The B. F. Goodrich Company

Bausch-lomb Incorporated

Edison Polymer Innovation Corporation

Virgil Percec

Paul P Nicholas

Jay Friedrich Kunzler

Gary S Huvard

Lee Traynor

Floyd L Ramp

Dana S Garcia

A process for preparing poly(p-phenylene)s comprises reacting dihydroxy aromatic compounds such as orthoquinone and bisphenols with halogen-substituted aliphatic sulfonic acids, halogen sulfonic acid, or their anhydrides. The monomers thus formed are subsequently polymerized with Ni(0) catalysts to yield the desired polymers. The monomers or polymers may be functionalized with reactive groups.

Soluble poly(p-phenylene)s

Oligomers of polyarylene polyethethers (PAPE) having a mol wt Mn in the range from 1000 to about 10,000 are converted to monofunctionalized macromers, so as, in the first instance, to provide a reactive double bond (for example, a vinylbenzyl group) at only one end of the PAPE; and, in the second instance, to provide a triple bond (benzylethynyl group) at only one end of the PAPE. The macromer may be a polysulfone, a polyketone, or a copolymer containing both sulfone and ketone-containing units; or, the macromer may be monofunctionalized PPO. The synthesis of macromers with terminal double bonds is carried out with a fast and quantitative modified Williamson etherification of the PAPE with an electrophilic haloalkyl reactant ('HAR') such as chloromethylstyrene ('C1MS') in the presence of a major molar amount (more than 50 mol % based on the number of moles of OH group originally present in the oligomer) of a phase transfer catalyst such as tetrabutylammonium hydrogen sulfate ('TBAH'). The vinyl groups at the end of the marcomer may then be converted to an ethynyl group by bromination of the macromer in CH.sub.2 Cl.sub.2 or CHCl.sub.3, followed by dehydrobromination in the presence of potassium-tert-butoxide ('K-t-Bu'). The glass transition temperature (T.sub.g) of the comb-like polymer produced from (monostyrenated) macromer after curing, is unexpectedly higher than that of the terminally halogenated macromer which the comb-like polymer is derived.

Comb-like polymers and graft copolymers from polyarylene polyether

Polyarylene polyethers ('PAPE') with vinyl chain ends may be crosslinked to form networks with excellent physical and chemical properties except they tend to be brittle. In particular, a polysulfone ('PSU' made from bisphenol A and dichlorodiphenyl sulfone) with vinylbenzyl chain ends ('di-VB-PSU') is too brittle for many applications where impact resistance is essential. This brittleness is combatted by inserting a thermally stable rubbery poly(dimethylsiloxane) ('PDMS') segment having a number average molecular weight in the range from about 600 to about 5000 connected to di-VB-PSU segments by hydrosilylation in the presence of a Pt catalyst, to form a thermoplastic linear predominantly triblock oligomer with vinylbenzyl chain ends which are thermally crosslinkable. When crosslinked, the network formed has improved impact resistance and toughness, with only a little loss in the upper glass transition temperature if the relative lengths of the PDMS and PAPE are such as to provide the desired degree of phase microincompatibility sufficient to improve toughness. The triblock may be blended with a polymer with which the triblock may be crosslinked upon curing. If the VB-PSU-PDMS-PSU-VB triblock is blended with di-VB-PSU the polyblend may be crosslinked to provide improved toughness.

Triblock polyarylene polyether with polysiloxane segment and

A polymer represented by the general formula ##STR1## where m is the average degree of polymerization of the polymer, y is an integer from 1 to 3, x is an integer from 1 to 10, A denotes a halogen atom and R denotes an alkyl radical with 1 to 6 carbon atoms.

Oxygen permeable polymeric materials

When two 4-naphthoxyphenyl moieties are connected through a polar linking group, Y, it does not interfere with an oxidation process which results in dehydrogenative polymerization to yield polyarylene polyether (PAPE) polymers having a weight average mol wt greater than 10,000. Homo- and copolymers having a repeating unit in which a 4,4'-di(1-naphthoxyphenyl) moiety is connected through its phenyl rings to a bivalent polar residue are described. A specific monomer is selected from the group consisting of 4,4'-di(1-naphthoxy)diphenyl sulfone (DNDPS, Y=SO.sub.2) and, 4,4'-di(1-naphthoxy)benzophenone (DNBP, Y=CO). Because the process provides thermoplastic PAPE polymers having a Tg in the range from about 250.degree. C. to about 350.degree. C. with excellent physical properties, the polymers are suitable for use in the fabrication of composites for aerospace vehicles subjected to elevated temperatures.

Poly(dinaphthyl arylene ether) and preparation thereof

A method for the synthesis of polyarylene polyether (PAPE) oligomers with pendant vinyl groups is presented. Aromatic polyether sulfone (APS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) backbones are used for specific examples. Terminal vinyl groups may also be provided on the APS by forming the .alpha., .omega.-di(benzyl)APS before the first step of a synthesis to form a pendant groups which step involves the chloromethylation of APS and PPO to provide oligomers with chloromethyl groups. PPO containing bromomethyl groups was obtained by radical bromination of the PPO methyl groups. Both chloromethylated and bromomethylated starting materials are converted to their phosphonium salts, and then subjected to a phase transfer catalyzed Wittig reaction to provide the pendant vinyl groups. An APS containing pendant ethynyl groups is prepared by bromination of the APS with pendant vinyl groups, followed by a phase transfer catalyzed dehydrobromination. Differential scanning calorimetry analysis of the thermal curing of the oligomers containing pendant vinyl groups, and, ethynyl groups, showed that the curing reaction is much faster for the former. The resulting network polymers were flexible when the starting oligomer contained pendant vinyl groups, and very rigid when it contained pendant ethynyl groups.

Polyarylene polyethers with pendant vinyl and ethynyl groups and process

A modified Williamson etherification in the presence of phase transfer catalyst is used to synthesize alternating block copolymers and regular copolymers. Unsaturated polyethers of a polynuclear dihydric phenol containing chloroallylic (electrophilic) end groups (prepared from cis- or trans-1,4-dichloro-2-butene and Bisphenol A) and aromatic poly(ether sulfone)s containing terminal phenol (nucleophilic) groups are polycondensed in the presence of tetrabutylammonium hydrogen sulfate as phase transfer catalyst to give alternating block copolymers. The same telechelic polymers were chain-extended with dinucleophilic or dielectrophilic monomers under similar reaction conditions. Both the regular copolymers and the alternating block copolymers were characterized by gel permeation chromatography and DSC.

Alternating block copolymers of polyarylene polyethers and process for

Oligomers of polyarylene polyethethers (PAPE) having a mol wt Mn in the range from 1000 to about 10,000 are converted to difunctionalized oligomers so as, in the first instance, to provide a reactive double bond (for example, a vinylbenzyl group) at each end of the PAPE; and, in the second instance, to provide a triple bond (benzylethynyl group) at each end of the PAPE. The PAPE most preferably has a repeating unit which is the residuum of two dihydric phenols or thiophenols ('DHP') linked through a C=O, --S--S--, or --SO.sub.2 -group, or a Si or C atom, and or ether O, or thioether S atoms. The preferred repeating unit is formed by reaction of a DHP such as bisphenol A (BPA) with a halogenated DHP such as dichlorophenyl sulfone (DCPS) so as to provide an alternating configuration. The repeating unit may also include a linking residue of a reactive solvent which residue provides chain extension in the backbone. An oligomer which is a homopolymer having a repeating unit in which at least four benzenoid rings are connected through ether O atoms, may also be difunctionalized. In particular, .alpha.,.omega.-di(phenol)aromatic polyether sulfone oligomers ('APS') are esterified so as to have terminal methacrylyl groups; and, etherified so as to have styryl end groups which are thermally crosslinkable. Illustrated are APS oligomers having BPA-DPS repeating units. The BPA moiety may be replaced with other diphenols. The synthesis of PAPE oligomers with terminal double bonds is carried out with a fast and quantitative modified Williamson etherification of the PAPE with an electrophilic haloalkyl reactant ('HAR') such as chloromethylstyrene ('CIMS') in the presence of a major molar amount (more than 50 mol% based on the number of moles of OH or SH groups originally present in the APS) of a phase transfer catalyst ('PTC') such as tetrabutylammonium hydrogen sulfate ('TBAH'). The vinyl groups at each end of the oligomer may then be converted to ethynyl groups by bromination of the DAPS in CH.sub.2 Cl.sub.2 or CHCl.sub.3, followed by dehydrobromination in the presence of potassium-tertbuoxide (K--t--Bu'). The glass transition temperature (T.sub.g) of the di(styrenated)APS after thermal curing is unexpectedly much higher than that of the APS from which it is derived.

Difunctionalized polyarylene polyethers and process for preparation

A process is disclosed for converting .alpha.,.omega.-bis(2,6-dimethylphenol)poly(2,6-dimethyl-1,4-phenylene oxide) ('PPO--2OH' for brevity), and the corresponding thiophenol-poly(phenylene sulfide) ('PPS--2SH'), by the oxidative copolymerization of 2,6-dimethylphenol (DMP) with 2,2'-di)4-hydroxy-3,5-dimethylphenyl propane ('TMBPA'), or, of 2,6-dimethylthiophenol (DMTP) with 2,2-di(4-thiol-3,5-dimethylthiophenyl propane ('TMBTPA') respectively. Specifically, a mixture of water-methanol or chlorobenzene-methanol is used as the medium in which the reaction of DMP with TMBPA is carried out. By using a particular range of ratios of DMP to TMBPA and different solvent mixtures, the molecular weight of the PPO--2OH is tailored to be in the range from about 1000 to about 5000. The PPO--2OH is then difunctionalized at its chain ends, so that in the first instance, there is provided a reactive double bond (for example, a vinylbenzyl group) at each end of the PPO--2OH; and, in the second instance, a triple bond (benzylethynyl group) at each end of the PPO--2OH. The thermal polymerization of the PPO--2VB has exceptionally desirable characteristics. The corresponding PPS--2VB is also crosslinkable and has high reactivity, but has quite different characteristics.

Crosslinkable difunctionalized poly(phenylene oxide) and process for

A non-catalytic process converts oligomers of polyarylene polyethers (PAPE) having a mol wt Mn in the range from 1000 to about 10,000 to difunctionalized oligomers so as, in the first instance, to provide a reactive double bond (for example, a vinylbenzyl group) at each end of the PAPE; and, in the second instance to provide a triple bond (benzylethynyl group) at each end of the PAPE. The solubility of intermediate bisphenolates of (i) a dihydric phenol, and of (ii) the PAPE oligomer in particular solvents which allow (a) water of reaction to be removed without being degraded, and (b) essentially complete end-capping of the oligomer chains with vinyl chain ends, are the keys to the novel process. The PAPE most preferably has a repeating unit which is the residuum of two dihydric phenols or thiophenols ('DHP') linked through a C.dbd.O, --S--S--, or --SO.sub.2 - group, or a Si or C atom, and/or ether O, or thioether S atoms. The preferred repeating unit is formed by reaction of a DHP such as bisphenol A (BPA) with a halogenated DHP such as dichlorophenyl sulfone (DCPS) so as to provide an alternating configuration. The repeating unit may also include a linking residue of a reactive solvent which residue provides chain extension in the backbone. An oligomer which is a homopolymer having a repeating unit in which at least four benzenoid rings are connected through ether O atoms, may also be difunctionalized. In particular, .alpha..omega.-di(phenol)aromatic polyether sulfone oligomers ('APS') are esterified so as to have terminal methacrylyl groups; and, etherified so as to have styryl end groups which are thermally crosslinkable.

Non-catalytic process for the preparation of difunctionalized

A method for the synthesis of polyarylene polyether (PAPE) oligomers with pendant vinyl groups is presented. Aromatic polyether sulfone (APS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) backbones are used for specific examples. Terminal vinyl groups may also be provided on the APS by forming the .alpha., .omega.-di(benzyl)APS before the first step of a synthesis to form pendant groups which step involves the chloromethylation of APS and PPO to provide oligomers with chloromethyl groups. PPO containing bromomethyl groups was obtained by radical bromination of the PPO methyl groups. Both chloromethylated and bromomethylated starting materials are converted to their phosphonium salts, and then subjected to a phase transfer catalyzed Wittig reaction to provide the pendant vinyl groups. An APS containing pendant ethynyl groups is prepared by bromination of the APS with pendant vinyl groups, followed by a phase transfer catalyzed dehydrobromination. Differential scanning calorimetry analysis of the thermal curing of the oligomers containing pendant vinyl groups, and, ethynyl groups, showed that the curing reaction is much faster for the former. The resulting network polymers were flexible when the starting oligomer contained pendant vinyl groups, and very rigid when it contained pendant ethynyl groups.

Polyarylene polyethers with pendant vinyl groups and process for

Oligomers of polyarylene polyethers (PAPE) having a mol wt Mn in the range from 1000 to about 10,000 are converted to difunctionalized oligomers so as, in the first instance, to provide a reactive double bond (for example, a vinylbenzyl group) at each end of the PAPE; and, in the second instance, to provide a triple bond (benzylethynyl group) at each end of the PAPE. The PAPE most preferably has a repeating unit which is the residuum of two dihydric phenols or thiophenols ('DHP') linked through a C.dbd.O, --S--S--, or --SO.sub.2 -group, or a Si or C atom, and or ether O, or thioether S atoms. The preferred repeating unit is formed by reaction of a DHP such as bisphenol A (BPA) with a halogenated DHP such as dichlorophenyl sulfone (DCPS) so as to provide an alternating configuration. The repeating unit may also include a linking residue of a reactive solvent which residue provides chain extension in the backbone. An oligomer which is a homopolymer having a repeating unit in which at least four benzenoid rings are connected through ether O atoms, may also be difunctionalized. In particular, .alpha.,.omega.-di(phenol)aromatic polyether sulfone oligomers ('APS') are esterified so as to have terminal methacrylyl groups; and, etherified so as to have styryl end groups which are thermally crosslinkable. Illustrated are APS oligomers having BPA-DPS repeating units. The BPA moiety may be replaced with other diphenols. The synthesis of PAPE oligomers with terminal double bonds is carried out with a fast and quantitative modified Williamson etherification of the PAPE with an electrophilic haloalkyl reactant ('HAR') such as chloromethylstyrene ('ClMS') in the presence of a major molar amount (more than 50 mol % based on the number of moles of OH or SH groups originally present in the APS) of a phase transfer catalyst ('PTC') such as tetrabutylammonium hydrogen sulfate ('TBAH'). The vinyl groups at each end of the oligomer may then be converted to ethynyl groups by bromination of the DAPS in CH.sub.2 Cl.sub.2 or CHCl.sub.3, followed by dehydrobromination in the presence of potassium-tert-butoxide ('K-t-Bu'). The glass transition temperature (T.sub.g) of the di(styrenated)APS after thermal curing is unexpectedly much higher than that of the APS from which it is derived.

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Pepper Pike, OH, United States of America

Virgil Percec