WO2001021588A2

WO2001021588A2 - Cycloalkyl bicycloheptene dicarboximides

Info

Publication number: WO2001021588A2
Application number: PCT/US2000/023526
Authority: WO
Inventors: Jack Warren
Original assignee: Eagleview Technologies, Inc.
Priority date: 1999-09-21
Filing date: 2000-08-24
Publication date: 2001-03-29
Also published as: AU7079500A; JP2003509492A; WO2001021588A3; CA2347837A1

Abstract

The invention provides a compound of formula (I) in which R?1 and R2¿ are independently hydrogen, (C¿1?-C7)-alkyl, (C2-C7)-alkenyl, or (C2-C7)-alkynyl; X?1 and X2¿ can be independently present or absent, and if present are independently (C¿1?-C7)-alkylene or (C2-C7)-alkenylene; Y?1 and Y2¿ are independently (C¿4?-C8)-cycloalkylene or (C4-C8)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C1-C7)-alkyl, (C2-C7)-alkenyl, or carboxyl; and Z is (C1-C12)-alkylene; (C2-C12)-alkenylene; D-E-F, where D and F are independently (C1-C12)-alkylene or (C2-C12)-alkenylene, and E is (C4-C8)-cycloalkylene or (C4-C8)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C1-C7)-alkyl or (C2-C7)-alkenyl; or G-H-I, where G and I are independently (C1-C12)-alkylene or (C2-C12)-alkenylene, and H is N-(C1-C7)-alkyl; N-(C2-C7)-alkenyl; N-(C4-C8)-cycloalkyl or N-(C4-C8)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C1-C7)-alkyl or (C2-C7)-alkenyl; or N-(C1-C7)-alkyl-(C4-C8)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C1-C7)-alkyl or (C2-C7)-alkenyl.

Description

CYCLOALKYL BICYCLOHEPTENE DICARBOXIMIDES

FIELD OF THE INVENTION This invention relates to cycloalkyl bicycloheptene dicarboximides. These compounds are useful for making polymers such as heat resistant polyimide polymers.

BACKGROUND OF THE INVENTION Cycloalkyl bicycloheptene dicarboximides and polymers of these compounds are known. See U.S. Patent No. 5,049,632 to Asrar. The Asrar patent describes these polymers as having high heat resistance, low dielectric constant and low moisture absorption. See col. 1, lines 5 to 9. U.S. Patent No. 5,502,207 to Futaesaku et al. describes alkenyl-substituted bisnadimides containing a linking group which contains a phenylene group. See the abstract. These compounds are used to make polymers such as adhesives and coating materials. Col. 1, lines 9 to 25.

U.S. Patent No. 4,742,166 to Renner and U.S. Patent No. 4,022,954 to Kurosawa et al. also describe cycloalkyl bicycloheptene dicarboximides. However, none of these patents describe cycloalkyl bicycloheptene dicarboximides having two bicycloheptene dicarboximide groups and two or more cycloalkyl groups.

SUMMARY OF THE INVENTION The invention provides a compound of the formula I

in which R¹ and R² are independently hydrogen, (C,-C₇)-alkyl, (C₂-C₇)-alkenyl, or (C₂-C₇)-alkynyl;

X¹ and X² can be independently present or absent, and if present are independently (C,-C₇)-alkylene or (C₂-C₇)-alkenylene;

Y¹ and Y² are independently (C₄-C₈)-cycloalkylene or (C₄-C₈)- cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)-alkyl, (C₂-C₇)-alkenyl or carboxyl; and

Z is (C C₁₂)-alkylene; (C₂-C₁₂)-alkenylene; D-E-F, where D and F are independently (C_rCι₂)-alkylene or (C₂-C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C_rC,₂)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C,-C₇)-alkyl; N-(C₂-C₇)-alkenyl; N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C,-C₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)-alkyl or (C₂-C₇)-alkenyl.

The invention also provides methods of making these compounds, polymers containing units of these compounds, and polymers made by polymerizing or copolymerizing these compounds.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention provides a compound of formula I given above. In different embodiments of the compound of formula I, Y¹ and Y² are identical, Y¹ and Y² are cyclohexylene monosubstituted by methyl, Y¹ and Y² are cyclohexylene, and Y¹ and Y² are cyclohexenylene. In other embodiments, Z is -CH₂-, or Z is (C,-C_]2)-alkylene or (C₂-C₁₂)-alkenylene. In another embodiment, X¹ and X² are not present, Y¹ and Y² are cyclohexylene monosubstituted by methyl, and Z is -CH₂-. In a preferred embodiment of the compound of formula I, the compound is N ,N'-3, 3' -dimethyl - dicyclohexylmethane-4,4'-bis-(bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide). In another preferred embodiment, the compound of formula I is N,N'-3,3'- dicarboxyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3- dicarboximide).

