CA2059988C - Process for preparing compound of unsaturated dicarboxylic acid imides and resin of the same imides - Google Patents
Process for preparing compound of unsaturated dicarboxylic acid imides and resin of the same imidesInfo
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- CA2059988C CA2059988C CA002059988A CA2059988A CA2059988C CA 2059988 C CA2059988 C CA 2059988C CA 002059988 A CA002059988 A CA 002059988A CA 2059988 A CA2059988 A CA 2059988A CA 2059988 C CA2059988 C CA 2059988C
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- unsaturated dicarboxylic
- distillation
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- anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
- C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/121—Preparatory processes from unsaturated precursors and polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Pyrrole Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
A process for preparing a compound of unsaturated dicarboxylic acid imides allows the compound of a following formula obtained through a dehydrating cyclization of an unsaturated dicarboxylic amic acid compound in the presence of catalysts and thereafter a vacuum distillation of the ring-closed compound:
Description
"PROCESS FOR PREPARING COMPOUND OF UNSATERATED
DICARBOXYLIC ACID IMIDES AND
RESIN OF THE SAME IMIDES"
SPECIFICATION
BACKGROUND OF THE INVENTION
This invention relates to a process for preparing compounds of unsaturated dicarboxylic acid imides and resins of the same imides.
The compounds of unsaturated dicarboxylic acid imides of the kind referred to can be effectively utilized as a material for laminates and the like which are employable as printed circuit boards.
DESCRIPTION OF RELATED ART
As a typical one of the processes for preparing the compounds of unsaturated dicarboxylic acid imides, there may be enumerated a process in which unsaturated dicarboxylic amic acid is subjected to a cyclization for obtaining the compounds. According to this chemical cyclization process, generally, a dehydrating cyclization with such dehydrating agent as acetic anhydride or the like employed has been practiced. With this process, required reaction can be attained at a lower temperature and in a short time, so that the eventually obtained compounds of unsaturated dicarboxylic acid imides are of such high level of the purity as to be about 90 weight %, contained amount of polymeric component in the compound is smaller, and the compound itself may be regarded to be satisfactory.
DICARBOXYLIC ACID IMIDES AND
RESIN OF THE SAME IMIDES"
SPECIFICATION
BACKGROUND OF THE INVENTION
This invention relates to a process for preparing compounds of unsaturated dicarboxylic acid imides and resins of the same imides.
The compounds of unsaturated dicarboxylic acid imides of the kind referred to can be effectively utilized as a material for laminates and the like which are employable as printed circuit boards.
DESCRIPTION OF RELATED ART
As a typical one of the processes for preparing the compounds of unsaturated dicarboxylic acid imides, there may be enumerated a process in which unsaturated dicarboxylic amic acid is subjected to a cyclization for obtaining the compounds. According to this chemical cyclization process, generally, a dehydrating cyclization with such dehydrating agent as acetic anhydride or the like employed has been practiced. With this process, required reaction can be attained at a lower temperature and in a short time, so that the eventually obtained compounds of unsaturated dicarboxylic acid imides are of such high level of the purity as to be about 90 weight %, contained amount of polymeric component in the compound is smaller, and the compound itself may be regarded to be satisfactory.
- 2 - *
However, in the known chemical cyclization, normally a reactive solution is poured into water to have a reaction product separated out of the solution, the product is further processed through a filtration, water 5treatment, neutralization of by-produced acid and so on, respective steps of which are extremely laborious and render the process to be complicated, and the known process has involved a problem in the productivity and manufacturing economy.
10As further known processes for preparing the unsaturated dicarboxylic acid imide compounds in which no such measure for simplifying the processing steps as in the present invention which will be described in the followings, there may be enumerated such ones as have been 15suggested in U.S. Patent No. 4,855,450 to John M. Butler et al, Japanese Laid-Open Publication No. 63-69829 of Shuichi Kanekawa et al and so on, but they still involve problems in respect of the treatment simplification and the improvement in the productivity and economy.
Accordingly, a primary object of the present invention is to provide the process for preparing compound of unsaturated dicarboxylic acid imides, which process can be attain the high yield and purity without requiring any complicated processing steps.
According to the present invention, this object can be realized by means of a process for preparing the compound of unsaturated dicarboxylic acid imides in which such unsaturated dicarboxylic amic acid as represented by a following general formula (I) is subjected to the dehydrating cyclization in the presence of three of acid anhydride as a dehydrating agent, basic catalyst and metallic salt catalyst, characterized in that an acid and solvent produced after the dehydrating cyclization are subjected to a vacuum distillation, upon which 50 to 70%
of solution component is distilled off at a distilling temperature below 70C, a cooling is thereafter carried out to separate a solid component, and the distillation is again performed to obtain such compound as represented by a following general formula (II):
/ CONH R
D ....... (I) COOH n -- CO
N R ----.. (II) CO n in which formulas (I) and (II), D denoting bivalent organic group having at least one carbon-carbon double bonding, Rl denoting n-valent organic group having at least one carbon atom, and n denoting an integer more that 1.
Further according to the present inventiol, polyamine and a solvent are added to the compound of unsaturated dicarboxylic acid imides obtained through the above process to have them polymerized and a resin of unsaturated dicarboxylic acid imides is obtained.
Other objects and advantages of the present invention will be made clear as the description of preferred examples advances in the followings.
While the present invention shall now be described with reference to the certain preferred examples, it should be appreciated that the intention is not to limit the invention only -to these examples described but rather to include all alterations, modifications and equivalent arrangements possible within the scope of appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EXAMPLES
In obtaining the compound of unsaturated dicarboxylic acid imides in the present invention, unsaturated dicarboxylic amic acid compound is employed.
While this unsaturated dicarboxylic amic acid compound is not specifical~y limited, the same can be obtained through a reaction caused between such unsaturated dicarboxylic anhydride as represented by a following general formula (III) and such amine or polyamine as represented by a following general formula (IV), preferably in the presence of inert organic solvent or the like with respect to a reaction system or non-solvent system:
CO
D O ....... (III) CO
[ 2 1 n Rl ....... (IV) in which formulas (III) and (IV), D denoting bivalent organic group having at least one carbon-carbon double bonding, R denoting n-valent organic group having at least one carbon atom, and n denoting an integer more than S 1.
For the unsaturated dicarboxylic anhydride employable in this reaction system, while not required to be specifically limited, it is possible to employ maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic tetrahydro anhydride, nudic anhydride, their halogen substituted products, alkyl substituted products or the like alone or in a mixture of two or more.
For amine or polyamine, while not particularly limited, it is possible to employ one or a mixture of two or more of methylamine, ethylamine, l-propylamine, 1,2-dimethyl propylamine, 3-methoxypropylamine, 3-eth-oxypropylamine, 3-propoxypropylamine, 3-isopropoxy-propylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3-(2-ethylhexyloxy!propylamine, 3-rauryl oxypropylamine, 3-mirystyl oxypropylamine, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibu-tylaminopropylamine, 2-hydroxyethyl aminopropylamine, dimethylaminoethoxy propylamine, raurylaminopropylamine, diethanolaminopropylamine, imino-bis-propylamine, methyl amino-bis-propylamine, n-butylamine, isobutylamine, sec-butylamine, hexylamine, 2-ethylhexylamine, dodecy-lamine, cyclohexylamine, arylamine, 3-decichloxyamine, diethylaminoethyl amine, ethylaminoethyl amine, ~-phenethylamine, ~-phenethylamine, furfurylamine, methoxylamine, m-aminobenzylamine, methaphenylenediamine, 4-chloromethaphenylenediamine, 5-nitromethaphenylenedia-mine, 4,6-dimethylmethaphenylenediamine, paraphenylenedi-amine, 2-chloroparaphenylenediamine, 2-nitroparaphenylene-diamine, 2-cyanoparaphenylenediamine, 2,5-dichloroparaphe-nylenediamine, 2,6-dichloroparaphenylenediamine, 2,5-die-thylparaphenylenediamine, 5-chloro-2-methylparaphenylen-ediamine, tetrafluorophenylenediamine, torylenediamine, 3,5-diethyl-2,4-torylenediamine, 2-picolylamine, 3-picol-ylamine, 4-picolylamine, methaxylenediamine, paraxylen-ediamine, hexamethylenediamine, heptamethylenediamine, 4,4-dimethylheptamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, penta-ethylenehexamine, 4,4'-diaminodiphenylmethane, 3,4'-diam-inodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3',4, 4'-tetraaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldi-phenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimeth-ylphenylmethane, 4,4'-bis(p-aminophenoxy)diphenylmethane, 4,4'-bis(m-aminophenoxy)diphenylmethane, 