WO1992011309A1 - Polymeres de carbonate a terminaisons arylcyclobutene - Google Patents

Polymeres de carbonate a terminaisons arylcyclobutene Download PDF

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Publication number
WO1992011309A1
WO1992011309A1 PCT/US1991/009325 US9109325W WO9211309A1 WO 1992011309 A1 WO1992011309 A1 WO 1992011309A1 US 9109325 W US9109325 W US 9109325W WO 9211309 A1 WO9211309 A1 WO 9211309A1
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Prior art keywords
arylcyclobutene
carbonate
compound
polymer
carbonate polymer
Prior art date
Application number
PCT/US1991/009325
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English (en)
Inventor
Maurice J. Marks
Alan K. Schrock
Thomas H. Newman
Original Assignee
The Dow Chemical Company
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Filing date
Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to JP4502406A priority Critical patent/JPH06504305A/ja
Publication of WO1992011309A1 publication Critical patent/WO1992011309A1/fr
Priority to KR1019930701937A priority patent/KR930703376A/ko

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule

Definitions

  • This invention relates to novel carbonate polymers having at least one terminal arylcyclobutene moiety. These polymeric compositions are well suited for use in preparing molded articles, composite or blend materials and extruded articles such as sheet or film.
  • the invention is a carbonate polymer possessing good combinations of product properties, including toughness, solvent resistance, heat resistance, and thermal stability.
  • a carbonate polymer prepared from one or more multi-hydric compounds and having an average degree of polymerization of at least 2 based on multi-hydric compound and having terminal arylcyclobutene moieties.
  • Other embodiments of the invention include such carbonate polymers having an average degree of polymerization of from 2 to 100 and carbonate polymers having polymerized therein from 0.01 to 1 mole of terminal arylcyclobutene-containing compound per mole of multi-hydric compound.
  • the present invention is a carbonate polymer as described above having terminal arylcyclobutene moieties and having essentially complete arylcyclobutene compound chain termination, preferably having, on the average, at least 2 terminal arylcyclobutene moieties per polymer molecule.
  • a further aspect of the present invention is a carbonate polymer as described above having terminal arylcyclo ⁇ butene moieties and having less than complete arylcyclo ⁇ butene compound chain termination.
  • an arylcyclobutene chain terminating compound and additional chain terminating agent(s) are employed in the preparation of the polymer.
  • at least 0.01 mole of an aryl ⁇ cyclobutene chain terminating compound is employed per mole of additional chain terminating agent(s).
  • the carbonate polymers according to the present invention can be easily handled and melt processed according to the techniques generally utilized with carbonate polymer resins and, when subjected to sufficient crosslinking conditions, result in shaped articles having improved combinations of physical properties such as heat resistance, solvent resistance, toughness and thermal stability.
  • different properties of the crosslinked or branched carbonate polymers according to the present invention can be optimized and improved.
  • Carbonate polymers having two or more terminal arylcyclobutene moieties per chain and a low degree of polymerization in the precrosslinked phase are as easily processed as low molecular weight thermoset resins while providing molded or shaped articles having good mechanical properties which are similar in many respects to high molecular weight linear thermoplastic carbonate polymers.
  • Carbonate polymers having less than two arylcyclobutene units per chain can be used to provide branched carbonate polymers with improved melt processability.
  • Carbonate polymers are well known in the literature and can be prepared by well known techniques. In general, the carbonate polymers can be prepared from -It-
  • one or more multi-hydric compounds by reacting the multi-hydric compound(s) such as a dihydric phenol with a carbonate precursor such as phosgene, a haloformate or a carbonate ester such as diphenyl carbonate.
  • the carbonate polymers can be prepared from these raw materials by an appropriate process selected from one of the known polymerization processes such as the known interfacial, solution or melt processes.
  • Such carbonate polymers generally possess reoccurring structural units as shown in formula I:
  • A is a radical having at least 2 valences which is a remnant of a multi-hydric compound, (-) represents valences of A connecting to a carbonate moiety as shown and v is the number of valences of A in excess of 1 , an integer greater than or equal to 1.
  • A is predominantly a dihydric compound remnant (v is 1) but, if branched polymers are intended, A can include amounts of a tri- or tetra-hydric compound remnant at low levels (v is greater than 1).
  • Dihydric phenols are preferred multi-hydric compounds. The use of a dihydric phenol results in an aromatic carbonate polymer, the most typical of the carbonate polymers.
  • the carbonate polymer molecules are usually terminated with the remnant of a monohydric compound or other monofunctional chain terminating compound.
  • Such carbonate polymers can be generally represented according to formula II:
  • T is independently the chain terminating remnant of a monohydric compound or other monofunctional chain terminating compound with or without an arylcyclobutene moiety and q is the average number of polymer chain branches per polymer molecule, preferably from 0 to 0.05. In cases where branched polymer is specifically desired, q is preferably from 0.01 to 0.05.
  • n is usually from 30 to 315, representing aromatic polycarbonates with weight average molecular weights of from 20,000 to 200,000. See for example, "Polycarbonates", Encyclopedia of Polymer Science and Technology, Vol. 11, p. 6 ⁇ 8 (1987).
