom or a lower alkyl group, and D is an integer of 1 to 4. When n' and n are 2 or more, two or more R' and t may be the same. The aromatic bis-amic acid represented by the general formula (1) (in the formula, A, D, R', Bi', n' and R' have the same meanings as in general formula (n)).

The starting material used in the production method of the present invention is bis-
This is an amic acid compound represented by the above general formula (■). These compounds have the general formula ('yD (wherein A, R',
Maleic anhydride or 5-norbornene-2,3-dicarboxylic anhydride is added to an aromatic diamine represented by f (', n', and R' have the same meanings as in general formula (1)) in a solvent such as acetone. It is obtained by adding at 0 to 40°C in a medium temperature. In order to advantageously carry out the production process of the present invention, bis-amic acid obtained by the addition reaction of diamine with maleic anhydride or 5-norbornene-2,3-dicarboxylic anhydride in an organic bath agent is preferably used. It is directly used in the cyclization (imidization) reaction without separation, which is the production method of the present invention.

The aromatic diamine of the general formula (IID) is 2-(4'-
aminophenyl) 2 (4#-hydroxyphenyl)propane, 2 (!l'lnor-4'-aminophenyl) -2-(4''-hydroxyphenyl)propane, 2-(2'-methyl-4'-amino phenyl)
2 (47/-hydroxyphenyl)furopane, 2
-(3'-ethyl-4'-aminophenyl)-2-(4
″-hydroxyphenyl)furopane, 2-(2′-propyl-4′-aminophenyl)-2=(3″-hydroxyphenyl)chromy, 2-(3′-aminophenyl)
-2-(4"-hydroxyphenyl)furopane, 2-(
3'-7minophenyl)-2-(3"-hydroxyphenyl)furopane, 2-(4'-aminophenyl)-2-
(5”-hydroxyphenyl)propane, 2-(5’-
Methyl-37-aminophenyl) 2 (4//-
hydroxyphenyl)propane, 2-(5'-ethyl-
chloro'-aminophenyl)propane, 2- ('3'-chloro4'-ami/phenyl) 2 (4//-hydroxyphenyl)propane, 2 (s/, s/-
dichloro-47-amylafx = l) -2-(4'
/-hydroxyphenyl)furopane, 2-(6'-promo4'-aminophenyl)2 (t, //-hydroxyphenyl)furopane, 2-(ge5'-dibromo4
7-aminophenyl)-2(t,l/-hydroxyphenyl)propane etc. 2-(aminophenyl)-42-(
Hydroxyphenyl)propanes (one type at a time,
4,4'-dichlorodiphenyl sulfone, 4,4'-dibromodiphenyl sulfone, 3,4'-dichlorodiphenyl sulfone, 3,3'-dichlorodiphenyl sulfone, 3,4'-dibromodiphenyl sulfone, "r,
5'-dibromodiphenyl sulfone, 4,4'-dichlorodiphenyl ketone, 4.4'-)furomodiphenyl ketone, 3.4'-dichlorodiphenyl ketone, 3.3
'-Zin0rodiphenylketone, i,4'-dibromodiphenylketone, 3,3'-dibromodiphenylketone, 4,4'-difluorodiphenyl sulfo7,4,4'
- one of the dihalogen compounds such as difluorodiphenyl ketone in the presence of an alkali metal or a basic compound such as an alkali metal hydroxide, carbonate, bicarbonate, nitrate or alcoholade in an organic solvent. 10
It can be obtained by reacting at 0 to 200°C.

Among such aromatic diamines, bis[p,
p'-(α,α-dimethylv'-aminobenzyl)phenoxyphenyldisulfone, bis(4,4'-(
α,α-dimethyl-6″-methyl-4″-aminobenzyl)phenoxyphenyldisulfone, bis(p,p-(
α,α-dimethyl-6″-aminobenzyl)phenoxyphenylkoketone and nobis[4,4′-(α,α-dimethyl-6″-methylbenzyl)phenoxyphenylkoketone are preferred.

In the method of the present invention, maleic anhydride or 5-norbornene-2 anhydride,
General formula (11) obtained by adding 3-dicarboxylic acid
The aromatic bis-amic acid represented by is cyclodehydrated.