2,2',3,3'-tet-rachloro-4,4'-diaminodiphenylmethane, diaminodicyclo-hexylmethane, 4,4'-bis(p-aminophenoxy)diphenylmethane, 4,4'-bis(m-aminophenoxy)diphenylethane, 1,2-bis-(3-ami-nopropoxy)-ethane, 2-aminopropanol, 3-aminopropanol, 1,2-diaminopropane, 3,3'-diaminodiphenylpropane, 1,2-bis-(3-aminopropoxy)-2,2'-dimethylpropane, 4,4'-bis(p-am-inophenoxy)diphenylpropane, 4,4'-bis(m-aminophenoxy)dip-henylpropane, 2,2'-bis(4-aminophenyl)propane, 1,4-diamino-butane, 1,4-diaminocyclohexane, bis-(3-aminopropyl)ether, ~,w-bis-(3-aminopropyl)polyethylene glycol ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4,4'-triaminodiphenyl ether, 3,3',4,4'-tetraminodiphenyl ether, bis(p-Ramino-tert-buty-lphenyl) ether, toluidine, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-6-bromo-2-toluidine, aniline, ethy-laniline, dichloroaniline, 4,4'-methylenedi-2,6-diethyla-niline, 4,4'-methylenedi-2,6-isopropylaniline, isopropo-xyaniline, chloroaniline, bromoaniline, iodoaniline,nitroaniline, 4,4'-methylenedi-2,6-bromoaniline, 4,4' methylenedi-2-bromo-6-chloroaniline, bis-p-aminophenyla-niline, methylene-bis-anthraanilic acid, methy-lene-bis-methyl anthranilate, 3,3'-diaminodiphenyl sulfone, [4,4'-diaminodiphenyl] sulfone, 3,3',4,4'-tetraa-minodiphenyl sulfone, p-bis(4-aminophenoxy)diphenyl sulfone, p-bis(3-aminophenoxy)diphenyl sulfone, 2,2'-bis- 4-(4-aminophenoxy)phenyl sulfone, orthotolidine sul-fone, 4,4'-diaminodiphenyl sulfide, bis-(4-amino-phenyl)disulfide, 3,3',4,4'-tetraaminodiphenyl sulfide, N-aminoethyl piperidine, N-aminoethyl-4-pipecoline, N-aminoethyl morpholine, N-aminopropyl piperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropyl morpholine, 2-aminoethyl piperidine, 4-aminomethyl piperidine, N-aminopiperidine, l-amino-4-methyl piperazine, l,4-bis-aminopropyl piperazine, 2-aminopiperazine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diamino-pyridine, 2,6-diaminopyridine, 2,3,6-triaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-ami-no-5-methylpyridine, 2-amino-6-methylpyridine, 2-ami-no-4-ethylpyridine, 2-amino-4-propylpyridine, 2-ami-no-4,6-dimethylpyridine, 2,6-diamino-4-methylpyridine, 2-amino-3-nitropyridine, 2-amino-5-nitropyridine, 2-chlo-ro-4-aminopyridine, 2-chloro-5-aminopyridine, 2-ami-no-3,5-dichloropyridine, 4-amino-3,5-dichloropyridine, 2-amino-3,5-dichloro-6-methylpyridine, 2-amino-3,5-dich-loro-4-methylpyridine, 2-amino-5-chloro-3-methylpyridine, 2-amino-3,5-dichloro-4,6-dimethylpyridine, 2,4-diamino pyridine, 2,4-diamino-6-(4-pyridyl)-5-triazine, p-bis(4-aminophenoxy)benzene, m-bis(4-aminophenoxy)benzene, p-bis (3-aminophenoxy)benzene, m-bis(3-aminophenoxy)benzene, 1,3,5-triaminobenzene, 4,4'-diamino-3-methoxyazobenzene, 1,5-diaminonaphthalene, 1,3,5-triaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiph-enyl, 2,5-diaminoterephthalic acid, 3,4'-diaminobenzani-lide, 4,4'-diaminobenzanilide, 4-(p-aminophenoxy)-4-amino-benzanilide, 3,3'-dimethoxybenzidine, 3,3'-dimethylbenzi-dine, 3,3'-diaminobenzidine, 3,3'-dihydroxybenzidine, 2,2'-dichloro-5,5'-dimethoxybenzidine, 2,2',5,5'-tetrach-lorobenzidine, 2,4-diaminotoluene, 2,4-bis(~amino-tert-butyl)toluene, 4,4'-diaminobenzophenone, polytetrame-thyleneoxido-di-p-aminoobenzoate, trimethylene-bis-(4-aminobenzoate), bis(4-aminophenyl)diphenylsilane bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)phenylpho-sphinic oxide, bis(4-aminophenyl)methylphosphinic oxide, melamine, 4,4'-diaminostilbene, 9,9-bis(4-aminophe-nyl)-10-hydroanthracene, 2,6-diaminoanthraquinone, 1,5-diaminoanthraquinone, 9,9-bis(4-aminophenyl)fluorene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1(4'-aminophenyl)-1,3,3-trimethylindane, anisidine, phen-etidine, aminophenol, 2-aminothiophenol, 4-aminothio-phenol, aminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, xylidine, 4,4'-methylenedi-2,6-xylidine, 2,6-diaminobenzothiazole, m-aminobenzoic acid hydrazide, 2,4-diaminomesitylene, hexaaminocyclophos-phazine, l,l-diamino-3,3,5,5-tetraphenoxycyclophosphazine, 1,3,5-tris(p-aminophenoxy)-1,3,5-triphenoxycyclophosphazi-ne, hexakis(p-aminophenoxy)-cyclophosphazine and the like.
For the acid anhydride used as the dehydrating agent in subjecting the unsaturated dicarboxylic amic acid compound such as represented by the foregoing formula (I) to the dehydrating cyclization, while not limited particularly, such lower monoalkyl carboxylic anhydride as acetic anhydride, propionic anhydride, butyric anhydride or the like. The amount in which this dehydrating agent is used is made to be in a range of 1 to 5mol, preferably, 1 or 3mol with respect to 1 equivalent amount of amic acid group. For the basic catalyst employed upon the dehydrating cyclization, while not particularly limited, such trialkyl amines having trialkyl group of a carbon number of 1 to 10 as trimethylamine, triethylamine, tri-n-butyl amine and the like, N,N-dimethylbenzylamine, N-methyl morpholine, 1,8-diaza-bicyclo[5,4,0]7-undecen and the like may be employed. The amount in which this basic catalyst is used is preferably in a range of 0.01 to 0.5mol with respect to 1 equivalent amount of the amic acid group.
For the metallic salt catalyst employed upon the dehydrating cyclization, while not particularly limited, such bivalent or trivalent cobalt compound as cobalt chloride, cobalt carbonate, cobalt sulfate, cobalt naphthenic acid or the like, such bivalent nickel compound as nickel acetate, nickel (acetyl acetate), nickel carbonate or the like, such bivalent magnesium compound as magnesium chloride, magnesium carbonate, magnesium acetate, magnesium perchlorate or the like, and such monovalent sodium compound as sodium acetate can be employed. The amount in which this metallic salt catalyst other than cobalt naphthenic acid is employed is preferably in a range of 0.2 to 0.0001 equivalent amount with respect to 1 equivalent amount of the amic acid group, while the amount of cobalt naphthenic acid the molecular weight of which is not easily definable should preferably be in a range of 0.2 to O.OOOlwt.% with respect to the amic acid compound.
For the organic solvent employed in the reaction system, further, while not particularly limited, it is possible to employ one or a mixture of two or more of, for example, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, acetone, dioxane, benzene, toluene, xylene, cyclohexane, methyl 20~9988 ethyl ketone, methyl isobutyl ketone, tetrahydrofuran and the like. The amount in which this organic solvent is used is preferably about 1.0 to 4.0 times in weight as much as the unsaturated dicarboxylic amic acid compound.
The reaction of the dehydrating cyclization, on the other hand, is carried out preferably at a temperature in a range of 20 to 100 C and, more preferably in a range of 40 to 70 C. In the event when the compound of unsaturated dicarboxylic acid imides is obtained in such manner, there is produced alkyl carboxylic acid as a by-product, and this alkyl carboxylic acid is subjected to the distilling removal together with the solvent employed for the reaction, so as to obtain the compound of unsaturated dicarboxylic acid imides. In removing alkyl carboxylic acid and the solvent through the distillation, it is necessary that such conditions as follows are settled. That is, 50 to 70% of the solution component is first removed as distilled through the distillation carried out at a distilling temperature adjusted to be below about 70 C, preferably below 60C, while regulating the distilling temperature in accordance with the degree of vacuum pressure, since the temperature exceeding 70C
causes a polymerization reaction of the compound of unsaturated dicarboxylic acid imides to occur during the distillation so that a polymerization product will render the purity of the compound of unsaturated dicarboxylic acid imides to be lowered.
When 50 to 70% of the solution component of alkyl carboxylic acid and solvent are thus removed through the distillation, the solution is once cooled down to be below 50C preferably, or below 30C more preferably, or the compound of unsaturated dicarboxylic acid imides is made to separate out with such poor solvent as water added to the solution, and thereafter the solution is again subjected to the distillation. When in the initial distillation the amount of removal as distilled of the solution component is less than 50%, the compound of unsaturated dicarboxylic acid imides can hardly separate out. When the amount exceeds 70%, on the other hand, the solution component is made to be a highly concentrated solution, whereby the polymerization reaction of the compound of unsaturated dicarboxylic acid imides is caused to occur to produce a polymerization product which renders the purity of the thus obtained compound of unsaturated dicarboxylic acid imides to be lowered.
For other poor solvent than water, though not to be particularly limited, xylene, toluene, benzene, hexane, cyclohexane or the like may be used. Further, it is preferable that the distillation is carried out to an extent of eventually removing more than 93% of the solution component, since the removal less than 93% may involve a risk that the resultant resin obtained with the thus prepared compound of unsaturated dicarboxylic acid imides is deteriorated in the heat-resistance.
Accordingly, in manufacturing the resin with the compound of unsaturated dicarboxylic acid imides, a polymerization is carried out with some other composition of the compound of unsaturated dicarboxylic acid imides added at a proper ratio. Here, the polymerization itself is executed under the same conditions as those in known art. Here, the some other composition used is the foregoing polyamine, solvent or the like. The resin manufacturing can be performed with an isolated compound of unsaturated dicarboxylic acid imides used. It will be also possible to sequentially execute the resin menufacture within the same container employed for preparing the compound of unsaturated dicarboxylic acid imides without subjecting it to the isolation.
