CA1246584A - Substituted, unsaturated, bicyclic imides and polymers thereof - Google Patents
Substituted, unsaturated, bicyclic imides and polymers thereofInfo
- Publication number
- CA1246584A CA1246584A CA000473017A CA473017A CA1246584A CA 1246584 A CA1246584 A CA 1246584A CA 000473017 A CA000473017 A CA 000473017A CA 473017 A CA473017 A CA 473017A CA 1246584 A CA1246584 A CA 1246584A
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- Prior art keywords
- formula
- atoms
- group
- allyl
- imide
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/72—4,7-Endo-alkylene-iso-indoles
- C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
-
- 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
- C08G73/122—Preparatory processes from unsaturated precursors and polyamines containing chain terminating or branching agents
-
- 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
- C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
Abstract
Substituted, unsaturated, bicyclic imides and polymers thereof Abstract Imides of the formula I
(I) in which E is allyl or methallyl and n is 1 or 2 and, if n is 1, R is hydrogen, alkyl having 1-12 C atoms, alkenyl having 3-6 C atoms, cycloalkyl having 5-8 C atoms, aryl having 6-10 C atoms or benzyl, or, if n is 2, R is -CmH2m-in which m is 2-20, arylene having 6-10 C atoms or a group of the formula II
(I) in which E is allyl or methallyl and n is 1 or 2 and, if n is 1, R is hydrogen, alkyl having 1-12 C atoms, alkenyl having 3-6 C atoms, cycloalkyl having 5-8 C atoms, aryl having 6-10 C atoms or benzyl, or, if n is 2, R is -CmH2m-in which m is 2-20, arylene having 6-10 C atoms or a group of the formula II
Description
~;~4~;S~3~
3-14753 /1 ~2 Substituted, unsaturated, bicyclic imides and polymers thereof __ The invent;on relates to allyl-substituted or methallyl-subst;tuted methylbicyclo~2~2.1]hept-5-ene-2,3-dicarboximides, to their preparation and to the polymerswhich can be obtained therefrom by heating.
Maleim;des and bismaleimides and also N-allylmono-maleimides are known~
The curing of halogenated, olefinic rubber polymers by means of selected polymaleimide compounds, such as N,N -m-phenylene-bismaleimide, is described in U.S. Patent 3,334,075.
These polymaleimides do not contain any allyl or norbornenyl groups, and the male;m;de radicals do not carry any sub-stituents.
~esin-form;ng compositions containing maleimide or bismaleimide derivatives, such as N-phenylmaleimide and methylene-bis-(N-phenylmaleimide), are known from ~ritish Patent 1,277,790. ~lone of these compounds contains norbor-nenyl or allyl groups.
A process for the preparation of bismaleimides by reacting a bismaleamic acid w;th the anhydrlde of a lower carboxylic acid in the presence of a tertiary amine, an organic solvent and a nickel catalyst is described in U.S.
Patent 3,839,3S8. A process for the preparation of mono-25 maleim;des and bismaleimides containing aliphatic substituents on the nitrogen atom is known from U.S. Patent 4,229,351.
The preparation of compounds containing allyl-substituted and methyl-substituted norbornenyl groups is not described or suggested either in the former or in the latter patent.
~9 iL2465~34 Z
U~S. Patent 3,450,711 relates to bisimide compounds prepared by reacting endo-cis-bicycloC2.2.1~hept-5-ene-2,3-dicarboxylic anhydride t= 5-norbornene-Z,3-dicarboxylic anhydride) with selected organic diamines. These bisimides do not contain either methyl or allyl substituents in the imide radical and are distinguished from the present com-pounds both by their structure and by thleir chemical reac-tivity. The compounds according to this U.S. patent are used as intermediates in the preparation of epoxide compounds.
It is also known that it is possible to prepare poly-irnide oligomers which are used as adhesives by addition of 3,3'~4,4'-benzophenonetetracarboxylic dianhydride onto d;amino diphenylmethane ;n the presence of various compounds capable of causing crossl;nk;ng and end group masking, such as chlori-nated or unchlorinated 5-norbornenecarboxylic anhydride and 5-vinylphthal;c anhydride Ccf., for example, Polym. Eng. Sci., 22, 9-14 t1982)]. These polyimide oligomers do not contain __ any allyl groups.
Silanes prepared from imide intermediates including, for example, N-allyl-Z,3-dimethylmaleimide, are described in U.S. Patent 4,271,074. The monomers according to the inven-tion do not contain any norbornenyl group which is substituted by an allyl group and a methyl group, and are therefore entirely different in structure and are not suggested by this patent.
The preparation of the starting materials for the compounds according to the invention is described ;n U.S.
Patent 3,105,839.
The allyl-substituted or methallyl-substituted methyl-b;cycloC2.2.1]hept-5-ene-Z,3-dicarboximides according to the ;nvention are valuable start;ng materials for polymers which have excellent properties. They are characterised by formula I below:
~24658~
¦ ~ ~ L ~ R (I) in wh;ch E is allyl or methallyl and n is 1 or 2 and, ;f n i5 1, R is hydrogen, alkyl having 1-12 C atomsO alkenyl having 3-6 C atoms, cycloalkyl having 5-8 C atoms~ aryl having 6-10 C
atoms or benzyl, or, if n is 2, R ;s -CmH2m- ;n which m is
3-14753 /1 ~2 Substituted, unsaturated, bicyclic imides and polymers thereof __ The invent;on relates to allyl-substituted or methallyl-subst;tuted methylbicyclo~2~2.1]hept-5-ene-2,3-dicarboximides, to their preparation and to the polymerswhich can be obtained therefrom by heating.
Maleim;des and bismaleimides and also N-allylmono-maleimides are known~
The curing of halogenated, olefinic rubber polymers by means of selected polymaleimide compounds, such as N,N -m-phenylene-bismaleimide, is described in U.S. Patent 3,334,075.
These polymaleimides do not contain any allyl or norbornenyl groups, and the male;m;de radicals do not carry any sub-stituents.
~esin-form;ng compositions containing maleimide or bismaleimide derivatives, such as N-phenylmaleimide and methylene-bis-(N-phenylmaleimide), are known from ~ritish Patent 1,277,790. ~lone of these compounds contains norbor-nenyl or allyl groups.
A process for the preparation of bismaleimides by reacting a bismaleamic acid w;th the anhydrlde of a lower carboxylic acid in the presence of a tertiary amine, an organic solvent and a nickel catalyst is described in U.S.
Patent 3,839,3S8. A process for the preparation of mono-25 maleim;des and bismaleimides containing aliphatic substituents on the nitrogen atom is known from U.S. Patent 4,229,351.
The preparation of compounds containing allyl-substituted and methyl-substituted norbornenyl groups is not described or suggested either in the former or in the latter patent.
~9 iL2465~34 Z
U~S. Patent 3,450,711 relates to bisimide compounds prepared by reacting endo-cis-bicycloC2.2.1~hept-5-ene-2,3-dicarboxylic anhydride t= 5-norbornene-Z,3-dicarboxylic anhydride) with selected organic diamines. These bisimides do not contain either methyl or allyl substituents in the imide radical and are distinguished from the present com-pounds both by their structure and by thleir chemical reac-tivity. The compounds according to this U.S. patent are used as intermediates in the preparation of epoxide compounds.
It is also known that it is possible to prepare poly-irnide oligomers which are used as adhesives by addition of 3,3'~4,4'-benzophenonetetracarboxylic dianhydride onto d;amino diphenylmethane ;n the presence of various compounds capable of causing crossl;nk;ng and end group masking, such as chlori-nated or unchlorinated 5-norbornenecarboxylic anhydride and 5-vinylphthal;c anhydride Ccf., for example, Polym. Eng. Sci., 22, 9-14 t1982)]. These polyimide oligomers do not contain __ any allyl groups.
Silanes prepared from imide intermediates including, for example, N-allyl-Z,3-dimethylmaleimide, are described in U.S. Patent 4,271,074. The monomers according to the inven-tion do not contain any norbornenyl group which is substituted by an allyl group and a methyl group, and are therefore entirely different in structure and are not suggested by this patent.
The preparation of the starting materials for the compounds according to the invention is described ;n U.S.
Patent 3,105,839.
The allyl-substituted or methallyl-substituted methyl-b;cycloC2.2.1]hept-5-ene-Z,3-dicarboximides according to the ;nvention are valuable start;ng materials for polymers which have excellent properties. They are characterised by formula I below:
~24658~
¦ ~ ~ L ~ R (I) in wh;ch E is allyl or methallyl and n is 1 or 2 and, ;f n i5 1, R is hydrogen, alkyl having 1-12 C atomsO alkenyl having 3-6 C atoms, cycloalkyl having 5-8 C atoms~ aryl having 6-10 C
atoms or benzyl, or, if n is 2, R ;s -CmH2m- ;n which m is
2-20, arylene having 6-10 C atoms or a group of the formuLa II
-T-~
~ 5~
in wh;ch T is methylene, isopropylidene, C0, 0, S or S02.
E is preferably the allyl group.
R can be a linear or branched-chain alkyl group hav;ng 1 12 C atoms, such as methyL, ethyl, isopropyl, n-butyl, isopentyl, n-hexyl, 2-ethylhexyl, n-decyl and n dodecyl, pre-ferably alkyl having 1-8 C atoms.
R can also be a linear or branched-chain alkenyl group having 3-6 C atoms, such as allyl, methallyl, 2-butenyl and 3-hexenyl, preferably allyl.
As a cycloalkyl group, R can be a cyclopentyl, cyclo-hexyl, cycloheptyl or cyclooctyl group~ preferably cyclohexyl.
As an aryl group, R can be unsubstituted phenyl or a zn phenyl group which ;s subst;tuted by one or two methyl groups, such as tolyl or xylyl, or naphthyl too. The phenyl group is preferred. As a group -CmH2m-, R can be a linear or branched rad;cal, such as ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene and dodecamethy-lene. As a group of the formula II, R is preferably attachedto the N atoms in the 4~4'-pos;tion.
R ;s preferably a group -(CH2)rn_ in which m is Z to 12.
~24~
As an arylene group having 6-10 C atoms, R can be, for example, an m-phenylene, p-phenylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene or 2,6-naphthylene group.
If R is a group of the formula II, T is preferably the methylene group, 0 or S02.
Preferred compounds of the formula I are those in which, if n is 1, R is hydrogen, alkyl having 1-~ C atoms, cyclohexyl, allyl or phenyl, or, if n is 2, R is -~CHz)6-or a group of the formula II in which T is the methylene group or S02O
Compounds of the formula I which are particularly preferred are those in which n is the number 2 and R is -(CH2)6~ CH2 \ _ ~ or -~ -S02--~
Compounds of the formula I which are very particu-larly preferred are those in which E is the allyl group and,if n is 1, R is allyl, or, if n is 2, R is -(CH2)6- or -CH2- ~
The imides according to the invention can be prepared in a manner known per se, for example by reacting an anhydride of the formula III
o
-T-~
~ 5~
in wh;ch T is methylene, isopropylidene, C0, 0, S or S02.
E is preferably the allyl group.
R can be a linear or branched-chain alkyl group hav;ng 1 12 C atoms, such as methyL, ethyl, isopropyl, n-butyl, isopentyl, n-hexyl, 2-ethylhexyl, n-decyl and n dodecyl, pre-ferably alkyl having 1-8 C atoms.
R can also be a linear or branched-chain alkenyl group having 3-6 C atoms, such as allyl, methallyl, 2-butenyl and 3-hexenyl, preferably allyl.
As a cycloalkyl group, R can be a cyclopentyl, cyclo-hexyl, cycloheptyl or cyclooctyl group~ preferably cyclohexyl.
As an aryl group, R can be unsubstituted phenyl or a zn phenyl group which ;s subst;tuted by one or two methyl groups, such as tolyl or xylyl, or naphthyl too. The phenyl group is preferred. As a group -CmH2m-, R can be a linear or branched rad;cal, such as ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene and dodecamethy-lene. As a group of the formula II, R is preferably attachedto the N atoms in the 4~4'-pos;tion.
R ;s preferably a group -(CH2)rn_ in which m is Z to 12.
~24~
As an arylene group having 6-10 C atoms, R can be, for example, an m-phenylene, p-phenylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene or 2,6-naphthylene group.
If R is a group of the formula II, T is preferably the methylene group, 0 or S02.
Preferred compounds of the formula I are those in which, if n is 1, R is hydrogen, alkyl having 1-~ C atoms, cyclohexyl, allyl or phenyl, or, if n is 2, R is -~CHz)6-or a group of the formula II in which T is the methylene group or S02O
Compounds of the formula I which are particularly preferred are those in which n is the number 2 and R is -(CH2)6~ CH2 \ _ ~ or -~ -S02--~
Compounds of the formula I which are very particu-larly preferred are those in which E is the allyl group and,if n is 1, R is allyl, or, if n is 2, R is -(CH2)6- or -CH2- ~
The imides according to the invention can be prepared in a manner known per se, for example by reacting an anhydride of the formula III
o
3 \X ~ ~C~ ( I I I ) ~!,! /
O
with a compound of the formula IV
~H2N)n R ~IV) ;n which E, R and n are as defined under formula I, at an elevated temperature and with removal by distillation c,f the water formed in the reaction. If the compounds bf the formula IV are ammonia or low-boiling monoamines, an excess of these reactants is advisable. It is advantageous to employ ~465~3~
diamines 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 the azeotropic removal of the water (entraining agent). The temperature of the reaction can be between 100 and 250C. The imides of the formula I
are preferably prepared in the melt under a pressure of not more than 4~500 Pa and at temperatures between 130 and 220C, in particular 180 and 220r~.
As already mentioned, the starting materials of the formula III can be prepared in accordance with the process described in U.S. Patent Specification 3,105,839 by react;ng sodium methylcyclopentadienide with an allyl or methallyl halide, foLlowed by a Diels-Alder reaction with maleic anhydride. Although it is stated in the U.S. Patent Specification that the allyl group is attached in the 7-position of the bicyclic system, recent investiga~ions show that an isomeric m;xture is formed in respect of the position of the allyl group (;n the 1-position and the 6-position) and also in respect of the endo-configuration and exo-configuration of the anhydride moiety. Hitherto it has only been possible to isolate the isomeric components by preparative gas chroma-tography.
The monoamines or diamines of the formula IV which are used are known or can be prepared by processes known per se.
The compounds according to the invention are liquid, or low-melting solid substances which can be polymerised to give solid products having high glass transition points and good resistance to heat and water. These products can be used for many purposes, for example as casting resins or adhesives and, in particular, for the preparation of glass fibre-reinforced or carbon fibre-reinforced plastics and heat-resistant composite materials, and as electrical insulating materials and whirl-sintered powder paints.
The compounds according to the invention can be used and polymerised without further treatment, or they can first be dissolved in an organic solvent, such as toluene, xylene, ~Z4~58~
- b -methyL ethyL ketone, ethylene glycol monoalkyl and dialkyl ethers having 1-4 C atoms ;n the alkyl groups or a similar solvent, ~ustomary in the paint industry. Solutions of this type can be used as ;mpregnating agents or coating agents or as a form of dispatch to the consumer.
The compounds, according to the ;nvention, of the formula I can be reacted to give novel poLymers, and, sur-pr;singly, the methyl substituent hardly impairs the capac-ity of the allylnorbornene system for polymerisation~
Accordingly, the ;nvent;on also relates to the novel poly-mers which can be obtained by heating an imide of the formula I at a temperature between 180 and 300C, prefer ably between 200 and 250C, for 6 to 60 hours. In th;s respect, what has been stated above applies in respect of the preFerred meanings of E, R and n. Polymers which are particularLy preferred are those wh;ch can be obtained by heating an imide of the formula I in which n is the number 2 and R is the group -(C~2~6~ / 2 ~ / -u~ SO -~,=. .=. ~,=. =--.
at 200 to 250C for 6-2h hours.
It is~ of course, possible to add inert and stable substances, such as fillers, pigments, dyes and other addi-tives, to the imides of the formula I before they are poly-merised to give crosslinked structures.
PREPARATION EXAMPLES
Example 1: Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicar-box;mide.
A mixture of 30 9 of allylmethylbicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic anhydride, prepared in accor-dance with Example 2 of UuS. Patent Specification 3,105,839, and 10.2 9 of 25 % aqueous ammonia solution is heated at 100-108 ~ for 2.5 hours, with stirring and reflux cooling.
According to a gas chromatogram, this gives a mixture of Ç;5~34 - 6a -12 isomers having varying positions for the allyl group and the methyl group in the 1-, 4-, 5- and 6-positions in the bicycLoheptene ring, and also exo-anhydr;des and endo-anhydrides. Since this - -.. :
~246S~
mixture of isomers cannot be separated by fractional dis-tillation, it is used for further purposes as such. ~Jater is then removed by distillation, excess ammonia is expelled and the imide is rectified at 14û-145C and 2.0 Pa.
21.5 g of a mixture o~ isomers of allylmethylbicyclo-C2.2.1]hept-5-enedicarboxylic acid 2,3-imide are obtained, corresponding to a yield of 71.3% of theory. The imide is a yellow syrup and has a viscosity of 96.18 mPa.s at 80C.
Analysis % C % H % N
calculated for C13H15N2 71.87 6.96 6.45 found 71.41 6.94 6.42 IR spectru~:
1639.2 cm 1 cyclic double bond 1653.4 cm~1 allyl group 1708.9 cm~1 carbonyl group 177~0 cm~1 carbonyl ;n the cyclic imide 3210.3 cm 1 NH vibrat;on Polymerisation for 48 hours at 250C gives a solid having a gl3ss transition temperature (6TT) of 125C. The IR
spectrum contains no absorption bands for ~C=C double bonds (1639.2 and 1653.4 cm~1) ExampLe 2: AllylmethylbicycloC2.2.1]hept-5-ene-2,3-__ _ d;carboxylic acid N-allylimide.
A mixture of 30 g of allylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 9.41 9 of allylamine is heated at reflux temperature for 2 hours, water is removed by distillation, and the product is rectified at 119~127C and 2.66 Pa. This gives 30.24 g (85.5% of theory) of a pale yellow oil having the follow;ng characteristic data:
n20 = 1.5202, ~25 = 0.135 Pa.s.
Analysis % C % H % N
calculated for C16H19N2 74.68 7.84 5.44 found 74.66 7.55 5.22 Polymerisation for 48 hours at 250C gives a solid having a GTT > 250C and an IR spectrum which shows no C=C absorption frequéncies (1639.2 and 1653.4 cm~1).
658~
Example_3. AllylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic acid N-(2-ethylhexyl)-imide.
30 9 of anhydride are reacted with 21.3 9 of 2-ethyl-hexylamine as described in Example 2 above. Distillation at 3.3 Pa gives~ between 149 and 162C, 40.74 9 of a yellow oil (90% of theory) having a refractive index n20 = 1.5090 and a viscosity of 0.306 Pa.s at 25C.
Analysis % C % H % N
calculated for Cz1H31NO2 76.55 9.48 ~.52 found 76.32 9.48 4.16 Polymerisation for 40 hours at 250C gives a solid having a GTT of 128C. The IR bands for double bonds at 1639.2 and 1653.4 cm 1 can no longer be detected.
Example 4-. AllylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic acid N-phenylimide.
3û g of anhydride are reacted with 15.4 9 of aniline as described in Example 2. The anilide is distilled between 161 and 165C at 6.65 Pa to give 23.2 g ~57.5% of theory) of a viscous liquid having a viscosity of 4.2 Pa.s at 40C
and a refractive index n2D0 = 1.5647 at 20C
Analysis % C % H % N
calculated for C1gH19N02 77.79 6.53 4.77 found 77.92 6.46 4.68 Polymerisation for 48 hours at 250C gives a solid having a GTT of 132.5C and an IR spectrum which has no \C=C
absorption frequencies (1639.2 and 1653.4 cm~1).
Example 5: N,N'-Hexamethylene-bis-(allylmethylbicyclo~2.2.1]-hept-5-ene-2,3-dicarboximide) 300 9 of allylmethylbicycloC2.2.1]hept-5-ene-2r3-dicarboxylic anhydride are taken and heated to 130C, and 7~.9 9 of melted hexamethylene diamine are added dropwise, with stirring. Water is removed by dis~illation, the temperature is raised to 180C and the pressure is reduced to 53 Pa. 180C and 53 Pa are maintained for 15 minutes. This gives 345 9 t97% of theory) of a brown, v;scous res;n hav;ng a viscosity of 1.356 Pa.s at 80C.
~6S~
Analysis % C % H % N
calculated for C32H40N2~4 7.80 5.42 found 73.8Z 7.74 5.47 Example 6: Bis-C4-(allylmethylbicyclo~2.2.1]hept-S~ene-2,3-dicarboximidophenyl)]-methane ¦ ~ ~ \C0 ~ ~ ~ / 2 \ _ / \
H2C=CH-CH2 ' CH2-CH=CH2 300 9 of anhydride and 136.2 9 of 4,4'-diaminodiphenyl-methane are reacted as described in Example 5. This gives 403.2 9 (98.0% of theory) of a dark brown solid res;n having a glass transit;on temperature of 66C.
Analysis: % C X H X N
calculated for C39H38N24 78.24 6.40 4.68 found: 78.41 6.49 4.68 Example 7: Bis-C4-(methallylmethylbicycloC2.2.1~hept-5-ene-____ 2,3-d;carboximidophenyl~] sulfone N C l~ / 2 \ _ / \C0/ ~ ~ ~3 124.15 9 of 4,4'-diaminodiphenyl sulfone and 232 9 of methallylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride are heated to 180C~ and the pressure is reduced in stages to 25 Pa~ After 90 minutes at 180C and 25 Pa, 319.55 9 of a brown solid resin having a glass transition temperature of 87C are obtained.
Analysis: % C % H % N % S
calculated for C40H40N206S 70.98 5.96 4.14 4.74 found: 69O98 5.91 4.35 4.98 ~2~6~84 The anhydride is prepared analogously to Examples 1 and 2 of U.S. Patent Specification 3,105,839. 994 9 of methallyl chloride are used instead of 840 9 of allyl chloride. The anhydride, which has not hitherto been des-cribed in the literature, distills at 125-140C and 25 Pa, and has n20 = 1.508 and a viscosity of 195 mPaOs.
Example 8. 8is-[4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2~3-dicarboximidophenyL~ methane ~ CH2 ~
116 9 of methallylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 49.5 g of 4,4'-dialninodiphenyl-methane are heated to 200C, with stirring, in an atmosphere of N2. 9 cm3 of water are distilled off. In the course of ` 35 minutes at 2~0C the glass transition temperature rises from 67.5 to 78.5C. Yield 155 9 (99% of theory)O
Analys;s: % C % H % N
calculated for C41H42~l24 78.57 6.75 4.47 found: 77.41 6.71 4.39 _ mple 9: Allylmethylb;cyclo~2.2.1~hept-5-ene-2,3-d;carboxylic acid N-cyclohexylimide.
A mixture of 20 9 of allylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 9.09 g of cyclohexylamine ;s heated at 135C for 3 hours, and the product is then dist;lled in vacuo. 16 9 of a yellow, v;scous oil d;still over between 128 and 138C at 2.5 Pa, corresponding to a yield of 58.2%.
Analysis: % C % H % N
calculated for C1gH2sN02: 76.25 8.36 4.68 found: 76.46 8.52 4.38 -30 Thermal polymerisation for 48 hours at 250C gives a solid resin having a glass transition temperature of 72.5C.
:~246584~
~ 11 -The molecule of the compounds according to the inven-tion contains two or more olefinic double bonds which make them capable of polymerisation. Crosslinked polymers having valuable physicaL properties are obtained on heating, cf.
Examples 1-4.
U _ EXAMPLES_ _ Example I
The imide prepared in accordance with Example 5 is poured, in the form of a hot, low-viscosity melt, into a steel mould measuring 12 x 12 x 0.4 cm and cured for 3 hours at 200, 3 hours at 225 and 12 hours at 250C. After cooling, test rods are cut from the sheet. The follo~ing properties are measured on these:
Flexural strength as specified in DIN 53,452: 81.5 N/mm2 Deflection as specif;ed in DIN 53,452: 5.2 mm Impact strength as specified in DIN 53,455: 13.2 kJ/m2 Glass transition temperature ~TA 2000 made by Mettler) 201C
Water absorpt;on (1 hour/100C) 0.48æ
20 TensiLe shear strength on Anticorodal as specified in DIN 53,Z83 9.9 N/mm2 Example II
The imide resin prepared in accordance with Example 6 is melted, poured into a steel mould measuring 12 x 12 X 0.4 cm and cured for 3 hours at 200, 3 hours at 225 and 12 hours at 250C. After cooling, the plate is cut into test rods, on which the following properties are measured:
Flexural strength as specified in DIN 53,452: 95 N/mm2 Deflection as specified in DIN 53,452: 4~5 mm Impact strength as specified in DIN 53,455: 9.5 kJ/m2 Glass transition temperature (TA 20D0 made by Mettler) 192C
Water absorption (1 hour/100C): OD35%
Tens;le shear strength on Anticorodal as specified in DIN 53,283: 7.6 N/mm2 The following properties were measured on a test sheet (12 X 12 X 0.2 cm):
~L24~;5~4 Volume resistivity (DIN 53,432) 5.0 x 1016 cm Dissipation factor (DIN 53,483) 0.25%
Dielectric constant (DIN 53,483) 3.2 Example III:
After curing for 24 hours at 250C, the resin pre-pared in accordance with Example 7 has a glass transi~ion temperature >250C and a tensile shear strength on Anticorodal as speci-fied in DIN 53,283 o~f 9.5 N/mm2.
O
with a compound of the formula IV
~H2N)n R ~IV) ;n which E, R and n are as defined under formula I, at an elevated temperature and with removal by distillation c,f the water formed in the reaction. If the compounds bf the formula IV are ammonia or low-boiling monoamines, an excess of these reactants is advisable. It is advantageous to employ ~465~3~
diamines 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 the azeotropic removal of the water (entraining agent). The temperature of the reaction can be between 100 and 250C. The imides of the formula I
are preferably prepared in the melt under a pressure of not more than 4~500 Pa and at temperatures between 130 and 220C, in particular 180 and 220r~.
As already mentioned, the starting materials of the formula III can be prepared in accordance with the process described in U.S. Patent Specification 3,105,839 by react;ng sodium methylcyclopentadienide with an allyl or methallyl halide, foLlowed by a Diels-Alder reaction with maleic anhydride. Although it is stated in the U.S. Patent Specification that the allyl group is attached in the 7-position of the bicyclic system, recent investiga~ions show that an isomeric m;xture is formed in respect of the position of the allyl group (;n the 1-position and the 6-position) and also in respect of the endo-configuration and exo-configuration of the anhydride moiety. Hitherto it has only been possible to isolate the isomeric components by preparative gas chroma-tography.
The monoamines or diamines of the formula IV which are used are known or can be prepared by processes known per se.
The compounds according to the invention are liquid, or low-melting solid substances which can be polymerised to give solid products having high glass transition points and good resistance to heat and water. These products can be used for many purposes, for example as casting resins or adhesives and, in particular, for the preparation of glass fibre-reinforced or carbon fibre-reinforced plastics and heat-resistant composite materials, and as electrical insulating materials and whirl-sintered powder paints.
The compounds according to the invention can be used and polymerised without further treatment, or they can first be dissolved in an organic solvent, such as toluene, xylene, ~Z4~58~
- b -methyL ethyL ketone, ethylene glycol monoalkyl and dialkyl ethers having 1-4 C atoms ;n the alkyl groups or a similar solvent, ~ustomary in the paint industry. Solutions of this type can be used as ;mpregnating agents or coating agents or as a form of dispatch to the consumer.
The compounds, according to the ;nvention, of the formula I can be reacted to give novel poLymers, and, sur-pr;singly, the methyl substituent hardly impairs the capac-ity of the allylnorbornene system for polymerisation~
Accordingly, the ;nvent;on also relates to the novel poly-mers which can be obtained by heating an imide of the formula I at a temperature between 180 and 300C, prefer ably between 200 and 250C, for 6 to 60 hours. In th;s respect, what has been stated above applies in respect of the preFerred meanings of E, R and n. Polymers which are particularLy preferred are those wh;ch can be obtained by heating an imide of the formula I in which n is the number 2 and R is the group -(C~2~6~ / 2 ~ / -u~ SO -~,=. .=. ~,=. =--.
at 200 to 250C for 6-2h hours.
It is~ of course, possible to add inert and stable substances, such as fillers, pigments, dyes and other addi-tives, to the imides of the formula I before they are poly-merised to give crosslinked structures.
PREPARATION EXAMPLES
Example 1: Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicar-box;mide.
A mixture of 30 9 of allylmethylbicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic anhydride, prepared in accor-dance with Example 2 of UuS. Patent Specification 3,105,839, and 10.2 9 of 25 % aqueous ammonia solution is heated at 100-108 ~ for 2.5 hours, with stirring and reflux cooling.
According to a gas chromatogram, this gives a mixture of Ç;5~34 - 6a -12 isomers having varying positions for the allyl group and the methyl group in the 1-, 4-, 5- and 6-positions in the bicycLoheptene ring, and also exo-anhydr;des and endo-anhydrides. Since this - -.. :
~246S~
mixture of isomers cannot be separated by fractional dis-tillation, it is used for further purposes as such. ~Jater is then removed by distillation, excess ammonia is expelled and the imide is rectified at 14û-145C and 2.0 Pa.
21.5 g of a mixture o~ isomers of allylmethylbicyclo-C2.2.1]hept-5-enedicarboxylic acid 2,3-imide are obtained, corresponding to a yield of 71.3% of theory. The imide is a yellow syrup and has a viscosity of 96.18 mPa.s at 80C.
Analysis % C % H % N
calculated for C13H15N2 71.87 6.96 6.45 found 71.41 6.94 6.42 IR spectru~:
1639.2 cm 1 cyclic double bond 1653.4 cm~1 allyl group 1708.9 cm~1 carbonyl group 177~0 cm~1 carbonyl ;n the cyclic imide 3210.3 cm 1 NH vibrat;on Polymerisation for 48 hours at 250C gives a solid having a gl3ss transition temperature (6TT) of 125C. The IR
spectrum contains no absorption bands for ~C=C double bonds (1639.2 and 1653.4 cm~1) ExampLe 2: AllylmethylbicycloC2.2.1]hept-5-ene-2,3-__ _ d;carboxylic acid N-allylimide.
A mixture of 30 g of allylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 9.41 9 of allylamine is heated at reflux temperature for 2 hours, water is removed by distillation, and the product is rectified at 119~127C and 2.66 Pa. This gives 30.24 g (85.5% of theory) of a pale yellow oil having the follow;ng characteristic data:
n20 = 1.5202, ~25 = 0.135 Pa.s.
Analysis % C % H % N
calculated for C16H19N2 74.68 7.84 5.44 found 74.66 7.55 5.22 Polymerisation for 48 hours at 250C gives a solid having a GTT > 250C and an IR spectrum which shows no C=C absorption frequéncies (1639.2 and 1653.4 cm~1).
658~
Example_3. AllylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic acid N-(2-ethylhexyl)-imide.
30 9 of anhydride are reacted with 21.3 9 of 2-ethyl-hexylamine as described in Example 2 above. Distillation at 3.3 Pa gives~ between 149 and 162C, 40.74 9 of a yellow oil (90% of theory) having a refractive index n20 = 1.5090 and a viscosity of 0.306 Pa.s at 25C.
Analysis % C % H % N
calculated for Cz1H31NO2 76.55 9.48 ~.52 found 76.32 9.48 4.16 Polymerisation for 40 hours at 250C gives a solid having a GTT of 128C. The IR bands for double bonds at 1639.2 and 1653.4 cm 1 can no longer be detected.
Example 4-. AllylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic acid N-phenylimide.
3û g of anhydride are reacted with 15.4 9 of aniline as described in Example 2. The anilide is distilled between 161 and 165C at 6.65 Pa to give 23.2 g ~57.5% of theory) of a viscous liquid having a viscosity of 4.2 Pa.s at 40C
and a refractive index n2D0 = 1.5647 at 20C
Analysis % C % H % N
calculated for C1gH19N02 77.79 6.53 4.77 found 77.92 6.46 4.68 Polymerisation for 48 hours at 250C gives a solid having a GTT of 132.5C and an IR spectrum which has no \C=C
absorption frequencies (1639.2 and 1653.4 cm~1).
Example 5: N,N'-Hexamethylene-bis-(allylmethylbicyclo~2.2.1]-hept-5-ene-2,3-dicarboximide) 300 9 of allylmethylbicycloC2.2.1]hept-5-ene-2r3-dicarboxylic anhydride are taken and heated to 130C, and 7~.9 9 of melted hexamethylene diamine are added dropwise, with stirring. Water is removed by dis~illation, the temperature is raised to 180C and the pressure is reduced to 53 Pa. 180C and 53 Pa are maintained for 15 minutes. This gives 345 9 t97% of theory) of a brown, v;scous res;n hav;ng a viscosity of 1.356 Pa.s at 80C.
~6S~
Analysis % C % H % N
calculated for C32H40N2~4 7.80 5.42 found 73.8Z 7.74 5.47 Example 6: Bis-C4-(allylmethylbicyclo~2.2.1]hept-S~ene-2,3-dicarboximidophenyl)]-methane ¦ ~ ~ \C0 ~ ~ ~ / 2 \ _ / \
H2C=CH-CH2 ' CH2-CH=CH2 300 9 of anhydride and 136.2 9 of 4,4'-diaminodiphenyl-methane are reacted as described in Example 5. This gives 403.2 9 (98.0% of theory) of a dark brown solid res;n having a glass transit;on temperature of 66C.
Analysis: % C X H X N
calculated for C39H38N24 78.24 6.40 4.68 found: 78.41 6.49 4.68 Example 7: Bis-C4-(methallylmethylbicycloC2.2.1~hept-5-ene-____ 2,3-d;carboximidophenyl~] sulfone N C l~ / 2 \ _ / \C0/ ~ ~ ~3 124.15 9 of 4,4'-diaminodiphenyl sulfone and 232 9 of methallylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride are heated to 180C~ and the pressure is reduced in stages to 25 Pa~ After 90 minutes at 180C and 25 Pa, 319.55 9 of a brown solid resin having a glass transition temperature of 87C are obtained.
Analysis: % C % H % N % S
calculated for C40H40N206S 70.98 5.96 4.14 4.74 found: 69O98 5.91 4.35 4.98 ~2~6~84 The anhydride is prepared analogously to Examples 1 and 2 of U.S. Patent Specification 3,105,839. 994 9 of methallyl chloride are used instead of 840 9 of allyl chloride. The anhydride, which has not hitherto been des-cribed in the literature, distills at 125-140C and 25 Pa, and has n20 = 1.508 and a viscosity of 195 mPaOs.
Example 8. 8is-[4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2~3-dicarboximidophenyL~ methane ~ CH2 ~
116 9 of methallylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 49.5 g of 4,4'-dialninodiphenyl-methane are heated to 200C, with stirring, in an atmosphere of N2. 9 cm3 of water are distilled off. In the course of ` 35 minutes at 2~0C the glass transition temperature rises from 67.5 to 78.5C. Yield 155 9 (99% of theory)O
Analys;s: % C % H % N
calculated for C41H42~l24 78.57 6.75 4.47 found: 77.41 6.71 4.39 _ mple 9: Allylmethylb;cyclo~2.2.1~hept-5-ene-2,3-d;carboxylic acid N-cyclohexylimide.
A mixture of 20 9 of allylmethylbicycloC2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 9.09 g of cyclohexylamine ;s heated at 135C for 3 hours, and the product is then dist;lled in vacuo. 16 9 of a yellow, v;scous oil d;still over between 128 and 138C at 2.5 Pa, corresponding to a yield of 58.2%.
Analysis: % C % H % N
calculated for C1gH2sN02: 76.25 8.36 4.68 found: 76.46 8.52 4.38 -30 Thermal polymerisation for 48 hours at 250C gives a solid resin having a glass transition temperature of 72.5C.
:~246584~
~ 11 -The molecule of the compounds according to the inven-tion contains two or more olefinic double bonds which make them capable of polymerisation. Crosslinked polymers having valuable physicaL properties are obtained on heating, cf.
Examples 1-4.
U _ EXAMPLES_ _ Example I
The imide prepared in accordance with Example 5 is poured, in the form of a hot, low-viscosity melt, into a steel mould measuring 12 x 12 x 0.4 cm and cured for 3 hours at 200, 3 hours at 225 and 12 hours at 250C. After cooling, test rods are cut from the sheet. The follo~ing properties are measured on these:
Flexural strength as specified in DIN 53,452: 81.5 N/mm2 Deflection as specif;ed in DIN 53,452: 5.2 mm Impact strength as specified in DIN 53,455: 13.2 kJ/m2 Glass transition temperature ~TA 2000 made by Mettler) 201C
Water absorpt;on (1 hour/100C) 0.48æ
20 TensiLe shear strength on Anticorodal as specified in DIN 53,Z83 9.9 N/mm2 Example II
The imide resin prepared in accordance with Example 6 is melted, poured into a steel mould measuring 12 x 12 X 0.4 cm and cured for 3 hours at 200, 3 hours at 225 and 12 hours at 250C. After cooling, the plate is cut into test rods, on which the following properties are measured:
Flexural strength as specified in DIN 53,452: 95 N/mm2 Deflection as specified in DIN 53,452: 4~5 mm Impact strength as specified in DIN 53,455: 9.5 kJ/m2 Glass transition temperature (TA 20D0 made by Mettler) 192C
Water absorption (1 hour/100C): OD35%
Tens;le shear strength on Anticorodal as specified in DIN 53,283: 7.6 N/mm2 The following properties were measured on a test sheet (12 X 12 X 0.2 cm):
~L24~;5~4 Volume resistivity (DIN 53,432) 5.0 x 1016 cm Dissipation factor (DIN 53,483) 0.25%
Dielectric constant (DIN 53,483) 3.2 Example III:
After curing for 24 hours at 250C, the resin pre-pared in accordance with Example 7 has a glass transi~ion temperature >250C and a tensile shear strength on Anticorodal as speci-fied in DIN 53,283 o~f 9.5 N/mm2.
Claims (8)
1. An imide of the formula I
(I) in which E is allyl or methallyl and n is 1 or 2 and, if n is 1, R is hydrogen, alkyl having 1-12 C atoms, alkenyl having 3-6 C atoms, cycloalkyl having 5-8 C atoms, aryl having 6-10 C atoms or benzyl, or, if n is 2, R is -CmH2m- in which m is 2-20, arylene having 6-10 C atoms or a group of the formula II
(II) in which T is methylene, isopropylidene, CO, O, S or SO2.
(I) in which E is allyl or methallyl and n is 1 or 2 and, if n is 1, R is hydrogen, alkyl having 1-12 C atoms, alkenyl having 3-6 C atoms, cycloalkyl having 5-8 C atoms, aryl having 6-10 C atoms or benzyl, or, if n is 2, R is -CmH2m- in which m is 2-20, arylene having 6-10 C atoms or a group of the formula II
(II) in which T is methylene, isopropylidene, CO, O, S or SO2.
2. An imide of the formula I, according to claim 1, in which E is the allyl group.
3. An imide of the formula I, according to claim 1, in which, if n is 1, R is hydrogen, alkyl having 1-8 C atoms, cyclohexyl, allyl or phenyl, or, if n is 2, R is -(CH2)6-or a group of the formula II
(II) in which T is the methylene group or SO2.
(II) in which T is the methylene group or SO2.
4. An imide of the formula I, according to claim 1, in which n is the number 2 and R is -(CH2)6-,
5. An imide of the formula I, according to claim 1, in in which E is the allyl group and, if n is 1, R is allyl or, if n is 2, R is -(CH2)6- or
6. A process for the preparation of an imide of the formula I, according to claim 1, which comprises reacting an anhydride of the formula III
(III) with a compound of the formula IV
(IV) at an elevated temperature and with removal by distillation of the water formed in the reaction, E, R and n being as defined in claim 1.
(III) with a compound of the formula IV
(IV) at an elevated temperature and with removal by distillation of the water formed in the reaction, E, R and n being as defined in claim 1.
7. A polymer obtainable by heating an imide of the formula I, according to claim 1, at a temperature between 180 and 300°C for 6 to 60 hours.
8. A polymer according to claim 7, wherein a compound of the formula I in which n is the number 2 and R is -(CH2)6-, is heated at 200 to 250°C for 6 to 24 hours.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH45084 | 1984-01-31 | ||
| CH450/84-9 | 1984-10-05 | ||
| CH479684 | 1984-10-05 | ||
| CH4796/84-0 | 1984-10-05 |
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| Publication Number | Publication Date |
|---|---|
| CA1246584A true CA1246584A (en) | 1988-12-13 |
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ID=25684610
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000473017A Expired CA1246584A (en) | 1984-01-31 | 1985-01-29 | Substituted, unsaturated, bicyclic imides and polymers thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US4604437A (en) |
| EP (1) | EP0152372B1 (en) |
| JP (1) | JPH0611757B2 (en) |
| BR (1) | BR8500407A (en) |
| CA (1) | CA1246584A (en) |
| DE (1) | DE3584982D1 (en) |
Families Citing this family (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
| US5155206A (en) * | 1987-09-03 | 1992-10-13 | The Boeing Company | Crosslinkable polyamideimide oligomers and a method of preparation |
| US5367083A (en) * | 1987-09-03 | 1994-11-22 | The Boeing Company | Extended acid halide capping monomers |
| US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
| US5116935A (en) * | 1987-05-04 | 1992-05-26 | The Boeing Company | Polyimide oligomers and blends and method of curing |
| US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
| US5216117A (en) * | 1987-09-03 | 1993-06-01 | The Boeing Company | Amideimide blends |
| US5516876A (en) | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
| US5210213A (en) * | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
| US5521014A (en) | 1981-11-13 | 1996-05-28 | The Boeing Company | Extended multidimensional ether or ester oligomers |
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US5104967A (en) * | 1987-09-03 | 1992-04-14 | The Boeing Company | Amideimide oligomers and blends |
| US4851495A (en) * | 1987-02-20 | 1989-07-25 | The Boeing Company | Polyetherimide oligomer |
| US5286811A (en) * | 1983-09-27 | 1994-02-15 | The Boeing Company | Blended polyimide oligomers and method of curing polyimides |
| US5175234A (en) * | 1983-09-27 | 1992-12-29 | The Boeing Company | Lightly crosslinked polyimides |
| DE3479510D1 (en) * | 1984-01-31 | 1989-09-28 | Ciba Geigy Ag | Process for preparing cross-linked polymers by cationic polymerisation of unsaturated bicyclic imides |
| US4728742A (en) * | 1984-06-27 | 1988-03-01 | Ciba-Geigy Corporation | Substituted, unsaturated, bicyclic imides containing hydroxyl groups, and polymers thereof |
| US5082905A (en) * | 1984-09-18 | 1992-01-21 | The Boeing Company | Blended heterocycles |
| US4868270A (en) * | 1986-08-04 | 1989-09-19 | The Boeing Company | Heterocycle sulfone oligomers and blends |
| US5120819A (en) * | 1984-09-18 | 1992-06-09 | Boeing Company | High performance heterocycles |
| US4709047A (en) * | 1985-01-29 | 1987-11-24 | Ciba-Geigy Corporation | Substituted unsaturated, sulfonyloxy group-containing bicyclic imides as catalysts for cationic polymerization |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| US5610317A (en) | 1985-09-05 | 1997-03-11 | The Boeing Company | Multiple chemically functional end cap monomers |
| US4847333A (en) * | 1985-09-30 | 1989-07-11 | The Boeing Company | Blended polyamide oligomers |
| US5151487A (en) * | 1985-09-30 | 1992-09-29 | The Boeing Company | Method of preparing a crosslinking oligomer |
| US4985568A (en) * | 1985-09-30 | 1991-01-15 | The Boeing Company | Method of making crosslinking imidophenylamines |
| DE3679883D1 (en) * | 1985-10-25 | 1991-07-25 | Ciba Geigy Ag | TRISIMIDES OF ALLYL- OR METHALLYL-SUBSTITUTED BICYCLO (2.2.1) HEPT-5-EN-2,3-DICARBONIC ACID IMIDES AND THEIR USE. |
| GB8628003D0 (en) * | 1986-11-22 | 1986-12-31 | Ciba Geigy Ag | Polymerisable compounds |
| EP0272210A3 (en) * | 1986-12-08 | 1988-07-27 | Ciba-Geigy Ag | (Poly)oxaalkylene-alpha-, omega-bisimides of allyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acids, and their use |
| US5268519A (en) * | 1987-02-20 | 1993-12-07 | The Boeing Company | Lightly crosslinked etherimide oligomers |
| US5144000A (en) * | 1987-02-20 | 1992-09-01 | The Boeing Company | Method for forming crosslinking polyetherimide oligomers |
| US5175304A (en) * | 1987-02-20 | 1992-12-29 | The Boeing Company | Halo- or nitro-intermediates useful for synthesizing etherimides |
| US4876328A (en) * | 1987-05-18 | 1989-10-24 | The Boeing Company | Polyamide composition |
| EP0292434B1 (en) * | 1987-05-22 | 1992-07-08 | Ciba-Geigy Ag | Unsaturated bisimides and their polymers |
| US5109105A (en) * | 1987-06-12 | 1992-04-28 | The Boeing Company | Polyamide oligomers |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| DE58906877D1 (en) * | 1988-09-02 | 1994-03-17 | Ciba Geigy | Bisimides of allyl or methallyl bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid. |
| EP0376884A3 (en) * | 1988-12-21 | 1991-06-05 | Ciba-Geigy Ag | Pourable granulate |
| US5120823A (en) * | 1989-02-17 | 1992-06-09 | Basf Aktiengesellschaft | Toughened thermosetting structural materials |
| US5075456A (en) * | 1989-03-07 | 1991-12-24 | Ciba-Geigy Corporation | Substituted, unsaturated, bireactive bicycle imides and the use thereof |
| GB8924143D0 (en) * | 1989-10-26 | 1989-12-13 | Ciba Geigy | Novel oligomers |
| EP0504109A1 (en) * | 1991-03-11 | 1992-09-16 | Ciba-Geigy Ag | Aromatic monoanhydride-esters |
| US5191088A (en) * | 1991-03-11 | 1993-03-02 | Ciba-Geigy Corporation | Aromatic monoanhydride-esters |
| US5502207A (en) * | 1993-08-13 | 1996-03-26 | Maruzen Petrochemical Co., Ltd. | Alkenyl-substituted bisnadimides, process for manufacturing the same, process for curing the same, and adhesives and coating materials utilizing the same |
| JP3506395B2 (en) * | 1994-10-26 | 2004-03-15 | 丸善石油化学株式会社 | Thermosetting water-based emulsion |
| US5914385A (en) * | 1996-10-03 | 1999-06-22 | Mitsubishi Jukogyo Kabushiki Kaisha | Polyimide resin composition and method for producing prepreg and paint and method for curing resin using the same |
| CA2347837A1 (en) * | 1999-09-21 | 2001-03-29 | Jack Warren | Cycloalkyl bicycloheptene dicarboximides |
| US6521731B2 (en) * | 2001-02-07 | 2003-02-18 | Henkel Loctite Corporation | Radical polymerizable compositions containing polycyclic olefins |
| JP4030499B2 (en) * | 2003-01-22 | 2008-01-09 | セントラル硝子株式会社 | Glass fiber for rubber reinforcement |
| JP2009132668A (en) * | 2007-11-08 | 2009-06-18 | Dainippon Jochugiku Co Ltd | Effect-enhancing agent of incense stick for repelling mosquito or fly, and method for producing the same |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH407097A (en) * | 1960-12-16 | 1966-02-15 | Ciba Geigy | Process for the production of new dicarboxylic acid anhydrides |
| US3334075A (en) * | 1964-10-23 | 1967-08-01 | Exxon Research Engineering Co | Multimaleimide cure of halogenated isoolefin-multiolefin copolymers |
| US3450711A (en) * | 1965-07-01 | 1969-06-17 | American Cyanamid Co | Bis-imide containing diepoxide compounds |
| FR2020542A1 (en) * | 1968-09-27 | 1970-07-17 | Tokyo Shibaura Electric Co | |
| BE754723A (en) * | 1969-08-12 | 1971-02-11 | Rhone Poulenc Sa | PROCESS FOR PREPARING |
| FR2400014A1 (en) * | 1977-08-09 | 1979-03-09 | Rhone Poulenc Ind | PREPARATION OF OLIGOIMIDES |
| CH634558A5 (en) * | 1978-04-06 | 1983-02-15 | Ciba Geigy Ag | METHOD FOR PRODUCING ALIPHATIC N-SUBSTITUTED MALEINIMIDES. |
| CH641470A5 (en) * | 1978-08-30 | 1984-02-29 | Ciba Geigy Ag | SILANES CONTAINING IMID GROUPS. |
| JPS56103162A (en) * | 1980-01-21 | 1981-08-18 | Hitachi Ltd | Ether-imide and its preparation |
| US4515962A (en) * | 1982-08-05 | 1985-05-07 | Ciba Geigy Corporation | Allyl or methallyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imides and bisimides |
| JPS6071067A (en) * | 1983-09-27 | 1985-04-22 | Dainippon Toryo Co Ltd | Method for coating multi-color pattern |
| US4579916A (en) * | 1983-11-15 | 1986-04-01 | Ciba-Geigy Corporation | Curable mixtures containing an epoxide resin, an imide and a curing catalyst |
| EP0175648B1 (en) * | 1984-09-14 | 1991-05-22 | Ciba-Geigy Ag | Heat-hardenable compositions containing a polymaleinimide and a bicyclo[2.2.1]heptene-5-2,3-dicarboximide, and their use |
-
1985
- 1985-01-22 US US06/693,640 patent/US4604437A/en not_active Expired - Fee Related
- 1985-01-25 EP EP85810024A patent/EP0152372B1/en not_active Expired - Lifetime
- 1985-01-25 DE DE8585810024T patent/DE3584982D1/en not_active Expired - Lifetime
- 1985-01-29 CA CA000473017A patent/CA1246584A/en not_active Expired
- 1985-01-30 BR BR8500407A patent/BR8500407A/en unknown
- 1985-01-31 JP JP60017706A patent/JPH0611757B2/en not_active Expired - Lifetime
-
1986
- 1986-04-17 US US06/853,265 patent/US4742166A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0152372A2 (en) | 1985-08-21 |
| US4604437A (en) | 1986-08-05 |
| DE3584982D1 (en) | 1992-02-06 |
| JPS60178862A (en) | 1985-09-12 |
| EP0152372A3 (en) | 1988-04-27 |
| BR8500407A (en) | 1985-09-10 |
| JPH0611757B2 (en) | 1994-02-16 |
| US4742166A (en) | 1988-05-03 |
| EP0152372B1 (en) | 1991-12-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |