Phosphorus- Or Sulfur-containing Reactant Patents (Class 528/352)
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Patent number: 5262516Abstract: A process for preparing a polyetherimide-polyimide copolymer by (a) reacting a bis (ether anhydride) with a stoichiometric excess of an organic diamine in an inert, non-polar solvent to form an amine-terminated oligomer-solvent mixture; (b) removing unreacted organic diamine from the oligomer-solvent mixture; and (c) reacting the oligomer with an aromatic dianhydride.Type: GrantFiled: November 26, 1991Date of Patent: November 16, 1993Assignee: General Electric CompanyInventor: Brent A. Dellacoletta
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Patent number: 5260412Abstract: A terminal-modified imide oligomer composition, comprising(A) 100 parts by weight of a terminal-modified imide oligomer obtained by a reaction in a solvent of a biphenyltetracarboxylic acid compound with an aromatic diamine compound and a monoamine compound containing a carbon-carbon triple bond, and having an unsaturated terminal group at the terminal of the oligomer and an imide bond in the oligomer, and having a logarithmic viscosity number at 30.degree. C., as determined at a concentration of 0.5 g/100 ml of N-methyl-2-pyrrolidone as a solvent, of from 0.1 to 1 and;(B) 5 to 180 parts by weight of an unsaturated imide compound obtained by a reaction in a solvent of a substituent-containing nadic anhydride with a monoamine compound having a carbon-carbon triple bond in an equimolar ratio, and having an unsaturated terminal group at the terminal thereof and an imide bond therein.Type: GrantFiled: September 24, 1990Date of Patent: November 9, 1993Assignee: Ube Industries, Ltd.Inventors: Shinji Yamamoto, Hideho Tanaka, Kazuyoshi Fujii
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Patent number: 5260411Abstract: A method for the preparation of a polyimide containing reversible crosslinks comprising the step of curing a monomer having the formula ##STR1## wherein R and R' may be the same or different and each is H or lower alkyl having 1-5 carbon atoms under conditions conducive to the formation of a polyimide and thereby forming a polyimide having the formula ##STR2## R and R' are as defined above and n is an integer from 10 to 100. The polyimide may be converted to a soluble polymer by cleaving the disulfide bond in the presence of a solvent and a reducing agent. The reduced polymer may be reformed into the polymer in an oxidation step or into a modified polyimide in other reaction steps. Copolymerization processes are also disclosed.Type: GrantFiled: April 20, 1988Date of Patent: November 9, 1993Assignee: Polytechnic UniversityInventors: Giuliana C. Tesoro, Vinod R. Sastri
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Patent number: 5260404Abstract: Polyetherketoneimides and copolymers thereof having an imide repeat unit of formula ##STR1## wherein Ri is ##STR2## in which A is a direct bond or --O--or another substantially non-electron-withdrawing group, and/or Ra is an at least partly arylene moiety other than m- or P-phonylene.These polymers tend to have improved melt stability and other properties, especially when made from a pre-existing imide monomer, instead of by the known amic acid route which results in uncyclised amic acid residues in the polymer.Type: GrantFiled: July 24, 1992Date of Patent: November 9, 1993Assignee: Raychem LimitedInventors: Richard Whiteley, Christopher Borrill
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Patent number: 5247060Abstract: Curing of phthalonitrile monomers and prepolymers is accelerated by inclusion of an acid curing agent. Cured phthalonitrile polymers have high thermal oxidative stability and are useful as resins in various compositions and as adhesives.Type: GrantFiled: January 9, 1992Date of Patent: September 21, 1993Assignee: The United States of America as represented by the Secretary of the NavyInventor: Teddy M. Keller
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Patent number: 5243024Abstract: Improved imide-containing copolymers comprising, in the aromatic diamine component, p-phenylene diamine and at least one additional aromatic diamine have increased rigidity and useful processability. The copolymers of this invention also may exhibit improved resistance to the detrimental effects of humid environments and retain mechanical properties at elevated temperatures after exposure to humid environments.Type: GrantFiled: December 21, 1990Date of Patent: September 7, 1993Assignee: Amoco CorporationInventors: Ronald E. Bockrath, Edward J. Gordon
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Patent number: 5239049Abstract: Poly(dianhydride) compounds having formulae (I) and (II): ##STR1## where m is 0 to 50. ##STR2## wherein n is 0 to 20 and X is bond junction, oxygen atom, sulfur atom, SO.sub.2, C(CF.sub.3), CO, C(CH.sub.3).sub.2, CF.sub.2 --O--CF.sub.2, CH.sub.2, and CHOH.Type: GrantFiled: November 23, 1992Date of Patent: August 24, 1993Assignee: Olin CorporationInventors: Bruce A. Marien, Keith O. Wilbourn