The invention also provides a polymer produced by polymerizing or copolymerizing the compound of formula I. The invention also provides a polymer comprising units of the compound of formula I. In different embodiments, the polymer is a polyimide, a polyester, or a polyimide ester. In a preferred embodiment, the polymer is produced from N,N'-3,3'-dimethyl- dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide). In another preferred embodiment, the polymer is produced from N,N'-3,3'- dicarboxyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3-

dicarboximide). One polyimide produced can have the following structure:

One polyester produced can have the following structure:

The invention also provides a process for making a compound of formula I, wherein

is reacted with H₂N-X¹-Y¹-Z-Yⁱ-Xⁱ-NH₂, in which

R¹ and R² are independently hydrogen, (C,-C₇)-alkyl, (C₂-C₇)-alkenyl, or (C₂-C₇)-alkynyl

X¹ and X² can be present or absent, and if present are independently (C C₇)-alkylene or (C₂-C₇)-alkenylene;

Y¹ and Y² are independently (C₄-C₈)-cycloalkylene or (C₄-C₈)- cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or carboxyl; and Z is (C₁-C_]2)-alkylene; (C₂-C_]2)-alkenylene; D-E-F, where D and F are independently (C C₁₂)-alkylene or (C₂-C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C_rC₁₂)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C,-C₇)-alkyl; N-(C₂-C₇)-alkenyl; N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C_rC₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)-alkyl or (C₂-C₇)-alkenyl. The invention also provides a compound of the formula II

in which R¹ and R² are independently hydrogen, (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or (C₂-C₇)-alkynyl;

X¹ and X² can be independently present or absent, and if present are independently (C_rC₇)-alkylene or (C₂-C₇)-alkenylene;

Y¹ and Y² are independently (C₄-C₈)-cycloalkylene or (C₄-C₈)- cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or carboxyl; and Z is (C,-C₁₂)-alkylene; (C₂-C₁₂)-alkenylene; D-E-F, where D and F are independently (C,-C₁₂)-alkylene or (C₂-C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C,-C₁₂)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C_rC₇)-alkyl; N-(C₂-C₇)-alkenyl; N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C,-C₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)-alkyl or (C₂-C₇)-alkenyl. The preferred structures are analogous to those of formula I. The invention also provides a polymerizable composition comprising a mixture of a compound of formula I or II and an additional unsaturated monomer having at least one double bond.

The invention also provides a compound of the formula III

H₂N-X¹-Y^,-Z-Y²-X²-NH₂ (III)

in which

R¹ and R² are independently hydrogen, (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or (C₂-C₇)-alkynyl;

Y¹ and Y² are independently (C₄-C₈)-cycloalkylene or (C₄-C₈)- cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or carboxyl; and

Z is (C,-C₁₂)-alkylene; (C₂-C₁₂)-alkenylene; D-E-F, where D and F are independently (C,-C₁₂)-alkylene or (C -C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C,-C₁₂)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C,-C₇)-alkyl; N-(C₂-C₇)-alkenyl;

N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C_rC₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C₁-C₇)-alkyl or (C₂-C₇)-alkenyl, wherein Y¹ and Y² are not cyclohexylene. The preferred structures are analogous to those of formula I.

The details for making the compounds and polymers of the invention are known to those skilled in the art. U.S. Patent No. 5,049,632 to Asrar, U.S. Patent No. 5,502,207 to Futaesaku et al, U.S. Patent No. 4,742,166 to Renner, and U.S. Patent No. 4,022,954 to Kurosawa et al. are hereby incorporated by reference.

In addition to the polymers described above, the compounds of the invention can be used as modifiers for a polyester resin, high impact additives for PVC plastics, dye site receptors for textile fibers, plasticizers for inks or coatings, and as intermediates for pharmaceuticals or metal catalysts.

The polymers of the invention can be in the endo form, exo form, or a mixture of endo and exo forms. If the polymerization is performed under vacuum, a pure endo form can be obtained. If the polymerization is performed above about 180°C at atmospheric pressure, a pure exo form can be obtained. The imides according to the invention can be prepared in a manner which is known, for example by reacting the anhydride with the diamine at elevated temperature, with the water formed during the reaction being distilled off. Diamines are preferably used in a stoichiometric ratio. The reaction can be carried out without a solvent or in the presence of an inert solvent, which can be used for azeotropic removal of water. The temperature of the reaction preferably is between 100° and 250°C. The imides of the formula I are preferably prepared in the melt under a pressure of 4,500 Pa or less and at temperatures between 130° and 220°C, more preferably between 180° and 220°C.