  • n can advantageously be from 2 to 100. This represents, for example, aromatic carbonate polymer molecular weights (uncrosslinked) of from 500 to 65,000.
  • the degree of polymerization for a particular carbonate polymer resin according to the present invention depends on the average number of terminal arylcyclobutene moieties per polymer molecule.
  • Carbonate polymers having two or more terminal arylcyclobutene moieties per chain usually become heavily crosslinked to drastically increase the effective molecular weight and provide the desired balance of physical properties.
  • Such polymers need only a low degree of polymerization in the precrosslinked phase.
  • Branched carbonate polymers can be prepared from a carbonate polymer having less than two arylcyclobutene units per chain and a molecular weight within the ranges generally desired for branched carbonate polymers.
  • the precrosslinking degree of polymerization for the carbonate polymers according to this invention can advantageously vary across relatively broad ranges but is at least 2, preferably greater than 2, more preferably at least 2.5, and most preferably at least 3.
  • the precrosslinking degree of polymerization for the carbonate polymers according to this invention is generally up to 50, preferably less than or equal to 35, more preferably less than or equal to 30, and most preferably less than or equal to 20.
  • n is the degree of polymerization
  • r is the mole ratio of reactive groups
  • p is the extent of reaction
  • X a is the mole fraction of the dihydric chain extending compound
  • X_ is the mole fraction of the monohydric chain terminating compound.
  • the dihydric phenols which are preferably employed as the multi-hydric compound to provide the aromatic carbonate polymers may contain one or more aromatic rings and contain as functional groups two or more hydroxyl moieties which are reactive with the carbonate precursor compound, each of which hydroxyl moiety is preferably attached directly to a carbon atom of an aromatic ring.
  • Typical dihydric phenols are 2,2-bis-(4-hy- droxyphenyl)-propane ("Bisphenol A”); hydroquinone; resorcinol; 2,2-bis-(4-hydroxyphenyl)-pentane; 2,4'-dihydroxy diphenyl methane; bis-(2-hydroxyphenyl) methane; bis-(4-hydroxyphenyl)-methane; bis(4-hydroxy-5- nitrophenyl)-methane; 1 , 1-bis-(4-hydroxyphenyl)-ethane; 3,3-bis-(4-hydroxyphenyl)-pentane; 2,2*-dihydroxydi- phenyl; 2,6-dihydroxy naphthalene; bis-(4-hydroxypehnyl) sulfone; 2,4'dihydroxydiphenyl sulfone; 5'-chloro-2,4 '- -dihydroxydiphenyl sulf
  • the carbonate copolymers according to the present invention would contain less than 50, preferably less than 20, more preferably less than 10 percent and most preferably less than 5 percent of an ester linking group.
  • the carbonate polymers according to the present invention consist essentially of dihydric phenols which contain one or more aromatic rings and contain as functional groups two or more hydroxyl moieties which are attached directly to a carbon atom of an aromatic ring.
  • the materials are reacted at temperatures of from 100°C or higher for times varying from 1 to 15 hours. Under such conditions ester interchange occurs between the carbonate ester and the multi-hydric compound used.
  • the ester interchange is advantageously done at reduced pressures of the order of from 10 to 100 millimeters (mm) of mercury.
  • arylcyclobutene moieties which are otherwise pendant from the polymer backbone to the extent that their irregular and inconsistent distribution along the polymer molecules detrimentally affects the polymer properties, such as by causing gels or reduced physical properties.
  • the arylcyclobutene moieties in carbonate polymers according to the present invention consist essentially of terminal arylcyclobutene moieties and more preferably there are essentially no pendant arylcyclobutene moieties.
  • an arylcyclobutene terminated carbonate polymer corresponds to the formula III below:
  • B is a carbonate polymer
  • Ar is an aromatic radical which may be substituted with an electron- withdrawing substituent or electron-donating substituent, the carbon atoms represented by C are bonded to adjacent carbon atoms of the aromatic radical Ar, R is independently in each occurrence hydrogen or an electron-withdrawing substituent or electron-donating substituent;
  • x is an integer of. 1 or greater, and
  • y is an integer of 1 or greater, preferably 1.
  • a benzocyclobutene-functionalized carbonate polymer according to the present invention corresponds to the following formula IV:
  • P is a carbonate polymer
  • R-- is independently in each occurrence hydrogen or an electron-withdrawing substituent or electron-donating substituent
  • z is an integer of 1 or greater.
  • is always hydrogen, is also referred to as bicyclo[4.2.0]-octa-1,3 > 5-triene.
  • Providing the backbone chains of all or part of the carbonate polymer molecules with terminal arylcyclobutene moieties can be accomplished by a number of techniques including the use of an arylcyclobutene- functionalized chain terminating compound in a carbonate polymer polymerization reaction or the use of a suitably functionalized arylcyclobutene compound to react with terminally located reactive moieties on an existing carbonate polymer.
  • Compounds suitable for use as chain terminating compounds in carbonate polymerization processes are well known in the literature.
  • techniques for preparing arylcyclobutene-containing molecules are well known in the literature, for example U.S. Patents 4,540,763 and 4,708,994.
  • the terminal arylcyclobutene moieties are effectively and efficiently incorporated into the carbonate polymers according to the present invention by the use of arylcyclobutene-functionalized chain terminating compounds.
  • the arylcyclo ⁇ butene moieties are located on molecules which react into but terminate the growing carbonate polymer molecules.
  • arylcyclobutene-containing molecules with a single acyl chloride or hydroxy functionality are desirably employed in the carbonate polymer polymerization process.
  • acid chloride functionalized and hydroxy functionalized arylcyclobutene compounds are described. See also Lloyd et al., Tetrahedron , vol. 21, pp.
  • Hydroxybenzocyclobutene and particularly 4-hydroxy- benzocyclobutene, is a preferable arylcyclobutene- functionalized chain terminating compound for use in preparing the carbonate polymers according to the present invention.
  • 4-Hydroxybenzocyclobutene is also referred to as 3-hydroxy-bicyclo[4.2.0]-octa-1 ,3 > 5- triene.
  • the hydroxy moiety in hydroxybenzocyclobutene reacts very effectively in the carbonate polymerization process to provide the desired levels of terminal benzocyclobutene moiety.
  • the concentration of the arylcyclobutene groups and the molecular weight of the carbonate polymer can be optimized for a particular set of properties. In this way, the total concentration of terminating compound(s) statistically determines the chain length of the carbonate polymer molecules as indicated above where the Flory equations for this calculation are reproduced.
  • the amount of the arylcyclobutene chain terminating compound relative to the amount of any other chain terminating compound(s) will determine, on the average, what percentage of the carbonate polymer molecule ends will be terminated with an arylcyclobutene moiety and thus the amount of branching that will take place.
  • branched carbonate 0 polymers can be prepared by the use of branching compounds having three or more hydroxyl groups. This situation is represented by formula I above wherein v is 2 or 3- In these cases the relative concentrations of a chain-terminating arylcyclobutene compounds and any other chain-terminating compounds can be determined to provide the theoretical amount which would be required to provide the desired molecular weight and percentage of chain ends with a terminal arylcyclobutene moiety.
  • Carbonate polymers having a relatively low molecular weight prior to crosslinking and being completely terminated with all arylcyclobutene terminal groups can be very desirably employed in applications where the molten polymer must flow quickly and easily into a mold, for example, relatively large, complicated molds. Then, upon further heating and crosslinking, in the mold or subsequently, the shaped articles possess good levels of toughness and other properties. It is very unexpected to be able to obtain a readily processable polymer which can be crosslinked to such a high degree and still provide shaped polymer articles which are relatively tough and heat and solvent resistant.
  • the mole ratio of the arylcyclobutene compound per mole of the multi-hydric compound is at least 0.02, more preferably at least 0.03 and most preferably at least 0.1.
  • the mole ratio of the arylcyclobutene compound per mole of the multi-hydric phenol compound is desirably less than or equal to to 1 , preferably less than or equal to 0.99, more preferably less than or equal to 0.5.
  • a polycarbonate precursor compound such as phosgene and a dihydric phenolic compound such as bisphenol A
  • a molar ratio of 1 mole hydroxybenzocyclobutene per mole of dihydric phenolic compound results in a degree of polymerization of 2, based on dihydric compound as calculated by the Flory equations given above and determined prior to the crosslinking of the polymer.
  • a molar ratio of 0.03 mole hydroxybenzocyclobutene per mole of dihydric phenolic compound can be used to obtain a degree of polymerization of 34 when using these compounds to prepare a carbonate polymer which is completely terminated with the arylcyclobutene moiety.
  • one embodiment of the present invention includes polymers where less than all of the chain ends are terminated with the arylcyclobutene moiety. Since the arylcyclobutene moieties react with multiple other arylcyclobutene moieties upon activation, the resulting carbonate polymer will be branched around a connecting point of inter-reacted arylcyclobutene moieties. It has been found that very desirable branched carbonate polymers can be provided by this partial crosslinking (that is, branching) of the carbonate polymer via the arylcyclo ⁇ butene reaction.
  • suitable reactive arylcyclobutene compounds can be reacted onto terminal reactive sites or, more preferably, an arylcyclobutene chain terminating compound is employed in the polycarbonate polymerization process together with one or more other chain terminating compound(s).
  • an arylcyclobutene chain terminating compound is employed in the polycarbonate polymerization process together with one or more other chain terminating compound(s).
  • branched polymers can be obtained by the use of chain terminating compound (aryl ⁇ cyclobutene and other) in total amounts in the range of from 0.04 to 0.01 mole per mole of multi-hydric aromatic compound.
  • chain terminating compound aryl ⁇ cyclobutene and other
  • the desired amount of branching typically from 0.01 to 0.05 branches per polymer molecule, is then determined by the relative amounts of the arylcyclobutene and other type chain terminating compound which are employed.
  • the arylcyclobutene chain terminating compound can be used in amounts of up to 0.5 moles arylcyclobutene chain terminating compound per mole of additional chain terminating agent, preferably up to 0.3 and more preferably up to 0.2 mole arylcyclo ⁇ butene chain terminating compound per mole of additional chain terminating agent.
  • the cyclobutene ring of the arylcyclobutene moiety can open by subjecting the functionalized polymers to sufficient heat. Typically, temperatures from 200°C to 300°C are sufficient to open the ring. Polymerization solvents or catalysts are unnecessary, although a copper salt catalyst may lower the required temperature. Electromagnetic radiation, such as microwave, infrared, ultraviolet, electron beam and gamma radiation, may also be used to open the ring, but thermal radiation is preferred since it can be applied by conventional methods.
  • the carbonate polymers according to the present invention can be employed in mixtures, alloys or blends with other polymer resins, including mixtures with polyester.
  • other additives can be included x, r- in the carbonate polymer of the present invention such as fillers (that is, glass fibers), pigments, dyes, antioxidants, heat stabilizers, ultraviolet light absorbers, mold release agents, impact modifiers and other additives commonly employed in carbonate polymer 0 compositions.
  • a glass reactor was fitted with a mechanical stirrer, a baffle, a thermometer, a pH electrode connected to a pH meter/controller, a liquid inlet tube, a gas inlet tube and a gas outlet tube connected to a phosgene scrubber, the scrubber containing an aqueous solution of 50 weight percent sodium hydroxide and 1 percent by weight triethylamine.
  • a mechanical stirrer a baffle
  • a thermometer connected to a pH meter/controller
  • a liquid inlet tube a gas inlet tube and a gas outlet tube connected to a phosgene scrubber
  • the scrubber containing an aqueous solution of 50 weight percent sodium hydroxide and 1 percent by weight triethylamine.
  • To the reactor was added 68.5 weight parts (0.3 mole parts) bisphenol A, 2.16 weight parts (0.018 mole parts) 4-hydroxy- benzocyclobutene (BCB-0H), 360 weight parts water and 240 weight parts dichloromethan
  • the polymer molecular weight was determined by gel permeation chromatographic analysis, the weight average molecular weight (Mw) being 18,190. Liquid chromatographic analysis of the reaction mixture residue showed complete reaction of the 4-hydroxybenzocyclo- butene. The resulting polycarbonate, before any crosslinking, was therefore determined to contain 0.06 moles benzocyclobutene per mole bisphenol A and have a degree of polymerization of 27.
  • This material was compression molded at 585°F (307°C) to form a crosslinked polycarbonate which was completely insoluble in dichloromethane.
  • Differential scanning calorimetry analysis showed a glass transition temperature (Tg) of 165°C.
  • Tg glass transition temperature
  • the pH of the mixture was increased to 12.5 with the addition of sodium hydroxide in the form of a 50 percent aqueous solution and 360 weight parts dichloromethane and 0.10 weight parts (0.001 mole parts) triethylamine
  • the tensile testing is performed on 1.6 millimeter (mm), that is, 1/16 inch, samples that have been compression molded at 307°C.
  • the analyses were performed according to ASTM D-638 on type V sample dimensions.
  • the tensile modulus is shown as "Ten Mod” and the value given in megaPascals (MPa) with the value in kilopounds per square inch (kpsi) being given in 0 parentheses.
  • the stress required to the point of sample yield and sample breaking are shown as "Yield stress” and "Break stress” and the values are given in MPa with the value in kpsi being given in parentheses.
  • the E - percent of sample elongation at sample yield and sample break are shown as "Yield elong” and "Break elong” with the values shown being the percentages of original sample length that the sample has been elongated.
  • the flexural modulus (“Flex Mod”) is tested according to ASTM D-790 and given in MPa with the value in kpsi being given in parentheses.
  • the notched Izod impact resistance is tested according to ASTM D-256-72A on on 3-18 millimeter (1/8 inch) samples that have been compression molded at
  • the percent swelling shows the resistance to solvent of the polymer and was measured on 0.254 mm (1/100 inch) film samples soaked in dichloromethane. The indicated results are the percentage increase in the polymer surface area due to solvent absorption. All of the samples were found to be insoluble in dichloromethane.
  • Thermogravimetric analysis is used to measure the char yield (“5&Char”), the weight percentage of the residue remaining after heating to 800°C in air and the decomposition temperature (“Td”), the temperature at which 5 percent of the sample material is lost.
  • the resistance to ignition of the polymer compositions is shown by the Limiting Oxygen Index (LOI) and UL-94 tests performed according to ASTM A-2863-87 and D-4804-88 respectively on 3-18 millimeter (1/8 inch) samples.
  • LOI Limiting Oxygen Index
  • CLTE coefficient of linear thermal expansion
  • Hardness shows the abrasion resistance of the samples and is tested according to ASTM D-3363 with H being the hardest and F, HB, B, 2B and 3B indicating progressively less hardness. As shown, a typical carbonate polymer has a hardness value of 3B and a hardness value of B is recognized to be significantly better hardness than standard carbonate polymers.
  • the R* 5 value is an indication of the blow moldability of the polymer, branched polycarbonates being generally recognized as superior in blow molding applications to linear polycarbonate resins.
  • Table II 0 compares the properties of the branched polycarbonate according to the present invention with the properties of a linear bisphenol A polycarbonate resin.
  • acyl chloride of benzocyclobutene was used to prepare a functionalized polycarbonate.
  • a glass reactor was fitted with a mechanical stirrer, a stirrer baffle, a thermometer, a pH electrode connected to a Fisher Model 805 pH meter/controller, a caustic inlet tube, a phosgene inlet and a gas outlet tube connected to a phosgene scrubber, the scrubber containing an aqueous solution of 50 weight percent sodium hydroxide and 1 percent by weight triethylamine.
  • the reactor and solvents were thoroughly purged with nitrogen prior to phosgenation.
  • the stirrer was set to give turbulent mixing throughout the vessel.
  • the reactor temperature was maintained below 30°C.
  • the mixture was agitated for 20 minutes to produce the BCB terminated polycarbonate.
  • the pH of the mixture was reduced to 7 with addition of 9 weight parts of phosgene.
  • the polymer solution was washed with 1 N HCl and with water and the polymer was then isolated.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

On décrit des polymères de carbonate présentant des fractions terminales d'arylcyclobutène. De tels polymères de carbonate sont préparés à partir d'un ou plusieurs composés multihydriques et présentent un degré de polymérisation moyen de 2 au minimum, basé sur le composé multihydrique. Ces polymères, y compris des mélanges les comprenant, peuvent être aisément traités et dotés de profils et de structures variées selon les techniques connues. Au cours du traitement, ou après celui-ci, les polymères peuvent être réticulés, par exemple par exposition à la chaleur ou à un rayonnement, de manière à produire des compositions polymères réticulées. Ces compositions présentent une bonne combinaison de caractéristiques, y compris, notamment, la possibilité d'être traitées de façon à produire des articles profilés présentant des combinaisons étonnamment avantageuses de robustesse, de résistance aux solvants et à l'allumage, de coefficient de conversion et de résistance à l'expansion linéaire thermique.
PCT/US1991/009325 1990-12-24 1991-12-17 Polymeres de carbonate a terminaisons arylcyclobutene WO1992011309A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP4502406A JPH06504305A (ja) 1990-12-24 1991-12-17 アリールシクロブテン末端カーボネートポリマー
KR1019930701937A KR930703376A (ko) 1990-12-24 1993-06-23 아릴사이클로부텐 말단화된 카보네이트 중합체

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US63374090A 1990-12-24 1990-12-24
US633,740 1990-12-24

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5318827A (en) * 1992-06-15 1994-06-07 The Dow Chemical Company Carbonate polymer laminate structure
US5362838A (en) * 1993-02-19 1994-11-08 Virginia Polytechnic Institute And State University Carbonate polymers containing ethenyl aryl moieties
WO1995014742A1 (fr) * 1993-11-22 1995-06-01 The Dow Chemical Company Compositions a base de melanges de polymeres de carbonate comprenant un constituant polymere de carbonate ramifie a poids moleculaire eleve et leurs procedes de preparation
WO1995014743A1 (fr) * 1993-11-22 1995-06-01 The Dow Chemical Company Resine polymere de carbonate presentant une fluidite amelioree et sa fabrication, articles de faible epaisseur de paroi obtenus a partir de ladite resine

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5965792B2 (ja) * 2012-09-05 2016-08-10 三菱瓦斯化学株式会社 芳香族ポリカーボネート樹脂組成物および成形品

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4708990A (en) * 1986-06-18 1987-11-24 Shell Oil Company Anionic polymerization process
US4708994A (en) * 1986-06-30 1987-11-24 Shell Oil Company Engineering thermoplastics containing pendant benzocyclobutene groups
US4937287A (en) * 1988-02-17 1990-06-26 Amoco Corporation Elastomeric polyarylate graft copolymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4708990A (en) * 1986-06-18 1987-11-24 Shell Oil Company Anionic polymerization process
US4708994A (en) * 1986-06-30 1987-11-24 Shell Oil Company Engineering thermoplastics containing pendant benzocyclobutene groups
US4937287A (en) * 1988-02-17 1990-06-26 Amoco Corporation Elastomeric polyarylate graft copolymers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5318827A (en) * 1992-06-15 1994-06-07 The Dow Chemical Company Carbonate polymer laminate structure
US5362838A (en) * 1993-02-19 1994-11-08 Virginia Polytechnic Institute And State University Carbonate polymers containing ethenyl aryl moieties
WO1995014742A1 (fr) * 1993-11-22 1995-06-01 The Dow Chemical Company Compositions a base de melanges de polymeres de carbonate comprenant un constituant polymere de carbonate ramifie a poids moleculaire eleve et leurs procedes de preparation
WO1995014743A1 (fr) * 1993-11-22 1995-06-01 The Dow Chemical Company Resine polymere de carbonate presentant une fluidite amelioree et sa fabrication, articles de faible epaisseur de paroi obtenus a partir de ladite resine

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EP0564517A1 (fr) 1993-10-13
KR930703376A (ko) 1993-11-29
JPH06504305A (ja) 1994-05-19
CA2093903A1 (fr) 1992-06-25

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