This technology is available from Temarex Corporation.

HIGH PERFORMANCE POLYIMIDES: Composites, Microelectronics

Title: THERMOPLASTIC COPOLYIMIDES AND COMPOSITES THEREFROM

Inventor(s):F. Harris, P. Gabori

Disclosure 200 U.S. Patent 5,328,979

The invention allows polymers with Tg's above 300¯C to be consolidated into laminates with autoclave temperatures (150-250 psi).Such polymers otherwise could not be melt-processible at these low pressures.

Another advantage of this invention is the application of a "reactive plasticizer approach" as an aid in processing the polyimide resins.This approach is especially useful in the reactive monomer technique used in the fabrication of fiber-reinforced composites.In addition, the premature or inadvertent build-up of a few very high molecular weight chains in the copolymers' melt, that would greatly increase their viscosity is avoided.

Still another advantage of this invention is that the copolyimides structure changes from a more-or-less random arrangement of repeat units to one in which similar repeat units are arranged in blocks during processing.The random arrangement can disrupt the early development of crystallinity, thus facilitating processing at lower temperatures.

The invention additionally encompasses copolyimides precursors, reinforced polyimide composites and laminates made from said polyimides where the composite is reinforced by fibrous materials. This is achieved by reacting at least one aromatic dianhydride where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another, with at least one diamine which is capable of a transimidization reaction upon incorporation into the polyimide backbone, and with at least one other diamine which is not capable of undergoing such reaction, the diamine which is capable of undergoing the transimidization reaction being present in an amount of from 1-50 mole percent in relation to the diamine that is not susceptible to transimidization.

These thermoplastic copolyimides and reinforced copolyimide molecular or laminated composites have high fracture resistance, outstanding modulus, tensile, excellent oxidative stability, excellent energy absorption characteristics, very low coefficient of expansion, excellent thermal stability, excellent dielectric properties at less expense than most existing polymers.These properties will make the polyimides and polyimide components ideally suited for use in the production of high performance compositions.

The polyimides are suitable for the manufacture of shaped articles of very diverse types, such as fibers, films, coatings, foams, laminates, molding powders, pressed articles and the like with the use of customary additives, such as pigments, fillers and the like.The composites may be formed by any technique which is generally known in the art such as compression molded, autoclaving, injection molding, etc.

Using these polyimides it is now possible to produce 32 ply laminates using an autoclave process that has reproducible properties.

Title:THERMOPLASTIC POLYIMIDES AND COMPOSITES THEREFROM

Inventor(s):F. Harris

Disclosure 138-DIV U.S. Patent 5,360,671 Disclosure 138-DIV-CIP U.S. Patent not yet issued

A new class polyimide and polyimide precursor based on diaryl oxyalkylene diamines, such as 1,3-bis[4-aminophenoxy]-2,2-dimethyl propane, a process for their preparation and their use as the continuous phase for the manufacture of composites and composite laminates reinforced by reinforcing agents such as carbon fiber, Kevlar) and other similar high strength reinforcing agents.The polyimides and molecular composites obtained from the diamines according to the invention show thermoplastic properties, excellent flex fatigue and fracture resistance, and excellent thermal and oxidative stability.

This technology provides a new way to make composites, which typically could only be compression molded, processable by less dramatic means through the incorporation of a reactive plasticizer.This technology is suitable for the manufacture of shaped articles of very diverse types, such as fibers, films, sheets, coatings, foams, laminates, molding powders, press articles and the like.The composites may be formed by any technique which is generally known in the art such as compression molded, autoclaving, injection molding, etc.

Applications that samples were prepared and tested for were (1) the next generation fan blades for aircraft (panels were 100 ply laminates), and (2) High Speed Civil Transport Car and\or Fast Rail Car.Prior to product commercialization incorporating this technology, the composite market bottomed out in 1991/92 time frame and major new products were canceled by both industry and government.The same and similar type applications remain viable today for this technology.

Title:ORGANO-SOLUBLE POLYIMIDES FROM SUBSTITUTED DIANHYDRIDES

Inventor(s):F. Harris

Disclosure 225 U.S. Patent 5,395,918

This invention relates to new biphenyl dianhydrides, and new polyimides and copolyimides made from the dianhydrides.The synthesized polyimides exhibit significantly enhanced solubility when the dianhydrides are substituted, particularly at the 2 and 2' positions on the phenyl rings.

The main advantages of this new class of polyimides are their very unusual solubility in common organic solvents, and the films display very high negative birefringence.These polyimide greatly improve the processability of polymers with outstanding properties.

These polyimides are ideally suitable as negative birefringence films in liquid crystal displays, dielectric layers in VLSIC microelectronics, and as fibers.

Title:HEAT RESISTANT THERMOPLASTIC POLYIMIDE BLENDS AND LAMINATES

Inventor(s):F. Harris, H. Furutani

Disclosure 195-A-CIP U.S. Patent 5,397,847

This invention relates to novel heat-resistant laminate materials using novel thermoplastic polyimide blend compositions , which have excellent heat resistance, are satisfactorily soluble in organic solvents and are best suited for [copper-clad] laminating and molding.

The blends contain a thermoplastic polyimide component and a thermosetting imide oligomer.The weight ratio of the thermoplastic component to the thermosetting component is selected in the range of 99/1 to 5/95.The thermoplastic polyimide component has a number average molecular weight of 10,000 or more.

These materials are ideally suitable for meeting the demands for (micro)electronic apparatuses such as (1) copper-clad laminates, which are satisfactorily processable, for instance less subject to smear generation during drilling processing; (2) productivity improvement and cost reduction; (3) over comes the following prior art limitations in that (a) diaminodiphenyl methane is highly reactive, thus posing a problem that varnish and prepreg using it can be used for a short period of time, and (b) there is sometimes a problem of the toxicity of diaminodiphenyl methane to the human body; (4) overcomes inferior moisture resistance of unsaturate dicarboxylic acid and amiophenyl as reaction components.

Title:POLYIMIDES COMPRISING SUBSTITUTED BENZIDINES

Inventor(s):F. Harris

Disclosure 126 U.S. Patent 5,071,997

A new class of polyimides and copolyimides made from substituted benzidines, aromatic dianhydrides and other aromatic diamines.The polyimides obtained with said diamines are distinguished by excellent thermal, soluble, and electrical properties (such as very low dielectric constants), excellent clarity and mechanical properties.

These polyimides are ideally suited as coating materials for microelectronic apparatii, as membranes for selective molecular or gas separation, as fibers in molecular composites, as high tensile strength, high compression strength fibers, as film castable coatings, or as fabric components.

Title:SELF POLYMERIZABLE PHENYLQUINOXALINES, THEIR PREPARATION AND USE IN POLYPHENYLQUINOXALINE HOMOPOLYMERS AND COPOLYMERS

Inventor(s):F. Harris, J. Korleski

Disclosure 124 U.S. Patent 5,030,704 Disclosure 124-CON U.S. Patent 5,115,078

A polyphenylquinoxaline which consists of 1 to 100 mole percent of structural elements of the formula (IV)

3 3 ³ ³ ³O2ÄÄÄÅÄÄ0 ³ ³ ³ ³ ³ N ³ ³ ³ (IV) ³ ³ ³ N ³ ³ ³ ³ ³ ³R³ 1 1 and of 0-99 mole percent of the following repeat unit of formula (V)

3 3 2ÄÅÄ0AR12Ä0O2Ä0B2Ä0O2ÄÅÄ0 (V) 1 1

where R is selected from the group consisting of H, an alkyl group, a carbocyclic aromatic group, a heterocyclic aromatic group, or an alkoxy group; AR1 is a carbocyclic aromatic or heterocyclic aromatic group, and B is selected from the representative group consisting of: Ar22Ä0Z2Ä0Ar3(i)

where Ar2 and Ar3 are the same or different carbocyclic aromatic or heterocyclic aromatic group and Z is selected from the representative group consisting of CO, SO or SO2

Z'2Ä0Ar42Ä0Z' (ii)

where Z' is an activated carbocyclic aromatic or heterocyclic aromatic group and Ar4 is an aliphatic group, a carbocyclic aromatic or heterocyclic aromatic group.A process for manufacture of a self polymerizable phenylquinoxaline subject to polymerization by aromatic nucleophilic substitution.

These polyphenylquinoxalines and their copolymers are useful as stable thermal plastics for use in aerospace, high temperature adhesives, microelectronics and membrane (gas and/or molecular separation membrane) applications.

Title:PHENYLATED POLYIMIDES PREPARED FROM 3,6-DIARYLPYROMELLITIC DIANHYDRIDE AND AROMATIC DIAMINES

Inventor(s):F. Harris

Disclosure 106 U.S. Patent 5,175,242

A new class of soluble phenylated polyimides made from 3,6-diarylpyromellitic dianhydride and a process for the manufacture of the 3,6-diarylpyromellitic dianhydride starting material.The polyimides obtained with said dianhydride are readily soluble in appropriate organic solvents and are distinguished by excellent thermal, electrical and/or mechanical properties.

These polyimides are ideally suited as coating materials for microelectronic apparatii, as membranes for selective molecular separation or permeation, for selective gas separation or permeation, as reinforcing fibers in molecular composites, or as high modulus, high tensile strength fibers.

Title:POLY-PHENYLATED DIAMINES AND THEIR USE AS POLYCONDENSATION MONOMERS IN THE SYNTHESIS OF POLYAMIDE,POLY(AMIDE-IMIDE) AND POLYIMIDE POLYMERS

Inventor(s):F. Harris

Disclosure 105 U.S. Patent 5,087,691

New polyphenylated polynuclear aromatic diamines, such as 1,4-bis[4-aminophenyl]-2,3,5-triphenylbenzene; a process for their manufacture and their use as polycondensation components for the manufacture of polyamide, polyamide-imide and polyimide polymers. The polymers obtained with the aromatic diamines according to the invention are readily soluble, rigid-rod polymers distinguished by outstanding modulus, tensile compression strength, excellent energy absorption characteristics, very low coefficient of expansion, excellent thermal stability, non-conduction, excellent film processability and relatively less expensive than existing polymers.

These polyimides are ideally suited for use in the production of anti-ballistics, reinforced molecular composites, microelectronic coatings and gas, liquid and solid membrane separation applications.

Title:MOLDABLE AND/OR EXTRUDABLE POLY(ENAMINE KETONE-CO-ALKYLENE ETHER) BLOCK COPOLYMERS

Inventor(s):F. Harris, D. Russell

Disclosure 104 U. S. Patent 5,061,764

A moldable and/or extrudable poly(enamine ketone-co-alkylene ether)block copolymer is disclosed which has the formula shown below:

3R' RHO OHRR'3³|||º º||| ³2ÄÅÄ0N20C64C20C20A20C20C64C20N20B2ÄÅÄ0³³11n

wherein R' is H or alkyl, alkoxyl, cycloalkyl, cycloalkoxyl and aryl and aryloxyl; A is a poly(enamine ketone) sequence and B is a polyalkylene ether sequence.The poly(enamine ketone-co-alkyleneether) block copolymer is preferably prepared under mild conditions by reacting a bispropynone with an amine-terminated poly(alkyleneether); a bispropynone with an organic diamine and an amine-terminated poly(alkylene ether); or by reacting a preformed propynone-terminated poly(enamine ketone) with an amine-terminated poly(alkylene ether).

These new block copolymers were discovered to overcome deficiencies in the homopolymers made from poly(enamine ketones).

The copolymers have excellent mechanical properties, are moldable and extrudable and are useful for the manufacture of articles such as films, sheaths, fibers (anti-static agents) for textile products,tubes, pipes, and other moldable and/or extrudable articles and RIM shaping.These materials are also useful as bonded or welded linings and as hot-melt adhesives.

Title:POLY-PYRIDINIUM SALTS

Inventor(s):F. Harris

Disclosure 96-CIP-CIP U.S. Patent 5,763,563

A new class of pyrylium salts and process for their manufacture. The use of new pyrylium salts as polycondensation components for anew class of poly pyridinium salts and a new class of conducting polypyridinium salts manufactured by doping the polypyridinium salts with a conducting dopant.The new polypyridinium salts and conducting doped analogs are stable, positively charged polymers, resistant to base attack and distinguished by water insolubility.

The salts are ideally suited as metal anti-corrosion coating, and as separation membranes for anions.The doped salts form stable conducting polymers ideally suited for making electrically conducting materials and as redox (oxidation reduction) catalysts.