The imides of the present invention can also be copolymerized with other unsaturated monomers containing at least one double bond. Typical monomers include acrylic and methacrylic derivatives such as the (C_rC₁₈)- alkyl esters as well as the (C₂-C₆)-hydroxyalkyl esters. The biscarboximides of the present invention can be also be copolymerized with other imides such as maleimides selected from the group consisting of N,N'-ethyl-ene-bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismale-imide, N,N'- phenylene bismaleimide, N,N'-4,4'-diphenyιmethane-bismaleimide, N,N'-4,4'- 3 ,3'-dichlorodiphenylmethane-bismaleimide, N,N'-4,4'-diphenyl ether- bismaleimide, N,N'-4,4'-diphenylsulfone-bismaleimide, N,N'-m-xylylene- bismale-imide, N,N'-p-xylylene-bismaleimide, N,N'-4,4'-2,2-diphenylpropane- bismale-imide, the N,N'-bismaleimide of 4,4'-di-aminotriphenylphosphate, the N,N'-bis-maleimide of 4,4'-diaminotri-phenylphosphite, the N,N'-bismaleimide of 4,4'-di-aminotriphenyl-thiophosphate, the N,N',N"-trismaleimide of tris(4- aminophenyl)-phosphate, the N,N',N"-trismaleimide of tris(4- aminophenyl)phosphite, the N,N',N"-trimaleimide of tris(4- aminophenyl)phosphite, and the N,N',N"-tris-maleimide of tris(4- aminophenyl)thiophosphate.

The compounds according to the invention can be polymerised directly, or they can first be dissolved in an organic solvent, such as toluene, xylene, methyl ethyl ketone, an ethylene glycol monoalkyl or dialkyl ether having 1 to 4 carbon atoms in the alkyl groups, or a similar solvent conventional in the coatings industry. Such solutions can be used as impregnating agents or coating agents.

Typically, the polymers of the invention are preferably obtained by heating an imide of the formula I at a temperature between 100° and 300°C, preferable between 175° and 275°C, and more preferably between 200° and 250°C, for 6 to 24 hours. Particularly preferred polymers are those which can be obtained by heating an imide of the formula I at 200° to 250°C for 6 to 12 hours. Inert and stable substances, such as fillers, pigments, dyes and other additives can, of course, be added to the imides of the formula I before they are polymerized to form crosslinked structures.

The curing or processing of the bisimides of the formula I and of compositions of matter containing them can be carried out in an inert organic solvent, but is preferably carried out from the melt and, if appropriate, in the presence of a curing catalyst. Examples of suitable inert organic solvents are dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, toluene, xylenes, methyl ene chloride, tetrahydrofuran, methyl ethyl ketone, and ethylene glycol monoalkyl or dialkyl ethers having 1 to 4 carbon atoms in the alkyl groups. Depending on the intended use, examples of suitable curing catalysts are organic peroxides, such as ditert-butyl peroxide, dicumyl peroxide or tert- butyl perbenzoate, or basic catalysts, in particular primary, secondary and tertiary amines, for example diethyl-amine, tributylamine, triethylamine, benzylamine, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, N,N- diisobutylaminoacetonitrile or N,N-dibutylaminoacetonitrile, and heterocyclic bases, such as quinoline, N-methylpyrrolidine and imidazole. The concentration of the catalyst which can be used is appropriately between 0.1 and 15.0, preferably between 0.25 and 5.0, and particularly preferably between 0.5 and 2.0 percent by weight, relative to the total weight of the imide of the formula I and the other unsaturated imides or additional unsaturated monomers which can be present in the mixture. The invention also provides a process for the preparation of a polymer which comprises subjecting a composition of the invention to actinic radiation until it is photopolymerized. The radiation can be exclusively ultraviolet radiation or it may be radiation having wavelengths in both the ultraviolet and visible regions of the spectrum. Radiation having a wavelength of 200 to 600 nm, especially 200 to 400 nm, is preferred. The selection, from commercially available equipment, of a suitable radiation source emitting radiation within this wavelength range is a routine matter for those skilled in the art of photopolymerization. Suitable sources include medium pressure mercury arc lamps and metal halide lamps. Suitable irradiation times may similarly be determined readily by those familiar with photopolymerization techniques.

