DE4202281A1 - High yield ring closure prepn. of di:carboxylic imide for resin - involving prod. sepn. by vacuum distn. or spraying - Google Patents

Abstract

Dehydration ring-closure prepn. of unsatd. dicarboxylic acid imides of formula (II) from dicarboxylic acid amides of formula (I) uses an acid anhydride as dehydrating agent in the presence of a basic catalyst and a metal salt catalyst. Either (A) the acid formed and the solvent are (vacuum) distilled such that at a pre-determined temp. (pref. below 70 deg.C.) more than a pre-determined amt. (pref. 50-70%) of the solvent is distilled off and the residue is cooled to separate off imide (II) as a solid prod.; or (B) the ring-closed reaction prod. soln. is sprayed so as to produce (II). Also claimed are resins of imides (II) produced in the form of a lacquer. n = 1 or more; D = divalent residue with at least one C=C double bond; and R1 = n-valent organic residue contg. at least 1C atom. USE/ADVANTAGE - The resins from (II) are useful in mfr. of prepregs for laminates. Imides (II) are obtd. in high yields at high purity without the need for complex treatment.

Description

The invention relates to a method for producing un saturated dicarboximides and resins of these imides.

The unsaturated dicarboximides in question Art can in particular as a material for laminates and the same can be used that can be used as printed circuit boards are.

As a typical process for the production of unsaturated Dicarboximides can be used as a method which is an unsaturated dicarboxamide for production these compounds are subjected to a cyclization. To this chemical cyclization process is generally ge says using a ring closure with dehydration  a dehydrating agent such as acetic anhydride or the like Chen carried out. With this procedure the desired one Reaction achieved at low temperature and in a short time be so that the unsaturated Di carboximides a high degree of purity of about 90 wt .-% have, the amount of polymeric components contained therein ten is low and the respective connection itself as too can be viewed as peaceful.

In the well-known chemical cyclization is usually the reaction solution is poured into water to complete the reaction separating product from the solution, after which the product knows by filtration, water treatment, neutralization of the acid treated as a by-product is treated, wherein these steps are extremely labor intensive and that Complicate the process so that the known method out Obviously, productivity and economy are disadvantageous is.

Other processes for the production of unsaturated dicarbon acid imides, where no measures to simplify the Process steps as in the present invention, which in are described, are taken from the following US-PS 48 55 450 and JP-OS 63-69 829 known; these are but still problematic in terms of simplification treatment and improvements in productivity and of economy.

The object of the present invention is therefore a Ver drive to the production of unsaturated dicarboximides with which high yields and high purity can be aimed without difficult procedural steps require.

According to the invention, this object is achieved by a method for Production of unsaturated dicarboximides dissolved in the unsaturated dicarboxamides of the general formula I in the presence (1) of an acid anhydride as a dehydrating  Agent, (2) a basic catalyst and (3) a metal salt catalyst a ring closure with elimination of water un be thrown and that is characterized in that Säu re and solvents after the dehydrating cycle be obtained, subjected to vacuum distillation become, in the course of 50 to 70% of the distilled Solution components at a distillation temperature below 70 ° C are distilled, after which to separate the solid Component is cooled, then again is distilled to give compounds of general formula II to obtain:

where in formulas (I) and (II)

D is a divalent organic radical with at least one carbon-carbon double bond,
R¹ is an n-valent organic radical with at least one carbon atom and
n is an integer greater than 1

mean.

According to the invention, polyamine and a solvent are also used to the unsaturated dicarboximides caused by the above were obtained, added to this polymerize and a resin from unsaturated dicarboxylic acid to get imid.

Other objects and advantages of the present invention were achieved ben from the following description of preferred Aus leadership examples.  

Although the invention now relates to certain preferred ones Exemplary embodiments are not described tends to limit the invention only to these examples, rather, all deviations, changes and equiva lente embodiments within the scope of the claims are possible to be included.

To produce the unsaturated dicarboximides according to the invention use an unsaturated dicarboxamide det. Although not specifically limited to this, the ses unsaturated dicarboxamide by reacting an un saturated dicarboxylic acid anhydride of the general formula III with an amine or polyamine of the general formula IV ten, preferably in the presence of an inert organi 's solvent or the like., wherein a reaction system or a solvent-free system is included:

where in formulas (III) and (IV)

D is a divalent organic radical with at least one carbon-carbon double bond,
R¹ is an n-valent organic radical with at least one carbon atom and
n is an integer greater than 1

mean.

As unsaturated dicarboxylic acid anhydride, which in this Reaction system can be used, it is possible whether equally not specifically limited to maleic anhydride, Citraconic anhydride, itaconic anhydride, tetrahydrophthal acid anhydride, nudic anhydride, their halogen-substituted Derivatives, alkyl-substituted derivatives or the like, in each case al alone or in a mixture of two or more of them use.  