The organic solvents used in the dehydration cyclization, which is the production method of the present invention, include chloroform, methylene chloride, carbon tetrachloride, halogenated hydrocarbons such as trichloroethylene, acetone,
Ketones such as methyl ethyl ketone and cyclohexanone,
Organic carboxylic acids such as formic acid, acetic acid, butyric acid, methyl acetate, ethyl acetate and their esters, methyl alcohol, ethyl alcohol, flobyl alcohol, ether, 1.
Alcohols and ethers such as 4-dioxane, tetrahydrofuran, cellosolve, methyl cellosol, cyclohexane, benzene, toluene, xylene (0-,
? ? 'L7, p-), alicyclic and aromatic hydrocarbons such as mesitylene, chlorobenzene, cresol (0-1m-
1p-), aromatic compounds such as dichlorobenzene (o=, m-1p-), acetonyl), pyridine, N,
N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoramide, N-methyl-2-
These include nitrogen-containing and yellow-containing compounds such as pyrrolidone, N-methylcaprolactam, and dimethyl sulfoxide. Particularly preferred organic solvents are acetone, methyl ethyl ketone,
Acetonitrile or N,N-dimethylformamide. It is also possible to use a mixture of two or more of these organic solvents. The amount of organic solvent used is preferably 11 to 80 times the weight of diamine or bis-amic acid.

Further, the catalyst used in the dehydration cyclization reaction of the production method of the present invention is sodium bicarbonate, carbonate, sulfate,
nitrates, phosphates, birophosphates, acetates and butyrates; bicarbonates, carbonates, sulfates, nitrates, phosphates, pyrophosphates, chlorides, bromides, iodides, acetates of lithium; Butyrate; magnesium, iron (■ and I)
, nickel (II), manganese (■ and I), copper (■
and ■) or cobalt (■ and i) carbonates, sulfates, phosphates, chlorides, bromides, iodides, formates,
Hydrates and non-hydrates of acetates, butyrates, stearates and naphthenates, as well as copper, nickel (11),
Cobalt (■ and I) and manganese (■ and l)
acetylacetonate complexes, etc. These catalysts are 1
Seeds are effective enough, but 2!1! It is also possible to use a mixture of the above. Particularly preferred catalysts are sodium acetate, hydrated and non-hydrated nickel(II) acetate,
or hydrates and non-hydrates of cobalt (It) acetate. The amount of catalyst used is 10 x 10'' to 12 mol, preferably 2.0 x 10 mol per mol of bismaleamic acid used.
'' to 05 mol.If the amount of catalyst used is 10 x 10
When the amount is less than -3 moles, the reaction rate is low and the dehydration cyclization reaction takes a long time. On the other hand, when it is more than 12 moles, undesirable side reactions occur and the yield of bis-imide decreases.

Further, the tertiary amines used in the present invention include trialkylamines having an alkyl group having 3 to 20 carbon atoms such as trimethylamine, triethylamine, tributylamine, N,N-diethylcyclobexylamine,
N,N-dimethylbenzylamine, N-methylpiperidine, 1,4-diazabicyclo(2,2,2)-octane, 1,8-diazabicyclo(5,4,0)-7-undecene, N-methylmorpholine, etc. It is. Two or more of these 6th class amines may be used in combination. A particularly desirable tertiary amine is triethylamine. The amount of tertiary amine used is 001 to 1.1 per mole of bisamide liquid.
It is in the molar range, preferably in the range of 0.005 to 0.06 molar.

If the amount of the 6th class amine used is below the above range, the reaction rate will be low, while if it is above the above range, undesirable side reactions will occur. Further, the 6th class amine can also be added in the step of producing the amic acid.

Furthermore, the dehydrating agent in the present invention is a compound that acts on the amic acid group of bis-amic acid to form an imide group, and is itself hydrated or hydrolyzed, or a compound that has an extremely large dehydrating ability. Typical compounds as dehydrating agents are acetic anhydride,
Propionic anhydride, butyric anhydride, valeric anhydride, Kono anhydride
Calcium such as phosphoric acid, glutaric anhydride, benzoic anhydride, 7-taric anhydride, etc.: 1. ... Bonic acid anhydride. It is also possible to use a mixture of two or more of these dehydrating agents. A particularly preferred dehydrating agent is acetic anhydride because it is easy to handle and easy to post-process after the dehydration and cyclization reaction. The amount of the dehydrating agent used is in the range of 0.2 to 5 moles, preferably in the range of 1.0 to 2 moles, per equivalent of the amic acid group of the bis-amic acid.