EXAMPLE 1:
197g (0.5mol) of unsaturated dicarboxylic amic acid (compound name: N,N-4,4'-diphenylmethane-bis-maleamic acid) having such structure as ~CONH ~ CH2 ~ NHCO~
COOH HOOC
were solved in 394g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.1g (0.05mol) of triethylamine and 0.2g (0.001mol) of nickel acetate were added, and this solution was made to execute a reaction for 30 minutes while keeping the reaction temperature at 60C. After completion of this reaction, a distillation was initiated while vacuumizing gradually.
The distillation was carried out for 1 hour under a degree of vacuum of 10mmHg and at a distillating temperature of 52 C, thereafter the distillation was stopped, and the solution was cooled down to 40C. At this time, the amount of distillation was 345g, which corresponds to 61%
of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 1 hour to distill off 97% of the solution component, and a solid matter was then obtained. The structure of this solid matter was confirmed by means of 13C-MMR, and it was found that the solid matter was a compound of unsaturated dicarboxylic imides (compound name: N,N-4,4'-diphenylmethane-bis-maleimide) having a following structure:
~ / N ~ CH2 ~ ~ N
The purity of this compound was measured by means of a liquid chromatography, the measurement having been shown to be 91.5%.
EXAMPLE 2:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid used in Example 1 were solved in 394g of N,N'-methyl formomide, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methyl morpholine and 0.2g (O.OOlmol) of cobalt acetate were added, and a reaction was then made to take place for 1 hour while the reaction temperature was maintained at 60C Upon completion of the reaction, the distillation was initiated while vacuumizing gradually. After this distillation carried out for 75 minutes under the degree of vacuum of 10mmHg and at the distillating temperature of 52C, the distillation was then terminated, and the solution was cooled down to 40C, upon which the amount of distillation was 367g, the amount corresponding to 68% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 45 minutes to distill off 95% of the solution component, and a solid matter of N,N-4,4'-diphenylmethane-bis-maleimide was obtained in the same manner as in Example 1. The purity of this compound was measured with the liquid chromatography, the result of which was 90.3%.
EXAMPLE 3:
l91g (lmol) of unsaturated dicarboxylic amic acid (compound name: N-phenylmaleamic acid) of a following structure ¢CONH
COOH
were solved in 287g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 10.lg (0.lmol) of triethylamine and 0.2g (0.1wt.%) of cobalt naphthenic acid (a reagent of special grade made by a Japanese manufacturer WAKO PURE CHEMICAL INDUSTRY, LTD., Art. NO.
038-03745) were added and, thereafter, the reaction was made to take place for 30 minutes while maintaining the solution at a reaction temperature of 60C. After completion of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 60 minutes under the degree of vacuum of lOmmHg and distillation temperature of 52C, the distillation was stopped, and the solution was cooled down to 30C, upon which the amount of distillation was 275g.
This corresponds to 60% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 60 minutes to distill off 93~ of the solution component, and a solid matter was obtained.
The structure of this solid matter was confirmed by means of 13C-MMR, and it was found that this solid matter was unsaturated dicarboxylic acid imide compound (compound name: N-phenylmaleimide) of a following structure:
¢,o/~ G~
Liquid chromatographic measurement of the purity of this compound was 92.1%.
EXAMPLE 4:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid used in the foregoing Example 1 were solved in 394g of N,N'-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.1g (0.05mol) of triethylamine and 0.2g (O.OOlmol) of nickel acetate were added, and the solution was made to execute a reaction for 30 minutes while maintaining the reaction temperature of 60 C. After completion of this reaction, the distillation was initiated while vacuumizing gradually. The distillation was carried out for 1 hour under the degree of vacuum of lOmmHg and at a distillating temperature of 52C, thereafter the distillation was stopped, and 300g of water was added. At this time, the amount of distillation was 345g, which corresponds to 61%
of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 1 hour to distill off 97% of the solution component and, thereafter, a solid matter of N,N-4,4'-diphenylmethane-bis-maleimide was obtained in the same manner as in Example 1.
The purity of this compound as measured by means of the liquid chromatograph was 91.5%.
EXAM~LE 5:
197g (0.5mol) of N,N-4,4'-diphenylmethan-bis-maleamic acid used in Example 1 was solved in 394g of N,N -dimethylformamide, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methyl morpholine and 0.2g (O.OOlmol) of cobalt acetate were added and, thereafter, the reaction was made to take place for 1 hour while keeping the reaction temperature at 60C. .~fter completion of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 75 minutes under the degree of lOmmHg and distillation temperature of 52C, the distillation was terminated, and 300g of xylene were added, upon which the amount of distillation was 367g. This corresponds to 68~
of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation for 45 minutes under the same conditions to distill off 95% of the solution component, and solid N,N-4,4'-diphenylmethane-bis-maleimide was obtained in the same manner as in Example 1.
The purity of this compound as measured by means of the liquid chromatograph was 90.3%.
EXAMPLE 6:
l91g (lmol) of N-phenylmaleamic acid was solved in 287g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, lO.lg (O.lmol) of triethylamine and 0.2g (O.lwt.%) of cobalt naphthenic acid (special grade reagent of WAKO PURE CHEMICAL INDUSTRY, LTD., Art. No. 038-03745) were added and, thereafter, the reaction was made to take place for 30 minutes while keeping the reaction temperature at 60C After completion of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 60 minutes under the degree of vacuum of lOmmE~g and distillation temperature of 52C, the distillation was terminated, and 400g of toluene was added to the solution, upon which the amount of distillation was 275g which corresponding to 60% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation for 60 minutes under the same conditions to distill off 93% of the solution component, and solid N-phenylmaleimide was obtained in the same manner as in Example 3.
The purity of this compound as measured by the liquid chromatograph was 92.1%.
COMPARATIVE EXAMPLE 1:
197g (0.5mol) of N,N-4,4'-diphenylmethan-bis-maleamic acid used in Example 1 was solved in 394g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.001mol) were added and, thereafter, the reaction was made to take place for 1 hour while keeping the reaction temperature at 60C. After completion of the reaction, the solution was cooled down to 20C, 500g of water was added to the reacted solution, and a precipitate was separated. This precipitate was then filtered off, linsed, neutralized with an aqueous solution of sodium carbonate, again washed after the neutralization and dried, and thereby 163g of N,N-4,4'-diphenylmethane-bis-maleimide were obtained. At this occasion, about 3,000g of waste liquid were yielded, which amount was 6 times as much as that in the case of Example 1.
The purity of this compound as measured with the liquid chromatograph was 91.5%, but it was found that such excessive amount of the waste liquid as above rendered this compound to be not adaptable to the mass production 2~9988 line.
COMPARATIVE EXAMPLE 2:
197g (0.5mol~ of N,N-4,4'-diphenylmethane-bis-maleamic acid used in Example 1 were solved in 394g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.OOlmol) of nickel acetate were added and, thereafter, the reaction was made to take place for 30 minutes while keeping the reaction temperature at 60C. After termination of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 1 hour under the degree of vacuum of 30mmHg and distillation temperature of 75C, the distillation was terminated and the solution was cooled down to 40C, upon which the distilled amount was 356g which corresponding to 63% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation for 1 hour under the same conditions, 97% of the solution component were distilled off, and a solid compound was obtained.
The purity of this compound as measured with the liquid chromatograph was 75.6%, and no sufficiently high purity could be attained.
COMPARATIVE EXAMPLE 3:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid used in Example 1 were solved in 394g of N,N-dimethylformamide, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methylmorpholine and 0.2g (O.OOlmol) of cobalt acetate were added and, thereafter, the reaction was carried out for 1 hour while keeping the reaction temperature at 60C. After completing the reaction, the distillation was initiated while gradually vacuumizing. Carrying out this distillation for 2 hours under the degree of vacuum of lOmmHg and at distillating temperature of 52C, 97% of the solution component were distilled off and a solid compound was obtained.
The purity of this compound as measured with the liquid chromatograph was 80.9~, and no sufficiently high purity could be attained.
Manufacturing examples of the resin of unsaturated dicarboxylic acid imides shall now be referred to, further.
EXAMPLE 7:
lOOg of N,N-4,4'-diphenylmethane-bis-maleimide obtained in Example 1 were taken out and were put in another reaction vessel, into which 75g of N,N-dimethylacetamide were added and solved, 27.7g of diaminodiphenylmethane were further added, and their reaction was taken place for 3 hours at 80C. Thus obtained varnish was employed for impregnation of a glass cloth, and the impregnated glass cloth was dried for 5 minutes at 150C to prepare a prepreg. Four of the thus obtained prepregs were stacked on one another, copper foils were stacked onto both sides of the stacked prepregs, the whole stack of such prepregs and copper foils was subjected to a molding at a temperature of 140C, for a period of 60 minutes and under a pressure of 40kgf/cm2 and then to a curing for 2 hours at 230C, and a double-surface copper-clad laminate was obtained.
Tg temperature of this laminate was measured through TMA analysis and was shown to be 250C. Further, the interlaminar strength between the stacked prepregs was measured to be 1.3kgf/cm, showing that the laminate was satisfiable in the heat resistance and peeling resistance.
EXAMPLE 8:
179g of N,N-4,4'-diphenylmethane-bis-maleimide obtained in Example 1 was kept not isolated but left in the same reaction vessel to be solved together with 134g of N,N-dimethylacetamide added, thereafter 49.6g of diaminodiphenylmethane were added, and a reaction of them was carried out for 3 hours at 80C. A varnish thus obtained was employed for impregnation of glass cloths, the thus impregnated glass cloths were dried at 150C for 5 minutes to obtain prepregs. Four of such prepregs were stacked, copper foils were stacked on both sides of the stacked prepregs, and the whole stack of the prepregs and copper foils were then subjected to the molding at a temperature of 140C for a period of 60 minutes and under a pressure of 40kgf/cm and then to the curing at 230C
for 2 hours, and a both-surface copper-clad laminate was obtained.
Measured Tg temperature by the TMA analysis of this laminate was 250C. Further, measured interlaminar strength between the respective prepregs was 1.3kgf/cm, showing the satisfiable heat resistance and peeling resistance.
EXAMPLE 9:
lOOg of N,N-4,4'-diphenylmethane-bis-maleimide obtained through Example 4 were taken out and put in another reaction vessel, 75g of N,N'-dimethylacetamide were then added, they were solved, thereafter 27.7g of diaminodiphenylmethane were added, and they were subjected to the reaction at 80C for 3 hours. Thus obtained varnish was employed for impregnation of glass cloths, thus impregnated cloths were dried for 5 minutes at 150C
and prepregs were thereby prepared. Four of such prepregs were stacked, copper foils were further stacked on both sides of the stacked prepregs, and, through a curing carried out at 230C for 2 hours, a both-surface copper-clad laminate was obtained.
The Tg temperature measurement by the TMA
analysis of this laminate was 250C, and the interlaminar strength between the respective prepregs was measured to be 1.3kgf/cm, showing the satisfiable heat resistance and peeling resistance.
EXAMPLE 10:
179g of N,N-4,4'-diphenylmethane-bis-maleimide obtained through Example 4 were left in the same reaction vessel, without isolation, 134g of N,N'-dimethylacetamide were added thereto and they were solved. 49.6g of diaminodiphenylmethane were further added and their reaction was carried out at 80C for 3 hours. Glass cloths were impregnated with the thus obtained varnish and were then dried at 150C for 5 minutes and prepregs were thereby prepared. Four of such prepregs were stacked on each other, copper foils were stacked onto both sides of the stacked prepregs, the whole stack of the prepregs and copper foils were then subjected to the molding at a temperature of 140C for a period of 60 minutes under a pressure of 40kgf/cm2 and then to the curing at 230C for 2 hours, and a both-surface copper-clad laminate was obtained.
The Tg temperature measurement through the TMA
analysis of this laminate was 248C, and the interlaminar strength between the respective prepregs was measured to be 1.3kgf/cm, showing thus satisfiable heat resistance and peeling resistance.
COMPARATIVE EXAMPLE 4:
100g of N,N-4,4'-diphenylmethane-bis-maleimide obtained through Comparative Example 1 were solved with 75g of N,N-dimethylacetamide added, then 27.7g of diaminodiphenylmethane were added and their reaction was executed at 80C for 3 hours. Glass cloths were impregnated with thus obtained varnish and were dried at 150C for 5 minutes to prepare prepregs. Four of such prepregs were stacked on one another, copper foils were further stacked on both sides of the stacked prepregs, the whole stack of the prepregs and copper foils was subjected " 2059988 to the molding at a temperature of 140C for a period of 60 minutes under a pressure of 40kgf/cm and then to the curing at 230C for 2 hours, and a both-surface copper-clad laminate was then obtained.
The Tg temperature measurement through the TMA
analysis of this laminate was 252C, and the interlaminar strength measurement between the respective prepregs was 1.3kgf/cm, showing the heat resistance and peeling resistance to be satisfiable. In the present instance, however, there has involved a problem at a stage of obtaining the resin of unsaturated dicarboxylic acid imides.
According to another feature of the present invention, there is provided a process for preparing conveniently the compound of unsaturated dicarboxylic acid imides by subjecting the unsaturated dicarboxylic amic acid to the dehydrating cyclization in the presence of such three dehydrating agents as acid anhydride, basic catalyst and metallic salt catalyst, and spraying a reaction product liquid.
For unsaturated dicarboxylic acid amic acid or unsaturated dicarboxylic acid anhydride, amine or polyamine made to be contributive to the reaction, basic catalyst, metallic salt catalyst, organic catalyst and so on may be the ones which have been described with reference to the foregoing Examples, while not required to be particularly limited, and their using ratio also may be as has been described.
20~9988 In spraying the reactions product liquid, it is preferable that the spray is executed under any one of such conditions as being heated, vacuumized or heated while being vacuumized. The heating should preferably be carried out at a temperature below 180C, since the heating at a temperature above 180C involves a risk that the compound of unsaturated dicarboxylic acid imides becomes apt to carry out homopolymerization so as to cause the resultant compound to be deteriorated in the purity.
EXAMPLE 11:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid employed in Example 1 were solved in 394g of N,N-methylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.001mol~ of nickel acetate were added and, thereafter, their reaction was made to take place for 30 minutes while keeping the reaction temperature at 65C. Upon completion of the reaction, the spray of the reaction product liquid was carried out by means of a spray drier (made by Japanese manufacturer HOSOKAWA MICRON, "Clacks System") for 5 minutes under the conditions of heating temperature at 180C and vacuum degree of 10 Torr, whereby N,N-4,4'-diphenylmethane-bis-maleimide yellow and similarly solid to that in Example 1 was obtained.
The purity of this compound as measured by the liquid chromatograph was shown to be 95.5%.
EXAMPLE 12:
205g988 197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid employed in Example 1 were solved in 500g of methyl ethyl ketone, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methyl morpholine and 0.2g (O.OOlmol) of cobalt acetate were added and, thereafter, their reaction was made to take place for 3 hours while keeping the reaction temperature at 60C. Upon completion of the reaction, the spray of the reaction product was carried out by means of the same spray drier as that in Example 11, for 5 minutes under the conditions of heating temperature of 160C and vacuum degree of 40 Torr, whereby N,N-4,4'-diphenylmethane-bis-maleimide yellow and similarly solid to that in Example 1 was obtained.
The purity of this compound as measured by the liquid chromatograph was 93.3%.
EXAMPLE 13:
l91g (lmol) of N-phenylmaleamic acid were solved in 287g of methyl ethyl ketone, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of triethylamine and 0.2g (O.lwt.%) of cobalt naphthenic acid (the reagent by WAKO PURE CHEMICAL, Art. No. 038-03745) were added and, thereafter, they were caused to react for 60 minutes while keeping the reaction temperature of 60C.
Upon completion of the reaction, the reaction product was subjected to the spray with the same spray drier as in Example 11, for 5 minutes under the conditions of the heating temperature of 140C and vacuum degree of 7 Torr, whereby N,N-4,4'-diphenylmethane-bis-maleimide yellow and similarly solid to that in Example 1 was obtained.
The purity of this product as measured by the liquid chromatograph was 92.1%.
EXAMPLE 14:
198g (0.5mol) of unsaturated dicarboxylic acid amic acid (compound name: N,N-4,4'-diphenylether-bis-maleamic acid) of such structure as ~CONH ~ H2O ~ NHCO
COOH HOOC
were solved in 396g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.001mol) of cobalt acetate were added and, thereafter, they were made to react for 60 minutes while keeping the reaction temperature at 70C.
Upon completion of the reaction, the reaction product liquid was subjected to the spray with the same spray drier as in Example 11, for 5 minutes under the conditions of the heating temperature of 180C and vacuum degree of 10 Torr, whereby the compound of unsaturated dicarboxylic acid imides (compound name: N,N-4,4'-diphenylether-bis-maleimide) was obtained, the compound being yellow, solid and of such structure as follow:
~ N ~ ~ O ~ N/C -~
The purity of this compound as measured by the liquid chromatograph was 94.1%.
However, in the known chemical cyclization, normally a reactive solution is poured into water to have a reaction product separated out of the solution, the product is further processed through a filtration, water 5treatment, neutralization of by-produced acid and so on, respective steps of which are extremely laborious and render the process to be complicated, and the known process has involved a problem in the productivity and manufacturing economy.
10As further known processes for preparing the unsaturated dicarboxylic acid imide compounds in which no such measure for simplifying the processing steps as in the present invention which will be described in the followings, there may be enumerated such ones as have been 15suggested in U.S. Patent No. 4,855,450 to John M. Butler et al, Japanese Laid-Open Publication No. 63-69829 of Shuichi Kanekawa et al and so on, but they still involve problems in respect of the treatment simplification and the improvement in the productivity and economy.
Accordingly, a primary object of the present invention is to provide the process for preparing compound of unsaturated dicarboxylic acid imides, which process can be attain the high yield and purity without requiring any complicated processing steps.
According to the present invention, this object can be realized by means of a process for preparing the compound of unsaturated dicarboxylic acid imides in which such unsaturated dicarboxylic amic acid as represented by a following general formula (I) is subjected to the dehydrating cyclization in the presence of three of acid anhydride as a dehydrating agent, basic catalyst and metallic salt catalyst, characterized in that an acid and solvent produced after the dehydrating cyclization are subjected to a vacuum distillation, upon which 50 to 70%
of solution component is distilled off at a distilling temperature below 70C, a cooling is thereafter carried out to separate a solid component, and the distillation is again performed to obtain such compound as represented by a following general formula (II):
/ CONH R
D ....... (I) COOH n -- CO
N R ----.. (II) CO n in which formulas (I) and (II), D denoting bivalent organic group having at least one carbon-carbon double bonding, Rl denoting n-valent organic group having at least one carbon atom, and n denoting an integer more that 1.
Further according to the present inventiol, polyamine and a solvent are added to the compound of unsaturated dicarboxylic acid imides obtained through the above process to have them polymerized and a resin of unsaturated dicarboxylic acid imides is obtained.
Other objects and advantages of the present invention will be made clear as the description of preferred examples advances in the followings.
While the present invention shall now be described with reference to the certain preferred examples, it should be appreciated that the intention is not to limit the invention only -to these examples described but rather to include all alterations, modifications and equivalent arrangements possible within the scope of appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EXAMPLES
In obtaining the compound of unsaturated dicarboxylic acid imides in the present invention, unsaturated dicarboxylic amic acid compound is employed.
While this unsaturated dicarboxylic amic acid compound is not specifical~y limited, the same can be obtained through a reaction caused between such unsaturated dicarboxylic anhydride as represented by a following general formula (III) and such amine or polyamine as represented by a following general formula (IV), preferably in the presence of inert organic solvent or the like with respect to a reaction system or non-solvent system:
CO
D O ....... (III) CO
[ 2 1 n Rl ....... (IV) in which formulas (III) and (IV), D denoting bivalent organic group having at least one carbon-carbon double bonding, R denoting n-valent organic group having at least one carbon atom, and n denoting an integer more than S 1.
For the unsaturated dicarboxylic anhydride employable in this reaction system, while not required to be specifically limited, it is possible to employ maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic tetrahydro anhydride, nudic anhydride, their halogen substituted products, alkyl substituted products or the like alone or in a mixture of two or more.
For amine or polyamine, while not particularly limited, it is possible to employ one or a mixture of two or more of methylamine, ethylamine, l-propylamine, 1,2-dimethyl propylamine, 3-methoxypropylamine, 3-eth-oxypropylamine, 3-propoxypropylamine, 3-isopropoxy-propylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3-(2-ethylhexyloxy!propylamine, 3-rauryl oxypropylamine, 3-mirystyl oxypropylamine, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibu-tylaminopropylamine, 2-hydroxyethyl aminopropylamine, dimethylaminoethoxy propylamine, raurylaminopropylamine, diethanolaminopropylamine, imino-bis-propylamine, methyl amino-bis-propylamine, n-butylamine, isobutylamine, sec-butylamine, hexylamine, 2-ethylhexylamine, dodecy-lamine, cyclohexylamine, arylamine, 3-decichloxyamine, diethylaminoethyl amine, ethylaminoethyl amine, ~-phenethylamine, ~-phenethylamine, furfurylamine, methoxylamine, m-aminobenzylamine, methaphenylenediamine, 4-chloromethaphenylenediamine, 5-nitromethaphenylenedia-mine, 4,6-dimethylmethaphenylenediamine, paraphenylenedi-amine, 2-chloroparaphenylenediamine, 2-nitroparaphenylene-diamine, 2-cyanoparaphenylenediamine, 2,5-dichloroparaphe-nylenediamine, 2,6-dichloroparaphenylenediamine, 2,5-die-thylparaphenylenediamine, 5-chloro-2-methylparaphenylen-ediamine, tetrafluorophenylenediamine, torylenediamine, 3,5-diethyl-2,4-torylenediamine, 2-picolylamine, 3-picol-ylamine, 4-picolylamine, methaxylenediamine, paraxylen-ediamine, hexamethylenediamine, heptamethylenediamine, 4,4-dimethylheptamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, penta-ethylenehexamine, 4,4'-diaminodiphenylmethane, 3,4'-diam-inodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3',4, 4'-tetraaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldi-phenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimeth-ylphenylmethane, 4,4'-bis(p-aminophenoxy)diphenylmethane, 4,4'-bis(m-aminophenoxy)diphenylmethane, 2,2',3,3'-tet-rachloro-4,4'-diaminodiphenylmethane, diaminodicyclo-hexylmethane, 4,4'-bis(p-aminophenoxy)diphenylmethane, 4,4'-bis(m-aminophenoxy)diphenylethane, 1,2-bis-(3-ami-nopropoxy)-ethane, 2-aminopropanol, 3-aminopropanol, 1,2-diaminopropane, 3,3'-diaminodiphenylpropane, 1,2-bis-(3-aminopropoxy)-2,2'-dimethylpropane, 4,4'-bis(p-am-inophenoxy)diphenylpropane, 4,4'-bis(m-aminophenoxy)dip-henylpropane, 2,2'-bis(4-aminophenyl)propane, 1,4-diamino-butane, 1,4-diaminocyclohexane, bis-(3-aminopropyl)ether, ~,w-bis-(3-aminopropyl)polyethylene glycol ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4,4'-triaminodiphenyl ether, 3,3',4,4'-tetraminodiphenyl ether, bis(p-Ramino-tert-buty-lphenyl) ether, toluidine, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-6-bromo-2-toluidine, aniline, ethy-laniline, dichloroaniline, 4,4'-methylenedi-2,6-diethyla-niline, 4,4'-methylenedi-2,6-isopropylaniline, isopropo-xyaniline, chloroaniline, bromoaniline, iodoaniline,nitroaniline, 4,4'-methylenedi-2,6-bromoaniline, 4,4' methylenedi-2-bromo-6-chloroaniline, bis-p-aminophenyla-niline, methylene-bis-anthraanilic acid, methy-lene-bis-methyl anthranilate, 3,3'-diaminodiphenyl sulfone, [4,4'-diaminodiphenyl] sulfone, 3,3',4,4'-tetraa-minodiphenyl sulfone, p-bis(4-aminophenoxy)diphenyl sulfone, p-bis(3-aminophenoxy)diphenyl sulfone, 2,2'-bis- 4-(4-aminophenoxy)phenyl sulfone, orthotolidine sul-fone, 4,4'-diaminodiphenyl sulfide, bis-(4-amino-phenyl)disulfide, 3,3',4,4'-tetraaminodiphenyl sulfide, N-aminoethyl piperidine, N-aminoethyl-4-pipecoline, N-aminoethyl morpholine, N-aminopropyl piperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropyl morpholine, 2-aminoethyl piperidine, 4-aminomethyl piperidine, N-aminopiperidine, l-amino-4-methyl piperazine, l,4-bis-aminopropyl piperazine, 2-aminopiperazine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diamino-pyridine, 2,6-diaminopyridine, 2,3,6-triaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-ami-no-5-methylpyridine, 2-amino-6-methylpyridine, 2-ami-no-4-ethylpyridine, 2-amino-4-propylpyridine, 2-ami-no-4,6-dimethylpyridine, 2,6-diamino-4-methylpyridine, 2-amino-3-nitropyridine, 2-amino-5-nitropyridine, 2-chlo-ro-4-aminopyridine, 2-chloro-5-aminopyridine, 2-ami-no-3,5-dichloropyridine, 4-amino-3,5-dichloropyridine, 2-amino-3,5-dichloro-6-methylpyridine, 2-amino-3,5-dich-loro-4-methylpyridine, 2-amino-5-chloro-3-methylpyridine, 2-amino-3,5-dichloro-4,6-dimethylpyridine, 2,4-diamino pyridine, 2,4-diamino-6-(4-pyridyl)-5-triazine, p-bis(4-aminophenoxy)benzene, m-bis(4-aminophenoxy)benzene, p-bis (3-aminophenoxy)benzene, m-bis(3-aminophenoxy)benzene, 1,3,5-triaminobenzene, 4,4'-diamino-3-methoxyazobenzene, 1,5-diaminonaphthalene, 1,3,5-triaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiph-enyl, 2,5-diaminoterephthalic acid, 3,4'-diaminobenzani-lide, 4,4'-diaminobenzanilide, 4-(p-aminophenoxy)-4-amino-benzanilide, 3,3'-dimethoxybenzidine, 3,3'-dimethylbenzi-dine, 3,3'-diaminobenzidine, 3,3'-dihydroxybenzidine, 2,2'-dichloro-5,5'-dimethoxybenzidine, 2,2',5,5'-tetrach-lorobenzidine, 2,4-diaminotoluene, 2,4-bis(~amino-tert-butyl)toluene, 4,4'-diaminobenzophenone, polytetrame-thyleneoxido-di-p-aminoobenzoate, trimethylene-bis-(4-aminobenzoate), bis(4-aminophenyl)diphenylsilane bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)phenylpho-sphinic oxide, bis(4-aminophenyl)methylphosphinic oxide, melamine, 4,4'-diaminostilbene, 9,9-bis(4-aminophe-nyl)-10-hydroanthracene, 2,6-diaminoanthraquinone, 1,5-diaminoanthraquinone, 9,9-bis(4-aminophenyl)fluorene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1(4'-aminophenyl)-1,3,3-trimethylindane, anisidine, phen-etidine, aminophenol, 2-aminothiophenol, 4-aminothio-phenol, aminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, xylidine, 4,4'-methylenedi-2,6-xylidine, 2,6-diaminobenzothiazole, m-aminobenzoic acid hydrazide, 2,4-diaminomesitylene, hexaaminocyclophos-phazine, l,l-diamino-3,3,5,5-tetraphenoxycyclophosphazine, 1,3,5-tris(p-aminophenoxy)-1,3,5-triphenoxycyclophosphazi-ne, hexakis(p-aminophenoxy)-cyclophosphazine and the like.
For the acid anhydride used as the dehydrating agent in subjecting the unsaturated dicarboxylic amic acid compound such as represented by the foregoing formula (I) to the dehydrating cyclization, while not limited particularly, such lower monoalkyl carboxylic anhydride as acetic anhydride, propionic anhydride, butyric anhydride or the like. The amount in which this dehydrating agent is used is made to be in a range of 1 to 5mol, preferably, 1 or 3mol with respect to 1 equivalent amount of amic acid group. For the basic catalyst employed upon the dehydrating cyclization, while not particularly limited, such trialkyl amines having trialkyl group of a carbon number of 1 to 10 as trimethylamine, triethylamine, tri-n-butyl amine and the like, N,N-dimethylbenzylamine, N-methyl morpholine, 1,8-diaza-bicyclo[5,4,0]7-undecen and the like may be employed. The amount in which this basic catalyst is used is preferably in a range of 0.01 to 0.5mol with respect to 1 equivalent amount of the amic acid group.
For the metallic salt catalyst employed upon the dehydrating cyclization, while not particularly limited, such bivalent or trivalent cobalt compound as cobalt chloride, cobalt carbonate, cobalt sulfate, cobalt naphthenic acid or the like, such bivalent nickel compound as nickel acetate, nickel (acetyl acetate), nickel carbonate or the like, such bivalent magnesium compound as magnesium chloride, magnesium carbonate, magnesium acetate, magnesium perchlorate or the like, and such monovalent sodium compound as sodium acetate can be employed. The amount in which this metallic salt catalyst other than cobalt naphthenic acid is employed is preferably in a range of 0.2 to 0.0001 equivalent amount with respect to 1 equivalent amount of the amic acid group, while the amount of cobalt naphthenic acid the molecular weight of which is not easily definable should preferably be in a range of 0.2 to O.OOOlwt.% with respect to the amic acid compound.
For the organic solvent employed in the reaction system, further, while not particularly limited, it is possible to employ one or a mixture of two or more of, for example, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, acetone, dioxane, benzene, toluene, xylene, cyclohexane, methyl 20~9988 ethyl ketone, methyl isobutyl ketone, tetrahydrofuran and the like. The amount in which this organic solvent is used is preferably about 1.0 to 4.0 times in weight as much as the unsaturated dicarboxylic amic acid compound.
The reaction of the dehydrating cyclization, on the other hand, is carried out preferably at a temperature in a range of 20 to 100 C and, more preferably in a range of 40 to 70 C. In the event when the compound of unsaturated dicarboxylic acid imides is obtained in such manner, there is produced alkyl carboxylic acid as a by-product, and this alkyl carboxylic acid is subjected to the distilling removal together with the solvent employed for the reaction, so as to obtain the compound of unsaturated dicarboxylic acid imides. In removing alkyl carboxylic acid and the solvent through the distillation, it is necessary that such conditions as follows are settled. That is, 50 to 70% of the solution component is first removed as distilled through the distillation carried out at a distilling temperature adjusted to be below about 70 C, preferably below 60C, while regulating the distilling temperature in accordance with the degree of vacuum pressure, since the temperature exceeding 70C
causes a polymerization reaction of the compound of unsaturated dicarboxylic acid imides to occur during the distillation so that a polymerization product will render the purity of the compound of unsaturated dicarboxylic acid imides to be lowered.
When 50 to 70% of the solution component of alkyl carboxylic acid and solvent are thus removed through the distillation, the solution is once cooled down to be below 50C preferably, or below 30C more preferably, or the compound of unsaturated dicarboxylic acid imides is made to separate out with such poor solvent as water added to the solution, and thereafter the solution is again subjected to the distillation. When in the initial distillation the amount of removal as distilled of the solution component is less than 50%, the compound of unsaturated dicarboxylic acid imides can hardly separate out. When the amount exceeds 70%, on the other hand, the solution component is made to be a highly concentrated solution, whereby the polymerization reaction of the compound of unsaturated dicarboxylic acid imides is caused to occur to produce a polymerization product which renders the purity of the thus obtained compound of unsaturated dicarboxylic acid imides to be lowered.
For other poor solvent than water, though not to be particularly limited, xylene, toluene, benzene, hexane, cyclohexane or the like may be used. Further, it is preferable that the distillation is carried out to an extent of eventually removing more than 93% of the solution component, since the removal less than 93% may involve a risk that the resultant resin obtained with the thus prepared compound of unsaturated dicarboxylic acid imides is deteriorated in the heat-resistance.
Accordingly, in manufacturing the resin with the compound of unsaturated dicarboxylic acid imides, a polymerization is carried out with some other composition of the compound of unsaturated dicarboxylic acid imides added at a proper ratio. Here, the polymerization itself is executed under the same conditions as those in known art. Here, the some other composition used is the foregoing polyamine, solvent or the like. The resin manufacturing can be performed with an isolated compound of unsaturated dicarboxylic acid imides used. It will be also possible to sequentially execute the resin menufacture within the same container employed for preparing the compound of unsaturated dicarboxylic acid imides without subjecting it to the isolation.
EXAMPLE 1:
197g (0.5mol) of unsaturated dicarboxylic amic acid (compound name: N,N-4,4'-diphenylmethane-bis-maleamic acid) having such structure as ~CONH ~ CH2 ~ NHCO~
COOH HOOC
were solved in 394g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.1g (0.05mol) of triethylamine and 0.2g (0.001mol) of nickel acetate were added, and this solution was made to execute a reaction for 30 minutes while keeping the reaction temperature at 60C. After completion of this reaction, a distillation was initiated while vacuumizing gradually.
The distillation was carried out for 1 hour under a degree of vacuum of 10mmHg and at a distillating temperature of 52 C, thereafter the distillation was stopped, and the solution was cooled down to 40C. At this time, the amount of distillation was 345g, which corresponds to 61%
of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 1 hour to distill off 97% of the solution component, and a solid matter was then obtained. The structure of this solid matter was confirmed by means of 13C-MMR, and it was found that the solid matter was a compound of unsaturated dicarboxylic imides (compound name: N,N-4,4'-diphenylmethane-bis-maleimide) having a following structure:
~ / N ~ CH2 ~ ~ N
The purity of this compound was measured by means of a liquid chromatography, the measurement having been shown to be 91.5%.
EXAMPLE 2:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid used in Example 1 were solved in 394g of N,N'-methyl formomide, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methyl morpholine and 0.2g (O.OOlmol) of cobalt acetate were added, and a reaction was then made to take place for 1 hour while the reaction temperature was maintained at 60C Upon completion of the reaction, the distillation was initiated while vacuumizing gradually. After this distillation carried out for 75 minutes under the degree of vacuum of 10mmHg and at the distillating temperature of 52C, the distillation was then terminated, and the solution was cooled down to 40C, upon which the amount of distillation was 367g, the amount corresponding to 68% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 45 minutes to distill off 95% of the solution component, and a solid matter of N,N-4,4'-diphenylmethane-bis-maleimide was obtained in the same manner as in Example 1. The purity of this compound was measured with the liquid chromatography, the result of which was 90.3%.
EXAMPLE 3:
l91g (lmol) of unsaturated dicarboxylic amic acid (compound name: N-phenylmaleamic acid) of a following structure ¢CONH
COOH
were solved in 287g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 10.lg (0.lmol) of triethylamine and 0.2g (0.1wt.%) of cobalt naphthenic acid (a reagent of special grade made by a Japanese manufacturer WAKO PURE CHEMICAL INDUSTRY, LTD., Art. NO.
038-03745) were added and, thereafter, the reaction was made to take place for 30 minutes while maintaining the solution at a reaction temperature of 60C. After completion of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 60 minutes under the degree of vacuum of lOmmHg and distillation temperature of 52C, the distillation was stopped, and the solution was cooled down to 30C, upon which the amount of distillation was 275g.
This corresponds to 60% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 60 minutes to distill off 93~ of the solution component, and a solid matter was obtained.
The structure of this solid matter was confirmed by means of 13C-MMR, and it was found that this solid matter was unsaturated dicarboxylic acid imide compound (compound name: N-phenylmaleimide) of a following structure:
¢,o/~ G~
Liquid chromatographic measurement of the purity of this compound was 92.1%.
EXAMPLE 4:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid used in the foregoing Example 1 were solved in 394g of N,N'-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.1g (0.05mol) of triethylamine and 0.2g (O.OOlmol) of nickel acetate were added, and the solution was made to execute a reaction for 30 minutes while maintaining the reaction temperature of 60 C. After completion of this reaction, the distillation was initiated while vacuumizing gradually. The distillation was carried out for 1 hour under the degree of vacuum of lOmmHg and at a distillating temperature of 52C, thereafter the distillation was stopped, and 300g of water was added. At this time, the amount of distillation was 345g, which corresponds to 61%
of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation carried out under the same conditions for 1 hour to distill off 97% of the solution component and, thereafter, a solid matter of N,N-4,4'-diphenylmethane-bis-maleimide was obtained in the same manner as in Example 1.
The purity of this compound as measured by means of the liquid chromatograph was 91.5%.
EXAM~LE 5:
197g (0.5mol) of N,N-4,4'-diphenylmethan-bis-maleamic acid used in Example 1 was solved in 394g of N,N -dimethylformamide, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methyl morpholine and 0.2g (O.OOlmol) of cobalt acetate were added and, thereafter, the reaction was made to take place for 1 hour while keeping the reaction temperature at 60C. .~fter completion of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 75 minutes under the degree of lOmmHg and distillation temperature of 52C, the distillation was terminated, and 300g of xylene were added, upon which the amount of distillation was 367g. This corresponds to 68~
of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation for 45 minutes under the same conditions to distill off 95% of the solution component, and solid N,N-4,4'-diphenylmethane-bis-maleimide was obtained in the same manner as in Example 1.