As an amine or polyamine, although not specifically limited to it is possible, individually or as a mixture of two or more Methylamine, ethylamine, 1-propylamine, 1,2- Dimethylpropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3-rauryloxypropylamine, 3-mirystyloxypropylamine, methylaminopropylamine, Dimethylaminopropylamine, diethylaminopropylamine, Dibutylaminopropylamine, 2-hydroxyethylaminopropylamine, dimethyl aminoethoxypropylamine, raurylaminopropylamine, diethanolaminopropylamine, Imino-bis-propylamine, methylamino-bis-propylamine, n-butylamine, isobutylamine, sec-butylamine, hexylamine, 2-ethylhexylamine, dodecylamine, cyclohexylamine, arylamine, 3-decichloxyamine, diethylaminoethylamine, ethylaminoethylamine, α-phenethylamine, β-phenethylamine, furfurylamine, methoxylamine, m-aminobenzylamine, m-phenylenediamine, 4-chloro-m-phenylenediamine, 5-nitro-m-phenylenediamine, 4,6-dimethyl-m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, 2-nitro-p- phenylenediamine, 2-cyano-p-phenylenediamine, 2,5-dichloro-p- phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2,5-diethyl-p- phenylenediamine, 5-chloro-2-methyl-p-phenylenediamine, tetra fluorophenylenediamine, tolylenediamine, 3,5-diethyl-2,4-tolylenediamine, 2-picolylamine, 3-picolylamine, 4-picolylamine, m-xylene diamine, p-xylene diamine, hexamethylene diamine, heptamethylene diamine, 4,4-dimethylheptamethylene diamine, diethylene triamine, Triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3 ', 4,4'-tetraaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino- 3,3'-diethyl-5,5'-dimethylphenylmethane, 4,4'-bis (p-aminophenoxy) diphenylmethane, 4,4′-bis (m-aminophenoxy) diphenylmethane, 2,2'-3,3'-tetrachloro-4,4'-diaminodiphenylmethane, diaminodicyclohexylmethane, 4,4′-bis (p-aminophenoxy) diphenylmethane, 4,4′-bis (m-aminophenoxy) diphenylethane, 1,2-bis (3-aminopropoxy) ethane, 2-aminopropanol, 3-aminopropanol, 1,2-diaminopropane, 3,3'-diaminodiphenylpropane, 1,2-bis (3-aminopropoxy) - 2,2′-dimethylpropane, 4,4′-bis (p-aminophenoxy) diphenylpropane, 4,4′-bis (m-aminophenoxy) diphenylpropane, 2,2′-bis (4-aminophenyl)  propane, 1,4-diaminobutane, 1,4-diaminocyclohexane, Bis (3-aminopropyl) ether, α, ω-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'-tetraaminodiphenyl ether, bis (p-β-amino-tert- butylphenyl) ether, toluidine, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-6-bromo-2-toluidine, aniline, ethylaniline, dichloroaniline, 4,4'-methylenedi-2,6-diethylaniline, 4,4'-methylenedi- 2,6-isopropylaniline, isopropoxyaniline, chloraniline, Bromaniline, iodaniline, nitroaniline, 4,4′-methylenedi-2,6-bromaniline, 4,4'-methylenedi-2-bromo-6-chloroaniline, bis-p-aminophenylaniline, Methylene-bis-anthranilic acid, methylene-bis-methylanthranilate, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3 ′, 4,4′-tetraaminodiphenyl sulfone, p-bis (4-aminophenoxy) diphenyl sulfone, p-bis (3-aminophenoxy) diphenyl sulfone, 2,2′-bis-4- (4-aminophenoxy) phenyl sulfone, o-toluidine sulfone, 4,4'-diaminodiphenyl sulfide, bis (4-aminophenyl) disulfide, 3,3 ', 4,4'-tetraaminodiphenyl sulfide, N-aminoethylpiperidine, N- Aminoethyl-4-pipecolin, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecolin, N-aminopropyl-4-pipecolin, N-aminopropylmorpholine, 2-aminoethylpiperidine, 4-aminomethylpiperidine, N-aminopiperidine, 1-amino-4-methylpiperazine, 1,4-bis-aminopropylpiperazine, 2-aminopiperazine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,3,6-triaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino- 5-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine, 2-amino-4,6-dimethylpyridine, 2,6-diamino-4-methylpyridine, 2-amino-3-nitropyridine, 2-amino-5-nitropyridine, 2-chloro-4-aminopyridine, 2-chloro-5- aminopyridine, 2-amino-3,5-dichloropyridine, 4-amino-3,5-dichloropyridine, 2-amino-3,5-dichloro-6-methylpyridine, 2-amino 3,5-dichloro-4-methylpyridine, 2-amino-5-chloro-3-methylpyridine, 2-amino-3,5-dichloro-4,6-dimethylpyridine, 2,4-diaminopyridine, 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'-diaminooctafluorobiphenyl, 2,5-diaminoterephthalic acid, 3,4'-diaminobenzanilide, 4,4'-diaminobenzanilide, 4- (p-aminophenoxy) - 4-aminobenzanilide, 3,3'-dimethoxybenzidine, 3,3'-dimethylbenzidine, 3,3'-diaminobenzidine, 3,3'-dihydroxybenzidine, 2,2′-dichloro-5,5′-dimethoxybenzidine, 2,2 ′, 5,5′-tetrachlorobenzidine, 2,4-diaminotoluene, 2,4-bis (β-amino-tert-butyl) toluene, 4,4'-diaminobenzophenone, polytetramethyleneoxido-di-p- aminobenzoate, trimethylene bis (4-aminobenzoate), bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) dimethylsilane, Bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) methylphosphine oxide, Melamine, 4,4′-diaminostilbene, 9,9-bis (4-aminophenyl) -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, Phenetidine, aminophenol, 2-aminothiophenol, 4-aminothiophenol, Aminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminosbenzoic acid, Xylidine, 4,4'-methylenedi-2,6-xylidine, 2,6-diaminobenzothiazole, m-aminobenzoic acid hydrazide, 2,4-diaminomesitylene, Hexaaminocyclophosphazine, 1,1-diamino-3,3,5,5-tetraphenoxycyclophosphazine, 1,3,5-tris (p-aminophenoxy) -1,3,5- triphenoxycyclophosphazine, Hexakis (p-aminophenoxy) cyclophosphazine and the like.

As an acid anhydride, which be as a dehydrating agent is used when the unsaturated dicarboxamide of all general formula I of dehydrating cyclization under can, although not in detail limits, lower monoalkyl carboxylic anhydrides such. B. Acet anhydride, propionic anhydride, butyric anhydride or the like. be used. The amount in which the dehydrating Agent used is in the range of 1 to 5 moles preferably 1 or 3 moles, based on one equivalent of the acid amidrestes.

As a basic catalyst used in the dehydrating Ring closure is used, although not in one  limited to trialkylamines that are a trialkyl Have group with a carbon number of 1 to 10, such as e.g. B. trimethylamine, triethylamine, tri-n-butylamine and the like, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diaza-bi cyclo (5,4,0) 7undecen and the like can be used. The amount in which basic catalyst is used is available preferably in the range of 0.01 to 0.5 mol, based on a Equivalent to the acid amide residue.

As a metal salt catalyst, which in the dehydrating Cyclization applies, although not in detail limited to a divalent or trivalent cobalt connection, such as B. cobalt chloride, cobalt carbonate, cobalt sulfate, cobalt naphthenate or the like, a divalent nickel connection such as B. nickel acetate, nickel acetylacetate, nickel carbonate or the like, a divalent magnesium compound such as e.g. B. magnesium chloride, magnesium carbonate, magnesium acetate, Magnesium perchlorate or the like and a monovalent sodium connection such as B. sodium acetate can be used. The men ge, with which the metal salt catalyst except cobalt naph then used is preferably in the range of 0.2 to 0.0001 equivalents based on one equivalent of acid reamidrestes, while the amount of cobalt naphthenate, its Molecular weight cannot be easily determined, preferably in the range of 0.2 to 0.0001% by weight, based on the Acid amide compound.

It is also possible, as an organic solvent, which is used in the reaction system, although not individually limited to one or a mixture of two or more of e.g. B. dimethylformamide, dimethylacetamide, Dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, acetone, Dioxane, benzene, toluene, xylene, cyclohexane, methyl ethyl ketone, To use methyl isobutyl ketone, tetrahydrofuran and the like. The amount in which the organic solvent is used is preferably 1.0 to 4 times the weight of the unsaturated dicarboxylic acid amide compound.  

The reaction of the dehydrating cyclization is different on the other hand preferably at a temperature in the range of 20 to 100 ° C, and, particularly preferably, in the range of 40 to 70 ° C carried out. If the unsaturated dicarboximides Made in this way is a by-product Alkyl carboxylic acid is formed, and this alkyl carboxylic acid is together with the solvent used for the reaction removed by distillation to give the unsaturated dicarbon to obtain acidimides. When removing the carboxylic acid and the solvent by distillation is necessary dig that the following conditions are met. As first 50 to 70% of the solution to be distilled off constituents distilled off, the distillation temperature to below about 70 ° C, preferably below 60 ° C is set and the distillation temperature corresponds is regulated according to the degree of negative pressure, because if the Temperature exceeds 70 ° C, a polymerization reaction of unsaturated dicarboximides that occur during the distillation takes place, so that the polymerization product reduces the purity of the unsaturated dicarboximides.

Once a share of 50 to 70% of the solution components, the Alkylcarboxylic acid and the solvent by distillation removed, the solution is preferably below 50 ° C, or particularly preferably cooled down below 30 ° C., or the Unsaturated dicarboximides are obtained by adding a bad solvent, such as. B. water, excreted, and then the solution is again subjected to distillation throw. If in the initial distillation the amount of removed solution components is less than 50%, can the unsaturated dicarboximides are hardly separated the. On the other hand, if the amount exceeds 70%, the Solution so highly concentrated that a polymerization reaction of unsaturated dicarboximides occurs, one Po Lymerisation product is formed, which the purity of the unsaturated dicarboximides thus obtained is reduced.  

Solvents other than water are bad for the imides Although not specifically limited to xylene, Toluene, benzene, hexane, cyclohexane or the like can be used. It is further preferred that the distillation up to one Degree is carried out, at which possibly more than 93% of the Lö Solution components are removed because less than 93% involves the risk that the resulting resin, which from the unsaturated dicarboxylic acid so represented rhyme is produced, a deteriorated heat resistance shows In the production of the resin from the un The polymerization with saturated dicarboximides a slightly different composition of the unsaturated dicar bäurimide carried out in the correct ratio will give. The polymerization itself is among the same Chen conditions carried out as in the prior art are known. Here is the slightly different composition the above polyamine, solvent or the like. The Her position of the resin can with an isolated connection of the unsaturated dicarboximides are carried out. It is also possible to manufacture the resin below in to carry out the same reaction vessel which is used for the manufacture unsaturated dicarboximides, without isolating them.

example 1

197 g (0.5 mol) of the unsaturated acid amide (compound name: N, N-4,4'-diphenylmethane-bis-maleic acid amide) with the structure

are dissolved in 394 g of N, N-dimethylformamide. 153 g (1.5 mol) of acetic anhydride, 5.1 g (0.05 mol) of triethylamine and 0.2 g (0.001 mol) of nickel acetate are added to this solution, and the solution is left to react for 30 minutes, the reaction temperature temperature is kept at 60 ° C. After completion of this reaction, distillation is started, gradually applying vacuum. The distillation is carried out for one hour under a vacuum of 10 mm Hg and at a distillation temperature of 52 ° C, after which the distillation is stopped and the solution is cooled to 40 ° C. At this time, the amount of distillate is 345 g, which corresponds to 61% of the solution components to be distilled. After the deposition of a solid component, the solution is again subjected to a distillation, which is carried out for 1 hour under the same conditions, 97% of the solution components being distilled off and then a solid residue being obtained. The structure of this solid residue was confirmed by ¹³ C-NMR, and it was found that the solid residue is an unsaturated dicarboximide (compound name: N, N-4,4'-diphenylmethane-bis-maleimide) of the following structure:

The purity of this compound was determined using liquid chromatography graph determined, the measurement a purity of 91.5% revealed.

Example 2

197 g (0.5 mol) of N, N-4,4'-diphenylmethane-bis-maleic acid amide are dissolved in 394 g of N, N'-dimethylformamide, including 127.5 g (1.25 mol) acetic anhydride, 10.1 g (0.1 mol) N-methylmorpholine and 0.2 g (0.001 mol) of cobalt acetate are added and then Is reacted for 1 hour, the reaction temperature at 60 ° C is maintained. After the reaction is complete a distillation started, gradually being vacuum is laid. After this distillation is under for 75 minutes a vacuum of 10 mm Hg and at a distillation temperature distilled is stopped and the solution cooled to 40 ° C, after which the amount of De stillats is 367 g, this amount being 68% of that too distilled corresponding solution components. After the disgust  tion of the solid component, the solution becomes the still again lation, which under the same conditions for 45 Minutes, 95% of the solution component be distilled off and a solid residue of N, N-4,4'-di phenylmethane-bis-maleimide in the same way as is obtained in Example 1. The purity of this connection was determined by means of liquid chromatography, the Er result was 90.3%.

Example 3

191 g (1 mole) of unsaturated dicarboxamide (compound na me: N-phenyl maleic acid amide) with the following structure:

are dissolved in 287 g of N, N-dimethylformamide, including 153 g (1.5 mol) acetic anhydride, 10.1 g (0.1 mol) triethylamine and 0.2 g (0.1% by weight) cobalt naphthenate (a reagent of the Japanese Manufacturer WAKO PURE CHEMICAL INDUSTRY, LTD., Art. 038-03745), and then one for 30 minutes Reaction is carried out, the solution at a reak tion temperature of 60 ° C is maintained. After completion distillation is started, whereby vacuum is gradually applied. After the distillation 60 minutes under a vacuum of 10 mm Hg and a still lation temperature of 52 ° C, the De Stillation ended and the solution cooled to 30 ° C, after which the amount of distillate was 275 g. This corresponds to 60% the component to be distilled. After the deposition of the solid component, the solution is again a distillation subject to 60 minutes under the same conditions gene is performed to cover 93% of the solution component breastfeed, and then a solid residue is obtained.

The structure of this solid residue was confirmed by ¹³ C-NMR, and it was found that the solid residue was an unsaturated dicarboximide compound (compound name: N-phenylmaleimide) of the following structure:

The purity of this compound was determined using a liquid Chromatography measurement determined to be 92.1%.

Example 4

197 g (0.5 mol) of N, N-4,4'-diphenylmethane-bis-maleic acid amide are dissolved in 394 g of N, N'-dimethylformamide, including 153 g (1.5 mol) acetic anhydride, 5.1 g (0.05 mol) triethylamine and 0.2 g (0.001 mol) of nickel acetate and this solution is reacted for 30 minutes, the Reak tion temperature is kept at 60 ° C. After completion distillation is started, whereby vacuum is gradually applied. The distillation is 1 Hour under a vacuum of 10 mm Hg and at a still tion temperature of 52 ° C, then the De Stillation ended and 300 g of water are added. To the This time the amount of distillate is 345 g, which is 61% of solution components to be distilled. After Separation of a solid, the solution becomes one again Subjected to distillation, which for 1 hour among them Conditions is carried out to 97% of the solution component to distill off, and then a solid residue of N, N-4,4'-Di phenylmethane-bis-maleimide in the same way as is obtained in Example 1.

The purity of this compound, which by means of liquid chroma topography was determined was 91.5%.  

Example 5

197 g (0.5 mol) of N, N-4,4'-diphenylmethane-bis-maleic acid amide are dissolved in 394 g of N, N-dimethylformamide, including 127.5 g (1.25 mol) acetic anhydride, 10.1 g (0.1 mol) N-methylmorpholine and 0.2 g (0.001 mol) of cobalt acetate are added, after which for 1 hour a reaction is carried out, the reaction temperature is kept at 60 ° C. After completing the A distillation reaction is started, gradually Vacuum is applied. The distillation is for 75 minutes under a vacuum of 10 mm Hg and with a distillation temperature of 52 ° C, then the distilla tion ended and 300 g of xylene are added, after which the Amount of distillate is 367 g. This corresponds to 68% of the components of the solution to be distilled. After the deposition The solid component is the solution again for 45 minutes subjected to distillation under the same conditions, to distill off 95% of the solution components, whereupon fe stes N, N-4,4'-diphenylmethane-bis-maleimide in the same Chen way as obtained in Example 1.

The purity of this compound, measured using liquid chro matography, is 90.3%.

Example 6

191 g (1 mol) of N-phenylmaleic acid amide are dissolved in 287 g of N, N-di dissolved methylformamide, for which purpose 153 g (1.5 mol) acetic anhydride, 10.1 g (0.1 mol) of triethylamine and 0.2 g (0.1% by weight) of cobalt naphthenate (reagent from WAKO PURE CHEMICAL INDUSTRY, Ltd., Art. No. 038-03745) are added, after which for 30 minutes a reaction is carried out, the reaction temperature is kept at 60 ° C. After completing the reak distillation is started, with gradual Va vacuum is applied. After distilling for 60 minutes a vacuum of 10 mm Hg and at a distillation temperature temperature of 52 ° C was carried out, the distillation terminated and 400 g of toluene are added to the solution, after which  the amount of distillate is 275 g, which is 60% of de correspond to lactating solution components. After the Ab separation of the solid component, the solution is again for Distilled for 60 minutes under the same conditions, by 93% remove the solution components, whereupon solid N-phenyl maleimide in the same manner as in Example 3 will hold.

The purity of this compound, measured using liquid chro matography, is 92.1%.

Comparative Example 1

197 g (0.5 mol) of N, N-4,4′-diphenylmethane-bis-maleic acid amide, as used in Example 1 are in 394 g of N, N-dimethyl Formamide dissolved, for which 153 g (1.5 mol) acetic anhydride, 5.1 g (0.05 mol) triethylamine and 0.2 g (0.001 mol) nickel acetate are given and then a reaction is carried out for 1 hour is carried out, the reaction temperature being kept at 60.degree becomes. After the reaction is complete, the solution is brought to 20 ° C cooled, 500 g of water are added to the reaction solution ben, whereupon precipitation occurs. This rainfall is then filtered off, washed, with an aqueous solution neutralized by sodium carbonate, after neutralization washed again and dried, whereupon 163 g of N, N-4,4'-diphe nylmethane-bis-maleimide can be obtained. At this Opportunity will receive about 3000 g of waste water, their amount is 6 times larger than in Example 1.

The purity of this compound, measured using liquid chro matography is 91.5%, but it has been found that the excessive waste water mass production impossible Lich.

Comparative Example 2

197 g (0.5 mol) of N, N-4,4'-diphenylmethane-bis-maleic acid amide are dissolved in 394 g of N, N-dimethylformamide, for which purpose 153 g (1.5 mol)  Acetic anhydride, 5.1 g (0.05 mol) triethylamine and 0.2 g (0.001 mol) of nickel acetate are added, followed by 30 minutes a reaction is carried out, the reaction tem temperature is kept at 60 ° C. After completing the reaction a distillation is started, gradually vacuum is created: After distillation for 1 hour under a Vacuum of 30 mm Hg and at a distillation temperature of 75 ° C has been carried out, the distillation is ended and the solution cooled to 40 ° C, the amount of distillate 365 g is 63% of the solution stock to be distilled parts correspond. After separation of the solid component the solution is again for 1 hour under the same conditions distilled gene, removing 97% of the solution components and a firm connection will be obtained.

The purity of this compound, measured using liquid chro matography, is 75.6%; a satisfactorily high Rein could not be achieved.

Comparative Example 3

197 g (0.5 mol) of N, N-4,4'-diphenylmethane-bis-maleic acid amide are dissolved in 394 g of N, N-dimethylformamide, including 127.5 g (1.25 mol) acetic anhydride, 10.1 g (0.1 mol) N-methylmorpholine and 0.2 g (0.001 mol) of cobalt acetate are added, followed by 1 hour a reaction is carried out, the reaction temperature is kept at 60 ° C. After completing the A distillation reaction is started, gradually Vacuum is applied. This distillation is carried out for 2 hours under a vacuum of 10 mm Hg and with a distillation temperature of 52 ° C, 97% of the solution compo be distilled off and the solid component obtained becomes.

The purity of this compound, measured using liquid chro matography, is 80.9%; it couldn't be high enough Purity can be achieved.  

The following are examples of the manufacture of resins unsaturated dicarboximides.

Example 7

100 g of the N, N-4,4'-diphenylmethane obtained in Example 1 bis-maleimides are taken out and into another Added reaction vessel in which 75 g of N, N-dimethylacetamide be given and dissolved, further 27.7 g of diaminodi phenylmethane added and their reaction for 3 hours 80 ° C carried out. The varnish thus obtained becomes an impregnation used a glass fabric and the impregnated glass weave is 5 minutes at 150 ° C to produce a prepreg dried. Four of the prepregs thus obtained are combined stacked and copper foils are on both sides of the ge stacked prepregs applied, the whole stack of prepregs and copper foils at a temperature of 140 ° C for 60 minutes pressed under a pressure of 3.9 MPa and then Hardened for 2 hours at 230 ° C, one copper on both sides coated laminate is obtained.

The glass transition temperature Tg of this laminate was determined by means of TMA analysis measured and determined at 250 ° C. Furthermore, de the interlaminar strength between the stacked Measured prepregs; it was 0.13 MPa, which shows that the Laminate with satisfactory heat resistance and peel strength was.

Example 8

179 g of the N, N-4,4′-diphenylmethane obtained in Example 1 bis-maleimide are not isolated, but in the leave the same reaction vessel and added together with 134 g given N, N-dimethylacetamide, after which 49.6 g of diamino Diphenylmethane be added and vice versa at 80 ° C for 3 hours is set. A varnish obtained in this way becomes an impregnation of a glass fabric and the glass so impregnated fabric is 5 minutes at 150 ° C to produce prepregs  dried. Four of these prepregs are stacked, copper foils Lines are placed on both sides of the stacked prepregs brings and the whole stack of prepregs and copper foils is then un at a temperature of 140 ° C for 60 minutes ter pressure of 3.9 MPa and then at 2 hours 230 ° C hardened, whereby a copper-coated La minat is obtained.

The glass transition temperature measured by TMA analysis this laminate is 250 ° C. Furthermore, the in terlaminar strength between the prepregs 0.13 MPa what the satisfactory heat resistance and peel strength shows.

Example 9

100 g of the N, N-4,4′-diphenylmethane obtained in Example 4 bis-maleimides are taken out and into another Given reaction vessel, 75 g of N, N-dimethylacetamide are then added and dissolved, after which 27.7 g of diaminodiphenylmethane given and reacted at 80 ° C for 3 hours. The so he Holding varnish is used to impregnate glass fabrics det, the so impregnated tissues are 5 minutes at 150 ° C. dried, producing prepregs. Four of these Prepregs are stacked and copper foils applied to both sides of the stacked prepregs, and a copper-coated laminate on both sides becomes after 2 hours obtained at 230 ° C.

The measurement of the glass transition temperature using TMA analysis this laminate gives 250 ° C and the interlaminar strength 0.13 MPa is measured between the respective prepregs, what the satisfactory heat resistance and peeling shows strength.  

Example 10

179 g of the N, N-4,4′-diphenylmethane obtained in Example 4 bis-maleimide are isolated without isolation in the same Re leave action vessel, and 134 g of N, N'-dimethylacetamide added give and solved. Furthermore, 49.6 g of diaminodiphe nylmethane added and reacted at 80 ° C for 3 hours. With the thus obtained varnish, glass fabrics are impregnated and then 5 Dried for minutes at 150 ° C, making prepregs will. Four of these prepregs are stacked on top of each other, Copper foils are stacked on both sides of the prepregs applied, the whole stack of prepregs and copper foils is then un at a temperature of 140 ° C for 60 minutes ter pressure of 3.9 MPa and then at 2 hours 230 ° C hardened, after which a copper-coated on both sides Laminate is obtained.

The measurement of the glass transition temperature using TMA analysis this laminate gives 248 ° C, and the interlaminar strength speed between the individual prepregs becomes 0.13 MPa true what is a satisfactory heat resistance and Peel strength shows.

Comparative Example 4

100 g of the N, N-4,4'-diphe obtained in Comparative Example 1 nylmethane-bis-maleimide are obtained by adding 75 g N, N-dimethylacetamide dissolved, then 27.7 g of diaminodi phenylmethane added and reacted at 80 ° C for 3 hours. With the lacquer obtained in this way is impregnated with glass cloth and Preparation of prepregs dried at 150 ° C. for 5 minutes. Four these prepregs are stacked on top of each other copper foils on both sides of the stacked prepregs applied, the whole stack of prepregs and copper foils is under at a temperature of 140 ° C for 60 minutes a pressure of 3.9 MPa and then pressed at 230 ° C for 2 hours hardened, creating a double-sided copper-coated laminate is obtained.  

The measurement of the glass transition temperature using TMA analysis this laminate gives 252 ° C and the measurement of the interlamina The force between the individual prepregs is 0.13 MPa, what a satisfactory heat resistance and peel shows stability. Nevertheless, in the present case there is a Problem in the production of the resin from the unsaturated Dicarboximide.

In another embodiment of the present invention is a process for the cheap production of unsaturated ten dicarboximides provided, the unsaturated ten dicarboxamides in the presence of a dehydrating Agents such as B. acetic anhydride, a basic catalyst and a metal salt catalyst from ring closure under water be subjected to cleavage and a reaction product is liquid is sprayed.

As unsaturated dicarboxylic acid amide or unsaturated dicar bonic anhydride, amine or polyamine, which contribute to the reaction wear, basic catalyst, metal salt catalyst, orga nical catalyst etc. can be used which has been described in relation to the preceding examples the, although not specifically limited to, and their Ratios can also be used as described will.

It is before spraying the reaction product liquid causes the spraying under one of the conditions such. B. Heating, vacuum or heating done under vacuum becomes. Heating should preferably be at one temperature below 180 ° C because the heating to a Temperature above 180 ° C contains the risk that the saturated dicarboximides to homopolymerization gene so that the resulting compound in its purity is affected.  

Example 11

197 g (0.5 mol) of N, N-4,4′-diphenylmethane-bis-maleic acid amide, as used in Example 1 are in 394 g of N, N-dimethyl Formamide dissolved, for which 153 g (1.5 mol) acetic anhydride, 5.1 g (0.05 mol) triethylamine and 0.2 g (0.001 mol) nickel acetate are given, followed by a reaction for 30 minutes is carried out, the reaction temperature being kept at 65.degree becomes. After completing the reaction, spraying the reaction product solution by means of a spray dryer (from the Japanese manufacturer HOSOKAWA MIGRON, "Clacks System") for 5 minutes under the conditions of a heating temperature 180 ° C and a vacuum of 10 torr, whereby N, N-4,4'-diphenylmethane-bis-maleimide yellow and in the same way as obtained in Example 1.

The purity of this compound, measured using liquid chro matography was determined to be 95.5%.

Example 12

197 g (0.5 mol) of N, N-4,4′-diphenylmethane-bis-maleic acid amide, as used in Example 1 are in 500 g of methyl ethyl ketone dissolved, for which purpose 127.5 g (1.25 mol) acetic anhydride, 10.1 g (0.1 mol) N-methylmorpholine and 0.2 g (0.001 mol) of cobalt acetate were added be used, and then a reaction is carried out for 3 hours is carried out, the reaction temperature being kept at 60.degree becomes. After completing the reaction, spraying the reaction product using the same spray dryer as in Example 11, 5 minutes under the conditions a heating temperature of 160 ° C and a vacuum of 40 Torr, whereby N, N-4,4'-diphenylmethane-bis-maleimide yellow and similarly as obtained in Example 1.

The purity of this compound, measured using liquid chro matography, was 93.3%.  

Example 13

191 g (1 mol) of N-phenyl maleic acid amide are converted into 287 g of methyl dissolved ethyl ketone, to which 127.5 g (1.25 mol) of acetic anhydride, 10.1 g (0.1 mol) triethylamine and 0.2 g (0.1% by weight) cobalt naphthenate (Reagent from WAKO PURE CHEMICAL, Art. No. 038-03745) be used, and then these for 60 minutes to react are brought, the reaction temperature being kept at 60 ° C will. When the reaction is complete, the reac tion product using the same spray dryer as in Example 11, 5 minutes under the conditions a temperature of 140 ° C and a vacuum of 7 torr where by N, N-4,4'-diphenylmethane-bis-maleimide, yellow and similarly as in Example 1.

The purity of this product, measured using liquid chroma topography, was 92.1%.

Example 14

198 g (0.5 mol) of unsaturated dicarboxamide (compound name: N, N'-4,4'-diphenylether-bis-maleic acid amide) of the structure

are dissolved in 396 g of N, N-dimethylformamide, for which purpose 153 g (1.5 Mol) acetic anhydride, 5.1 g (0.05 mol) triethylamine and 0.2 g (0.001 mol) cobalt acetate are added, and then this be reacted for 60 minutes, the Reak tion temperature is kept at 70 ° C. After completion tion of the reaction, the reaction product with the same Spray dryer as sprayed in Example 11, under 5 minutes the conditions of a temperature of 180 ° C and a vacuum of 1.3 kPa, whereby the unsaturated dicarboximide (Ver bond name: N, N′-4,4′-diphenylether-bis-maleimide) is obtained, the connection being yellow and solid and has the following structure:  

The purity of this compound, measured using liquid chro matography, is 94.1%.

Claims (16)

1. A process for the preparation of unsaturated dicarboxylic acid in which an unsaturated dicarboxamide of the general formula I is subjected to a ring closure under water cleavage in the presence of an acid anhydride as a dehydrating agent, a basic catalyst and a metal salt catalyst, characterized in that acid formed after the ring closure and solvents are subjected to a distillation, in the course of which more than a predetermined amount of the solution constituents to be distilled is distilled off at a predetermined distillation temperature, after which the corresponding unsaturated dicarboximide of the general formula II is cooled in the form of a solid residue to separate out: where in formulas (I) and (II) D a bivalent organic radical with at least one carbon-carbon double bond,
R¹ is an n-valent organic radical with at least one carbon atom and
n means a number greater than 1. 2. Process for the preparation of unsaturated dicarboxylic acid, in which an unsaturated dicarboxamide of the general formula I in the presence of an acid anhydride as a dehydrating agent, a basic catalyst and a metal salt catalyst is subjected to a ring closure with water separation, whereupon a vacuum distillation of the acid formed and of the solvent is carried out, in the course of which 50 to 70% of the solution constituents to be distilled are distilled off at a temperature below 70 ° C., after which the corresponding unsaturated dicarboxylic acid rhyme of the general formula II is cooled in the form of a solid residue: where in formulas (I) and (II) D a bivalent organic radical with at least one carbon-carbon double bond,
R¹ is an n-valent organic radical with at least one carbon atom and
n is an integer from 1 to 6. 3. The method according to claim 2, characterized in that the Cooling carried out at a temperature below 50 ° C. becomes. 4. The method according to claim 1, characterized in that after distillation to distill off the solution stock share a solvent with low solubility ben and after separation of the solid residue further distillation is carried out. 5. The method according to claim 4, characterized in that the poor solvents, one from the group water, xylene, Is toluene, benzene, hexane, cyclohexane and their equivalents. 6. The method according to claim 4, characterized in that the further distillation at a temperature below 70 ° C. leads. 7. The method according to claim 4, characterized in that the further distillation is carried out to more than 93% of the distillable solution components. 8. The method according to claim 1, characterized in that the unsaturated dicarboxamide compound by reaction egg unsaturated dicarboxylic acid anhydride selected from the Group maleic anhydride, citraconic anhydride, itaconic acid reanhydride, tetrahydrophthalic anhydride, nudic acid anhydride drid, Cyclodien, Diels-Alder addition products of this Anhy dride, their halogen-substituted derivatives and their alkyl substituted derivatives with amines and polyamines from the group diaminodiphenyl ether, 4,4′-methylenedi-o- toluidine, phenylenediamine, 4,4'-diaminodiphenylmethane, aniline, 1,3,5-triaminobenzene, hexamethylene diamine, 3,3'-dimethyl 4,4'-diaminobiphenyl, tolylenediamine, 3,3'-diaminobenzidine, 3,3 ′, 4,4′-tetraaminodiphenylmethane, diaminodicyclohexylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, the halogen-substituted derivatives and their alkyl-substituted Derivatives.   9. Resin from unsaturated dicarboximides, each consisting of an unsaturated dicarboxamide of the general formula I and which is separated by ring closure with water separation in the presence of an acid anhydride as a dehydrating agent, a basic catalyst and a metal salt catalyst, by vacuum distillation, to form the acid and solvent to be distilled off, with more than a predetermined amount of the solution components to be distilled off being distilled off at a predetermined distillation temperature, by cooling with separation of the corresponding compound of the formula II in the form of a solid residue: wherein the compound of formula II forms a varnish which is used for a prepreg to form a laminate. 10. A process for the preparation of unsaturated dicarboxylic acid, in which an unsaturated dicarboxamide of the general formula I in the presence of an acid anhydride as a dehydrating agent, a basic catalyst and a metal salt catalyst is subjected to a ring closure with elimination of water, and the reaction solution from this cyclization Formation of the unsaturated dicarboximides of the general formula II is sprayed: where in formulas (I) and (II) D a bivalent organic radical with at least one carbon-carbon double bond,
R¹ is an n-valent organic radical with at least one carbon atom and
n means a number greater than 1. 11. The method according to claim 10, characterized in that spraying is carried out with heating. 12. The method according to claim 11, characterized in that spraying is carried out at a temperature below 180 ° C. becomes. 13. The method according to claim 10, characterized in that spraying is carried out under reduced pressure. 14. The method according to claim 11, characterized in that spraying is carried out under reduced pressure. 15. The method according to claim 13, characterized in that the pressure is less than 100 torr. 16. The method according to claim 10, wherein the unsaturated di carboxamide by reacting an unsaturated dicarbon acid anhydride, which from the group consisting of malein acid anhydride, citraconic anhydride, itaconic anhydride, Tetrahydrophthalic anhydride, nudic anhydride, cyclodiene, Diels-Alder addition products of these anhydrides, their halo gene-substituted derivatives and their alkyl-substituted Is selected with amines and polyamines, which from the group consisting of diaminodiphenyl ethers, 4,4'-Me thylenedi-o-toluidine, phenylenediamine, 4,4'-diaminodiphenyl methane, aniline, 1,3,5-triaminobenzene, hexamethylene diamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, tolylenediamine, 3,3'-di aminobenzidine, 3,3 ', 4,4'-tetraaminodiphenylmethane, diamino dicyclohexylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diamino  diphenyl sulfide, its halogen substituted derivatives and whose alkyl-substituted derivatives are selected, receive will.