When the amount of the dehydrating agent used is less than the above range, the amount of residual bis-amic acid increases, while when it exceeds the above range, side reactions tend to occur.

In the production method of the present invention, the reaction temperature for cyclodehydrating bis-amic acid to produce bis-imide is 20 to 100°C.
The temperature is preferably 40 to 80°C. The reaction time is in the range of 0.5 to 9 hours, more preferably in the range of 1 to 5 hours, and the reaction proceeds under a pressure sufficient to maintain the reaction system in a liquid phase.

If the reaction temperature is less than 20°C or the reaction time is less than 0.5 hours, the reaction rate will be so low that the reaction will hardly proceed;
.

If the reaction time exceeds 9 hours, undesirable side reactions tend to occur.

After the reaction under the above reaction conditions is completed, the reaction solution is cooled and a precipitant is gradually added to the resulting homogeneous phase reaction solution to obtain a film.

However, the bis-imide produced by adding a precipitant such as water to the reaction solution or dropping the reaction solution into the precipitant has a tar-like appearance because of its strong affinity with organic solvents. Therefore, when water is used as a precipitant, in order to enhance the dispersion effect of bis-imide in water and obtain good particulate precipitation, alcohols are added to the homogeneous phase reaction solution after bis-imide formation.

Examples of alcohols include methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butyl alcohol. The amount used is 0.05 to 200 per 100g of reaction solution.
I, preferably in the range of 1.0 to 50 g.

If the amount of alcohol used is less than 0.05 g, the bis-imide becomes tar-like, and if it exceeds 200 g, the bis-imide becomes a colloid and becomes extremely difficult to filtrate. To the reaction solution to which alcohols have been added, either add a precipitant or
Alternatively, good particulate bis-imide can be obtained by dropping it into a precipitant. Precipitants that can be used include water, methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, etc., in which the bis-imide has a low solubility and the bath of the reaction solution. Examples include compounds that are compatible with the drug. Among these compounds, water or methyl alcohol are preferred precipitants in terms of ease of handling, low cost, and environmental hygiene. The amount of precipitant used is 0 of the reaction solution volume.
3 to 50 times the capacity is sufficient.

The following operation is performed to purify the obtained bis-imide. That is, a basic compound such as sodium carbonate or sodium hydrogen carbonate is added to the slurry liquid obtained by pouring the cake that is precipitated from the reaction solution and then separated from the mother liquor into water so that the pH of slurry i is in the range of 80 to 90. The cake is further separated and washed with water moderately, thoroughly washed and purified with methyl alcohol, and then dried to obtain the target compound. In this case, the precipitate sla I
Neutralizing J-4 with a basic compound such as sodium carbonate is not necessarily an essential condition (the purification effect can be fully demonstrated by washing the precipitate with water several times, followed by washing with alcohol). However, if the slurry of the precipitate is neutralized with a basic compound, the target compound, bis-imide, can be further purified due to the synergistic effect. are methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1-butanol, and 2-furinol.The amount of alcohol used is sufficient to be 11 to 30 times the weight of the obtained precipitate. Washing with alcohols has the advantage that the drying process of the obtained bis-imide is shortened.

It is a relatively high-molecular compound containing two double bonds in the molecule, and when used alone or in combination with other suitable monomers or polymers, it undergoes a polymerization reaction to form a so-called three-dimensional structure. A cured product of thermosetting resin is formed.

The cured product obtained using this aromatic bis-imide has characteristics such as excellent heat resistance, dimensional stability, high toughness, and easy molding, and is used in the fields of electronics, electrical insulation materials, and mechanical parts. Widely used for impregnated varnishes, laminates, paints, adhesives, molded products, etc. Furthermore, the bis-imide has utility value in fields where unique functions are required, such as agricultural chemicals and rubber drugs. The use of bis-imide takes advantage of the properties of this compound additive, such as its easy solubility in organic solvents and its low boiling point.11 It also simplifies the work process and saves energy.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 9.4 g of maleic anhydride was dissolved in 64 ml of acetone, and then the solution was dissolved in bis(p,
268 g of p'-(α,α-dimethyl-me'-aminobenzyl)phenoxyphenyl]sulfone was gradually added. After the addition was completed, stirring was continued for 2 hours at a temperature of 200C. Next, 012 g of cobalt tetrahydrate, 18 g of triethylamine, and 104 g of Kabutochoic acid were poured into the mixture, the temperature of the reaction solution was raised, and stirring was continued at 60° C. for 25 hours. Thereafter, the reaction solution was cooled to room temperature, thoroughly stirred, and gradually poured into 600 ml of filtered water at ℃ to obtain a precipitate. The precipitation is f
Separately, wash thoroughly with water, then wash with methanol and 55°
Dried under C1 vacuum to give 32.2 g of light brown powder (yield: 97
) was obtained. The melting point of this compound was 125-132°C.

In addition, this compound has the structure of the following formula according to infrared absorption spectrum, 'H nuclear magnetic resonance absorption spectrum, and elemental analysis.
It was confirmed to be maleimidobenzyl)phenoxyphenyl]sulfone.

Infrared absorption spectrum As shown in Figure 1, characteristic absorption of imidocarbonyl was observed at 173Qcm1.

'H nuclear magnetic resonance absorption spectrum (solvent DMS()-D6
) Chemical shift (δ value) is t 68 pT) m is 0H3, 7, and 12 ppm are maleimide groups -CI (1
At 7.00 and 7.30.7.9>ppm, a unique absorption attributed to -11 of the benzene nucleus was observed, and the absorption area intensity matched the proton number ratio.

Elemental analysis value (Complete CHN S calculated value 72,45 4.B6 3.38 3
．． 87 analysis value 72,29 4,80 3,31
3.94 Example 2 Bis(p,p'-(α,α-dimethyl-V'-aminobenzyl)phenoxyphenyl)sulfone 26.8.9 Instead of bis(p,p'-(α,α-dimethyl-V'-aminobenzyl) The procedure of Example 1 was repeated except that 277 g of σ'-aminobenzyl) phenoxyphenyl coketone was used, and 32 g of light brown powder was obtained.
．． 0 g (yield 92.2%) was obtained.

The melting point was 90-109°C.

Infrared absorption spectrum Shown in Figure 2.

'II nuclear magnetic resonance absorption spectrum (solvent DM S 0-
D6) Chemical shifts (δ values) are each 1.70 ppm
1〇H3,7,12ppm is -OH of maleimide group,
7,04,7,50,7,761)pn] was observed to be attributed to -H of the benzene nucleus, and the absorption area intensity matched the proton number ratio.

Elemental analysis value (→ OHN total first straight 77.26 5,08 3
．． 53 analysis value 77.08 5.04 3.
From the analysis results of 55 or more, bis [p,
157I of 5-norbornene-2,3-dicarboxylic anhydride was used in place of 9.4 g of maleic anhydride. Except for the above steps, the same procedure as in Example 1 was carried out to obtain 552 g of pale white powder (yield: 928 yen).

The melting point was 112-118°C (softer than 98°C).

Infrared absorption spectrum Shown in Figure 6.

'H nuclear magnetic resonance absorption spectrum (solvent DMSO-D6
) Each chemical shift (δ value) could be attributed to the resonance absorption of each proton in the obtained chemistry, and the absorption area intensity matched the proton number ratio.

From the above analysis results, it was confirmed that bis-nadic imide having the structure of the following formula was produced.

[Brief explanation of drawings]

Figure 12 and filter are the bis(s) obtained in Examples 12 and 3.
p,p'-(α,α-dimethylov/N-maleimidobenzyl)phenoxyphenyl]sulfone (Figure 1)
, bisCp, p'-(α,α-dimethyl-1:/'-
This figure shows the infrared absorption spectra of N-maleimidobenzyl) phenoxyphenyl coketone (Figure 2) and bis-nasic imide (Figure 6). Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) General formula (1) (wherein A represents -5o2- or -CO-, R' and R' are the same or different from each other, a hydrogen atom, and H and -' are 1- is an integer of 4. When n' and n' are 2 or more, two or more R' and bi' may be the same or different from each other. 2) General formula (II) (It) (wherein A represents -5o2- or -co-, R'
and R'' are the same or different from each other and are hydrogen atoms, and halo n' and tj' are integers from 1 to 4. 7L', ?
+, ” is 2 or more pieces, each has 2 or more B/,
B// may be the same or different from each other) is reacted with a dehydrating agent in the presence or absence of a solvent together with a catalyst and optionally a tertiary amine to obtain the general formula (1) A method for producing an aromatic bis-imide represented by the formula (wherein A, D, a', *', n' and n'' have the same meanings as in general formula (If)).