Photoinitiators may be used as the catalyst in the photochemical polymerization of the imides according to the invention. Examples of suitable photoinitiators are α-halogen-substituted acetophenones, such as trichloromethyl-4'-tert-butyl phenyl ketone, α-hydroxy-α-alkyl-substituted acetophenones, such as 2-hydroxy-2-methyl-l-phenylpropan-l-one, 1- hydroxycyclohexyl phenyl ketone, benzoin and alkyl ethers thereof (for example, the n-butyl ether), α-methylbenzoin or alkyl esters of α,α-dialkoxy- α-benzoylacetic acid, benzophenones, such as benzophenone itself and 4,4'-bis- (dimethylamino)-benzophenone, O-alkoxycarbonyl derivatives of an oxime of benzil or of l-phenylpropan-l,2-dione, such as benzil-(O-ethoxycarbonyl) α- monoxime and l-phenylpropane-l,2-dione-2-(0-ethoxycarbonyl) oxime, benzil ketals, for example, the dimethyl ketal thereof, substituted thioxanthones, for example 2-chlorothioxanfhone, anthraquinones, esters of phenylglyoxylic acid, 2-benzoyl-2-phenyl-l,3-dioxolanes and 4-benzoyl-4-phenyl-l,3-dioxolanes and also photoredox systems consisting of a mixture of a phenothiazine dye (for example methylene blue) or a quinoxaline (for example a metal salt of 2-(m-or p-methoxyphenyl)-quinoxaline-6'- or 7'-sulfonic acid) together with an electron donor, such as benzene sulfmic acid or another sulfϊnic acid or a salt thereof, for example, the sodium salt, or an arsine, a phosphine or thiourea. α- Aminoacetophenone derivatives, for example, 2-methyl-l-[4-(methylthio)- phenyl]-2-morpholinopropan-l-one, are also suitable photoinitiators. Preferred photoinitiators are benzil dimethyl ketal, 1 -hydroxycyclohexyl phenyl ketone and 2-methyl- 1 -[4-(methylthio)-phenyl]-2-moφholinopropan- 1 -one. In general, about 0.15 to 10% by weight, preferably about 2.5 to 5 percent by weight, of photoinitiator are added, relative to the total weight of the imides according to the invention and of the other compounds containing unsaturated groups which may, if appropriate, be present in the mixture.

The photopolymerized composition can be further cured by heating. A cured polymeric material can be produced by heating a polymeric material prepared by photopolymerization of a composition of the invention until it is cured. The temperature at which heat curing is effected and heating times may vary according to the use of the composition. In general, the photopolymerized composition is heated at a temperature of 70° to 300°C, usually for 10 minutes to 6 hours. When used in the production of laminates, for example, the photopolymerised composition is usually heated at 180° to 300°C, preferably 200° to 270°C, normally for 1 to 4 hours. When used in image formation, the photopolymerized composition may, if desired, be heat cured, usually by heating at a temperature of 80° to 120°C, normally for 5 minutes to 1 hour. The invention also provides a process for the preparation of a cured polymeric material which comprises heating a composition of the invention until it is cured. In such a direct heat-curing process, the composition is usually heated at 70° to 300°C, preferably 180° to 300°C, more preferably 200° to 270° C. It can be advantageous to carry out heat cure initially at a temperature at the lower end of this range, followed by subsequent heating at one or more higher temperatures within the range. When a cured material having maximum physical strength is required, the heat cure may be carried out for durations up to 24 hours. Cure time can be reduced by including an initiator in the composition.

The bisimides of the present invention can be homopolymerized or copolymerized in various manners. By heating above 200°C the bycyclic system undergoes a retro Diels Alder Reaction to yield cyclopentadiene and maleimide oligomer. The cyclopentadiene and maleimide oligomer then copolymerize through free radical copolymerization.

The bisimides according to the invention and compositions of matter containing them constitute low-melting, solid resins to viscous, liquid resins and are distinguished by high reactivity and good mechanical properties in the products thus cured, such as good flexural strength and impact strength. Products obtained in this manner have high glass transition temperatures and very good resistance to heat and, in addition, are also not brittle. The bisimides and compositions of matter according to the invention can also be applied readily from the melt, in particular without adding solvents of low volatility, for example for impregnating glass fibre, carbon fibre or aramide fibre fabrics, such as fiber fabrics composed of the poly-(l,4-phenylene terephthalamides) known under the tradename KEVLAR.

Another preferred field of application for the imides according to the invention is their use as matrix resins for composites. The invention therefore also relates to the use of the imides of the formula I for the preparation of prepregs and to a process for the preparation of prepregs, which comprises impregnating a fibrous material with an imide of the formula I or with a mixture containing an imide of the formula I and then exposing the impregnated material to actinic radiation, so that the imide or the mixture containing an imide is solidified by photopolymerization and becomes essentially tack-free, but still remains crosslinkable by heat. The bisimides according to the invention and compositions of matter containing them can be used in a versatile manner, for example as laminating resins or electrical resins, as high-temperature adhesives or for the production of coatings or mouldings. They are very particularly suitable for the preparation of prepregs and heat-resistant composite materials.

Example 1

Preparation ofN,N'-3,3'-dimethyl- dicyclohexylmethane-bis-(^'bicvclo 2.2.1]hept-5-ene-2.3-dicarboximide)

To a 500 ml flask replaced with nitrogen, 150 grams (approx. 1.74 mole) of bicyclo[2.2.1.]hept-5-ene-2,3-dicarboxylic acid anhydride and 200 ml of xylene are charged. To the mixture is added 50 grams (approx. 0.38 mole) of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane over 30 minutes with heating and stirring while refluxing xylene. The reaction is continued for four hours while separating and removing water produced by the reaction by a water separator. A trace amount of solid residue is separated by filtration and the solvent, xylene, is removed by distillation. The contents of the flask is treated with heat at 200°C under reduced pressure of 1 Torr for 1.5 hours while stirring, and 109 grams (0.37 mole) of N,N'-3,3'-dimethyl- dicyclohexylmethane- bis-(bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) dicarboximide is obtained. This is a yield of 97% based on the amine. Example 2

A bisimide prepared according to Example 1 is degassed at 200°C in vacuo and poured into a mould preheated to 200°C, of dimensions 120x120x4 mm. The mouldings are cured at 200°C for 3 hours, at 220°C for 3 hours and at 250°C for 6 hours. After cooling, the sheets are cut into test bars. The physical properties of the resulting bars are excellent.

Example 3

One hundred parts by weight of N,N'-3,3'-dimethyl- dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) is melted at 150°C and 4-tert-butyl- 1 ,2-dihydroxy-benzene (0.05 part) is added followed by 20 parts of 1 ,4-butanediol dimethacrylate to give a resinous syrup, whose viscosity is measured at 25°C, 40°C, or 80°C. The syrup is poured into 150x150x4 mm steel moulds having their surface treated with a silicone release agent. The moulds are degassed and cure is then effected by heating for 2 hours at 200°C, 2 hours at 225°C and 12 hours at 250°C to give hard plates of excellent quality. These plates are sawn to give test bars for physical property measurements.

The above description is provided for the purpose of describing embodiments of the invention and is not intended to limit the scope of the invention in any way. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims

What is claimed is:

A compound of the formula I

in which

R¹ and R² are independently hydrogen, (C C₇)-alkyl, (C₂-C₇)-alkenyl, or (C₂-C₇)-alkynyl;

Z is (C₁-C₁₂)-alkylene; (C₂-C₁₂)-alkenylene; D-E-F, where D and F are independently (C,-C₁₂)-alkylene or (C₂-C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C,-C₁₂)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C,-C₇)-alkyl; N-(C₂-C₇)-alkenyl; N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C C₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C C₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)-alkyl or (C₂-C₇)-alkenyl.

2. A compound of claim 1 , wherein Y¹ and Y² are identical.

3. A compound of claim 1, wherein Y¹ and Y² are cyclohexylene monosubstituted by methyl.

4. A compound of claim 1 , wherein Y¹ and Y² are cyclohexylene.

5. A compound of claim 1 , wherein Y¹ and Y² are cyclohexenylene.

6. A compound of claim 1, wherein Z is -CH₂-.

7. A compound of claim 1, wherein Z is (C_rC₁₂)-alkylene or (C₂-C₁₂)-alkenylene.

8. A compound of claim 1 , wherein X¹ and X² are not present, Y¹ and Y² are cyclohexylene monosubstituted by methyl, and Z is -CH₂-.

9. A compound of claim 1, wherein the compound is N,N'-3,3'- dimethyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3- dicarboximide).

10. A compound of claim 1 , wherein the compound is N,N'-3,3'- dicarboxyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3- dicarboximide).

11. A polymer produced by polymerizing or copolymerizing the compound of claim 1.

12. A polymer of claim 11, wherein the polymer is a polyimide, a polyester, or a polyimide ester.

13. A polymer of claim 11 , wherein in the compound of claim 1 , X¹ and X² are not present, Y¹ and Y² are cyclohexylene monosubstituted by methyl, and Z is -CH₂-.

14. A polymer of claim 11, wherein the compound of claim 1 is

N,N'-3,3'-dimethyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3- dicarboximide).

15. A polymer of claim 11 , wherein the compound of claim 1 is N,N'-3,3'-dicarboxyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3- dicarboximide).

16. A polymer comprising units of the compound of claim 1.

17. A polymer of claim 16, wherein the polymer is polyimide, a polyester, or a polyimide ester.

18. A polymer of claim 16, wherein in the compound of claim 1 , X¹ and X² are not present, Y¹ and Y² are cyclohexylene monosubstituted by methyl, and Z is -CH₂-.

19. A polymer of claim 16, wherein the compound of claim 1 is

20. A polymer of claim 16, wherein the compound of claim 1 is N,N'-3,3'-dicarboxyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3- dicarboximide).

21. A process for making the compound of claim 1 , wherein

is reacted with H₂N-X¹-Y¹-Z-Y²-X²-NH₂, in which

R¹ and R² are independently hydrogen, (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or (C₂-C₇)-alkynyl

X¹ and X² can be present or absent, and if present are independently (C,-C₇)-alkylene or (C₂-C₇)-alkenylene;

Y¹ and Y² are independently (C₄-C₈)-cycloalkylene or (C₄-C₈)- cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C C₇)-alkyl, (C₂-C₇)-alkenyl, or carboxyl; and

Z is (C,-C₁₂)-alkylene; (C₂-C₁₂)-alkenylene; D-E-F, where D and F are independently (C_rC₁₂)-alkylene or (C₂-C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C,-C_]2)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C_rC₇)-alkyl; N-(C₂-C₇)-alkenyl;

N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C,-C₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)-alkyl or (C₂-C₇)-alkenyl.

22. A process of claim 21 , wherein in the compound of claim 1,

X¹ and X² are not present, Y'and Y² are cyclohexylene monosubstituted by methyl, and Z is -CH₂-.

23. A process of claim 21, wherein the compound of claim 1 is N,N'- 3,3'-dimethyl-dicyclohexylmethane-bis-(bicyclo[2.2.1]hept-5-ene-2,3- dicarboximide).

24. A compound of the formula II

Y¹ and Y² are independently (C₄-C₈)-cycloalkylene or (C₄-C₈)- cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or carboxyl; and Z is (C,-C₁₂)-alkylene; (C₂-C₁₂)-alkenylene; D-E-F, where D and F are independently (C,-C₁₂)-alkylene or (C₂-C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C,-C_I2)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C,-C₇)-alkyl; N-(C₂-C₇)-alkenyl; N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C,-C₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)-alkyl or (C₂-C₇)-alkenyl.

25. A compound of the formula III

H₂N-X¹-Y^,-Z-Y²-X²-NH₂ (III)

X¹ and X² can be independently present or absent, and if present are independently (C_rC₇)-alkylene or (C₂-C₇)-alkenylene; Y¹ and Y² are independently (C₄-C₈)-cycloalkylene or (C₄-C₈)- cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C_rC₇)-alkyl, (C₂-C₇)-alkenyl, or carboxyl; and

Z is (C,-C₁₂)-alkylene; (C₂-C₁₂)-alkenylene; D-E-F, where D and F are independently (C,-C₁₂)-alkylene or (C₂-C₁₂)-alkenylene, and E is (C₄-C₈)- cycloalkylene or (C₄-C₈)-cycloalkenylene, which are unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)- alkyl or (C₂-C₇)-alkenyl; or G-H-I, where G and I are independently (C C₁₂)- alkylene or (C₂-C₁₂)-alkenylene, and H is N-(C,-C₇)-alkyl; N-(C₂-C₇)-alkenyl; N-(C₄-C₈)-cycloalkyl or N-(C₄-C₈)-cycloalkenyl, which are unsubstituted or substituted by up to four identical or different radicals selected from (C₁-C₇)- alkyl or (C₂-C₇)-alkenyl; or N-(C_rC₇)-alkyl-( C₄-C₈)-cycloalkyl, which is unsubstituted or substituted by up to four identical or different radicals selected from (C,-C₇)-alkyl or (C₂-C₇)-alkenyl, wherein Y¹ and Y² are not cyclohexylene.