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Patent number: 5237045Abstract: Polymerization or cure of di-phthalonitrile monomers or prepolymers by a curing agent selected from (a) an acid and an amine, (b) a salt of an acid and an amine, and (c) mixtures of (a) and (b). In a preferred embodiment, the curing agents are amine salts which are reaction products of an aromatic amine and an aromatic sulfonic acid. The use of the novel curing agents enhances curing rates and results in polymers which have high Tg.Type: GrantFiled: January 9, 1992Date of Patent: August 17, 1993Assignee: The United States of America as represented by the Secretary of the NavyInventors: Peter J. Burchill, Teddy M. Keller
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Patent number: 5233018Abstract: A perfluorinated polyimide comprising a repeating unit represented by general formula (1): ##STR1## and a perfluorinated poly(amic acid) comprising a repeating unit represented by general formula (6): ##STR2## wherein R.sub.1 is a tetravalent organic group; and R.sub.2 is a divalent organic group, provided that chemical bonds between carbon atoms and monovalent elements contained in R.sub.1 and R.sub.2 are exclusively carbon-to-fluorine bonds; methods for preparing them; and optical material including the perfluorinated polyimide. 1,4-Bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzene dianhydride, 1,4-difluoropyromellitic anhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzene, 1,4-difluoropyromellitic acid, and 1,4-bis(3,4-dicyanotrifluorophenoxy)tetrafluorobenzene as well as methods preparing them. The perfluorinated polyimide has a thermal stability and has a low optical loss in an optical communication wavelength region (0.8 to 1.7 .mu.m).Type: GrantFiled: September 26, 1991Date of Patent: August 3, 1993Assignee: Nippon Telegraph and Telephone CorporationInventors: Shinji Ando, Toru Matsuura, Shigekuni Sasaki, Fumio Yamamoto
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Patent number: 5231160Abstract: A novel aromatic diamine; a polyimide comprising 1,3-bis(3-aminobenzoyl)benzene or 4,4'-bis(3-aminobenzoyl)biphenyl as a diamine component and having recurring structural units represented by the formula (III): ##STR1## wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical having from 2 to 27 carbon atoms, alicyclic radical, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected each other with a direct bond or a bridge member, and X is a divalent radical of ##STR2## and a polyimide having a terminal aromatic group which is essentially unsubstituted or substituted with a radical having no reactivity with amines or dicarboxylic acid anhydrides or a composition comprising said polyimide.Type: GrantFiled: August 29, 1991Date of Patent: July 27, 1993Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Shoji Tamai, Keizaburo Yamaguchi, Yuko Ishihara, Saburo Kawashima, Hideaki Oikawa, Toshiyuki Kataoka, Akihiro Yamaguchi
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Patent number: 5229485Abstract: The invention relates to soluble homo- or copolyimides of formula I ##STR1## wherein Y is hydrogen or the substituents Y, together with the linking N atom, are a divalent radical of of formulae IIa to IIc ##STR2## and X is the radical of of an aromatic amine after removal of the amino end groups, and n is an integer from 5 to 150.The compounds of the invention are readily soluble in organic solvents and are suitable tougheners for epoxy, bismaleimide and triazine resin systems.Type: GrantFiled: September 26, 1991Date of Patent: July 20, 1993Assignee: Ciba-Geigy CorporationInventors: Andreas Kramer, Jean-Pierre Wolf, Rudolf Brunner
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Patent number: 5218077Abstract: A high-temperature stable, highly optically transparent-to-colorless, low dielectric linear aromatic polyimide is prepared by reacting an aromatic diamine with 3,3'bis(3,4-dicarboxyphenoxy)diphenylmethane dianhydride in an amide solvent to form a linear aromatic polyamic acid. This polyamic acid is then cyclized to form the corresponding polyimide, which has the following general structural formula: ##STR1## wherein Ar is any aromatic or substituted aromatic group, and n is 10-100.Type: GrantFiled: August 26, 1991Date of Patent: June 8, 1993Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space AdministrationInventors: Anne K. St. Clair, Harold G. Boston, J. Richard Pratt
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Patent number: 5212279Abstract: A hot-melt adhesive comprising a special polyamideimide or polyamide is excellent in heat resistance and adhesive strength and usable for providing substrates for printed circuit boards.Type: GrantFiled: October 22, 1990Date of Patent: May 18, 1993Assignee: Hitachi Chemical Co., Ltd.Inventors: Yoshihiro Nomura, Takashi Morinaga, Toshiaki Fukushima, Hiroshi Minamisawa, Kazuhito Hanabusa
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Patent number: 5212277Abstract: The present invention relates to new polyetherimideimides having imideimide group with the following structural formula(I) and inherent viscosity of 0.27.about.0.71 dl/g, which can be made by effecting reaction between an aromatic bis(ether anhydride) and an organic diamine or an aromatic bis(nitro imideimide) and a metal salt of diol.Type: GrantFiled: January 10, 1991Date of Patent: May 18, 1993Assignees: Korea Research Institute of Chemical Technology, Cheil Industries, Inc.Inventors: Kwang-Sup Lee, Kil-Yeong Choi, Jong C. Won, Byoung K. Park, In-Tae Lee
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Patent number: 5210174Abstract: In a process for the preparation of polyimide by reacting a diamine compound with tetracarboxylic dianhydride in a phenol based solvent, an improved process for reacting the diamine compound with tetracarboxylic dianhydride in a solution by forming separate solutions of the tetracarboxylic dianhydride and the diamine compound and mixing the solutions and/or by dissolving tetracarboxylic dianhydride in the phenol-based solvent containing an organic base.Type: GrantFiled: November 14, 1990Date of Patent: May 11, 1993Assignee: Mitsui Toatsu Chemicals, Inc.Inventors: Shoji Tamai, Hideaki Oikawa, Masahiro Ohta, Akihiro Yamaguchi
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Patent number: 5196506Abstract: A polyimide having a high heat-resistance good processability and recurring structural units of the formula (I): ##STR1## wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical having at least two carbon atoms, alicyclic radical, monocyclic aromatic radical, fused polycyclic aromatic radical and polycyclic aromatic radical bonded through a direct bond or a bridge member.Type: GrantFiled: July 15, 1992Date of Patent: March 23, 1993Assignee: Mitsui Toatsu Chemicals, Inc.Inventors: Shoji Tamai, Masahiro Ohta, Akihiro Yamaguchi
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Patent number: 5194568Abstract: It is advantageous to prepare oligomers of polybenzazole polymers by reaction of AA-PBZ monomer with an excess of BB-PBZ monomer. The resulting oligomer dopes may be stored at a temperature at which they remain pumpable until such time as the dope can be advanced to higher molecular weight by adding additional AA-PBZ monomer. The molecular weight of the polymer may be adjusted by controlling the amount of chain extender and/or chain terminator added to oligomer mixtures as they are advanced to final molecular weight.Type: GrantFiled: October 19, 1990Date of Patent: March 16, 1993Assignee: The Dow Chemical CompanyInventors: Thomas Gregory, Carl W. Hurtig, Harvey D. Ledbetter, Kenneth J. Quackenbush, Steven Rosenberg, Ying H. So
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Patent number: 5189137Abstract: A method for preparing high molecular weight polyethermide polymers in a dual solvent system is disclosed. The inventive method provides for polymerizing a diamine monomer and a dianhydride monomer in a solvent system comprised of at least two solvents, a first solvent is selected for its solubility characteristics such that the polyethermide polymer is highly soluble therein and a second solvent is selected for its relatively high boiling point characteristics such that when the second solvent and first solvent are mixed together, the boiling point of the dual solvent system is at least as high as the temperature at which polymerization of said monomers occurs. In one embodiment, a diamine monomer of 4,4'-sulfonyl dianiline (SDAN) is reacted with a dianhydride monomer of bisphenol A dianhydride (BPADA) in the presence of a catalyst and a chain stopper in a dual solvent system comprised of chloroform and ortho-dichlorobenzene. The resulting polyethermide has an intrinsic viscosity exceeding 0.Type: GrantFiled: October 7, 1991Date of Patent: February 23, 1993Assignee: General Electric CompanyInventors: Paul E. Howson, Patricia D. Mackenzie
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Patent number: 5175234Abstract: Polyimide oligomers include (1) linear, monofunctional crosslinking oligomers prepared by condensing a monoanhydride end cap with a diamine that includes alternating ether and "Sulfone" (--SO.sub.2 --, --S--, --CO--, --(CF.sub.3).sub.2 C--, or --(CH.sub.3).sub.2 C--) linkages connecting alternating aromatic radicals and with a dianhydride (or dianhydride mixture), particularly the unsaturated, aliphatic dianhydride commonly known as MCTC; (2) linear, mono- or difunctional crosslinking oligomers prepared by condensing an amine end cap with a diamine and a dianhydride; and (3) multidimensional, crosslinking oligomers having an aromatic hub and at least three radiating arms connected to the hub, each arm including a crosslinking end cap at its distal end and at least one imide linkage.Blends, prepregs, and composites can be prepared from the oligomers.Type: GrantFiled: November 7, 1989Date of Patent: December 29, 1992Assignee: The Boeing CompanyInventors: Hyman R. Lubowitz, Clyde H. Sheppard
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Patent number: 5175241Abstract: Polyimide resins, which have reduced anhydride content when molded, are prepared by a novel reaction process that includes reacting an esterified aromatic tetracarboxylic acid or anhydride monomer with a primary aromatic diamine until substantially no free monomer remains to form a polyamide-acid (the molar ratio of esterified monomer to diamine ranging from 1:1 to 1:2); reacting the polyamide-acid with a low molecular weight end-capping agent to form an end-capped polyamide-acid; and heating the end-capped polyamide-acid to form the polyimide.Type: GrantFiled: December 28, 1989Date of Patent: December 29, 1992Assignee: The Dexter CorporationInventor: David S. Darrow
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Patent number: 5171829Abstract: A copolymeric amphiphilic polyimide precursor having the recurring unit of the formula (1): ##STR1## wherein R.sup.1 is a tetravalent group having at least 2 carbon atoms, R.sup.2 is a bivalent group having at least 2 carbon atoms, and R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an aromatic group, or an alicyclic group, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, provided that at least one of R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is neither hydrogen atom nor the above-mentioned group which has 1 to 11 carbon atoms; a part of at least one of said R.sup.1 and said R.sup.2 being substituted with a group having a valence different therefrom.Type: GrantFiled: January 16, 1991Date of Patent: December 15, 1992Assignee: Kanegafuchi Kagaku Kogyo Kabushiki KaishaInventors: Masakazu Uekita, Hiroshi Awaji
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Patent number: 5164476Abstract: Soluble and/or fusible polyimides or polyamidoimides of the general formula I ##STR1## in which R denotes a divalent radical of the formula II ##STR2## Ar denotes trivalent or tetravalent aromatic radicals or mixtures thereof, X denotes the amide radical, if Ar is trivalent, and if Ar is tetravalent denotes the imide radical and R.sub.1 denotes divalent aromatic radicals, and a process for their preparation.Type: GrantFiled: June 12, 1990Date of Patent: November 17, 1992Assignee: Chemie Linz Gesellschaft m.b.H.Inventors: Gerd Greber, Heinrich Gruber, Marcel Sychra
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Patent number: 5153303Abstract: Fully cyclized polyimides based on aromatic tetracarboxylic acid dianhydrides with substitution in the positions ortho to the bridging moiety and aromatic diamines, exhibiting solubility in organic solvents, increased glass transition temperatures, low coefficients of thermal expansion and photoimagability; said polyimides being suitable for the production of films, protective coatings and photolithographic relief images.Type: GrantFiled: January 19, 1990Date of Patent: October 6, 1992Assignee: Ciba-Geigy CorporationInventors: Stanley J. Jasne, Pasquale A. Falcigno
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Patent number: 5149772Abstract: Polyimides having a high thermal and oxidative stability are prepared by reacting a mixture of monomers comprising (a) a dialkyl, trialkyl, or tetraalkylester of an aromatic tetracarboxylic acid, (b) an aromatic diamine, and (c) an end cap compound. The ratio of (a), (b), and (c) is chosen so that upon heating the mixtures, low molecular weight prepolymers are formed, the prepolymers having only one end cap radical and being suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides. Upon heating, the prepolymers form polyimide resins, which can have T.sub.g in excess of 600.degree. F. and superior physical properties.Type: GrantFiled: January 22, 1992Date of Patent: September 22, 1992Assignee: TRW Inc.Inventors: Tito T. Serafini, Paul G. Cheng, Kenneth K. Ueda, Ward F. Wright
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Patent number: 5149760Abstract: Polyimides having a high thermal and oxidative stability are prepared by reacting a mixture of monomers comprising (a) a dialkyl, trialkyl, or tetraalkylester of an aromatic tetracarboxylic acid, (b) an aromatic diamine, and (c) an end cap compound. The ratio of (a), (b), and (c) is chosen so that upon heating the mixtures, low molecular weight prepolymers are formed, the prepolymers having only one end cap radical and being suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides. Upon heating, the prepolymers form polyimide resins, which can have T.sub.g in excess of 600.degree. F. and superior physical properties.Type: GrantFiled: January 22, 1992Date of Patent: September 22, 1992Assignee: TRW Inc.Inventors: Tito T. Serafini, Paul G. Cheng, Kenneth K. Ueda, Ward F. Wright
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Patent number: 5145937Abstract: New polyimides have been prepared from the reaction of aromatic dianhydrides with novel aromatic diamines containing carbonyl and ether connecting groups between the aromatic rings. Several of these polyimides were shown to be semi-crystalline as evidenced by wide angle x-ray diffraction and differential scanning calorimetry. Most of the polyimides form tough solvent resistant films with high tensile properties. Several of these materials can be thermally processed to form solvent and base resistant moldings.Type: GrantFiled: November 9, 1989Date of Patent: September 8, 1992Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space AdministrationInventors: Paul M. Hergenrother, Stephen J. Havens
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Patent number: 5145942Abstract: Novel polyimides have been prepared from the reaction of aromatic diahydrides with novel aromatic diamines having carbonyl and ether groups connecting aromatic rings containing pendant methyl groups. The methyl substituent polyimides exhibit good solubility and form tough, strong films. Upon exposure to ultraviolet irradiation and/or heat, the methyl substituted polyimides crosslink to become insoluble.Type: GrantFiled: September 28, 1990Date of Patent: September 8, 1992Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space AdministrationInventors: Paul M. Hergenrother, Stephen J. Havens
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Patent number: 5132395Abstract: Polyimides having a high thermal and oxidative stability are prepared by reacting a mixture of monomers comprising (a) a dialkyl, trialkyl, or teThis invention was made with Government support under F33615-88-C-5409 awarded by the Department of the Air force. The Government has certain rights in this invention.Type: GrantFiled: January 30, 1990Date of Patent: July 21, 1992Assignee: TRW Inc.Inventors: Tito T. Serafini, Paul G. Cheng, Kenneth K. Ueda, Ward F. Wright
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Patent number: 5128444Abstract: A thermosetting resin composition, a solution composition of the resin and a thermosetting dry film formed out of the resin are disclosed. The thermosetting resin composition contains a specific resin component as the main component. The resin component consists of (A) 100 weight parts of an aromatic polyimide; and (B) 5 to 2,000 weight parts of (a) a terminal-modified imide oligomer or (b) an unsaturated imide compound. The aromatic polyimide (A) is formed from a tetracarboxylic acid ingredient which contains 2,3,3',4'-biphenyltetracarboxylic acid or its derivative in an amount of at least 60 mole % and an aromatic diamine ingredient. The polyimide has such a high molecular weight that the logarithmic viscosity (concentration: 0.5 g/100 ml of solvent; solvent: N-methyl-2-pyrrolidone; and temperature of measurement: 30.degree. C.) is not less than 0.2. The polyimide is soluble in an organic polar solvent.Type: GrantFiled: April 17, 1990Date of Patent: July 7, 1992Assignee: Ube Industries, Ltd.Inventors: Hiroshi Inoue, Tadao Muramatsu, Tetsuji Hirano
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Patent number: 5126462Abstract: Aromatic tetracarboxylic acids or derivatives thereof of the general formula I ##STR1## in which R denotes a divalent radical of the formula II ##STR2## Ar denotes tri- or tetravalent aromatic radicals or mixtures thereof, X, if Ar is trivalent, denotes an amide radical, and if Ar is tetravalent denotes an imide radical, and Y and Z either together denote the anhydride radical --CO--O--CO-- or by themselves and independently of one another denote the radicals --COOH, --COCL or --COOR.sub.1, and a process for their preparation.Type: GrantFiled: June 12, 1990Date of Patent: June 30, 1992Assignee: Chemie Linz Gesellschaft m.b.H.Inventors: Gerd Greber, Heinrich Gruber, Marcel Sychra
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Patent number: 5120826Abstract: The present invention provides for a novel heat stable class of polyamide-imide polymers having excellent flow properties and hydrolytic stability which are prepared by forming the polycondensation product of one or more aromatic or aliphatic diamines and a comonomer comprising a tri- or hexafluoro-substituted tricarboxylic acid anhydride (or acid derivative thereof) having the structure: ##STR1## wherein R is CF.sub.3 or a phenyl radical. In addition to improved flow properties, the polyamide-imide polymers of this invention also exhibit improved solubility properties in most organic solvents, good resistance to attack by chlorinated solvents such as trichloroethylene as compared with polyimides, improved hydrophobic properties as well as good thermal properties, including resistance to thermooxidative degradation.Type: GrantFiled: December 21, 1990Date of Patent: June 9, 1992Assignee: Hoechst Celanese Corp.Inventors: Rohitkumar H. Vora, Paul N. Chen, Sr.
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Patent number: 5116935Abstract: A preferred class of polyimide oligomers include (1) linear, difunctional crosslinking oligomers prepared by condensing an imidophenylamine end cap with a lower alkylene diamine or a polyaryldiamine such as 3,3'-phenoxyphenylsulfone diamine and with a dianhydride, particularly 4,4'-phenoxyphenylsulfone dianhydride; and (2) multidimensional, crosslinking, polyimide oligomers having an aromatic hub and at least two radiating arms connected to the hub, each arm including a crosslinking imidophenylamine end cap at its distal end and at least two imide linkages.Blends, prepregs, and composites can be prepared from the oligomers.Type: GrantFiled: May 18, 1989Date of Patent: May 26, 1992Assignee: The Boeing CompanyInventors: Hyman R. Lubowitz, Clyde H. Sheppard
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Patent number: 5116939Abstract: A process for preparing polyimides having enhanced melt flow properties is described. The process consists of heating a mixture of a high molecular weight poly(amic acid) or polyimide with a low molecular weight amic acid or imide additive in the range of 0.05 to 15% by weight of additive. The polyimide powders so obtained show improved processability, as evidenced by lower melt viscosity by capillary rheometry. Likewise, films prepared from mixtures of polymers with additives show improved processability with earlier onset of stretching by TMA.Type: GrantFiled: August 11, 1987Date of Patent: May 26, 1992Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space AdministrationInventors: James C. Fletcher, J. Richard Pratt, Terry L. St. Clair, Diane M. Stoakley, Harold D. Burks
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Patent number: 5115089Abstract: Disclosed herein are processes for the preparation of polyimide-isoindroquinazolinediones and precursor thereof. These polymers are useful as heat-resistant electric insulation materials, surface coating films for electronic instrument parts and especially suitable for manufacturing a photoresist. The above precursor is produced by reacting a an alkylenebistrimellitate dianhydride, a diaminoamide compound and the other amine. The precursor is readily dehydrated and ring-closed to produce polyimide-isoindroquinazolinedione, which is often conveniently conducted by producing a varnish of the precursor, applying it onto adequate substrates such as silicon wafers, glass plates, metal plates, etc. and then subjecting the coated film to dehydration. The resulting films have excellent physical properties such as good adherence, high tensile strength, low elasticity, etc.Type: GrantFiled: September 16, 1988Date of Patent: May 19, 1992Assignee: Hitachi Chemical Co., Ltd.Inventors: Masatoshi Yoshida, Katsuji Shibata, Mitsumasa Kojima, Hidetaka Satou, Toshihiko Kato, Yasuo Miyadera, Masami Yusa
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Patent number: 5112942Abstract: Copolyimides and their precursors are disclosed comprising units represented by the formula ##STR1## where R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or different and are hydrogen or C.sub.1 to C.sub.6 linear or branched alkyl, with the proviso that R.sub.1, R.sub.2, R.sub.3 and R.sub.4 cannot simultaneously be hydrogen and where Z is a chemical bond, ##STR2## Ar is the tetravalent residue of a tetracarboxylic acid or acid dianhydride or di- or tetraester thereof, where x and y are integers from about 100 to about 1,000, and the ratio of x to y is from about 1:99 to about 49:51, and z is 0-5.These copolymers have improved resistance to stress cracking. They may also be used in applications such as coatings, or adhesives.Type: GrantFiled: September 26, 1990Date of Patent: May 12, 1992Assignee: Ethyl CorporationInventor: Wesley C. Blocker
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Patent number: 5104944Abstract: A process for the synthesis of derivatives of materials containing an imide group conjugated to an aromatic moiety to form an ester, a thioester, an amide, a ketone, and silylesters. Electrons are supplied to redox sites to form a reduced imide material. The reduced imide material is contacted with a nucleophile which opens the imide ring of the reduced imide and chemically combines with a carbonyl carbon atom of the open imide ring to form an imide derivative.Type: GrantFiled: July 18, 1989Date of Patent: April 14, 1992Assignee: International Business Machines CorporationInventors: Martin J. Goldberg, Daniel P. Morris, Alfred Viehbeck
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Patent number: 5101005Abstract: The present invention provides cross-linkable polyimide polymers having at least one repeating unit of the sturcture of: ##STR1## wherein n is the number of repeating groups and A is a tetravalent aromatic organic radical wherein each pair of carbonyl groups are attached to adjacent carbons in the ring moiety A.It has been found that polyimides having the structure of formula I may be crosslinked at surprisingly low temperatures when heated from about 75 to about 110.degree. C. to form infusible and solvent resistant shapes, thereby rendering them useful in the preparation of films, laminates and composites where inertness to solvents is a prerequisite.Type: GrantFiled: May 18, 1989Date of Patent: March 31, 1992Assignee: Hoechst Celanese Corp.Inventors: Rohitkumar H. Vora, Dinesh N. Khanna, Wolfgang K. Appel
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Patent number: 5093453Abstract: A high-temperature stable, optically transparent, low dielectric aromatic polyimide is prepared by chemically combining equimolar quantities of an aromatic dianhydride reactant and an aromatic diamine reactant, which are selected so that one reactant contains at least one Si(CH.sub.3).sub.2 group in its molecular structure, and the other reactant contains at least one --CH.sub.3 group in its molecular structure. The reactants are chemically combined in a solvent medium to form a solution of a high molecular weight polyamic acid, which is then converted to the corresponding polyimide.Type: GrantFiled: December 12, 1989Date of Patent: March 3, 1992Assignee: Administrator of the National Aeronautics and Space AdministrationInventors: Anne K. St. Clair, Terry L. St. Clair, J. Richard Pratt
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Patent number: 5091505Abstract: Polyimides having a high thermal and oxidative stability are prepared by reacting a mixture of monomers comprising (a) a dialkyl, trialkyl, or tetraalkylester of an aromatic tetracarboxylic acid, (b) an aromatic diamine, and (c) an end cap compound. The ratio of (a), (b), and (c) is chosen so that upon heating the mixtures, low molecular weight prepolymers are formed, the prepolymers having only one end cap radical and being suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides. Upon heating, the prepolymers form polyimide resins, which can have T.sub.g in excess of 600.degree. F. and superior physical properties.Type: GrantFiled: January 30, 1990Date of Patent: February 25, 1992Assignee: TRW Inc.Inventors: Tito T. Serafini, Paul G. Cheng, Kenneth K. Ueda, Ward F. Wright
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Patent number: 5070182Abstract: A polyimide resin having a repeating unit of the formula: ##STR1## wherein R.sub.1 is a tetravalent organic group constituting a tetracarboxylic acid or its derivative, wherein four atoms directly bonded to the four carbonyl groups are carbon atoms having no unsaturated bond, and R.sub.2 is a bivalent organic group constituting a diamine.Type: GrantFiled: April 26, 1990Date of Patent: December 3, 1991Assignee: Nissan Chemical Industries Ltd.Inventors: Noriaki Kohtoh, Takashi Kobayashi, Masahiko Yukawa
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Patent number: 5070181Abstract: Disclosed is a film of polyimide having repeating units of formula (1) and a birefringence (.DELTA.n) of at least 0.13: ##STR1## wherein R.sup.1 is an aromatic group having a valency of 4, at carbon atoms constituting the aromatic ring, and R.sup.2 is an aromatic group having a valency of 2, at carbon atoms constituting the aromatic ring. This polyimide film exhibits good thermal dimensional stability.Type: GrantFiled: August 7, 1989Date of Patent: December 3, 1991Assignee: Kanegafuchi Chemical Ind. Co., Ltd.Inventors: Hideki Kawai, Kiyokazu Akahori, Hirosaku Nagano
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Patent number: 5061509Abstract: A polyimide thin film is formed on a substrate by imparting energy under vacuum, by means of heating, ultraviolet light or electron beam irradiation, or a combination thereof, to a polyimide having in the polymer main chain imide bonds and decomposable bonds such as carbon-carbon single bond differing from the imide bonds so as to break the decomposable bonds.Type: GrantFiled: August 23, 1990Date of Patent: October 29, 1991Assignee: Kabushiki Kaisha ToshibaInventors: Katsuyuki Naito, Shinya Aoki, Toshio Nakayama
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Patent number: 5055550Abstract: This invention relates to new fluorine-containing polyimides, polyamide-acids/esters, polyamides, addition polyimides and imide oligomers which exhibit low melting points, better solubilities, low dielectric constants, superior thermal and thermal oxidative stability, and improved processing characteristics.The products of this invention are characterized by the fact that they are derived from 4,4'-bis[2-(3,4-(dicarboxyphenyl)hexafluoroisopropyl]diphenyl ether dianhydride.Type: GrantFiled: March 21, 1990Date of Patent: October 8, 1991Assignee: Hoechst Celanese Corp.Inventors: Werner H. Mueller, Dinesh N. Khanna, Rohitkumar H. Vora, Ruediger J. Erckel
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Patent number: 5053480Abstract: A polyimide resin composed essentially of repeating units represented by the general formula: ##STR1## where R is a divalent aromatic hydrocarbon radical.Type: GrantFiled: April 2, 1990Date of Patent: October 1, 1991Assignee: Nissan Chemical Industries, Ltd.Inventors: Noriaki Koto, Toyohiko Abe, Hideo Suzuki, Kanji Otsuka
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Patent number: 5053478Abstract: Production of polyenaminonitriles including those which can be cyclized to very stable poly(aminoquinolines) without the evolution of any small molecules and thus in a manner free of volatiles. The polyenaminonitriles are polymers which have desirable dielectric properties, and include those which can be cyclized to poly(aminoquinolines) without the evolution of volatiles to make defect-free films and composites of similar dielectric properties because of this characteristic.Type: GrantFiled: August 2, 1990Date of Patent: October 1, 1991Inventors: James A. Moore, Douglas Robello
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Method for stabilizing polyamide acid solutions of pyromellitic dianhydride and coating compositions
Patent number: 5043418Abstract: A method is provided for stabilizing polyamide acids of pyromellitic dianhydride and pyromellitic dianhydride copolymers utilizing certain silicon nitrogen compounds such as hexamethyldisilazane.Type: GrantFiled: October 4, 1988Date of Patent: August 27, 1991Assignee: General Electric CompanyInventors: Daniel R. Olson, Elbridge A. O'Neil -
Patent number: 5037949Abstract: This invention relates to new fluorine-containing polyimides, polyamide-acids/esters, polyamides, addition polyimides and imide oligomers which exhibit low melting points, better solubilities, low dielectric constants, superior thermal and thermal oxidative stability, and improved processing characteristics.The products of this invention are characterized by the fact that they are derived from 4,4'-bis[2-(amino(halo)phenoxyphenyl)hexafluoroisopropyl]diphenyl ether.Type: GrantFiled: March 6, 1990Date of Patent: August 6, 1991Assignee: Hoechst Celanese Corp.Inventors: Werner H. Mueller, Dinesh N. Khanna, Rohitkumar H. Vora, Ruediger J. Erckel
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Patent number: 5025084Abstract: A polyimide-forming composition comprising(A) a polycarboxylic acid partial ester of formulaHOOC--R.sup.1 --COOR.sup.2 Iwhere R.sup.1 denotes a divalent ethylenically unsaturated aliphatic or cycloaliphatic group of 2 to 20 carbon atoms, and R.sup.2 denotes the residue, after removal of a hydroxyl group, of an alcohol having from 4 to 20 carbon atoms which has a cycloaliphatic, aromatic or heterocyclic ring and is polymerizable on heating in the presence of an acid,(B) a partial ester of formula I above in which R.sup.1 denotes a group of formula II ##STR1## where Ar.sup.1 denotes a tetravalent aromatic group of 6 to 20 carbon atoms linked through aromatic carbon atoms thereof to the indicated carbon atoms, and R.sup.2 is as defined above,(C) an aromatic primary polyamine and(D) a heat-activable substance which releases an acid at a temperature of 100.degree. C. or above.Type: GrantFiled: July 10, 1990Date of Patent: June 18, 1991Assignee: Ciba-Geigy CorporationInventors: Bryan Dobinson, Mark R. Southcott
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Patent number: 5025088Abstract: The present invention here disclosed is directed to a photosensitive polymer having an inherent viscosity of 0.1 to 5 dl/g and represented by the general formula ##STR1## wherein R.sup.1 is independently a trivalent or tetravalent carbon cyclic aromatic group or heterocyclic group; R.sub.2 is independently an aliphatic group having at least 2 carbon atoms, an alicyclic group, an aromatic aliphatic group, a carbon cyclic aromatic group, a heterocyclic group or a polysiloxane group; R.sub.3 and R.sub.4 are CH.sub.2 --CH.dbd.CH.sub.2 ; m is 1 or 2; n is 0 or 1; and m and n satisfy 1.ltoreq.m+n.ltoreq.2.The photosensitive polymer of the present invention is applicable as electronic materials such as passivation films of semiconductors and print circuits.Type: GrantFiled: July 19, 1990Date of Patent: June 18, 1991Assignee: Chisso CorporationInventors: Hirotoshi Maeda, Kouichi Kunimune
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Patent number: RE34431Abstract: Macrocyclic oligomers, including polycarbonates, polyesters, polyamides, polyimides, polyetherketones and polyethersulfones, are conveniently prepared from various spiro(bis)indane compounds, especially the 6,6'-difunctional 3,3',3'-tetramethylspiro(bis)indanes. The macrocyclic oligomers may be conveniently converted to linear polymers.Type: GrantFiled: May 8, 1992Date of Patent: November 2, 1993Assignee: General Electric CompanyInventors: Daniel J. Brunelle, Thomas L. Guggenheim, James A. Cella, Thomas L. Evans, Luca P. Fontana, Gary R. Faler, James M. Fukuyama, Eugene P. Boden, Jonathan D. Rich, Thomas G. Shannon, Sharon J. McCormick, Philip J. McDermott, Alice M. Colley, Joseph W. Guiles