The purity of this compound as measured by means of the liquid chromatograph was 90.3%.
EXAMPLE 6:
l91g (lmol) of N-phenylmaleamic acid was solved in 287g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, lO.lg (O.lmol) of triethylamine and 0.2g (O.lwt.%) of cobalt naphthenic acid (special grade reagent of WAKO PURE CHEMICAL INDUSTRY, LTD., Art. No. 038-03745) were added and, thereafter, the reaction was made to take place for 30 minutes while keeping the reaction temperature at 60C After completion of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 60 minutes under the degree of vacuum of lOmmE~g and distillation temperature of 52C, the distillation was terminated, and 400g of toluene was added to the solution, upon which the amount of distillation was 275g which corresponding to 60% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation for 60 minutes under the same conditions to distill off 93% of the solution component, and solid N-phenylmaleimide was obtained in the same manner as in Example 3.
The purity of this compound as measured by the liquid chromatograph was 92.1%.
COMPARATIVE EXAMPLE 1:
197g (0.5mol) of N,N-4,4'-diphenylmethan-bis-maleamic acid used in Example 1 was solved in 394g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.001mol) were added and, thereafter, the reaction was made to take place for 1 hour while keeping the reaction temperature at 60C. After completion of the reaction, the solution was cooled down to 20C, 500g of water was added to the reacted solution, and a precipitate was separated. This precipitate was then filtered off, linsed, neutralized with an aqueous solution of sodium carbonate, again washed after the neutralization and dried, and thereby 163g of N,N-4,4'-diphenylmethane-bis-maleimide were obtained. At this occasion, about 3,000g of waste liquid were yielded, which amount was 6 times as much as that in the case of Example 1.
The purity of this compound as measured with the liquid chromatograph was 91.5%, but it was found that such excessive amount of the waste liquid as above rendered this compound to be not adaptable to the mass production 2~9988 line.
COMPARATIVE EXAMPLE 2:
197g (0.5mol~ of N,N-4,4'-diphenylmethane-bis-maleamic acid used in Example 1 were solved in 394g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.OOlmol) of nickel acetate were added and, thereafter, the reaction was made to take place for 30 minutes while keeping the reaction temperature at 60C. After termination of the reaction, the distillation was initiated while vacuumizing gradually. After carrying out the distillation for 1 hour under the degree of vacuum of 30mmHg and distillation temperature of 75C, the distillation was terminated and the solution was cooled down to 40C, upon which the distilled amount was 356g which corresponding to 63% of the solution component to be distilled. After confirmation of a separation of solid component, the solution was again subjected to the distillation for 1 hour under the same conditions, 97% of the solution component were distilled off, and a solid compound was obtained.
The purity of this compound as measured with the liquid chromatograph was 75.6%, and no sufficiently high purity could be attained.
COMPARATIVE EXAMPLE 3:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid used in Example 1 were solved in 394g of N,N-dimethylformamide, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methylmorpholine and 0.2g (O.OOlmol) of cobalt acetate were added and, thereafter, the reaction was carried out for 1 hour while keeping the reaction temperature at 60C. After completing the reaction, the distillation was initiated while gradually vacuumizing. Carrying out this distillation for 2 hours under the degree of vacuum of lOmmHg and at distillating temperature of 52C, 97% of the solution component were distilled off and a solid compound was obtained.
The purity of this compound as measured with the liquid chromatograph was 80.9~, and no sufficiently high purity could be attained.
Manufacturing examples of the resin of unsaturated dicarboxylic acid imides shall now be referred to, further.
EXAMPLE 7:
lOOg of N,N-4,4'-diphenylmethane-bis-maleimide obtained in Example 1 were taken out and were put in another reaction vessel, into which 75g of N,N-dimethylacetamide were added and solved, 27.7g of diaminodiphenylmethane were further added, and their reaction was taken place for 3 hours at 80C. Thus obtained varnish was employed for impregnation of a glass cloth, and the impregnated glass cloth was dried for 5 minutes at 150C to prepare a prepreg. Four of the thus obtained prepregs were stacked on one another, copper foils were stacked onto both sides of the stacked prepregs, the whole stack of such prepregs and copper foils was subjected to a molding at a temperature of 140C, for a period of 60 minutes and under a pressure of 40kgf/cm2 and then to a curing for 2 hours at 230C, and a double-surface copper-clad laminate was obtained.
Tg temperature of this laminate was measured through TMA analysis and was shown to be 250C. Further, the interlaminar strength between the stacked prepregs was measured to be 1.3kgf/cm, showing that the laminate was satisfiable in the heat resistance and peeling resistance.
EXAMPLE 8:
179g of N,N-4,4'-diphenylmethane-bis-maleimide obtained in Example 1 was kept not isolated but left in the same reaction vessel to be solved together with 134g of N,N-dimethylacetamide added, thereafter 49.6g of diaminodiphenylmethane were added, and a reaction of them was carried out for 3 hours at 80C. A varnish thus obtained was employed for impregnation of glass cloths, the thus impregnated glass cloths were dried at 150C for 5 minutes to obtain prepregs. Four of such prepregs were stacked, copper foils were stacked on both sides of the stacked prepregs, and the whole stack of the prepregs and copper foils were then subjected to the molding at a temperature of 140C for a period of 60 minutes and under a pressure of 40kgf/cm and then to the curing at 230C
for 2 hours, and a both-surface copper-clad laminate was obtained.
Measured Tg temperature by the TMA analysis of this laminate was 250C. Further, measured interlaminar strength between the respective prepregs was 1.3kgf/cm, showing the satisfiable heat resistance and peeling resistance.
EXAMPLE 9:
lOOg of N,N-4,4'-diphenylmethane-bis-maleimide obtained through Example 4 were taken out and put in another reaction vessel, 75g of N,N'-dimethylacetamide were then added, they were solved, thereafter 27.7g of diaminodiphenylmethane were added, and they were subjected to the reaction at 80C for 3 hours. Thus obtained varnish was employed for impregnation of glass cloths, thus impregnated cloths were dried for 5 minutes at 150C
and prepregs were thereby prepared. Four of such prepregs were stacked, copper foils were further stacked on both sides of the stacked prepregs, and, through a curing carried out at 230C for 2 hours, a both-surface copper-clad laminate was obtained.
The Tg temperature measurement by the TMA
analysis of this laminate was 250C, and the interlaminar strength between the respective prepregs was measured to be 1.3kgf/cm, showing the satisfiable heat resistance and peeling resistance.
EXAMPLE 10:
179g of N,N-4,4'-diphenylmethane-bis-maleimide obtained through Example 4 were left in the same reaction vessel, without isolation, 134g of N,N'-dimethylacetamide were added thereto and they were solved. 49.6g of diaminodiphenylmethane were further added and their reaction was carried out at 80C for 3 hours. Glass cloths were impregnated with the thus obtained varnish and were then dried at 150C for 5 minutes and prepregs were thereby prepared. Four of such prepregs were stacked on each other, copper foils were stacked onto both sides of the stacked prepregs, the whole stack of the prepregs and copper foils were then subjected to the molding at a temperature of 140C for a period of 60 minutes under a pressure of 40kgf/cm2 and then to the curing at 230C for 2 hours, and a both-surface copper-clad laminate was obtained.
The Tg temperature measurement through the TMA
analysis of this laminate was 248C, and the interlaminar strength between the respective prepregs was measured to be 1.3kgf/cm, showing thus satisfiable heat resistance and peeling resistance.
COMPARATIVE EXAMPLE 4:
100g of N,N-4,4'-diphenylmethane-bis-maleimide obtained through Comparative Example 1 were solved with 75g of N,N-dimethylacetamide added, then 27.7g of diaminodiphenylmethane were added and their reaction was executed at 80C for 3 hours. Glass cloths were impregnated with thus obtained varnish and were dried at 150C for 5 minutes to prepare prepregs. Four of such prepregs were stacked on one another, copper foils were further stacked on both sides of the stacked prepregs, the whole stack of the prepregs and copper foils was subjected " 2059988 to the molding at a temperature of 140C for a period of 60 minutes under a pressure of 40kgf/cm and then to the curing at 230C for 2 hours, and a both-surface copper-clad laminate was then obtained.
The Tg temperature measurement through the TMA
analysis of this laminate was 252C, and the interlaminar strength measurement between the respective prepregs was 1.3kgf/cm, showing the heat resistance and peeling resistance to be satisfiable. In the present instance, however, there has involved a problem at a stage of obtaining the resin of unsaturated dicarboxylic acid imides.
According to another feature of the present invention, there is provided a process for preparing conveniently the compound of unsaturated dicarboxylic acid imides by subjecting the unsaturated dicarboxylic amic acid to the dehydrating cyclization in the presence of such three dehydrating agents as acid anhydride, basic catalyst and metallic salt catalyst, and spraying a reaction product liquid.
For unsaturated dicarboxylic acid amic acid or unsaturated dicarboxylic acid anhydride, amine or polyamine made to be contributive to the reaction, basic catalyst, metallic salt catalyst, organic catalyst and so on may be the ones which have been described with reference to the foregoing Examples, while not required to be particularly limited, and their using ratio also may be as has been described.
20~9988 In spraying the reactions product liquid, it is preferable that the spray is executed under any one of such conditions as being heated, vacuumized or heated while being vacuumized. The heating should preferably be carried out at a temperature below 180C, since the heating at a temperature above 180C involves a risk that the compound of unsaturated dicarboxylic acid imides becomes apt to carry out homopolymerization so as to cause the resultant compound to be deteriorated in the purity.
EXAMPLE 11:
197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid employed in Example 1 were solved in 394g of N,N-methylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.001mol~ of nickel acetate were added and, thereafter, their reaction was made to take place for 30 minutes while keeping the reaction temperature at 65C. Upon completion of the reaction, the spray of the reaction product liquid was carried out by means of a spray drier (made by Japanese manufacturer HOSOKAWA MICRON, "Clacks System") for 5 minutes under the conditions of heating temperature at 180C and vacuum degree of 10 Torr, whereby N,N-4,4'-diphenylmethane-bis-maleimide yellow and similarly solid to that in Example 1 was obtained.
The purity of this compound as measured by the liquid chromatograph was shown to be 95.5%.
EXAMPLE 12:
205g988 197g (0.5mol) of N,N-4,4'-diphenylmethane-bis-maleamic acid employed in Example 1 were solved in 500g of methyl ethyl ketone, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of N-methyl morpholine and 0.2g (O.OOlmol) of cobalt acetate were added and, thereafter, their reaction was made to take place for 3 hours while keeping the reaction temperature at 60C. Upon completion of the reaction, the spray of the reaction product was carried out by means of the same spray drier as that in Example 11, for 5 minutes under the conditions of heating temperature of 160C and vacuum degree of 40 Torr, whereby N,N-4,4'-diphenylmethane-bis-maleimide yellow and similarly solid to that in Example 1 was obtained.
The purity of this compound as measured by the liquid chromatograph was 93.3%.
EXAMPLE 13:
l91g (lmol) of N-phenylmaleamic acid were solved in 287g of methyl ethyl ketone, to which solution 127.5g (1.25mol) of acetic anhydride, lO.lg (O.lmol) of triethylamine and 0.2g (O.lwt.%) of cobalt naphthenic acid (the reagent by WAKO PURE CHEMICAL, Art. No. 038-03745) were added and, thereafter, they were caused to react for 60 minutes while keeping the reaction temperature of 60C.
Upon completion of the reaction, the reaction product was subjected to the spray with the same spray drier as in Example 11, for 5 minutes under the conditions of the heating temperature of 140C and vacuum degree of 7 Torr, whereby N,N-4,4'-diphenylmethane-bis-maleimide yellow and similarly solid to that in Example 1 was obtained.
The purity of this product as measured by the liquid chromatograph was 92.1%.
EXAMPLE 14:
198g (0.5mol) of unsaturated dicarboxylic acid amic acid (compound name: N,N-4,4'-diphenylether-bis-maleamic acid) of such structure as ~CONH ~ H2O ~ NHCO
COOH HOOC
were solved in 396g of N,N-dimethylformamide, to which solution 153g (1.5mol) of acetic anhydride, 5.lg (0.05mol) of triethylamine and 0.2g (0.001mol) of cobalt acetate were added and, thereafter, they were made to react for 60 minutes while keeping the reaction temperature at 70C.
Upon completion of the reaction, the reaction product liquid was subjected to the spray with the same spray drier as in Example 11, for 5 minutes under the conditions of the heating temperature of 180C and vacuum degree of 10 Torr, whereby the compound of unsaturated dicarboxylic acid imides (compound name: N,N-4,4'-diphenylether-bis-maleimide) was obtained, the compound being yellow, solid and of such structure as follow:
~ N ~ ~ O ~ N/C -~
The purity of this compound as measured by the liquid chromatograph was 94.1%.
Claims (9)
1. A process for preparing a compound of unsaturated dicarboxylic acid imides, wherein an unsaturated dicar-boxylic amic acid compound represented by a following general formula (I) is subjected to a dehydrating cycli-zation in the presence of acid anhydride as a dehydrating agent, basic catalyst and metallic salt catalyst, and thereafter to a vacuum distillation of produced acid and solvent, upon which distillation 50 to 70% of solution component is distilled off at a distilling temperature below 70°C, and a cooling is thereafter carried out to separate a solid matter obtained as said compound of unsaturated dicarboxylic acid imides as represented by general formula (II):
........ (I) ........ (II) in which formulas (I) and (II), D denotes a bivalent organic group having at least one carbon-carbon double bond, R1 denotes n-valent organic group having at least one carbon atom, and n denotes a number more than 1.
........ (I) ........ (II) in which formulas (I) and (II), D denotes a bivalent organic group having at least one carbon-carbon double bond, R1 denotes n-valent organic group having at least one carbon atom, and n denotes a number more than 1.
2. A process for preparing a compound of unsaturated dicarboxylic acid imides, wherein unsaturated dicarboxylic amic acid compound represented by a following general formula (I) is subjected to a dehydrating cyclization in the presence of three of acid anhydride as a dehydrating agent, basic catalyst and metallic salt catalyst and thereafter to a vacuum distillation of produced acid and solvent, upon which distillation 50 to 70% of solution component is distilled off at a temperature below 70°C, a cooling is thereafter carried out to separate a solid matter obtained as said compound of unsaturated dicarboxylic acid imides which is represented by a following general formula (II):
........ (I) ........ (II) in which formulas (I) and (II), D denoting bivalent organic group having at least one carbon-carbon double bonding, R1 denoting n-valent organic group having at least one carbon atom, and n being an integer from 1 to 6.
........ (I) ........ (II) in which formulas (I) and (II), D denoting bivalent organic group having at least one carbon-carbon double bonding, R1 denoting n-valent organic group having at least one carbon atom, and n being an integer from 1 to 6.
3. The process according to claim 2 wherein said cooling is carried out at a temperature below 50°C.
4. The process according to claim 1 wherein, after said distillation for distilling off said solution component, a poor solvent low in the solubility is added and, after said separation of said solid matter, a further distillation is carried out again.
5. The process according to claim 4 wherein said poor solvent is one selected from the group consisting of water, xylene, toluene, benzene, hexane, cyclohexane and their equivalents.
6. The process according to claim 4 wherein said further distillation is carried out at a temperature below 70°C.
7. The process according to claim 4 wherein said further distillation is carried out to distill off more than 93% of the solution component.
8. The process according to claim 1 wherein said unsaturated dicarboxylic amic acid compound is obtained through a reaction of an unsaturated dicarboxylic anhydride selected from the group consisting of maleic anhydride, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, nadic anhydride, cyclodiene, Diels-Alder addition products of these anhydrides, their halogenated substitution products and their alkyl substitution products, with amine and polyamine selected from the group consisting of diaminodiphenyl ethers, 4,4'-methylendi-o-toluidine, phenylendiamine, 4,4'-diaminodiphenylmethane, aniline, 1,3,5-triaminobenzene, hexamethylendiamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, toluylenediamine, 3,3'-diaminobenzidine, 3,3',4,4'-tetraaminodiphenylmethane, diaminodicyclohexylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, their halogenated substitution products and their alkyl substitution products.
9. A resin of unsaturated dicarboxylic acid imides, which consists of an unsaturated dicarboxylic amic acid compound represented by a following general formula (I) and made to be a compound represented by a following general formula (II) through a dehydrating cyclization of said compound of the formula (I) in the presence of acid anhydride as a dehydrating agent, basic catalyst and metallic salt catalyst, a vacuum distillation for distilling off of produced acid and solvent, upon which distillation 50 to 70% of solution component is distilled off at a distilling temperature below 70°C, a cooling of the compound distilled and a separation of solid matter obtained as said compound of the formula (II):
........ (I) ........ (II) in which formulas (I) and (II), D denotes a bivalent organic group having at least one carbon-carbon double bond, R1 denotes n-valent organic group having at least one carbon atom, and a denotes a number more than 1, which compound of the formula (II) is formed into a varnish for being employed as a prepreg for forming a laminate.
........ (I) ........ (II) in which formulas (I) and (II), D denotes a bivalent organic group having at least one carbon-carbon double bond, R1 denotes n-valent organic group having at least one carbon atom, and a denotes a number more than 1, which compound of the formula (II) is formed into a varnish for being employed as a prepreg for forming a laminate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8777/91 | 1991-01-28 | ||
| JP3008777A JPH085855B2 (en) | 1991-01-28 | 1991-01-28 | Process for producing unsaturated dicarboxylic acid imide compound and resin |
| JP148972/91 | 1991-06-20 | ||
| JP3148972A JPH085856B2 (en) | 1991-06-20 | 1991-06-20 | Process for producing unsaturated dicarboxylic acid imide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2059988C true CA2059988C (en) | 1997-03-25 |
Family
ID=26343367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002059988A Expired - Fee Related CA2059988C (en) | 1991-01-28 | 1992-01-24 | Process for preparing compound of unsaturated dicarboxylic acid imides and resin of the same imides |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2059988C (en) |
| DE (1) | DE4202281C2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0165574B1 (en) * | 1984-06-18 | 1992-08-19 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Method for production of maleimides |
| GB8825790D0 (en) * | 1988-11-03 | 1988-12-07 | Bp Chem Int Ltd | Synthesis of bisimides |
-
1992
- 1992-01-24 CA CA002059988A patent/CA2059988C/en not_active Expired - Fee Related
- 1992-01-28 DE DE4202281A patent/DE4202281C2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE4202281C2 (en) | 1996-07-11 |
| DE4202281A1 (en) | 1992-07-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |