Halogenated polyimide resins prepared by addition reactions

Claim 2

A composition of matter consisting essentially of low molecular weight prepolymers substituted with a halogen selected from the group consisting of chlorine and fluorine, the prepolymers having only one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR11## where R 1 is a tetravalent aryl radical, each R 2 is independently selected from the group consisting of alkyl and hydrogen, at least one R 2 being alkyl, R 3 is a divalent aryl radical, E 1 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 10,000.

Claim 3

A composition of matter consisting essentially of low molecular weight prepolymers substituted with a halogen selected from the group consisting of chlorine and fluorine, the prepolymers having only one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR12## where R 1 is a tetravalent aryl radical, each R 2 is independently selected from the group consisting of alkyl and hydrogen, at least one R 2 being alkyl, R 3 is a divalent aryl radical, E 2 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 10,000.

Claim 4

A composition of matter consisting essentially of low molecular weight prepolymers substituted with a halogen selected from the group consisting of chlorine and fluorine, the prepolymers having only one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR12## where R 1 is a tetravalent aryl radical, each R 2 is independently selected from the group consisting of alkyl and hydrogen, at least one R 2 being alkyl, R 3 is a divalent aryl radical, E 2 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 10,000.

Claim 5

A composition of matter consisting essentially of a mixture of the monomers: (a) a dialkyl,, trialkyl, or tetraalkylester of an aromatic tetracarboxylic acid, the ester being substituted with a halogen selected from the group consisting of fluorine and chlorine; (b) an aromatic diamine; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the aromatic diamine or the ester to form an end cap radical that precludes further reaction of the aromatic diamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), aromatic diamine (b), and end cap compound (c) are present in a molar ratio such that heating the mixture forms low molecular weight prepolymers having only one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula of either: ##STR13## where R 1 is a tetravalent aryl radical provided by the tetracarboxylic acid, each R 2 is independently selected from the group consisting of alkyl and hydrogen, at least one R 2 being alkyl, R 3 is a divalent aryl radical provided by the aromatic diamine, E 1 is an end cap radical provided by the end cap compound when the prepolymers are of formula (d), and E 2 is an end cap radical provided by the end cap compound when the prepolymers are of formula (e), the end cap radicals having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 10,000.

Claim 6

A composition of matter consisting essentially of a mixture of the monomers: (a) a dialkyl,, trialkyl, or tetraalkylester of an aromatic tetracarboxylic acid, the ester being substituted with a halogen selected from the group consisting of fluorine and chlorine; (b) an aromatic diamine; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the aromatic diamine or the ester to form an end cap radical that precludes further reaction of the aromatic diamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), aromatic diamine (b), and end cap compound (c) are present in a molar ratio such that heating the mixture forms low molecular weight prepolymers having only one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula of either: ##STR13## where R 1 is a tetravalent aryl radical provided by the tetracarboxylic acid, each R 2 is independently selected from the group consisting of alkyl and hydrogen, at least one R 2 being alkyl, R 3 is a divalent aryl radical provided by the aromatic diamine, E 1 is an end cap radical provided by the end cap compound when the prepolymers are of formula (d), and E 2 is an end cap radical provided by the end cap compound when the prepolymers are of formula (e), the end cap radicals having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 10,000.

Claim 7

A composition of matter consisting essentially of a mixture of compounds of the formulas: ##STR14## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and each R 2 is independently selected from the group consisting of alkyl and hydrogen; and at least two R 2 are alkyl; H.sub.2 N--R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and ##STR15## wherein R 2 is as defined in (a) and at least one R 2 is alkyl, and R 4 is a divalent radical of the formula: ##STR16## wherein each R 5 is independently selected from the group consisting of hydrogen and lower alkyls; and wherein the molar ratio of a:b:c is n:(n+1):1, wherein n is from about 2 to about 20.

Claim 8

A composition of matter consisting essentially of a mixture of compounds of the formulas: ##STR14## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and each R 2 is independently selected from the group consisting of alkyl and hydrogen; and at least two R 2 are alkyl; H.sub.2 N--R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and ##STR15## wherein R 2 is as defined in (a) and at least one R 2 is alkyl, and R 4 is a divalent radical of the formula: ##STR16## wherein each R 5 is independently selected from the group consisting of hydrogen and lower alkyls; and wherein the molar ratio of a:b:c is n:(n+1):1, wherein n is from about 2 to about 20.

Claim 9

A polyimide resin having a molecular weight greater than 10,000 prepared by crosslinking the prepolymers of claim 1 or 2.

Claim 10

An article of manufacture comprising fibers impregnating a polyimide resin matrix having a molecular weight greater than 10,000 and prepared by crosslinking the prepolymers of claim 1 or 2.

Claim 11

Fibers coating with the composition of matter of claim 1, 2, 3 or 4.

Claim 12

The polyimide resin of claim 5 having a T g greater than 600° F.

Claim 13

The polyimide resin of claim 8 having a weight loss of less than 10% when heated in air at 700° F. for 100 hours.

Claim 14

The invention of claim 1 or 3 wherein the end cap compound is: ##STR17## wherein each R 2 is independently selected from the group consisting of alkyl and hydrogen and at least one R 2 is alkyl, and R 4 is a divalent radical of the formula: ##STR18## wherein each R 5 is independently selected from the group consisting of hydrogen and lower alkyls.

Claim 15

The invention of claim 1, 2, 3 or 4 wherein the prepolymers have a molecular weight greater than 3,000 and are capable of flowing during heat processing to remove voids at temperature less than about 500° F. and pressures less than about 200 psi.

Claim 16

A process for preparing polyimide resin comprising the steps of: (1) reacting, by heating to at least about 375° F., a mixture of: (a) an ester having the formula: ##STR19## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine and R 2 is alkyl or hydrogen, and at least two of R 2 are alkyl, (b) an aromatic diamine of the formula [ 2 N--R 3 --NH 2 ]NH 2 --R 3 --NH 2 wherein R 3 is a divalent aryl radical; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the aromatic diamine or the ester to form an end cap radical that precludes further reaction of the aromatic diamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), aromatic diamine (b), and end cap compound (c) are present in a molar ratio such that the mixture forms low molecular weight polyimide prepolymers having an aromatic diamine end group and only one end cap radical, the prepolymers being suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the polyimide prepolymers having an average molecular weight in the range of about 2000 to about 10,000; and (2) heating the prepolymers to a temperature of at least about 690° F. to obtain polyimide resins having an average molecular weight in excess of 10,000.

Claim 17

A process for preparing polyimide resin comprising the steps of: (1) reacting, by heating to at least about 375° F., a mixture of: (a) an ester having the formula: ##STR19## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine and R 2 is alkyl or hydrogen, and at least two of R 2 are alkyl, (b) an aromatic diamine of the formula [ 2 N--R 3 --NH 2 ]NH 2 --R 3 --NH 2 wherein R 3 is a divalent aryl radical; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the aromatic diamine or the ester to form an end cap radical that precludes further reaction of the aromatic diamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), aromatic diamine (b), and end cap compound (c) are present in a molar ratio such that the mixture forms low molecular weight polyimide prepolymers having an aromatic diamine end group and only one end cap radical, the prepolymers being suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the polyimide prepolymers having an average molecular weight in the range of about 2000 to about 10,000; and (2) heating the prepolymers to a temperature of at least about 690° F. to obtain polyimide resins having an average molecular weight in excess of 10,000.

Claim 18

A process for preparing polyimide resins comprising the steps of: (1) reacting, by application of heat to at least about 375° F., a mixture of compounds of the formulas: ##STR20## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and R 2 is alkyl or hydrogen, and at least two of R 2 are alkyl, H.sub.2 N--R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and ##STR21## wherein R 2 is as defined in (a) and at least one R 2 is alkyl, and R 4 is a divalent radical of the formula: ##STR22## wherein R 5 is hydrogen or lower alkyl, and wherein the molar ratio of a:b:c is [n:(n):1] n:(n+1):1, wherein n is from 2 to about 20, and wherein said application of heat obtains from the mixture polyimide prepolymers having an average molecular weight in the range of about 200 to about 10,000; and (2) heating the prepolymers to a temperature of at least about 690° F. to obtain polyimide resins having an average molecular weight in excess of 10,000.

Claim 19

A process for preparing polyimide resins comprising the steps of: (1) reacting, by application of heat to at least about 375° F., a mixture of compounds of the formulas: ##STR20## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and R 2 is alkyl or hydrogen, and at least two of R 2 are alkyl, H.sub.2 N--R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and ##STR21## wherein R 2 is as defined in (a) and at least one R 2 is alkyl, and R 4 is a divalent radical of the formula: ##STR22## wherein R 5 is hydrogen or lower alkyl, and wherein the molar ratio of a:b:c is [n:(n):1] n:(n+1):1, wherein n is from 2 to about 20, and wherein said application of heat obtains from the mixture polyimide prepolymers having an average molecular weight in the range of about 200 to about 10,000; and (2) heating the prepolymers to a temperature of at least about 690° F. to obtain polyimide resins having an average molecular weight in excess of 10,000.

Claim 20

A process for preparing polyimide resins comprising the steps of: (1) heating a solution of solvent and from about 30 percent to about 90 percent by weight of a mixture of compounds of the following formulas: ##STR23## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and R 2 is alkyl or hydrogen; and at least two R 2 are alkyl; H.sub.2 N--R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and ##STR24## wherein R 2 is as defined in (a) and at least one R 2 is alkyl, and R 4 is a divalent radical of the formula: ##STR25## wherein R 5 is hydrogen or lower alkyl, and wherein the molar ratio of a:b:c is n:(n+1):1, wherein n is from 2 to about 20, wherein the solution is heated to a temperature sufficiently high to remove the solvent, the solvent being inert to the mixture, (2) thereafter heating the mixture to at least about 375° F. polyimide prepolymers having an average molecular weight in the range of about 2000 to about 10,000; (3) heating the prepolymers to a temperature of from about 690 to about 750° F. for a sufficiently long time to obtain crosslinked thermally stable polyimide resin having an average molecular weight in excess of 10,000; and (4) curing the polyimide resin at a temperature of at least about 700° F. for at least 12 hours to improve the thermal stability and physical properties of the polyimide resin.

Claim 21

A process for preparing polyimide resins comprising the steps of: (1) heating a solution of solvent and from about 30 percent to about 90 percent by weight of a mixture of compounds of the following formulas: ##STR23## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and R 2 is alkyl or hydrogen; and at least two R 2 are alkyl; H.sub.2 N--R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and ##STR24## wherein R 2 is as defined in (a) and at least one R 2 is alkyl, and R 4 is a divalent radical of the formula: ##STR25## wherein R 5 is hydrogen or lower alkyl, and wherein the molar ratio of a:b:c is n:(n+1):1, wherein n is from 2 to about 20, wherein the solution is heated to a temperature sufficiently high to remove the solvent, the solvent being inert to the mixture, (2) thereafter heating the mixture to at least about 375° F. polyimide prepolymers having an average molecular weight in the range of about 2000 to about 10,000; (3) heating the prepolymers to a temperature of from about 690 to about 750° F. for a sufficiently long time to obtain crosslinked thermally stable polyimide resin having an average molecular weight in excess of 10,000; and (4) curing the polyimide resin at a temperature of at least about 700° F. for at least 12 hours to improve the thermal stability and physical properties of the polyimide resin.

Claim 22

Thermally stable polyimide resin having an average molecular weight in excess of 10,000 prepared by the process of claim 12, 13 or 14.

Claim 23

An article of manufacture comprising fibers impregnating the polyimide resin of claim 15.

Claim 24

The polyimide resin of claim 15 having a T g greater than 600° F.

Claim 25

The polyimide resin of claim 17 having a weight loss of less about 10% when heated in air at 700° F. for 100 hours.

Claim 26

A process for preparing polyimide resins comprising the steps of: (1) heating a solution of solvent and from about 30 percent to about 90 percent by weight of a mixture of compounds of the following formulas: ##STR26## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and R 2 is alkyl or hydrogen; and at least two R 2 are alkyl; NH.sub.2 --R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the ester to form an end cap radical that precludes further reaction of the aromatic diamine with the ester, and (iii) being capable of undergoing addition polymerization, and wherein the molar ratio of a:b:c is n:n:1, wherein n is from 2 to about 20, wherein the solution is heated to a temperature sufficiently high to remove the solvent, the solvent being inert to the mixture, (2) thereafter heating the mixture to at least about 375° F. to obtain polyimide prepolymers having an average molecular weight in the range of about 2000 to about 10,000; (3) heating the prepolymers to a temperature of from about 690 to about 750° F. for a sufficiently long time to obtain crosslinked thermally stable polyimide resin having an average molecular weight in excess of 10,000; and (4) curing the polyimide resin at a temperature of at least about 700° F. for at least 12 hours to improve the thermal stability and physical properties of the polyimide resin.

Claim 27

A process for preparing polyimide resins comprising the steps of: (1) heating a solution of solvent and from about 30 percent to about 90 percent by weight of a mixture of compounds of the following formulas: ##STR26## wherein R 1 is a tetravalent aryl radical substituted with a halogen selected from the group consisting of chlorine and fluorine, and R 2 is alkyl or hydrogen; and at least two R 2 are alkyl; NH.sub.2 --R.sub.3 --NH.sub.2 ( b) wherein R 3 is a divalent aryl radical; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the ester to form an end cap radical that precludes further reaction of the aromatic diamine with the ester, and (iii) being capable of undergoing addition polymerization, and wherein the molar ratio of a:b:c is n:n:1, wherein n is from 2 to about 20, wherein the solution is heated to a temperature sufficiently high to remove the solvent, the solvent being inert to the mixture, (2) thereafter heating the mixture to at least about 375° F. to obtain polyimide prepolymers having an average molecular weight in the range of about 2000 to about 10,000; (3) heating the prepolymers to a temperature of from about 690 to about 750° F. for a sufficiently long time to obtain crosslinked thermally stable polyimide resin having an average molecular weight in excess of 10,000; and (4) curing the polyimide resin at a temperature of at least about 700° F. for at least 12 hours to improve the thermal stability and physical properties of the polyimide resin.

Claim 28

The process of claim 12 or 13 comprising the additional step of curing the polyimide resins at a temperature of at least about 700° F. for at least 12 hours to improve the thermal stability and physical properties of the polyimide resins.

Claim 29

A polyimide resin having a molecular weight greater than 10,000 prepared by the steps of heating the composition of matter of claim 3 to form prepolymers having the formula of either (d) or (e), and cross-linking the formed prepolymers.

Claim 30

A polyimide resin having a molecular weight greater than 10,000 prepared by the steps of heating the composition of matter of claim 4 to form a prepolymers, and crosslinking the formed prepolymers.

Claim 31

An article of manufacture comprising fibers impregnating a polyimide resin matrix having a molecular weight greater than 10,000 and prepared by the steps of heating the composition of matter of claim 3 to form prepolymers having the formula of either (d) or (e), and cross-linking the formed prepolymers.

Claim 32

An article of manufacture comprising fibers impregnating the polyimide resin matrix having a molecular weight greater than 10,000 and prepared by the steps of heating the composition of matter of claim 4 to from a prepolymer, and crosslinking the formed prepolymer.

Claim 33

The polyimide resin of claim 21 or 22 having a T g greater than 600° F.

Claim 34

The polyimide resin of claim 25 having a weight loss of less than 10 percent when heated in air at 700° F. for 100 hours.

Claim 35

The composition of matter of claim 3 wherein monomer (a) is one step of 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride).

Claim 36

The composition of matter of claim 4 wherein compound (a) is an ester of 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride).