Melt-fusible polyimides

Claim 2

A melt-fusible polyimide consisting essentially of the following repeating units (N) where Q in each repeating unit, independently of any other unit, is a divalent organic radical selected from the following: where G is O or S, and Z is hydrogen or phenyl; and, when Z is hydrogen, both terminal covalent bonds are either in the ortho or meta position with respect to G; while, when Z is phenyl, both terminal covalent bonds are in ortho, meta, or para position with respect to G; where G is O or S; and R is phenyl, biphenyl, or naphthyl; where G is O or S and both terminal covalent bonds are in the ortho or meta position with respect to G; and

Claim 3

A polyimide of Claim 1 represented by formula (N) of Claim 1, wherein Q is the radical remaining on removal of the amino groups from a diamine H 2 N-Q-NH 2 selected from the group consisting of: l,3-bis(2-aminophenoxy)benzene, 1,2-bis(3-aminophenoxy)benzene, 1,2-bis(2-aminophenoxy)benzene, l,4-bis(3-aminophenoxy)benzene, l,4-bis(2-aminophenoxy)benzene, l,3-bis(3-aminophenoxy)benzene, 2,4-diaminodiphenyl ether, 1-(2,4-diaminophenoxy)naphthalene, 2-(2,4-dianinophenoxy)naphthalene, 2-(2,4-diaminophenoxy)biphenyl, 4-(2,4-diaminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)-2-phenylbenzene, 2,2-bis[4-(2-aminophenoxy)phenyl]propane, and 2,2-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]propane.

Claim 4

A polyimide of Claim 2 wherein Q is the radical remaining on removal of the amino groups from a diamine H 2 N-Q-NH 2 selected from the group consisting of: l,3-bis(3-aminophenoxy)benzene, l,3-bis(2-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, l,4-bis(4-aminophenoxy)-2-phenylbenzene, 2,2-bis[4-(2-aminophenoxy)phenyl]propane, and 2-(2,4-diaminophenoxy)biphenyl.

Claim 5

A polyimide of Claim 1, wherein G in each repeating unit Q is 0.

Claim 6

any one of to 4 5. A polyimide of/Claimsl/which contains an excess of up to 10% of diamine H 2 N-Q-NH 2 .

Claim 7

A polyimide of Claim 5 wherein the excess of diamine is end-capped.

Claim 8

A polyimide of/Claimsl/which contains an excess of up to 10% of pyromellitic dianhydride.

Claim 9

A polyimide of Claim 7 wherein the excess of dianhydride is end-capped.

Claim 10

A polyimide of any one of/Claims 1/to 8 which is melt-processible. compression-moulding,

Claim 11

An article obtained by extruding/or injection-molding a polyimide of any one of/Claims/1 to 9.

Claim 12

ll. A monofilament or fiber made from a polyimide of any one of/Clains/1 to 9.

Claim 13

ll. A monofilament or fiber made from a polyimide of any one of/Clains/1 to 9.

Claim 14

A substantially void-free composite structure consisting essentially of a fibrous substrate impregnated with a melt-fusible polyimide containing up to about 10% of end-capped amino or anhydride groups and consisting essentially of the following repeating units (N): where Q in each repeating unit, independently of any other unit, is a divalent organic radical selected from the following: where G is O or S; and Z is hydrogen or phenyl: and, when Z is hydrogen, both terminal covalent bonds are either in the ortho or meta position with respect to G; while, when Z is phenyl, both terminal covalent bonds are in ortho, meta, or para position with respect to G; where G is O or S; and R is phenyl, biphenyl, or naphthyl; where G is O or S; and

Claim 15

A substantially void-free composite structure consisting essentially of a fibrous substrate impregnated with a melt-fusible polyimide containing up to about 10% of end-capped amino or anhydride groups and consisting essentially of the following repeating units (N): where Q in each repeating unit, independently of any other unit, is a divalent organic radical selected from the following: where G is O or S; and Z is hydrogen or phenyl: and, when Z is hydrogen, both terminal covalent bonds are either in the ortho or meta position with respect to G; while, when Z is phenyl, both terminal covalent bonds are in ortho, meta, or para position with respect to G; where G is O or S; and R is phenyl, biphenyl, or naphthyl; where G is O or S; and

Claim 16

A composite of Claim 12 wherein Q is a divalent radical remaining on removal of the amino groups from the diamine: H 2 N-Q-NH 2 selected from the group consisting of: 1,3-bis(2-aminophenoxy)benzene, 1,2-bis(3-aminophenoxy)benzene, 1,2-bis(2-aminophenoxy)benzene, l,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1.4-bis(2-aminophenoxy)benzene, 2,4-diaminodiphenyl ether, 1-(2,4-diaminophenoxy)naphthalene, 2-(2,4-diaminophenoxy)naphthalene, 2-(2,4-diaminophenoxy)biphenyl, 4-(2,4-diaminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)-2-phenylbenzene, 2,2-bis[4-(2-aminophenoxy)phenylpropane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane,and 2,2-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]propane.

Claim 17

A composite of Claim 13 wherein H 2 N-Q-NH 2 is selected from the group consisting of: 1, 3 -bis(3-aminophenoxy)benzene, U122060 1,3-bis(2-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)-2-phenylbenzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2-(2,4-diaminophenoxy)biphenyl.

Claim 18

A composite of Claim 14 wherein the repeating unit of the polyimide is of two types, H 2 N- Q-NH 2 for one type being l,3-bis(3-aminophenoxy)benzene and for the other type 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

Claim 19

A composite structure which is a substantially void-free prepreg consisting essentially of a fibrous substrate impregnated with a concentrated solution of a polyamide acid, which is a precursor of a melt-fusible polyimide, the volatiles content of the prepreg being at most about 25% of its total weight, the melt-fusible polyimide which can be obtained by heating the precursor to a sufficiently high temperature consisting essentially of the following repeating units (N): where Q in each repeating unit, independently of any other unit, is a divalent organic radical selected from the following: where G is O or S, and Z is hydrogen or phenyl; and, when Z is hydrogen, both terminal covalent bonds are either in the ortho or meta position with respect to G; while, when Z is phenyl, both terminal covalent bonds are in ortho, meta, or para position with respect to G; where G is 0 or S; and R is phenyl, biphenyl, or naphthyl; where G is O or S; and

Claim 20

A composite structure which is a substantially void-free prepreg consisting essentially of a fibrous substrate impregnated with a concentrated solution of a polyamide acid, which is a precursor of a melt-fusible polyimide, the volatiles content of the prepreg being at most about 25% of its total weight, the melt-fusible polyimide which can be obtained by heating the precursor to a sufficiently high temperature consisting essentially of the following repeating units (N): where Q in each repeating unit, independently of any other unit, is a divalent organic radical selected from the following: where G is O or S, and Z is hydrogen or phenyl; and, when Z is hydrogen, both terminal covalent bonds are either in the ortho or meta position with respect to G; while, when Z is phenyl, both terminal covalent bonds are in ortho, meta, or para position with respect to G; where G is 0 or S; and R is phenyl, biphenyl, or naphthyl; where G is O or S; and

Claim 21

A prepreg of Claim 16 wherein Q is a divalent radical remaining on removal of the amino groups from a diamine H 2 N-Q-NH 2 selected from the group consisting of: 1,3-bis(2-aminophenoxy)benzene, 1,2-bis(3-aminophenoxy)benzene, l,2-bis(2-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenaxy)benzene, 1,4-bis(2-aminophenoxy)benzene, 2,4-diaminodiphenyl ether, l-(2,4-diaminophenoxy)naphthalene, 2-(2,4-diaminophenoxy)naphthalene, 2-(2,4-diaminophenoxy)biphenyl, 4-(2,4-diaminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-aminophenoxy)phenyl]propane 1,4-bis(4-aminophenoxy)-2-phenylbenzene, and 2,2-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]propane.

Claim 22

A prepreg of Claim 17, wherein the repeating unit of the polyimide is of two types, H 2 N-Q-NH 2 for one type being 1,3-bis(3-aminophenoxy)benzene and for the other type 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

Claim 23

A composite structure selected from the composites of any of the Claims 12-15 and prepregs of any of the Claims 16-18, wherein the fibrous substrate is a preformed woven, non-woven, or felted material. any one of 12 to

Claim 24

A composite structure of/Clains/19 wherein the fibrous substrate is in the form of unidirectional continuous fibers.

Claim 25

A composite structure of/Clains/19 wherein the fibrous substrate is in the form of unidirectional continuous fibers.

Claim 26

A composite structure of any of the Claims 12-20, wherein the fibrous substrate is selected from the group consisting of carbon, aramid, glass, boron, and asbestos fibers.

Claim 27

A composite structure of any of the Claims 12-21 wherein the fiber content is about 40-65 volume percent.

Claim 28

A composite structure of any of the Claims 12-22, which is in tape form.

Claim 29

A shaped article formed from any of the composite structures of Claims 12-23.

Claim 30

A polyimide composition comprising a polyimid of any one of /Claim 1/to 9 containing a reinforcing additive in fiber or particulate form.

Claim 31

A polyimide composition of Claim 25, wherein the volume proportion of reinforcing additive is 5-70%.

Claim 32

A composition of Claim 26 wherein the volume proportion of reinforcing additive is 5-50%.

Claim 33

A composition of Claim 27 wherein the volume proportion of reinforcing additive is 5-25%.

Claim 34

A film of a polyimide of any of the Claims 1-9.

Claim 35

A solution in a polar solvent of a pyromellitic diester diacid and of a diamine, either component being present in a 0-10% molar excess, the diamine being either a single species or more than one species selected from the following classes (a) through (d): where 3 is O or S, and Z is hydrogen or phenyl; and, when Z is hydrogen, both terminal amine groups are either in the ortho or meta position with respect to G; while, when Z is phenyl, both terminal amine groups are in ortho, meta, or para position with respect to G; where G is O or S; and R is phenyl, biphenyl, or naphthyl; where G is 0 or S, and both amine groups are in the ortho or meta position with respect to G; and

Claim 36

A solution in a polar solvent of a pyromellitic diester diacid and of a diamine, either component being present in a 0-10% molar excess, the diamine being either a single species or more than one species selected from the following classes (a) through (d): where 3 is O or S, and Z is hydrogen or phenyl; and, when Z is hydrogen, both terminal amine groups are either in the ortho or meta position with respect to G; while, when Z is phenyl, both terminal amine groups are in ortho, meta, or para position with respect to G; where G is O or S; and R is phenyl, biphenyl, or naphthyl; where G is 0 or S, and both amine groups are in the ortho or meta position with respect to G; and

Claim 37

A solution of Claim 30 wherein the diamine is selected from the group consisting of: 1,3-bis(2-aminophenoxy)benzene, 1,2-bis(3-aminophenoxy)benzene, 1,2-bis(2-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(2-aminophenoxy)benzene, 2,4-diaminodiphenyl ether, 1-(2,4-diaminophenoxy)naphthalene, 2-(2,4-diaminophenoxy)naphtbalene, 2-(2,4-diaminophenoxy)bipbenyl, 4-(2,4-diaminophenoxy)bipbenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)-2-phenylbenzene, and 2,2-bis[3,5-dichlaro-4-(4-aminophenoxylphenyl]propane.

Claim 38

A solution of Claim 30 wherein G in each repeating unit Q is O.

Claim 39

A polyimide of any one of the Claims 1-9 which has reversible crystallinity.

Claim 40

A diamine selected from the class consisting of: 1,4-bis(4-aminophenoxy)-2-phenylbenzene; 1,4-bis(2-aminophenoxy)benzene; 1,3-bis(2-aminophenoxy)benzene; 2-(2,4-diaminophenoxy)biphenyl; and 4-(2,4-diaminophenoxy)biphenyl.

Claim 41

A diamine selected from the class consisting of: 1,4-bis(4-aminophenoxy)-2-phenylbenzene; 1,4-bis(2-aminophenoxy)benzene; 1,3-bis(2-aminophenoxy)benzene; 2-(2,4-diaminophenoxy)biphenyl; and 4-(2,4-diaminophenoxy)biphenyl.

Claim 42

A diamine of Claim 34 which is 1,4-bis (4-aminophenoxy)-2-phenylbenzene.

Claim 43

A diamine of Claim 34 which is 1,4-bis (2-aminophenoxy)benzene.

Claim 44

A diamine of Claim 34 which is 1,3-bis (2-aminophenoxy)benzene.

Claim 45

A diamine of Claim 34 which is 2-(2,4-diaminophenoxy)biphenyl.

Claim 46

A diamine of Claim 34 which is 4-(2,4-diaminophenoxy)biphenyl.

Claim 47

A composite structure which is a substantially void-free prepreg consisting essentially of a fibrous substrate impregnated with a concentrated solution of any one of Claims 30 to 32, the volatiles content of the prepreg being at most about 25% of its total weight.

Claim 48

A composite structure of any one of Claims 12 to 23 wherein G in each repeating unit Q is 0.