CA1036747A - Soluble polyimides derived from phenylindane diamines and dianhydrides - Google Patents
Soluble polyimides derived from phenylindane diamines and dianhydridesInfo
- Publication number
- CA1036747A CA1036747A CA209,783A CA209783A CA1036747A CA 1036747 A CA1036747 A CA 1036747A CA 209783 A CA209783 A CA 209783A CA 1036747 A CA1036747 A CA 1036747A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
- C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
- C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Abstract
Abstract of the Disclosure Polyimides with phenylindane diamines and/or dianhydrides incorporated into the polyimide backbone have been found to b- soluble in high concentration in polar organic solvents. Solutions of the phenylindane polyimides are suitable as adhesives and as laminating, coating and impregnating resins.
Description
`` T}1i.5 inverltion relates to novel soluble polyimides t;hich are _haracteri2ed by a recurring unit having the following struc'ural formula:
~N ~ ~ Z \ N-Z' ~ I
wherein the four carbonyl groups are attached directly to separate carbon atoms, the carbonyl ~roups being oxtho or peri to each cther so that five or six membered imide rings are ~ormed respectively;
wherein Z is a tetravalent radical containing at least one aromatic ring; and wherein Z' is a divalent organic radical selected from aromatic, aliphatic, alkyl aromatic, cycloaliphatic, and heterocyclic radicals, combinations of these, and radicals with heteroa'om-containincJ bridgin~ groups where the heteroatom in the bridge is oxygen,-sulfur, nitrogen, siliGon or phosphorus, (1) pro~ided that out of the total number o~ polyimide recurring units ~A) 0 to 100 percent of such units have Z equal to a phenylindane radical of the structu_al formula II
Rl CH3 wherein Rl is hydrogen or an al~y]. group of from 1 to 5 carbon atoms, and ~
(B) 0 to 100 percent of such units have Z' equal to a phenylindane radical of the structural formula Rl R2 ~ R ~ R3 wherein Rl is hydrogen or an alkyl group of from 1 to 5 carbon atoms, and R2, R3, R4 and R5 are independently hydrogen, halogen or (lower) alkyl having 1 to 4 carbon atoms, and
~N ~ ~ Z \ N-Z' ~ I
wherein the four carbonyl groups are attached directly to separate carbon atoms, the carbonyl ~roups being oxtho or peri to each cther so that five or six membered imide rings are ~ormed respectively;
wherein Z is a tetravalent radical containing at least one aromatic ring; and wherein Z' is a divalent organic radical selected from aromatic, aliphatic, alkyl aromatic, cycloaliphatic, and heterocyclic radicals, combinations of these, and radicals with heteroa'om-containincJ bridgin~ groups where the heteroatom in the bridge is oxygen,-sulfur, nitrogen, siliGon or phosphorus, (1) pro~ided that out of the total number o~ polyimide recurring units ~A) 0 to 100 percent of such units have Z equal to a phenylindane radical of the structu_al formula II
Rl CH3 wherein Rl is hydrogen or an al~y]. group of from 1 to 5 carbon atoms, and ~
(B) 0 to 100 percent of such units have Z' equal to a phenylindane radical of the structural formula Rl R2 ~ R ~ R3 wherein Rl is hydrogen or an alkyl group of from 1 to 5 carbon atoms, and R2, R3, R4 and R5 are independently hydrogen, halogen or (lower) alkyl having 1 to 4 carbon atoms, and
(2) provided further that out of the total number of Z and Z' radical units, at least 10 percent are phenyl-indane radical units, and
(3) the polyamide acid, from which the soluble polyimide is produced, has an inherent viscosity of at least 0.1, measured at 25C
at a concentration of 0.5% by weight of the polymer in N,N-dimethylacetamide, N-methylpyrrolidone, or dimethylfoTmamide.
The polyimides are prepared by reacting an aromatic tetracarboxylic acid dianhydride of the formula O O
Il 11 /c\ /c \
O Z O
C/ \C
Il ll O O
wherein Z is as defined previously, with equimolar or about equimolar amounts of a diamine having the formula 1~)3~;747 H2N _ Z'--NH2 wherein Z' is as defined above, in an organic reaction medium which is a solvent for at least one of the reactants, preferably under substantially anhydrous conditions, at a temperature below 100C and preferably at 20C to 50C. The product of this reaction is a polyamide acid consisting of units having the formula:
~ HO ~ OH
_ - HN- C C -NH- Z' \ O 1' .
lo wherein Z and Z' are as defined above, s~id polyamide acid is then subsequently converted to the polyimide by methods which are well-known in the art.
The phenylindane diamine component of the novel soluble polyimide can consist of any combination of the isomeric or substituted isomeric diamino compounds repre-sented by formula III above. For example, the phenylindane diamine component can comprise from O to 100 % of 5-amino-` 1-(4'-aminophenyl)-1,3,3-trimethylindane in combination with from 100 to 0% of 6-amino-1-(4'-aminophenyl)-1,3,3-tri-methylindane.Further,either or both of these isomers can be substituted over the entire range from O to 100% by any of the substituted diamino isomers represented by 1036~47 lormula III wi~hcut impairing the novel soluble nature of these polyimides. Examples of such substituted diamino isomers are 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane, 5-amino-1-(4'-amino-Ar',Ar'-dichlorophenyl)-Ar,Ar-dichloro~1,3,3-trimethylindane, 6-amino-1-(4'-amino-Ar',Ar'-dichloro-phenyl)-Ar,~r-dichloro-1,3,3-trimethylindane, 4-amino-6-methyl-1-(3;-amino-4'-methylphenyl)-1,3,3-trimethyl-indane and Ar-amino-l-(Ar'-amino-2',4'-dimethylphenyl)-1,3,3,4,6-pentame~hylindane. The pre~ixes ~r and Ar' in the above formùlas indicate inde~inite positions for the given substituents in the phenyl rings.
Characteristic of the solubiliæing effect of the phenylindane diamlnes is their p~operty of impar~ing solubility to systems composed of aromatic dianhydrides and diamines through partial replacement of the diamine portion. ~lthough the prior art teaches aromatic polyimides are highly insoluble in organic solvents, it has been unexpectedly found that when as little as 20 mole percent of a diamine is replaced with a phenylindane diamine, a highly soluble polyimide is obtained. Thus, soluble polyimides are produced ~rom aromatic dianhydrides æuch as benzoDhenone tetrac2rboxylic acid dianhydride, pyromellitic dianhydride, etc. Such solubllizing effect may be less pronounced in the case of some difficultly soluble aromatic s~s~ems. However, in such systems, solubility can still be acnieved by further replacement 1`Q36~47 of the diamine portion; for example, by 50 to 100`mole percent replacement by a phenylindane diamine.
Among the phenylindane diamines of the formula III, those are preferrea in which Rl is hydrogen or methyl, R2 and R3 independently of one another axe hydrogen, methyl, chloro or bromo and R4 and R5 independently of one another are hydrogen, chloro or bromo. Moxe preferred phenylindane diamines of the formula III are those in which R is hydrogen or methyl, R2 and R3 independently of one another are hydrogen, methyl, chloro or b~omo, R4 and R5 inde-pendently of one another are hydrogen, chloro or bromo, and the amino groups are at positions 5, 6 or 7 and at positions 3' or 4'. Among the phenylindane diamines of the formula III those are most preferred in which Rl is hydrogen or methyl, R2, R3, R4 and R5 are hydrogen, and the ~ino groups are at positions 5 or 6 and at position 4'.
The phenylindane diamines of this invention may be prepared by Y2rioUS synthetic routes. The most preferable method of preparation is through the acid-catalyzed dimerization of styrene or substituted styrenes to produce the given phenylindane. Then, by subsequent nitration and reduction of the phenylindanes, the phenylindane di~mines are produced. One method of achieving al~;yl substitution on the aromatic rings of the phenylindane diamines is by subjecting alkyl sub-stituted compounds such as benzaldehyde, acetophenoneand the like to a Grignard reaction, followed by water ~036~47 removal to produce the alkyl substituted styrene compound.
Dimerization, nitration and reduction can then be effected as mentioned above. Additionally, it has been found tha~
chlorine gas effects direct chlorine substitution on the aromatic rings of diamino-1,3,3-trimethyl~
phenylindane dihydrochloride to produce chlorinated diaminophenylindanes.
The group Z', as defined above, may be selected from alkylene groups containing from 2 to 12 carbon ~toms; cycloalkylene groups containing from 4 to 6 carbon atoms; a xylylene group, arylene group~
selected from ortho, meta or para phenylene, xylene, tolylene, biphenylene, naphthylene or anthrylene;
a substituted arylene group of the formula ~W~
wherein W is a covalent bond, ~ulfur, carbonyl, -NH, -N-(lower)alkyl, O, S, SS, -N-phenyl, sulfonyl, a linear or branched alkylene group O r from 1 to 3 carbon atoms;
arylene, especially phenylene group; or a dialkyl or diaryl silyl group; R6 and R7 are independent and each is hydrogen; halogen; especially chloro or bromo; lower alkyl from 1 to 5 carbon atoms, especially methyl; lower alkoxy containing from 1 to 5 carbon atoms, espe~ially methoxy: or aryl, especially phenyl ~, More prc~erably, Z' en~races groups which are derived ~rom the aromatic diamines disclosed in the i~mediately preceding paragraph. Most preferably, ~` is a group having the formula ~W~
wherein ~ is a covalent bond, methylene, sulfur, oxy~en, or sulfone, and R6 and R7 are independently hydrogen, halogen, or lower alkyl of from 1 to 5 carbon atoms, especially methyl, or a g:oup having the formula R8 ~
- wherein R8 is hydrogen, halogen or lower alkyl of from l~to 5 carbon atoms, especially methyl.
Among the n~n-phenylindane diamines that can be employed in the preparation of the polyimides of ~his invention are aromatic diamines as illustrated below:
at a concentration of 0.5% by weight of the polymer in N,N-dimethylacetamide, N-methylpyrrolidone, or dimethylfoTmamide.
The polyimides are prepared by reacting an aromatic tetracarboxylic acid dianhydride of the formula O O
Il 11 /c\ /c \
O Z O
C/ \C
Il ll O O
wherein Z is as defined previously, with equimolar or about equimolar amounts of a diamine having the formula 1~)3~;747 H2N _ Z'--NH2 wherein Z' is as defined above, in an organic reaction medium which is a solvent for at least one of the reactants, preferably under substantially anhydrous conditions, at a temperature below 100C and preferably at 20C to 50C. The product of this reaction is a polyamide acid consisting of units having the formula:
~ HO ~ OH
_ - HN- C C -NH- Z' \ O 1' .
lo wherein Z and Z' are as defined above, s~id polyamide acid is then subsequently converted to the polyimide by methods which are well-known in the art.
The phenylindane diamine component of the novel soluble polyimide can consist of any combination of the isomeric or substituted isomeric diamino compounds repre-sented by formula III above. For example, the phenylindane diamine component can comprise from O to 100 % of 5-amino-` 1-(4'-aminophenyl)-1,3,3-trimethylindane in combination with from 100 to 0% of 6-amino-1-(4'-aminophenyl)-1,3,3-tri-methylindane.Further,either or both of these isomers can be substituted over the entire range from O to 100% by any of the substituted diamino isomers represented by 1036~47 lormula III wi~hcut impairing the novel soluble nature of these polyimides. Examples of such substituted diamino isomers are 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane, 5-amino-1-(4'-amino-Ar',Ar'-dichlorophenyl)-Ar,Ar-dichloro~1,3,3-trimethylindane, 6-amino-1-(4'-amino-Ar',Ar'-dichloro-phenyl)-Ar,~r-dichloro-1,3,3-trimethylindane, 4-amino-6-methyl-1-(3;-amino-4'-methylphenyl)-1,3,3-trimethyl-indane and Ar-amino-l-(Ar'-amino-2',4'-dimethylphenyl)-1,3,3,4,6-pentame~hylindane. The pre~ixes ~r and Ar' in the above formùlas indicate inde~inite positions for the given substituents in the phenyl rings.
Characteristic of the solubiliæing effect of the phenylindane diamlnes is their p~operty of impar~ing solubility to systems composed of aromatic dianhydrides and diamines through partial replacement of the diamine portion. ~lthough the prior art teaches aromatic polyimides are highly insoluble in organic solvents, it has been unexpectedly found that when as little as 20 mole percent of a diamine is replaced with a phenylindane diamine, a highly soluble polyimide is obtained. Thus, soluble polyimides are produced ~rom aromatic dianhydrides æuch as benzoDhenone tetrac2rboxylic acid dianhydride, pyromellitic dianhydride, etc. Such solubllizing effect may be less pronounced in the case of some difficultly soluble aromatic s~s~ems. However, in such systems, solubility can still be acnieved by further replacement 1`Q36~47 of the diamine portion; for example, by 50 to 100`mole percent replacement by a phenylindane diamine.
Among the phenylindane diamines of the formula III, those are preferrea in which Rl is hydrogen or methyl, R2 and R3 independently of one another axe hydrogen, methyl, chloro or bromo and R4 and R5 independently of one another are hydrogen, chloro or bromo. Moxe preferred phenylindane diamines of the formula III are those in which R is hydrogen or methyl, R2 and R3 independently of one another are hydrogen, methyl, chloro or b~omo, R4 and R5 inde-pendently of one another are hydrogen, chloro or bromo, and the amino groups are at positions 5, 6 or 7 and at positions 3' or 4'. Among the phenylindane diamines of the formula III those are most preferred in which Rl is hydrogen or methyl, R2, R3, R4 and R5 are hydrogen, and the ~ino groups are at positions 5 or 6 and at position 4'.
The phenylindane diamines of this invention may be prepared by Y2rioUS synthetic routes. The most preferable method of preparation is through the acid-catalyzed dimerization of styrene or substituted styrenes to produce the given phenylindane. Then, by subsequent nitration and reduction of the phenylindanes, the phenylindane di~mines are produced. One method of achieving al~;yl substitution on the aromatic rings of the phenylindane diamines is by subjecting alkyl sub-stituted compounds such as benzaldehyde, acetophenoneand the like to a Grignard reaction, followed by water ~036~47 removal to produce the alkyl substituted styrene compound.
Dimerization, nitration and reduction can then be effected as mentioned above. Additionally, it has been found tha~
chlorine gas effects direct chlorine substitution on the aromatic rings of diamino-1,3,3-trimethyl~
phenylindane dihydrochloride to produce chlorinated diaminophenylindanes.
The group Z', as defined above, may be selected from alkylene groups containing from 2 to 12 carbon ~toms; cycloalkylene groups containing from 4 to 6 carbon atoms; a xylylene group, arylene group~
selected from ortho, meta or para phenylene, xylene, tolylene, biphenylene, naphthylene or anthrylene;
a substituted arylene group of the formula ~W~
wherein W is a covalent bond, ~ulfur, carbonyl, -NH, -N-(lower)alkyl, O, S, SS, -N-phenyl, sulfonyl, a linear or branched alkylene group O r from 1 to 3 carbon atoms;
arylene, especially phenylene group; or a dialkyl or diaryl silyl group; R6 and R7 are independent and each is hydrogen; halogen; especially chloro or bromo; lower alkyl from 1 to 5 carbon atoms, especially methyl; lower alkoxy containing from 1 to 5 carbon atoms, espe~ially methoxy: or aryl, especially phenyl ~, More prc~erably, Z' en~races groups which are derived ~rom the aromatic diamines disclosed in the i~mediately preceding paragraph. Most preferably, ~` is a group having the formula ~W~
wherein ~ is a covalent bond, methylene, sulfur, oxy~en, or sulfone, and R6 and R7 are independently hydrogen, halogen, or lower alkyl of from 1 to 5 carbon atoms, especially methyl, or a g:oup having the formula R8 ~
- wherein R8 is hydrogen, halogen or lower alkyl of from l~to 5 carbon atoms, especially methyl.
Among the n~n-phenylindane diamines that can be employed in the preparation of the polyimides of ~his invention are aromatic diamines as illustrated below:
4,4'-methylenebis(o-chloroaniline) 3,3'-dichlorobenzidine 3,3'-sulfonyldianiline .
4,4'-diaminobenæophenone 1,5-diaminonaphthalene bis(4-aminophenyl)diethyl silane bis(4-aminophenyl)diphenyl silane bis(4-aminophenyl)ethyl phosphine oxide N-{bis(4-aminophenyl3}N-methyl amine N-{bis(4-am-nophenyl)}N-phenyl amine 4,4'-me~hylenehis(2-methylaniline) 4,4'-methylenebis(2-methoxyaniline) ~036747
4,4'-diaminobenæophenone 1,5-diaminonaphthalene bis(4-aminophenyl)diethyl silane bis(4-aminophenyl)diphenyl silane bis(4-aminophenyl)ethyl phosphine oxide N-{bis(4-aminophenyl3}N-methyl amine N-{bis(4-am-nophenyl)}N-phenyl amine 4,4'-me~hylenehis(2-methylaniline) 4,4'-methylenebis(2-methoxyaniline) ~036747
5,5'-methylenebis(2-aminophenol) 4,4'-methylcnekis(2-methylaniline) 4,4'-oxybis(2-methoxyaniline) 4;4'-oxybis(2-chloroaniline) 5,5'-oxybis(2-a~inophenol) 4,4'-thiobis(2-methylaniline) 4,4'-thiobis(2-me~-hoxyaniline) 4,4'-thiobis(2-chloroaniline) 4,4'-sulonylbis(2-methylaniline) 4,4'-sulfonylbis(2-ethoxyaniline) 4,4'-sulfonylbis(2-chloroaniline) 5,5'-sulfonylbis(2-aminophenol) 3,3'-dimethyl-4,4'-diamino~enzophenone 3,3'-dimethoxy-4,4'-diaminobenzophenone 3,3'-dichloro-4,4'-diamino~enzophenone 4,4'-diaminobiphenyl m-phenylenediamine p-phenylenediamine 4,4'-methylenedianiline 4,4'-oxydianiline 4,4'-~hiodianiline 4,4'-sulfonyldianiline 4,4'-isopropylidenedianiline 3,3'-dimethylbenzidine 3,3'-dimethoxybenzidine 3,3'-dicarboxybenzidine diaminotoluene The phenylindane diannydride component of the novel soluble polyimides useful in this inventi.on has the formula Rl CH3 wherein Rl is hydrogen or an alkyl group of from 1 to 5 carbon atoms. Illustrative examples of such dian-hydrid~s are 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-5,6-dicarboxylic acid dianhydride 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-~,7-dicarboxylic àcid dianhydride 1-(3',4`-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic acid dianhydride 1-(3',4'-dicarboxyphenyl)-3-methylindane-
6,7-dicarboxylic acid dianhydride.
These phenylindane dianhydrides are conveniently prepared according to the procedures set forth in U.S.
3,577,442. The individual isomers of th~se dianhydrides can be employed in this invention as well as the ~ixed isomers. Where economy in production of the instant polyimides is of para~ount importance the mixed isomers are preferable. In the soluble polyimides of this in vention these phenylindane dianhydrides can be used in combination with the previously d`iscussed phenylindane diamines and also with the broad range of diamines previously disclosed. Furthermore, from an economy and performance standpoint, it may be advantageo-ls to replace a portion of the phenylindane dianhydride by other dian-hydrides of this invention. Thus, it is seen that the phenylindane dianhydrides, whether in combination with other dianhydrides or not, form novel soluble polyimides ~036~47 with the disclose~ diamincs of tl-is invention, t~nether or not there is any phenylindane diamine component in 'he polymeric structure. The only restriction on the com-position of t~e resulting polyimides is that there be sufficient phenylilldane moiety in the backbone, whether derived from phenylindane diamine or dianhydride, to give solubility to the resulting polyimide. Thus, in ef~ecting the solubility of an easily solubilized poly-imide, the phenylindane moiety can be a relatively minor component of the total diamine and dianhydride content, as for example, 10 to 30 mole percent of the total. On the other hand, in effecting the solubility of a difficultly solubilized polyimide the phenylindane moiety can be a m~re significant part of the total diamine and dianhydride con_ent, as for example, 30 to 75 mole percent of the total. In an advantageous embodiment of this invention, wherein no phenylindane diamine is present, the phenylindane tetracarboxylic acid dianhydride comprises from 50 to 100 and preferably 75 to 100 mole percent of the aromatic dianhydrides employed.
The other dianhydrides useful in this invention are characterized by the general formula C/ \C /
Il 11 O O
wherein the tetravalen~ rad cal z 10;~6~47 is as heretofore defined and m~y be selected from the following gcneral groups; aro~atic, aliphatic, cyclo-aliphatic, heterocyclic, co~binations of aromatic and aliphatic, and substituted groups thereof. The Z groups may be characterized by the following structures:
~N
~ ~ - Rg ~
wherein Rg is selected from the group consisting of ~1 I 10 11 1l ~10 -0-~ -S-~ -S02-~ -C-N-, -C-~ -C-O-~ -7- -si-Rlo llO IRlo Rlo R
-0~ 0-, O O -N=N-, -N=N-, ,, 7 ~ lo l lo -C-N-, -CH2~, -CH-, -C-, and phenylene, wherein Rll Rlo and Rll are alkyl or aryl, and substi~uted groups thereof.
The preferred aromatic dianhydrides are those in which the carbon atoms of each pair of carbonyl groups are directly attached to ortho carbon atoms in the Z
roup to p.ovide a five-membered ring as follows:
O ~ O O
!I 11 11 11 C--O--C C--O--c l l or ¦ ¦
--C C-- --C = C--I I
The following species axe typical of tetra-carboxylic acid dianhydrides suitable for practicing the invention: .
2,3,9,10-perylene.tetracarboxylic acid dianhydride 1,4,5,8-naphthalene tetracarboxylic acid dianhydride , 2,6-dichloronaphthalene-1,4,5,8-tetracar~oxylic acid dianhydride 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetra-carboxylic acid dianhydride phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride 2,3,3`,4'-benzophenonetetracarboxylic acid dianhydride pyromellitic dianhydridè
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride 3,3',4,4'-biphenyltetracarboxylic acid dianhydride 2,2',3,3'-biphenyltetracarboxylic acid dianhydride ~()3~747 4,4'~isopropylidenediphthali.c an~ydride 3,3'-isopropylidenediphthalic anhydride 4,4'-oxydiphthalic anhydride 4,4'-sulfonyldiphthalic anhydride 3,3'-oxydiphthalic anhydride 4,4'-methylenediphthalic anhydride 4,4'-thiodiphthalic anhydride 4,4'-ethylidenediphthalic anhydride 2,3,6,7-naphthalenetetracarboxylic acid dianhydride 1,2,4,5-naphthalenetetracarboxylic acid dianhydride 1,2,5,6-naphthalenetetracarboxylic acid dianhydride benzene-1,2,3,4-tetracarboxylic acid dia~hydride pyrazine-2,3,5,6-tetracarboxylic acid dianhydride - .
thiophene-2,3,4,5-tetracarboxylic acid dianhydride, and dianhydrides having the general structure:
Yll ~ - HC -~Cl - CH C
Q \ I f-Y2 Ç - HC \ C-Y CH-C
where Yl, Y2, Y3 and Y4 are each members selected lrom hydro~en, alkyl, aryl and aralkyl.
... ,, .... .. . . . . . , . . ~ .. .. . .. ... . .. . ... . .......... .. . . . .. .. . . . .
The most preferred non-phenylindane aromatic d;.anhydrides are pyromellitic dianhydride, and aromatic dianhydrides characterized by the general formula ~ ~ R12 ~, where R12 is carbonyl, methylene, oxygen or sulfonyl.
The polyimides produced according to this in-vention are characterized by useful solubility in certain organic solvents. Polyimides heretofore known to the art have generally been extre~ely insoluble, and have not been shapeable after conversion from the polyamide-acid state to the polyimide fo~m. The polyimides of the invention are e~t-emely useful in that they can be dissol~ed in certain solvents, in relatively high concentration, and the solutions can be employed for further fabrication of the polyimides. In this way, it is possible to produce polyimide films, coatings, laminates and the like withou' the necessity of using a polyamide-acid intermediate with a follow-on conversion step. This is highly advantageous, because it permits the application of polyimide coatings to articles which mi~ht be damaged by heating ox chemical conversion techniques heretofore necessary.
The soluble polyimides display excellent physical, chemical and electrical propert.ies which render them capable of being used as adhesive~s, laminating resins, especially for prin~ed circuit boards, fibe.s, coat-30 ings, especially for decorative and electrical purposes, ~036~47 films, ~lire ename's and molding compounds. Solution.s ofthe phenylindane polyimides of this invention can be used to impregnate reinforcing fi~ers and fabrics li~e glass, boron, metal oxide whiskers and graphite. These prepregs can then be cured to form rigid polyimide laminates or composites or to form s~rong thermally resistant structural adhesive bonds between aluminum, 8tainless steel, titanium or other metals.
These polyimides have very good solubili~y in common organic solvents. Examples of such organic solvents are the following:
N,N-dimethylformamide N,N-dimethylacetamide N-methyl-2-pyrrolidone N,N-diethylformamide .N,N-diethylacetamide N-methylcaprolactam dioxane dimethylsulfoxide tetramethylurea pyridine dimethylsulfone r hexamethylphosphoram de ~-tetramethylene sulfone formamide N-methylformamide ~-butyrolactone tetrahydrofuran m-cresol 2-methoxyethyl acetaie 1,2-dimethoxyethane ~Q36~47 bis(2-met~oYyethyl) ether chloroform nitrobenzene.
.
- The solvents can be used alone, in combinations of solvents, or in combination with poor solvents such as benzene, benzonitrile, xylene, toluene and cycloheY.ane.
More specifically, these polyimides have been found to be soluble up to more than 60% in these solvents.
The particular solubility achieved depends on various factors such as the nature of the solvent, the nature of the dianhydride and diamine employed and the extent of any replacement of the phenylindane diamines or dianhydrides of the invention by other diamines or dianhydrides. ~he ~olubilities attained are unique because the phenyl-indane moieties contained in the novel soluble po3y-imides are themselves aromatic in character and might be expected to impart to their polyimides the generally found characteristic of insolubility among aromatic polyimides. Thus, it is most unusual that these phenylindane diamines and dianhydrides can be reacted with aromatic dianhydrides and diamines to produce the instant soluble polyimides.
The unusually high solubility of the novel polyimides of this invention is not completely under-~tood. However, it appears that the cor~.on phenylindane inner structure of both the phenylindane diamines and dianhydrides herein disclosed, said inner structure being represented by the formula .. ~, .
Rl~ CH3 significantly contributes to this solubility. Evidence of this solubilizing activity can be seen from the effect which phenylindane in either its diamine or dianhydride form has on the solubilities of otherwise difficulty soluble aromatic dianhydrides. Pyromellitic dianhydride and 4,4'-methylenedianiline are well known examples of materials, which, in combination with conventional aromatic diamines and dianhydrides generally yield poorly soluble high molecular weight polyimides. Yet, when 5t5)-amino-1-(4'-aminoPhenYl)-1,3,3-trimethylindane is polymeri~ed with py_omellit c dianhydride a highly soluble polyimide results, e.g., solubility greater than 40 weight percent in dimethyl-foxmamide is afforded. Again, when 1-(~',4'-dicarboxy-phenyl)-1,3,3-trimethylindane-5,6(6,7)-dicarboxylic acid dianhydride is polymerized with 4,4'-methylene-dianiline a very sol~le polyimide results.
The polyimides are prepared by a process com-prising reactins the abGve described aromatic primary diamino compounds with dianhydrides in an organic reaction medium which is a solvent for at least one of the reactants, preferably under substantially anhydrous conditions, at a temperature below 100C and con-~036~47 veniently at roo~ temperature. The product of this reaction is a polyamide acid represented by the follo~ing formula:
/ HOC \ / COH
t t This polyamide acid has a molecular weight such that its inherent viscosity is at least 0.1, preferably 0.~-5Ø The inherent viscosity is measured at 25C at a concentration of 0.5% by weight of the polymer in a suitable solvent, e.g., N,N-dimethyl-acetamide, N-methylpyrrolidone, dimethylforr,amide, etc.
The polyamide acid is subsequent]y converted to the polyimide by several methods which include heating the polyamide acid soluticn at temperatures bet~een 100C and 240C depending on the boiling point of the organic solvent, until imidization is com?lete; by ohemical means, e.g., by adding to the polyamide acid solution a dehydrating agent such as acetic anhydride alone or in combination with a tertiary a~ine catalyst such as pyridine and opt onally heating or not heating the resulting solution at about 120C until imidization i~; colnplete.
1a36747 More specifically, the preparation of the poly-amide acid which is subsequently converted to the polyimide can be conveniently carried out in a number of ways. The diamines and dianhydrides can be pre-mixed as dry solids in equivalent amounts and the resulting mixture can be added, in small portions and with agitation, to~an organic solvent. Alternately, this order of addition can be reversed, i.e., after premixing the diamine and the dianhydride the solvent may be added to the mixture with agitation. It i~
also possible to dissolve the diamine in the solvent while agitating ar.d to add slotYly the aianhydride in portions that provide a controllable rate of reaction.
However, this order of addition can also be varied.
Still another process involves dissolving the diamine in one portion of a solvent and the dianhydriàe in another portion of the same or another solvent and then mixing the two solutions.
~ To effect the conversion of the polyamide acids to the polyimides, the polyamide acids are heated above 50C and preferably in an inert atmosphere and mo e pre~erably in an inert atmosphere between 110C and 240C.
In the preferred process, the polyamide acids are prepared at a temperature below 50C and maintained at this temperature until maximum viscosity is obtained denotin~ maximum polymerization. The polyamide acid in solution and under an inert atmosphere is subsequently heated to about 110C to 240C to convert the polyamide ~ Q3674`~
acid to the polyimide. The soluble polyimide may be alternatively prepared by mixing the diamine and the dianhydride at room temperature in a solvent such as rlitrobenzene and then rapidly heating the mixture to reflux for about 2 to 12 hours.
` The soluble polyimides can be precipitated from their solutions by use of methanol, water, acetone, spray drying and the like. The resulting granular material can be molded or redissolved in a suitable solvent to yield a film-forming or varnish type com-position. Other appropriate ingredients can be added to the polyimide solutions or molding po~ders including fillers, dyes, pigments, thermal stabilizers and rein-forcing agents, such as glass fiber, carbon, '~oron and the like, depending on the end use.
The polyimides from phenylindane diamines and dianhydriaes are further characterized by high glass transition temperatures (Tg). This makes it possible for the phenylindane polyimides to be used at higher temperatures than many prior art polyimides. Since at temperatures above the transition temperature the polymers lose their stiffness and mechanical properties, any increase in transition temperature is of great importance.
To further illustrate the nature of this invention and the process employed in preparing the ~oluble polyimides, the following examples are given below.
.
~036747 Manufacture of the Starting Compounds Example A: 5(6)-Amino-1-(4'-aminophenyl)-1,3,3-trimethYlindane (a) Preparation of 1,3,3-Trimethyl-l-phenylindane To 6.0 kg. of 62% sulfuric acid at 50C was ad~ed 1.0 kg. of -methyl-styrene over a 5 minute period. The mixture was refluxed (145C) for 20 hours.
After cooling, the lower acid phase was drawn off and discarded. The organic phase was washed with sulfuric acid several times and then with water several times.
The product was recrystallized from methanol which afforded 750 g of white crystals with a melting point of 50.5C-52.0C. The yield was 75~.
By essentially following the ~bove procedure and substitutir~g a,3,4-trimethylstyrene for a-m~thyl-styrene there is obtained a mixture of tetramethyl phenylindanes in 95~ yield.
~036~747 (b) Preparation of 5,4'-dinitro- and 6,4'-d itro-1,3,3-~rimeth~ er~ylil~d~ne isomers To a solution of 236 g (1.0 mole) 1,3,3-trimeth~ phenylindane (~-methylstyrene dimer) in 750 ml chloroform at 2-8C was added a pxeviously mixed solution of 396 ml sulfuric acid and 132 ml ` nitric acid dropwise over a 2.5 hour period. The two phase reaction mixture was allowed to stir an additional 4 hours at 5C. The chloroform phase W2S
isolated and washed with aqeuous sodium bicarbonate until neutral and then with distilled water. A light yellow oil was obtained after drying and stripping the chloroform solution. Two triturations in hexane at room temperature afforded 295 g light yellow powder, melting point 109-125. This material was shown to be a mixture of the 5,4'-dinitro- and 6,4'-dinitro-1,3,3-trimethyl-l-phenylindane isomers by N~.~ analysis.
~nalysis for C18H18N24:
% Calculated: C, 66.25; H, 5.55; N, 8.58 ~ Found: C, 66.13; H, 5.50; N, 8.42 ~S)36'-~'47 ~c) Pre~aration of 5(6)-~mino-1-(4'-amino-p_en~ l,3,3-tri.meth~lir.d~ne A mixture of 250 g (0.t67 mole) of the ~ini~ro isomers and 250 g (4.60 g - ator~ls) reduced iron powdar in 1 liter 50~ a~ueous ethanol ~as brought to reflux and a previously prepared solution of 60 ml con~entrated hydrocllloric acid in 403 ml 50% aqueous ethanol was added over a 1 hou~ period. Reflux was continued an additional 3 hours, the reaction cooled to 50 an~ 50 ml conce.ntrated hydrochloric aci~ added. The reaction mixture was filtered. The filtrate was made basic with 20~ NaOH and extracted with ether, dried and stripped under vacuum to afford 145 g (71%) of a clear brown glassy solid, melting pOillt 47-54. NMR analys.is indicated the product was 62~ 6-amino- and 38`o 5-a~ino-1-(4'-aminophenyl)-1,3,3-trimethylindane.
~nalysiS fo~ C18H22~2 % Calculated: C, 81~18; H, 8.32; N, 10.52 % Found~ C, 81.27; H, 8.20; ~, 10.48 ~036!747 Example B:
1-(3',4'-Dicarboxyphenyl)-1,3,3-trimethylindane-5,6(6,7)-dicarboxylacid dianhydride A mixture of dimers (70 ~, 0.24 mole) prepared from à,3,4-trimethylstyrene as in Example A (a) was dis-sol~ed in 800 ml pyridine and 600 ml water. At reflux 76~ g (4.8~1 moles) KMnO4 was added to the reaction over a 4 hour period along with an additional 1500 ml ~Jater.
`After refluxing for an additional 2 hours, the pyridine and water were almost entirely removed by distillation and the reaction mixture filtered to remov~ MnO2. The ~iltrate was acidified, extracted, stripped and dried to afford ~6.5 g (8S%) of a mixture of tetra-acids.
Dehydration wa~ accompiished at 200C at 100 ~m Hg and afforded an analytically pure s~ple of dianhydrides:
~nalYSis for C22H16o6 % Calculated: C, 70.21; H, 4.29 % ~ound: C, 70.05; H, 4.24 1036!747 Example C:
.
6-Amino-1-(4'-aminophenyl)-1,3,3-trimethylindane -To a mixture of 16.2 g (50 n~oles) 1~
carboxyphenyl)-1,3,3-trimethyl-fi-indane carboxylic acid in 400 ml chloroform and 60 ~1 conc. H2SO4 at 40C was added portion~ise ovex a 1/2 hour period,
These phenylindane dianhydrides are conveniently prepared according to the procedures set forth in U.S.
3,577,442. The individual isomers of th~se dianhydrides can be employed in this invention as well as the ~ixed isomers. Where economy in production of the instant polyimides is of para~ount importance the mixed isomers are preferable. In the soluble polyimides of this in vention these phenylindane dianhydrides can be used in combination with the previously d`iscussed phenylindane diamines and also with the broad range of diamines previously disclosed. Furthermore, from an economy and performance standpoint, it may be advantageo-ls to replace a portion of the phenylindane dianhydride by other dian-hydrides of this invention. Thus, it is seen that the phenylindane dianhydrides, whether in combination with other dianhydrides or not, form novel soluble polyimides ~036~47 with the disclose~ diamincs of tl-is invention, t~nether or not there is any phenylindane diamine component in 'he polymeric structure. The only restriction on the com-position of t~e resulting polyimides is that there be sufficient phenylilldane moiety in the backbone, whether derived from phenylindane diamine or dianhydride, to give solubility to the resulting polyimide. Thus, in ef~ecting the solubility of an easily solubilized poly-imide, the phenylindane moiety can be a relatively minor component of the total diamine and dianhydride content, as for example, 10 to 30 mole percent of the total. On the other hand, in effecting the solubility of a difficultly solubilized polyimide the phenylindane moiety can be a m~re significant part of the total diamine and dianhydride con_ent, as for example, 30 to 75 mole percent of the total. In an advantageous embodiment of this invention, wherein no phenylindane diamine is present, the phenylindane tetracarboxylic acid dianhydride comprises from 50 to 100 and preferably 75 to 100 mole percent of the aromatic dianhydrides employed.
The other dianhydrides useful in this invention are characterized by the general formula C/ \C /
Il 11 O O
wherein the tetravalen~ rad cal z 10;~6~47 is as heretofore defined and m~y be selected from the following gcneral groups; aro~atic, aliphatic, cyclo-aliphatic, heterocyclic, co~binations of aromatic and aliphatic, and substituted groups thereof. The Z groups may be characterized by the following structures:
~N
~ ~ - Rg ~
wherein Rg is selected from the group consisting of ~1 I 10 11 1l ~10 -0-~ -S-~ -S02-~ -C-N-, -C-~ -C-O-~ -7- -si-Rlo llO IRlo Rlo R
-0~ 0-, O O -N=N-, -N=N-, ,, 7 ~ lo l lo -C-N-, -CH2~, -CH-, -C-, and phenylene, wherein Rll Rlo and Rll are alkyl or aryl, and substi~uted groups thereof.
The preferred aromatic dianhydrides are those in which the carbon atoms of each pair of carbonyl groups are directly attached to ortho carbon atoms in the Z
roup to p.ovide a five-membered ring as follows:
O ~ O O
!I 11 11 11 C--O--C C--O--c l l or ¦ ¦
--C C-- --C = C--I I
The following species axe typical of tetra-carboxylic acid dianhydrides suitable for practicing the invention: .
2,3,9,10-perylene.tetracarboxylic acid dianhydride 1,4,5,8-naphthalene tetracarboxylic acid dianhydride , 2,6-dichloronaphthalene-1,4,5,8-tetracar~oxylic acid dianhydride 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetra-carboxylic acid dianhydride phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride 2,3,3`,4'-benzophenonetetracarboxylic acid dianhydride pyromellitic dianhydridè
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride 3,3',4,4'-biphenyltetracarboxylic acid dianhydride 2,2',3,3'-biphenyltetracarboxylic acid dianhydride ~()3~747 4,4'~isopropylidenediphthali.c an~ydride 3,3'-isopropylidenediphthalic anhydride 4,4'-oxydiphthalic anhydride 4,4'-sulfonyldiphthalic anhydride 3,3'-oxydiphthalic anhydride 4,4'-methylenediphthalic anhydride 4,4'-thiodiphthalic anhydride 4,4'-ethylidenediphthalic anhydride 2,3,6,7-naphthalenetetracarboxylic acid dianhydride 1,2,4,5-naphthalenetetracarboxylic acid dianhydride 1,2,5,6-naphthalenetetracarboxylic acid dianhydride benzene-1,2,3,4-tetracarboxylic acid dia~hydride pyrazine-2,3,5,6-tetracarboxylic acid dianhydride - .
thiophene-2,3,4,5-tetracarboxylic acid dianhydride, and dianhydrides having the general structure:
Yll ~ - HC -~Cl - CH C
Q \ I f-Y2 Ç - HC \ C-Y CH-C
where Yl, Y2, Y3 and Y4 are each members selected lrom hydro~en, alkyl, aryl and aralkyl.
... ,, .... .. . . . . . , . . ~ .. .. . .. ... . .. . ... . .......... .. . . . .. .. . . . .
The most preferred non-phenylindane aromatic d;.anhydrides are pyromellitic dianhydride, and aromatic dianhydrides characterized by the general formula ~ ~ R12 ~, where R12 is carbonyl, methylene, oxygen or sulfonyl.
The polyimides produced according to this in-vention are characterized by useful solubility in certain organic solvents. Polyimides heretofore known to the art have generally been extre~ely insoluble, and have not been shapeable after conversion from the polyamide-acid state to the polyimide fo~m. The polyimides of the invention are e~t-emely useful in that they can be dissol~ed in certain solvents, in relatively high concentration, and the solutions can be employed for further fabrication of the polyimides. In this way, it is possible to produce polyimide films, coatings, laminates and the like withou' the necessity of using a polyamide-acid intermediate with a follow-on conversion step. This is highly advantageous, because it permits the application of polyimide coatings to articles which mi~ht be damaged by heating ox chemical conversion techniques heretofore necessary.
The soluble polyimides display excellent physical, chemical and electrical propert.ies which render them capable of being used as adhesive~s, laminating resins, especially for prin~ed circuit boards, fibe.s, coat-30 ings, especially for decorative and electrical purposes, ~036~47 films, ~lire ename's and molding compounds. Solution.s ofthe phenylindane polyimides of this invention can be used to impregnate reinforcing fi~ers and fabrics li~e glass, boron, metal oxide whiskers and graphite. These prepregs can then be cured to form rigid polyimide laminates or composites or to form s~rong thermally resistant structural adhesive bonds between aluminum, 8tainless steel, titanium or other metals.
These polyimides have very good solubili~y in common organic solvents. Examples of such organic solvents are the following:
N,N-dimethylformamide N,N-dimethylacetamide N-methyl-2-pyrrolidone N,N-diethylformamide .N,N-diethylacetamide N-methylcaprolactam dioxane dimethylsulfoxide tetramethylurea pyridine dimethylsulfone r hexamethylphosphoram de ~-tetramethylene sulfone formamide N-methylformamide ~-butyrolactone tetrahydrofuran m-cresol 2-methoxyethyl acetaie 1,2-dimethoxyethane ~Q36~47 bis(2-met~oYyethyl) ether chloroform nitrobenzene.
.
- The solvents can be used alone, in combinations of solvents, or in combination with poor solvents such as benzene, benzonitrile, xylene, toluene and cycloheY.ane.
More specifically, these polyimides have been found to be soluble up to more than 60% in these solvents.
The particular solubility achieved depends on various factors such as the nature of the solvent, the nature of the dianhydride and diamine employed and the extent of any replacement of the phenylindane diamines or dianhydrides of the invention by other diamines or dianhydrides. ~he ~olubilities attained are unique because the phenyl-indane moieties contained in the novel soluble po3y-imides are themselves aromatic in character and might be expected to impart to their polyimides the generally found characteristic of insolubility among aromatic polyimides. Thus, it is most unusual that these phenylindane diamines and dianhydrides can be reacted with aromatic dianhydrides and diamines to produce the instant soluble polyimides.
The unusually high solubility of the novel polyimides of this invention is not completely under-~tood. However, it appears that the cor~.on phenylindane inner structure of both the phenylindane diamines and dianhydrides herein disclosed, said inner structure being represented by the formula .. ~, .
Rl~ CH3 significantly contributes to this solubility. Evidence of this solubilizing activity can be seen from the effect which phenylindane in either its diamine or dianhydride form has on the solubilities of otherwise difficulty soluble aromatic dianhydrides. Pyromellitic dianhydride and 4,4'-methylenedianiline are well known examples of materials, which, in combination with conventional aromatic diamines and dianhydrides generally yield poorly soluble high molecular weight polyimides. Yet, when 5t5)-amino-1-(4'-aminoPhenYl)-1,3,3-trimethylindane is polymeri~ed with py_omellit c dianhydride a highly soluble polyimide results, e.g., solubility greater than 40 weight percent in dimethyl-foxmamide is afforded. Again, when 1-(~',4'-dicarboxy-phenyl)-1,3,3-trimethylindane-5,6(6,7)-dicarboxylic acid dianhydride is polymerized with 4,4'-methylene-dianiline a very sol~le polyimide results.
The polyimides are prepared by a process com-prising reactins the abGve described aromatic primary diamino compounds with dianhydrides in an organic reaction medium which is a solvent for at least one of the reactants, preferably under substantially anhydrous conditions, at a temperature below 100C and con-~036~47 veniently at roo~ temperature. The product of this reaction is a polyamide acid represented by the follo~ing formula:
/ HOC \ / COH
t t This polyamide acid has a molecular weight such that its inherent viscosity is at least 0.1, preferably 0.~-5Ø The inherent viscosity is measured at 25C at a concentration of 0.5% by weight of the polymer in a suitable solvent, e.g., N,N-dimethyl-acetamide, N-methylpyrrolidone, dimethylforr,amide, etc.
The polyamide acid is subsequent]y converted to the polyimide by several methods which include heating the polyamide acid soluticn at temperatures bet~een 100C and 240C depending on the boiling point of the organic solvent, until imidization is com?lete; by ohemical means, e.g., by adding to the polyamide acid solution a dehydrating agent such as acetic anhydride alone or in combination with a tertiary a~ine catalyst such as pyridine and opt onally heating or not heating the resulting solution at about 120C until imidization i~; colnplete.
1a36747 More specifically, the preparation of the poly-amide acid which is subsequently converted to the polyimide can be conveniently carried out in a number of ways. The diamines and dianhydrides can be pre-mixed as dry solids in equivalent amounts and the resulting mixture can be added, in small portions and with agitation, to~an organic solvent. Alternately, this order of addition can be reversed, i.e., after premixing the diamine and the dianhydride the solvent may be added to the mixture with agitation. It i~
also possible to dissolve the diamine in the solvent while agitating ar.d to add slotYly the aianhydride in portions that provide a controllable rate of reaction.
However, this order of addition can also be varied.
Still another process involves dissolving the diamine in one portion of a solvent and the dianhydriàe in another portion of the same or another solvent and then mixing the two solutions.
~ To effect the conversion of the polyamide acids to the polyimides, the polyamide acids are heated above 50C and preferably in an inert atmosphere and mo e pre~erably in an inert atmosphere between 110C and 240C.
In the preferred process, the polyamide acids are prepared at a temperature below 50C and maintained at this temperature until maximum viscosity is obtained denotin~ maximum polymerization. The polyamide acid in solution and under an inert atmosphere is subsequently heated to about 110C to 240C to convert the polyamide ~ Q3674`~
acid to the polyimide. The soluble polyimide may be alternatively prepared by mixing the diamine and the dianhydride at room temperature in a solvent such as rlitrobenzene and then rapidly heating the mixture to reflux for about 2 to 12 hours.
` The soluble polyimides can be precipitated from their solutions by use of methanol, water, acetone, spray drying and the like. The resulting granular material can be molded or redissolved in a suitable solvent to yield a film-forming or varnish type com-position. Other appropriate ingredients can be added to the polyimide solutions or molding po~ders including fillers, dyes, pigments, thermal stabilizers and rein-forcing agents, such as glass fiber, carbon, '~oron and the like, depending on the end use.
The polyimides from phenylindane diamines and dianhydriaes are further characterized by high glass transition temperatures (Tg). This makes it possible for the phenylindane polyimides to be used at higher temperatures than many prior art polyimides. Since at temperatures above the transition temperature the polymers lose their stiffness and mechanical properties, any increase in transition temperature is of great importance.
To further illustrate the nature of this invention and the process employed in preparing the ~oluble polyimides, the following examples are given below.
.
~036747 Manufacture of the Starting Compounds Example A: 5(6)-Amino-1-(4'-aminophenyl)-1,3,3-trimethYlindane (a) Preparation of 1,3,3-Trimethyl-l-phenylindane To 6.0 kg. of 62% sulfuric acid at 50C was ad~ed 1.0 kg. of -methyl-styrene over a 5 minute period. The mixture was refluxed (145C) for 20 hours.
After cooling, the lower acid phase was drawn off and discarded. The organic phase was washed with sulfuric acid several times and then with water several times.
The product was recrystallized from methanol which afforded 750 g of white crystals with a melting point of 50.5C-52.0C. The yield was 75~.
By essentially following the ~bove procedure and substitutir~g a,3,4-trimethylstyrene for a-m~thyl-styrene there is obtained a mixture of tetramethyl phenylindanes in 95~ yield.
~036~747 (b) Preparation of 5,4'-dinitro- and 6,4'-d itro-1,3,3-~rimeth~ er~ylil~d~ne isomers To a solution of 236 g (1.0 mole) 1,3,3-trimeth~ phenylindane (~-methylstyrene dimer) in 750 ml chloroform at 2-8C was added a pxeviously mixed solution of 396 ml sulfuric acid and 132 ml ` nitric acid dropwise over a 2.5 hour period. The two phase reaction mixture was allowed to stir an additional 4 hours at 5C. The chloroform phase W2S
isolated and washed with aqeuous sodium bicarbonate until neutral and then with distilled water. A light yellow oil was obtained after drying and stripping the chloroform solution. Two triturations in hexane at room temperature afforded 295 g light yellow powder, melting point 109-125. This material was shown to be a mixture of the 5,4'-dinitro- and 6,4'-dinitro-1,3,3-trimethyl-l-phenylindane isomers by N~.~ analysis.
~nalysis for C18H18N24:
% Calculated: C, 66.25; H, 5.55; N, 8.58 ~ Found: C, 66.13; H, 5.50; N, 8.42 ~S)36'-~'47 ~c) Pre~aration of 5(6)-~mino-1-(4'-amino-p_en~ l,3,3-tri.meth~lir.d~ne A mixture of 250 g (0.t67 mole) of the ~ini~ro isomers and 250 g (4.60 g - ator~ls) reduced iron powdar in 1 liter 50~ a~ueous ethanol ~as brought to reflux and a previously prepared solution of 60 ml con~entrated hydrocllloric acid in 403 ml 50% aqueous ethanol was added over a 1 hou~ period. Reflux was continued an additional 3 hours, the reaction cooled to 50 an~ 50 ml conce.ntrated hydrochloric aci~ added. The reaction mixture was filtered. The filtrate was made basic with 20~ NaOH and extracted with ether, dried and stripped under vacuum to afford 145 g (71%) of a clear brown glassy solid, melting pOillt 47-54. NMR analys.is indicated the product was 62~ 6-amino- and 38`o 5-a~ino-1-(4'-aminophenyl)-1,3,3-trimethylindane.
~nalysiS fo~ C18H22~2 % Calculated: C, 81~18; H, 8.32; N, 10.52 % Found~ C, 81.27; H, 8.20; ~, 10.48 ~036!747 Example B:
1-(3',4'-Dicarboxyphenyl)-1,3,3-trimethylindane-5,6(6,7)-dicarboxylacid dianhydride A mixture of dimers (70 ~, 0.24 mole) prepared from à,3,4-trimethylstyrene as in Example A (a) was dis-sol~ed in 800 ml pyridine and 600 ml water. At reflux 76~ g (4.8~1 moles) KMnO4 was added to the reaction over a 4 hour period along with an additional 1500 ml ~Jater.
`After refluxing for an additional 2 hours, the pyridine and water were almost entirely removed by distillation and the reaction mixture filtered to remov~ MnO2. The ~iltrate was acidified, extracted, stripped and dried to afford ~6.5 g (8S%) of a mixture of tetra-acids.
Dehydration wa~ accompiished at 200C at 100 ~m Hg and afforded an analytically pure s~ple of dianhydrides:
~nalYSis for C22H16o6 % Calculated: C, 70.21; H, 4.29 % ~ound: C, 70.05; H, 4.24 1036!747 Example C:
.
6-Amino-1-(4'-aminophenyl)-1,3,3-trimethylindane -To a mixture of 16.2 g (50 n~oles) 1~
carboxyphenyl)-1,3,3-trimethyl-fi-indane carboxylic acid in 400 ml chloroform and 60 ~1 conc. H2SO4 at 40C was added portion~ise ovex a 1/2 hour period,
7.8 g (120 mmoles) sodium azide. The resulting mixture was heatea for 2 hours at 55, cooled to room tem~
perature and aliowed to stand overnigh~. Water (200 ml) was added and the mixture stirred for 1 hour. The chlorofGr~ layer was drawn o~f r washed with water, dried over K2CO3 and stripped to afford a ~orowni~h oi l.
This oil was dissolved in 700 ml hot heptane, filtered and allo~?ed to crystalli~e. Filtration afforded 0.6 g (79~) of an off-white powder, meitin~ point 91-92, which was consister.t with the desired 6-~mino~ (4-aminophenyl)-1,3,3-trimethylindane.
Analys~s for C18X22N2 % Calcula'ed: ~, 81.18; H, 8.32; ~, 10.52 Found: C, 81.3C; H, 8.40; N, 10.47 ~036747 Example D: 5-Amino-6-methyl-1-(3'-amino-4'-methYlphenyl) 1,3,3-trimethylindane (a) Preparation of ~,p-Dimethylstyrene To 630 ml of a solution of 226.6 q (1.9 moles) of metllyl magnesium bromide in ether which was stirred in a reaction flask equipped with nitrogen inlet and dr~ing tube was added a solution o~ 214 g (1.6 moles) of 4'-methyl acetophenone in 5~0 ml ether. Addition ~as accomplished cver a 2.45 hour period while the internal temperature was maintained at 8-12C. The mixture was then ~tirred for 0.5 hour at room temperature and 1 hour at reflux. The mixture was cooled to 10C
a~d 300 ml 25% N~4Cl tJaS added over a 0.5 hour period while an in~ernal tempera~ure of ~5-20C was maintained.
The liquid top layer t~as decanted from the bottom layer.
This bottom layer ~las boiled t~ice in 300 ml ether each time. ~he eth r from these boilings was fi]tered, added to the initially decanted top layer, and the total ether solution was dried over MgSO4. Filtration and stripping off of volatiles at 50C and 14 ~ Flg produced 230 g o~
an oil (~6~ yieldj.
229 g (l.S moles) of the di~etnyl-p-methylphenyl-carbinol prodllced abo~re was added to a reaction flas};
which was equipped with nitrogen inlet and take~off con~enser. This carbinol was heated b~ means of an oil bath. When the oil bath temperature reached 115C, the r ~.o36~47 clear material became cloudy and the presence of water globules was noticed. Further heatin~ to an oil bath temperature of 140~C resulted in the distillation of 24 ml of ~7ater together ~7ith 11 ml of organi~ material.
On subsequent di3tillat.ion of the remaining material in the ~lask through a vigreaux col~l~n 158.5 g of ,p-dimethyls~yrene (80% yield) was produced, boiling point 75-77C/14 mm Hg.
~o36q47 (b) Preparation of 6-Methyl-1-(4'-methylphenyl)-1 3,3-trimethylindane A solution of 150 g ~1.14 moles) ~,p-dimethyl-styxene in 19C ml of toluene was added with stirring over a 1 hour period to a reaction flask containing 450 ml of toluene and 83 ml of concentrated H2SO4.
The reaction temperature ~u~ing this addition was n~aintained at 5-7C. The reaction mixture ~as allowed to stir for 1 hour at 5-10C and 1 hour at 20C. The upper toluene layer was then separated from the reaction mixture. The lower layer was ex-tracted with 100 ml toluene and then the combined toluene layers ~ere dried over a ~SgSO4-K2CO3 mixture.
The dried ~aterial was filtered and volatiles were removed at 75C and 14 ~ ~g to yield 145 g of a viscous yellow-brown oil. 15~ ml of ~ethanol was added to this oil. This mixture afforded 135 g o~
white crystals, melting point 37-38.5C ~89.5%
yield).
'lQ~q47 (c) Preparation of 5-Nitro-6-methyl-1-(3'-nitro-4'-meth~l-pheny~ 3~3-trimethylindane To a solution of 6.S g (.025 mole) 6-methyl~l-(4'~methylphenyl)-1,3,3-trimeth~lindane in 19 ~1 chloroform at 5C was added witll stirxing a pre-viously mixed solution of 10 ml sulfuric acid and 3.3 ml nitric acid over a 1.5 hour period. The resultant mixture was stirred 3 hours at 5C. The chloroform ~hase ~as isolatedr washed ~ith aqueous sodium bi-carbonate ~mtil neutral and then with water, and dried over MgSO4. 8.1 g of a thick oil was ohtained after stripping of the chloroform soluiion. T~is oil was taken up in 30 ml hexane and afforded 4.3 g crystalline solid, melting poillt 99-112C (50% yield).
Analysis for C20H22N2O4:
Calculated: Cr 67.78; H, 6.26; N, 7.90 Found: C, 67.S6; H, 6.65; N, 7.64 .. . .. .. . . ..... . . . . .... . ... . . ..... . . .
1036!747 (d) Preparati~n of 5-Amino-6-methyl-1-(3'-amino-4'-methyl-pheny~ 3~3-trimethylindane 0.4 g of 10% palladium on charcoal was added to a solution of 4 g (.011 mole) of the dinitro compound prepared above under (c) in 80 ml ethyl acetate under a nitrogen atmosphere. Reduction of the mixture was then carried out by means of the Paxr Hydrogenator ~vex a period of 20 hours. The mixture was filtered and the filtrate stripped to produce an oil. This oil was dissolved in ether, extracted with dllute acid, neutralized with base, and re-extracted witll additional ether. Subsequent drying, filtering and stripping afforded 3.~ g o~ a viscous s~rup. ~lR analysis indicated that 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethyl-indane was the predo~inant product.
. .
Example E: Chlorination of 5(6)-Amino-1-(4'-aminophenyl)-1 3 3-trimethylindane h~drochloride 102 g ~0.3 mole) of 5(6)-amino-1-(4'-aminophenyl)-1,3,3-trim~thylindane hydrochloride (prepared by acidi-ficatioll of the diamine) was dissolved in a previously mixed solution of 125 ml concentrated hydrochloric acid and 750 ml water; Chlori~e-was bu~bled into the brown solution maintained at 3-7C over a period of 50 minutes.
~ mild exother~ was noted and a brown solid separ~ted during the chlorine addition. After addition was complete the reaction mixture was stirred for 3 hsurs with a gradual increase of the temperature from 5 to 25C. The reac'ion mixture was next dilute~ t;ith 1250 ml water and the in-soluble brown solid filtered. The solid was triturated with water, filtered, further waslled with ~ater filtered and finaliy dried at 35-40C and 7 ~m Hg. for 132 hoùrs to constant weight. The yield ~as 110 g (91~), melting point 160-180C tdec!.
Calculated: C, 53.49; H, 4.49; N, 6.93; Cl, 35.09 Found: C, 52.07; H, 4.38; N, 7.76; Cl, 31.31 1036~747 Manufacture of the Polyimides Example 1 Preparation of Polyimide from 5(6)-Amino-1-(4'-amino-phenyl)-1,3,3,-trimethylindane and benzophenonetetra-carboxylic acid dianhYdride To a solution of 5.33 g (20 mmoles) of 5(6)-amino-1-(4l-amihophenyl)-l~3~3-trimethylindane as prepared in Example B in 67 g N-methylpyrrolidone (N~) was added lo 6.44 g (20 mmoles) benzophenonetetracarboxylic acid dianhydride (BTDA) over a 20 minute period. After 24 hours at room temperature, 20 ml acetic anhydride and 5 ml pyridine were added to imidize the amic acid polymer.
Coagulation into acetone afforded a 10.2 g (93~/0) yellow polyimide with an inherent viscosity (0.5%, NMP, 25) 0.55; 40% solubility in chloroform, N-methylpyrrolidone, dimethylformamide; TGA(thermal gravimetric analysis) mai.l break (5/min.) 425C in air, 500C in nitrogen; TG = 320C, measured by Torsional Braid Analysis (TBA)~
10;~6747 Example 2 Prepàration of Polvimide ~rom 5(6)-.~mino-1-(4'-aminophenyl)-1,3,3-tximeth lindane (~ID~), 4,4'~Meth~lenetlianiline (~A) and Benzo~henone-tetracarboxvl.ic Acid D~.anhyd-`de (BTD~) By essentially follo~ing the procedure of ~xample land successively replacing the phenylindane diamine mixture by 10, 20, 30, 40 and 50 mole percent 4l4'-methylenedianiline, the soluble p~lyimides set forth in the following table are obta~ned~ These polyimides are all soiuble in 20~ weight concentr&~.ion il. ~-methylpyrrolidone (NMP).
Mole% Mo'e~ Inherent Pol~ e Diamine Dianhvd-ide '7iscositv (u.5~ ~, 25C) MDA PID~ BTDA
1 S 45~ 50 0.45 2 10 ~050 O.SS
3 lS 3550 0.50 4 20 3050 0.61 S 25 2550 0.64 6 50 -- 50 insoluble 1()36!747 Example 3 Pxeparation of Polyimide fxom S (~) -Ami.no-1-(4'-amino-~henyl)-1,3,3-trimeth~lindane and -Pyromellitic Dianh~ride Pyromellitic dianhydride (P~DA), 5.37 g, was added QVer a 5 minute period to a stirring solution of 4.36 g 5(6)-amino-1-(4'-aminophenyl)-1,3,3-tri-methylindane in 55 g N~P at room temperature. A stronginitial exothexm was noticed but subsided after the last dianhydride addition. Stirring was continued at room temperature for 24 hours. The resu;ting amic acid was imidized with 20 ml acetic anhydride and 10 ml ~yridine ~y stirring overnight at room tempe ature.
The imidized material, which remained in scl~tion, was coagulated into water, washed wiih water and dried at 90~ for 24 ho~rs. The inherent viscosity (0.5% in ~, 25) of this material was 0.18. Torsional Braid Analysis (TB~) showed Tg=390C.
.
The weight percent sol~lbilities of this polyimide in various solvents at room tempe-ature are as ~ollo~
Solv~nt Solubility,Weight V/o dimethylformamide > 40 N,N-dimethylac2tamide > 50 N-methyl~yrrolidone > 40 m-cresol ~ ~ 30 ~-butyrolactone > 40 tetrahydrofuxan > 50 2-methoxyethyl acetate > 50 1,2-dimethoxyethane > 5.0 bis(2~methoxyethyl~ether > 50 dioxane > 50 chloroform > 40 ~036~47 , Example 4 Preparation of Polyimide from 5 (~ ino-l-(4 ' -aminophenyl) -1, 3, 3-trimetIlylindanc (PIDA), 4, 4 ' -Meth~lenediani].ine (~A) and Pvro~ellitic -Dianh~dride ~Pr~A) By essentially following the procedure of Example 2 and successively replacing the phenylindane diamine mixture by 10, 20, and 30 mole percent 4, 4 ' -m 3thylenedianiline the soluble polyimides set forth in the following table are obtained. These polyimides are all soluble in 20~ weight concentration in N-methyl-pyrrolidone (NMP).
Mole % Mole % Inhereni Po~yimide Diamine Dianhvdride Viscosi (0.5~, ~MP, 25C~
MD~ PII~A PMDA
0 . 27 2 10 40 50 0. 28 3 15 35 S0 0. 29 4 50 -- 50 insol~ible Example 5 Preparat.~on of Pol~imide from 1-(3',~
dicarbox~en~ 3,3-trimethylindane-5,6 -methylenc di.aniline A stoichiometric mixture of the phenylindane dianhydride o~tained in Example C and 4,4'-meths~lene 10dianiline was reacted at room temperature in N-met;.yl-pyrrolidona solvent and imidized as dascribed in Example 1. The light yellow polyimide product had an inherent viscosity (0.5g, N-methylpyrrolidone, 25) of . 0.31 and was soluble in N-methylpyrrolidone, dimethyl-formamide t dimethylacetamide, tetrahydrofuran and cresol.
! - 38 -1036~47 Example 6 By ~ssentially following the procedure of Example 5, soluhle polyimides are obtained by reacting equivalent amounts of 1-~3',4'-dicarboxy-phenyl)-l~3~-trimethylindane-5~6(6~7)-dicarboxylic acid dianhydride and the following aro~atic diamines:
(a) 4,4'-methylenebis(o-chloroaniline) (b) 4,4'-oxydianiline (c) 4,4'-thiodia~iline (d) 4,4'-sulfonyldianiline 1036q47 Example 7 By ess~nl-ially following the procedure of Exa~lple 6, and xeplacing the phenylindane dianhydr~de by 25 and 50 mole percent of ben20phenone tetracar-boxylic acid dianhydride soluble polyimides are obtained with the following aromatic diamines:
(a) 4,4'-methylenebis(o-chloroaniline) (b) 4,4'-oxydianiline ~ c) 4,4'-thiodi~niline (d) 4,4'-sulfonyldianiline ~036q47 Example 8 Preparati.on of Pol~imide from 6-Amino-1-(4'-am~nophenyl)-l,3,3-trimet.hvlindane and benzo-ph~.nonetetracarboxylic acid dianhydride To a solution in 50 g N-methylpyrrolidone of 5.168 g (19.4 mole) of the pure 6-amino diamine, prepared in Example D, was added, over a 5 minute period, 6.444 g (20 mmoles) benzophenone-~etracarboxylic acid dianhy~ride (BTD~). The solution immediately became warm and noticebly viscous. The ` solution was allowed to cool to room temperature and stand for 18 hours. 20 ml of acetic anhvdride and 10 ml pyridine were added and the reaction mi~ture heated on a ste~m plate for 5 hours. The solution was then coagulated into 1 liter aoetone to afford a light yellow fibrous pol~er. An I.R. spectrum showed no ~ic acid bands. Inherent viscosi~y (~.5% in N-methylpyrrolidone, 25) was 0.55. TBA sho~ed Ta--329. The material was 40~ soluble in N-methylpyr~olidone, N,N-dimethylacetamide, dimethylfcrmamide an~ CHC13.
1036!747 Example 9 By e~sontially following the p--ocedure of Example 1, and xeplacing the 5t6)-amino-1-(4'-amino-phenyl)~l,3,3-tritn~thylindane reacted in that example by the followin~ aromatic diamines:
~a) 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane; and (b) an isomeric mixture of 5-amino-1-(4'-amino-~r',Ar'-dichlorophenyl)-Ar,Ar-dichloro-1,3,3-trimethylindane and 6-amino-1-(4'-amino-Ar',Ar'-dichlorophenyl)-A~,Ar-dichloro-1,3,3-trimethylindane, there are obtained soluble polyimides.
Example 10 By essentially followin~ the procedure of Ex~nple 1, soluble polyimides arc obtained by reactin~ equivalent amounts of 5~6)-smino-1-(4'-a~ino-ph~nyl)-1,3,3-trimethylindane and the following aromatic dianhydrides:
(a) 4,4'-oxydiphthalic anhydride (b) 4,4'-thiodiphthalic anhydride ~ c) 4,4'-sulfonyldi~hthalic anhydride (d) 4,4'-methylene diphthalic ~.nhydride (e) 4,-~'-ethylidenediphthalic anhydride (f) `3,4,3',4'-t~tracarboxylic triphenylamine dianhydride (g) 3,4,3',4'-tetracarboxylic tetraphenylsilane dianhydride (h) 3,4,3',4'-tetracarboxylio tetraphenylsiloxanP
dianhydride ~i) 3,~,3',4'-tetracarhoxylic ~riphenyl~hospl;ine oxide dianhydride (j) 3,4,3',4'-tetracarboxylic triphenylphosphate dianhydride (k) 1-(3',41-dicarboxy~henyl~-1,3,3-trimethylin-dane-5,5(6,7~-dicarboxylic acid dianhydride -.. . . .. . . .
perature and aliowed to stand overnigh~. Water (200 ml) was added and the mixture stirred for 1 hour. The chlorofGr~ layer was drawn o~f r washed with water, dried over K2CO3 and stripped to afford a ~orowni~h oi l.
This oil was dissolved in 700 ml hot heptane, filtered and allo~?ed to crystalli~e. Filtration afforded 0.6 g (79~) of an off-white powder, meitin~ point 91-92, which was consister.t with the desired 6-~mino~ (4-aminophenyl)-1,3,3-trimethylindane.
Analys~s for C18X22N2 % Calcula'ed: ~, 81.18; H, 8.32; ~, 10.52 Found: C, 81.3C; H, 8.40; N, 10.47 ~036747 Example D: 5-Amino-6-methyl-1-(3'-amino-4'-methYlphenyl) 1,3,3-trimethylindane (a) Preparation of ~,p-Dimethylstyrene To 630 ml of a solution of 226.6 q (1.9 moles) of metllyl magnesium bromide in ether which was stirred in a reaction flask equipped with nitrogen inlet and dr~ing tube was added a solution o~ 214 g (1.6 moles) of 4'-methyl acetophenone in 5~0 ml ether. Addition ~as accomplished cver a 2.45 hour period while the internal temperature was maintained at 8-12C. The mixture was then ~tirred for 0.5 hour at room temperature and 1 hour at reflux. The mixture was cooled to 10C
a~d 300 ml 25% N~4Cl tJaS added over a 0.5 hour period while an in~ernal tempera~ure of ~5-20C was maintained.
The liquid top layer t~as decanted from the bottom layer.
This bottom layer ~las boiled t~ice in 300 ml ether each time. ~he eth r from these boilings was fi]tered, added to the initially decanted top layer, and the total ether solution was dried over MgSO4. Filtration and stripping off of volatiles at 50C and 14 ~ Flg produced 230 g o~
an oil (~6~ yieldj.
229 g (l.S moles) of the di~etnyl-p-methylphenyl-carbinol prodllced abo~re was added to a reaction flas};
which was equipped with nitrogen inlet and take~off con~enser. This carbinol was heated b~ means of an oil bath. When the oil bath temperature reached 115C, the r ~.o36~47 clear material became cloudy and the presence of water globules was noticed. Further heatin~ to an oil bath temperature of 140~C resulted in the distillation of 24 ml of ~7ater together ~7ith 11 ml of organi~ material.
On subsequent di3tillat.ion of the remaining material in the ~lask through a vigreaux col~l~n 158.5 g of ,p-dimethyls~yrene (80% yield) was produced, boiling point 75-77C/14 mm Hg.
~o36q47 (b) Preparation of 6-Methyl-1-(4'-methylphenyl)-1 3,3-trimethylindane A solution of 150 g ~1.14 moles) ~,p-dimethyl-styxene in 19C ml of toluene was added with stirring over a 1 hour period to a reaction flask containing 450 ml of toluene and 83 ml of concentrated H2SO4.
The reaction temperature ~u~ing this addition was n~aintained at 5-7C. The reaction mixture ~as allowed to stir for 1 hour at 5-10C and 1 hour at 20C. The upper toluene layer was then separated from the reaction mixture. The lower layer was ex-tracted with 100 ml toluene and then the combined toluene layers ~ere dried over a ~SgSO4-K2CO3 mixture.
The dried ~aterial was filtered and volatiles were removed at 75C and 14 ~ ~g to yield 145 g of a viscous yellow-brown oil. 15~ ml of ~ethanol was added to this oil. This mixture afforded 135 g o~
white crystals, melting point 37-38.5C ~89.5%
yield).
'lQ~q47 (c) Preparation of 5-Nitro-6-methyl-1-(3'-nitro-4'-meth~l-pheny~ 3~3-trimethylindane To a solution of 6.S g (.025 mole) 6-methyl~l-(4'~methylphenyl)-1,3,3-trimeth~lindane in 19 ~1 chloroform at 5C was added witll stirxing a pre-viously mixed solution of 10 ml sulfuric acid and 3.3 ml nitric acid over a 1.5 hour period. The resultant mixture was stirred 3 hours at 5C. The chloroform ~hase ~as isolatedr washed ~ith aqueous sodium bi-carbonate ~mtil neutral and then with water, and dried over MgSO4. 8.1 g of a thick oil was ohtained after stripping of the chloroform soluiion. T~is oil was taken up in 30 ml hexane and afforded 4.3 g crystalline solid, melting poillt 99-112C (50% yield).
Analysis for C20H22N2O4:
Calculated: Cr 67.78; H, 6.26; N, 7.90 Found: C, 67.S6; H, 6.65; N, 7.64 .. . .. .. . . ..... . . . . .... . ... . . ..... . . .
1036!747 (d) Preparati~n of 5-Amino-6-methyl-1-(3'-amino-4'-methyl-pheny~ 3~3-trimethylindane 0.4 g of 10% palladium on charcoal was added to a solution of 4 g (.011 mole) of the dinitro compound prepared above under (c) in 80 ml ethyl acetate under a nitrogen atmosphere. Reduction of the mixture was then carried out by means of the Paxr Hydrogenator ~vex a period of 20 hours. The mixture was filtered and the filtrate stripped to produce an oil. This oil was dissolved in ether, extracted with dllute acid, neutralized with base, and re-extracted witll additional ether. Subsequent drying, filtering and stripping afforded 3.~ g o~ a viscous s~rup. ~lR analysis indicated that 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethyl-indane was the predo~inant product.
. .
Example E: Chlorination of 5(6)-Amino-1-(4'-aminophenyl)-1 3 3-trimethylindane h~drochloride 102 g ~0.3 mole) of 5(6)-amino-1-(4'-aminophenyl)-1,3,3-trim~thylindane hydrochloride (prepared by acidi-ficatioll of the diamine) was dissolved in a previously mixed solution of 125 ml concentrated hydrochloric acid and 750 ml water; Chlori~e-was bu~bled into the brown solution maintained at 3-7C over a period of 50 minutes.
~ mild exother~ was noted and a brown solid separ~ted during the chlorine addition. After addition was complete the reaction mixture was stirred for 3 hsurs with a gradual increase of the temperature from 5 to 25C. The reac'ion mixture was next dilute~ t;ith 1250 ml water and the in-soluble brown solid filtered. The solid was triturated with water, filtered, further waslled with ~ater filtered and finaliy dried at 35-40C and 7 ~m Hg. for 132 hoùrs to constant weight. The yield ~as 110 g (91~), melting point 160-180C tdec!.
Calculated: C, 53.49; H, 4.49; N, 6.93; Cl, 35.09 Found: C, 52.07; H, 4.38; N, 7.76; Cl, 31.31 1036~747 Manufacture of the Polyimides Example 1 Preparation of Polyimide from 5(6)-Amino-1-(4'-amino-phenyl)-1,3,3,-trimethylindane and benzophenonetetra-carboxylic acid dianhYdride To a solution of 5.33 g (20 mmoles) of 5(6)-amino-1-(4l-amihophenyl)-l~3~3-trimethylindane as prepared in Example B in 67 g N-methylpyrrolidone (N~) was added lo 6.44 g (20 mmoles) benzophenonetetracarboxylic acid dianhydride (BTDA) over a 20 minute period. After 24 hours at room temperature, 20 ml acetic anhydride and 5 ml pyridine were added to imidize the amic acid polymer.
Coagulation into acetone afforded a 10.2 g (93~/0) yellow polyimide with an inherent viscosity (0.5%, NMP, 25) 0.55; 40% solubility in chloroform, N-methylpyrrolidone, dimethylformamide; TGA(thermal gravimetric analysis) mai.l break (5/min.) 425C in air, 500C in nitrogen; TG = 320C, measured by Torsional Braid Analysis (TBA)~
10;~6747 Example 2 Prepàration of Polvimide ~rom 5(6)-.~mino-1-(4'-aminophenyl)-1,3,3-tximeth lindane (~ID~), 4,4'~Meth~lenetlianiline (~A) and Benzo~henone-tetracarboxvl.ic Acid D~.anhyd-`de (BTD~) By essentially follo~ing the procedure of ~xample land successively replacing the phenylindane diamine mixture by 10, 20, 30, 40 and 50 mole percent 4l4'-methylenedianiline, the soluble p~lyimides set forth in the following table are obta~ned~ These polyimides are all soiuble in 20~ weight concentr&~.ion il. ~-methylpyrrolidone (NMP).
Mole% Mo'e~ Inherent Pol~ e Diamine Dianhvd-ide '7iscositv (u.5~ ~, 25C) MDA PID~ BTDA
1 S 45~ 50 0.45 2 10 ~050 O.SS
3 lS 3550 0.50 4 20 3050 0.61 S 25 2550 0.64 6 50 -- 50 insoluble 1()36!747 Example 3 Pxeparation of Polyimide fxom S (~) -Ami.no-1-(4'-amino-~henyl)-1,3,3-trimeth~lindane and -Pyromellitic Dianh~ride Pyromellitic dianhydride (P~DA), 5.37 g, was added QVer a 5 minute period to a stirring solution of 4.36 g 5(6)-amino-1-(4'-aminophenyl)-1,3,3-tri-methylindane in 55 g N~P at room temperature. A stronginitial exothexm was noticed but subsided after the last dianhydride addition. Stirring was continued at room temperature for 24 hours. The resu;ting amic acid was imidized with 20 ml acetic anhydride and 10 ml ~yridine ~y stirring overnight at room tempe ature.
The imidized material, which remained in scl~tion, was coagulated into water, washed wiih water and dried at 90~ for 24 ho~rs. The inherent viscosity (0.5% in ~, 25) of this material was 0.18. Torsional Braid Analysis (TB~) showed Tg=390C.
.
The weight percent sol~lbilities of this polyimide in various solvents at room tempe-ature are as ~ollo~
Solv~nt Solubility,Weight V/o dimethylformamide > 40 N,N-dimethylac2tamide > 50 N-methyl~yrrolidone > 40 m-cresol ~ ~ 30 ~-butyrolactone > 40 tetrahydrofuxan > 50 2-methoxyethyl acetate > 50 1,2-dimethoxyethane > 5.0 bis(2~methoxyethyl~ether > 50 dioxane > 50 chloroform > 40 ~036~47 , Example 4 Preparation of Polyimide from 5 (~ ino-l-(4 ' -aminophenyl) -1, 3, 3-trimetIlylindanc (PIDA), 4, 4 ' -Meth~lenediani].ine (~A) and Pvro~ellitic -Dianh~dride ~Pr~A) By essentially following the procedure of Example 2 and successively replacing the phenylindane diamine mixture by 10, 20, and 30 mole percent 4, 4 ' -m 3thylenedianiline the soluble polyimides set forth in the following table are obtained. These polyimides are all soluble in 20~ weight concentration in N-methyl-pyrrolidone (NMP).
Mole % Mole % Inhereni Po~yimide Diamine Dianhvdride Viscosi (0.5~, ~MP, 25C~
MD~ PII~A PMDA
0 . 27 2 10 40 50 0. 28 3 15 35 S0 0. 29 4 50 -- 50 insol~ible Example 5 Preparat.~on of Pol~imide from 1-(3',~
dicarbox~en~ 3,3-trimethylindane-5,6 -methylenc di.aniline A stoichiometric mixture of the phenylindane dianhydride o~tained in Example C and 4,4'-meths~lene 10dianiline was reacted at room temperature in N-met;.yl-pyrrolidona solvent and imidized as dascribed in Example 1. The light yellow polyimide product had an inherent viscosity (0.5g, N-methylpyrrolidone, 25) of . 0.31 and was soluble in N-methylpyrrolidone, dimethyl-formamide t dimethylacetamide, tetrahydrofuran and cresol.
! - 38 -1036~47 Example 6 By ~ssentially following the procedure of Example 5, soluhle polyimides are obtained by reacting equivalent amounts of 1-~3',4'-dicarboxy-phenyl)-l~3~-trimethylindane-5~6(6~7)-dicarboxylic acid dianhydride and the following aro~atic diamines:
(a) 4,4'-methylenebis(o-chloroaniline) (b) 4,4'-oxydianiline (c) 4,4'-thiodia~iline (d) 4,4'-sulfonyldianiline 1036q47 Example 7 By ess~nl-ially following the procedure of Exa~lple 6, and xeplacing the phenylindane dianhydr~de by 25 and 50 mole percent of ben20phenone tetracar-boxylic acid dianhydride soluble polyimides are obtained with the following aromatic diamines:
(a) 4,4'-methylenebis(o-chloroaniline) (b) 4,4'-oxydianiline ~ c) 4,4'-thiodi~niline (d) 4,4'-sulfonyldianiline ~036q47 Example 8 Preparati.on of Pol~imide from 6-Amino-1-(4'-am~nophenyl)-l,3,3-trimet.hvlindane and benzo-ph~.nonetetracarboxylic acid dianhydride To a solution in 50 g N-methylpyrrolidone of 5.168 g (19.4 mole) of the pure 6-amino diamine, prepared in Example D, was added, over a 5 minute period, 6.444 g (20 mmoles) benzophenone-~etracarboxylic acid dianhy~ride (BTD~). The solution immediately became warm and noticebly viscous. The ` solution was allowed to cool to room temperature and stand for 18 hours. 20 ml of acetic anhvdride and 10 ml pyridine were added and the reaction mi~ture heated on a ste~m plate for 5 hours. The solution was then coagulated into 1 liter aoetone to afford a light yellow fibrous pol~er. An I.R. spectrum showed no ~ic acid bands. Inherent viscosi~y (~.5% in N-methylpyrrolidone, 25) was 0.55. TBA sho~ed Ta--329. The material was 40~ soluble in N-methylpyr~olidone, N,N-dimethylacetamide, dimethylfcrmamide an~ CHC13.
1036!747 Example 9 By e~sontially following the p--ocedure of Example 1, and xeplacing the 5t6)-amino-1-(4'-amino-phenyl)~l,3,3-tritn~thylindane reacted in that example by the followin~ aromatic diamines:
~a) 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane; and (b) an isomeric mixture of 5-amino-1-(4'-amino-~r',Ar'-dichlorophenyl)-Ar,Ar-dichloro-1,3,3-trimethylindane and 6-amino-1-(4'-amino-Ar',Ar'-dichlorophenyl)-A~,Ar-dichloro-1,3,3-trimethylindane, there are obtained soluble polyimides.
Example 10 By essentially followin~ the procedure of Ex~nple 1, soluble polyimides arc obtained by reactin~ equivalent amounts of 5~6)-smino-1-(4'-a~ino-ph~nyl)-1,3,3-trimethylindane and the following aromatic dianhydrides:
(a) 4,4'-oxydiphthalic anhydride (b) 4,4'-thiodiphthalic anhydride ~ c) 4,4'-sulfonyldi~hthalic anhydride (d) 4,4'-methylene diphthalic ~.nhydride (e) 4,-~'-ethylidenediphthalic anhydride (f) `3,4,3',4'-t~tracarboxylic triphenylamine dianhydride (g) 3,4,3',4'-tetracarboxylic tetraphenylsilane dianhydride (h) 3,4,3',4'-tetracarboxylio tetraphenylsiloxanP
dianhydride ~i) 3,~,3',4'-tetracarhoxylic ~riphenyl~hospl;ine oxide dianhydride (j) 3,4,3',4'-tetracarboxylic triphenylphosphate dianhydride (k) 1-(3',41-dicarboxy~henyl~-1,3,3-trimethylin-dane-5,5(6,7~-dicarboxylic acid dianhydride -.. . . .. . . .
Claims (13)
1. Soluble polyimides consisting essentially of the recurring unit having the formula I
wherein the four carbonyl groups are attached directly to separate carbon atoms, the carbonyl groups being ortho or peri to each other so that five or six membered imide rings are formed respectively;
wherein Z is a tetravalent radical containing at least one aromatic ring; and wherein Z' is a divalent organic radical selected from aromatic, aliphatic, alkyl aromatic, cycloaliphatic, and heterocyclic radicals, combinations of these, and radicals with heteroatom-containing bridging groups where the hetero-atom in the bridge is oxygen, sulfur, nitrogen, silicon or phosphorus, provided that 1) out of the total number of polyimide recurring units (A) 0 to 100 percent of such units have Z
equal to a phenylindane radical of the structural formula II
wherein R1 is hydrogen or an alkyl group of from 1 to 5 carbon atoms, and (B) 0 to 100 percent of such units have Z' equal to a phenylindane radical of the structural formula III
wherein R1 is hydrogen or alkyl group of from 1 to 5 carbon atoms, and R2, R3, R4 and R5 are independently hydrogen, halogen or (lower)alkyl having 1 to 4 carbon atoms, (2) out of the total number of Z and Z' radical units, at least 10 percent are phenylindane radical units, and (3) the polyamide acid, from which the soluble polyimide is produced, has an inherent viscosity of at least 0.1, measured at 25°C at a concentration of 0.5% by weight of the polymer in N,N-dimethylacetamide, N-methylpyrrolidone, or dimethylformamide.
wherein the four carbonyl groups are attached directly to separate carbon atoms, the carbonyl groups being ortho or peri to each other so that five or six membered imide rings are formed respectively;
wherein Z is a tetravalent radical containing at least one aromatic ring; and wherein Z' is a divalent organic radical selected from aromatic, aliphatic, alkyl aromatic, cycloaliphatic, and heterocyclic radicals, combinations of these, and radicals with heteroatom-containing bridging groups where the hetero-atom in the bridge is oxygen, sulfur, nitrogen, silicon or phosphorus, provided that 1) out of the total number of polyimide recurring units (A) 0 to 100 percent of such units have Z
equal to a phenylindane radical of the structural formula II
wherein R1 is hydrogen or an alkyl group of from 1 to 5 carbon atoms, and (B) 0 to 100 percent of such units have Z' equal to a phenylindane radical of the structural formula III
wherein R1 is hydrogen or alkyl group of from 1 to 5 carbon atoms, and R2, R3, R4 and R5 are independently hydrogen, halogen or (lower)alkyl having 1 to 4 carbon atoms, (2) out of the total number of Z and Z' radical units, at least 10 percent are phenylindane radical units, and (3) the polyamide acid, from which the soluble polyimide is produced, has an inherent viscosity of at least 0.1, measured at 25°C at a concentration of 0.5% by weight of the polymer in N,N-dimethylacetamide, N-methylpyrrolidone, or dimethylformamide.
2. Polyimides of Claim 1 wherein the Z radical units are equal to (a) (b) (c) a mixture of and , or (d) any mixture of said radical units, and the Z' radical units are equal to (1) a radical of structural formula III wherein R1, R2, R3, R4 and R5 are independently hydrogen or methyl, (2) wherein W is a covalent bond, methylene, sulfur, oxygen or sulfone and R6 and R7 are independently hydrogen, halogen or lower alkyl of form 1 to 5 carbon atoms, (3) wherein R8 is hydrogen, halogen or lower alkyl of from 1 to 5 carbon atoms, or (4) any mixture of said radical units.
3. Polyimides of Claim 2, wherein the Z' radical units are exclusively equal to a radical of structural formula III and R1, R2, R3, R4 and R5 are as defined in Claim 2.
4. Polyimides of Claim 2, wherein 100 to 10 percent of the Z' radical units are equal to a radical of structural formula III and R1, R2, R3, R4 and R5 are as defined in Claim 2, while 0 to 90 percent of such units are equal to (a) wherein R6, R7 and W are as defined in Claim 2, (b) wherein R8 is defined as in Claim 2, or (c) any mixture of said radical units.
5. Polyimides of Claim 2, wherein 0 to 100 percent of the Z radical units are equal to (a) , or (b) while 100 to 0 percent of such units are equal to a mixture of and
6. Polyimidines of Claim 2, wherein the Z' radical units are exclusively equal to a radical of structural formula III and R1, R2, R3, R4 and R5 are as defined in Claim 2, and the Z radical units are equal to a mixture of and
7. Polyimides of Claim 2, wherein the Z' radical units are equal to a mixture of and , and the Z radical units are equal to
8. Polyimides of Claim 2, wherein the Z' radical units are equal to a mixture of and , and the Z radical units are equal to
9. Polyimides of Claim 2, wherein the Z' radical units are equal to a mixture of and and , and the Z radical units are equal to a mixture of and
10. Polyimides of Claim 2, wherein the Z' radical units are equal to and the Z radical units are equal to
11. Polyimides of Claim 2, wherein the Z' radical units are equal to and the Z radical units are equal to
12. Polyimides of Claim 2, wherein the Z' radical units are equal to (a) (b) , or (c) any mixture of said radical units, wherein R6, R7, R8 and W are as defined in Claim 2 and the Z radical units are equal to a mixture of and
13. A polyimide of Claim 2. wherein the Z' radical units are equal to
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00402646A US3856752A (en) | 1973-10-01 | 1973-10-01 | Soluble polyimides derived from phenylindane diamines and dianhydrides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1036747A true CA1036747A (en) | 1978-08-15 |
Family
ID=23592765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA209,783A Expired CA1036747A (en) | 1973-10-01 | 1974-09-23 | Soluble polyimides derived from phenylindane diamines and dianhydrides |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3856752A (en) |
| JP (1) | JPS5645420B2 (en) |
| CA (1) | CA1036747A (en) |
| CH (1) | CH599266A5 (en) |
| DE (1) | DE2446383C2 (en) |
| FR (1) | FR2246583B1 (en) |
| GB (1) | GB1470705A (en) |
| IT (1) | IT1022463B (en) |
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|---|---|---|---|---|
| US4026876A (en) * | 1975-01-20 | 1977-05-31 | Ciba-Geigy Corporation | Soluble polyamide-imides derived from phenylindane diamines |
| JPS57143329A (en) * | 1981-03-03 | 1982-09-04 | Nippon Telegr & Teleph Corp <Ntt> | Photosensitive resin and its production |
| US4362859A (en) * | 1981-08-19 | 1982-12-07 | Standard Oil Company (Indiana) | Polyimides from bicyclo[4.2.0]octane-7,8-dimethyl-3,4,7,8-tetracarboxylic acid dianhydride (I) and bicyclo [4.2.0]octane-2,5 diphenyl-7,8-dimethyl-3,4,7,8-tetracarboxylic dianhydride |
| US4360657A (en) * | 1981-08-19 | 1982-11-23 | Standard Oil Company (Indiana) | Tricyclo[6.4.0.02,7 ]-dodecane-1,8,2,7-tetracarboxylic acid dianhydride and polyimides therefrom |
| US4358580A (en) * | 1981-08-19 | 1982-11-09 | Standard Oil Company (Indiana) | Polyimides from tricyclo dodecane-3,6-diphenyl-1,8,4,5-tetracarboxylic acid dianhydride and tricyclo dodecane tetracarboxylic acid anhydride |
| US4358582A (en) * | 1981-08-19 | 1982-11-09 | Standard Oil Company (Indiana) | Novel nonaromatic dianhydride and polyimides from tricyclo [4.2.1.02,5 ] nonane-3,4 dimethyl-3,4,7,8-tetracarboxylic acid dianhydride |
| EP0092524B1 (en) * | 1982-04-21 | 1987-08-12 | Ciba-Geigy Ag | Radiation-sensible coating composition and its use |
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| US5015270A (en) * | 1989-10-10 | 1991-05-14 | E. I. Du Pont De Nemours And Company | Phenylindane-containing polyimide gas separation membranes |
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| US5178914A (en) * | 1990-10-30 | 1993-01-12 | International Business Machines Corp. | Means of seeding and metallizing polymide |
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| US6866977B2 (en) | 2000-05-19 | 2005-03-15 | Eastman Kodak Company | Photoconductive elements having a polymeric barrier layer |
| US6593046B2 (en) | 2000-05-19 | 2003-07-15 | Heidelberger Druckmaschinen Ag | Photoconductive elements having a polymeric barrier layer |
| US7264913B2 (en) * | 2002-11-21 | 2007-09-04 | Az Electronic Materials Usa Corp. | Antireflective compositions for photoresists |
| US7081511B2 (en) * | 2004-04-05 | 2006-07-25 | Az Electronic Materials Usa Corp. | Process for making polyesters |
| US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
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| US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
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| KR102219068B1 (en) | 2013-05-17 | 2021-02-23 | 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. | Novel polymer and thermosetting composition containing same |
| WO2015001422A2 (en) * | 2013-07-02 | 2015-01-08 | King Abdullah University Of Science And Technology | Dianhydrides, polyimides, methods of making each, and methods of use |
| RU2748127C2 (en) * | 2015-07-23 | 2021-05-19 | ХАНТСМАН ЭДВАНСТ МАТИРИАЛЗ АМЕРИКАС ЭлЭлСи | Curable benzoxazine compositions |
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| EP3401305A1 (en) | 2017-05-12 | 2018-11-14 | Dottikon Es Holding Ag | Indane derivatives and their use in organic electronics |
| TWI774767B (en) * | 2017-05-12 | 2022-08-21 | 瑞士商多蒂孔股份有限公司 | Indane derivatives and their use in organic electronics |
| JP7235317B2 (en) | 2017-06-16 | 2023-03-08 | フジフイルム エレクトロニック マテリアルズ ユー．エス．エー．， インコーポレイテッド | multilayer structure |
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| US11721543B2 (en) | 2019-10-04 | 2023-08-08 | Fujifilm Electronic Materials U.S.A., Inc. | Planarizing process and composition |
| CN111484412A (en) * | 2020-05-26 | 2020-08-04 | 上海华谊树脂有限公司 | Method for synthesizing compound containing indan structure |
| JP2021194641A (en) | 2020-06-17 | 2021-12-27 | エボニック ファイバース ゲゼルシャフト ミット ベシュレンクテル ハフツングEvonik Fibres GmbH | Crosslinked hollow fiber membrane and new production method for the same |
| CN112409187B (en) * | 2020-11-30 | 2022-09-02 | 山东华夏神舟新材料有限公司 | Synthesis method of 6-amino-1- (4-aminophenyl) -1,3,3-trimethylindane |
| JP2024501071A (en) | 2020-12-04 | 2024-01-10 | トウレ コンポジット マテリアルズ アメリカ，インコーポレイテッド | Prepreg and carbon fiber reinforced composites |
| CN115181115B (en) * | 2021-11-15 | 2023-10-10 | 同济大学 | Spiro-bisbenzoxazole cyclic diamine, colorless transparent polyimide derived from same and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3649596A (en) * | 1964-08-05 | 1972-03-14 | Du Pont | Polyamic acid from tricyclo-(4.2.2.0 2 5)-dec-7-ene - 3 4 9 10 - tetracarboxylic dianhydride |
| US3639356A (en) * | 1965-10-12 | 1972-02-01 | Chevron Res | Tricyclo-decene tetracarboxylic acid diimide polymers |
| DE2009739A1 (en) * | 1970-03-03 | 1971-09-30 | Bayer | Aromatic polyimides with increased solubility |
| US3748338A (en) * | 1972-05-01 | 1973-07-24 | Ciba Geigy Corp | Soluble polyimides from aromatic dianhydrides and 10,10-di-(p-aminophenyl)thioxanthene |
-
1973
- 1973-10-01 US US00402646A patent/US3856752A/en not_active Expired - Lifetime
-
1974
- 1974-09-23 CA CA209,783A patent/CA1036747A/en not_active Expired
- 1974-09-26 JP JP11138674A patent/JPS5645420B2/ja not_active Expired
- 1974-09-26 GB GB4193974A patent/GB1470705A/en not_active Expired
- 1974-09-27 CH CH1309474A patent/CH599266A5/xx not_active IP Right Cessation
- 1974-09-27 DE DE2446383A patent/DE2446383C2/en not_active Expired
- 1974-09-30 IT IT27895/74A patent/IT1022463B/en active
- 1974-09-30 FR FR7432837A patent/FR2246583B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1470705A (en) | 1977-04-21 |
| DE2446383C2 (en) | 1982-04-01 |
| JPS5062300A (en) | 1975-05-28 |
| US3856752A (en) | 1974-12-24 |
| CH599266A5 (en) | 1978-05-31 |
| FR2246583B1 (en) | 1983-07-01 |
| FR2246583A1 (en) | 1975-05-02 |
| IT1022463B (en) | 1978-03-20 |
| JPS5645420B2 (en) | 1981-10-26 |
| DE2446383A1 (en) | 1975-04-03 |
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