EP0000097B1 - Polyarylenester Formmassen, Verfahren zu ihrer Herstellung und so erhaltene Formkörper - Google Patents

Polyarylenester Formmassen, Verfahren zu ihrer Herstellung und so erhaltene Formkörper Download PDF

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Publication number
EP0000097B1
EP0000097B1 EP78300028A EP78300028A EP0000097B1 EP 0000097 B1 EP0000097 B1 EP 0000097B1 EP 78300028 A EP78300028 A EP 78300028A EP 78300028 A EP78300028 A EP 78300028A EP 0000097 B1 EP0000097 B1 EP 0000097B1
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Prior art keywords
bis
molding resin
hydroxyphenyl
resin according
diphenol
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French (fr)
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EP0000097A1 (de
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Oliver Desauze Deex
Virgil Wayne Weiss
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Monsanto Co
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Monsanto Co
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Priority claimed from US05/806,388 external-priority patent/US4127557A/en
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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass

Definitions

  • This invention relates to a molding resin, to a method of producing the molding resin and to shaped articles formed from the molding resin. More particularly, it pertains to molding resins comprising a polyarylene ester and a reinforcing filler, to a method of producing such molding resins and to shaped articles formed from such molding resins.
  • polyesters have been suggested for use as molding resins and engineering thermoplastics since the earliest practical development of such polymers by Whinfield and Dickson. Although several of such polyesters and copolyesters have found commercial success as film and fiber products, few have been successful as molding resins and engineering thermoplastics. Two of the more successful, polyethylene terephthalate and polytetramethylene terephthalate prepared from aliphatic diols and terephthalic acid, suffer from certain deficiencies as engineering thermoplastics. They are both quite flammable and have rather low glass transition temperatures which can limit their usefulness to relatively low temperatures.
  • the present invention discloses improved molding resins that yield molded articles possessing a) improved fire safety performance, particularly reduced afterglow, b) improved resistance to heat distortion and c) improved resistance to flow at elevated temperatures in comparison with reinforced polyalkylene terephthalates.
  • a molding resin comprising an intimate blend of a polyarylene ester and a reinforcing filler, characterised in that the polyarylene ester consists essentially of units derived from a C 8 to C 25 aromatic dicarboxylic acid and optionally a minor quantity of a C 2 to C 20 aliphatic dicarboxylic acid and a diphenol comprising from 60 to 100 mol percent 1,2-bis-(4-hydroxyphenyl) ethane and from 40 to 0 mol percent of a C 6 to C 25 diphenol, the inherent viscosity of said polyarylene ester at 30 °C being at least 0.5 as determined at a concentration of 0.5 grams polyester per 100 ml solution in a solvent mixture of 60 parts by
  • the molding resins of the present invention comprise an intimate blend of a polyarylene ester and a reinforcing filler preferably ranging from 2 to 60 weight percent of the total composition.
  • a polyarylene ester consist essentially of units derived from at least one C 8 to C 25 aromatic dicarboxylic acid and a diphenol comprising from 60 to 100 mol percent 1,2-bis-(4-hydroxyphenyl) ethane and from 40 to 0 mol percent of at least one C 6 to C 25 diphenol.
  • the polyarylene ester component of the molding resin of the present invention is the condensation product of at least one C 8 to C 25 aromatic dicarboxylic acid and a diphenol comprising from 60 to 100 mol percent 1,2-bis(4-hydroxyphenyl) ethane and from 40 to 0 mol percent of at least one C 6 to C 25 diphenol.
  • the polyesters are described in Belgian Patent 850,978 and have been found to possess superior fire safety performance and are capable of yielding crystalline compositions which have superior solvent resistance and stress cracking resistance.
  • the preferred aromatic dicarboxylic acids comprise at least one of isophthalic acid, terephthalic acid, 3,3'-, 3,4'- and 4,4'-bibenzoic acids and bis(carboxyphenyl) ethers, bis(carboxyphenyl) sulfides, bis(carboxyphenyl) sulfones, bis(carboxyphenyl) methanes, 1,2-bis(carboxyphenyl) ethanes and 2,2-bis(carboxyphenyl) propanes in which the carboxy groups are in the 3 or 4 positions.
  • Mixtures of one or more of the aromatic dicarboxylic diacids with minor quantities, generally less than 25 mol percent, of C 2 to C 20 aliphatic dicarboxylic acids can also be used.
  • the quantities of aliphatic dicarboxylic acids in general are selected so that they do not cause a significant loss in Tg of the resulting polyesters. Preferably the quantity is limited to a loss in Tg of not more than 10 °C.
  • the acid or admixture of acids is combined with 1,2-bis(4-hydroxyphenyl) ethane or with 1,2-bis(4-hydroxyphenyl) ethane in admixture with any other suitable C e to C 25 diphenol or mixture of diphenols to provide the aromatic polyesters of the present invention.
  • diphenols according to formula I include bis(4-hydroxyphenyl) methane, 1,2-bis(3-hydroxyphenyl) ethane, 1-(3-hydroxyphenyl)-2-(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfide and bis(4-hydroxyphenyl) sulfone.
  • diphenol must contain at least 60 mol percent 1,2-bis(4-hydroxyphenyl) ethane
  • a diphenol which comprises at least 90 mol percent, 1,2-bis(4-hydroxyphenyl) ethane because these polyesters are generally crystalline and exhibit a rather rapid rate of crystallization and polyarylene esters in which 1,2-bis(4-hydroxyphenyl) ethane is substantially the only diphenolic component can be used to advantage to obtain more rapid rates of crystallization.
  • the selection of acid and diphenol components is made so that the polyester preferably has a glass transition temperature of at least 100°C and a melt viscosity at 350 °C determined in a capillary rheometer at a shear rate of 110 sec- 1 of less than 10 5 poise.
  • the aromatic dicarboxylic acid is preferably selected so that the melting point of the polyarylene ester is less than 350 °C.
  • a preferred group of the polyarylene esters comprises those polyesters obtained by condensation of a diphenol comprising at least 90 mol percent 1,2-bis(4-hydroxyphenyl) ethane and a dicarboxylic acid comprising at least 67 mol percent isophthalic acid. Of this group, one of the preferred combinations is obtained from 1,2-bis(4-hydroxyphenyl) ethane and isophthalic acid without additional components. Such preferences are based on the availability and cost of the acid as well as on the desirable glass transition and melting points of the resulting polyesters.
  • the crystallization rate is expressed as the inverse of the time required for one half of the crystallization exotherm observed when a sample is cooled at a rate of 20 °C per minute.
  • a rate of crystallization of about 0.2 minutes -1 or greater as determined by this method is satisfactory in injection molding of polymers because the cooling rate in the molding operation is generally much faster than the cooling rate used in the determination of rate of crystallization.
  • a crystallization rate of about 0.5 minutes-' or greater is more preferable and for rapid molding cycles a crystallization rate of about one minute -1 or greater is even more preferred.
  • the polyarylene ester component of the present invention can be produced by a convenient method such as by melt condensation or solvent condensation of mixtures of aromatic dicarboxylic acids and diphenot diesters selected to provide polyarylene esters of the desired fire safety performance and processability. They can be produced by melt or solution polymerization of selected mixtures of phenol esters of aromatic dicarboxyiic acids and diphenols and by interfacial polymerization of salts of diphenols and aromatic dicarboxylic acid dihalides.
  • the reactants are diacids and diphenol esters, or phenyl esters of diacids and diphenols, or salts of diphenols and diacid halides.
  • One method of preparation is the melt condensation of mixtures of aromatic dicarboxylic' acids and diphenol diesters.
  • Another method is the melt condensation of mixtures of aromatic dicarboxylic acids and diphenol diesters to a prepolymer stage of inherent viscosity in the range of 0.1 to 0.4 followed by solid state polymerization to advance the polymer to an inherent viscosity above 0.5. ' .
  • the molding resins of the present invention are prepared by intimately blending the polyarylene ester with sufficient reinforcing filler which is preferably from 2 to 60 weight percent of the total composition.
  • the amount of reinforcing filler is in the range of from 5 to 40 weight percent of the total composition to achieve a sufficient degree of reinforcement without an excessive increase in melt viscosity. It is to be understood that the indicia of reinforcement are increases in the tensile strength, stiffness or impact strength of the filled composition in comparison with the unfilled composition.
  • any reinforcement can be used such as granular, plate-like, acicular or fibrous fillers of suitable size for reinforcement.
  • the fillers may be metallic such as aluminum, iron, nickel, copper or zinc or may be non-metallic such as carbon filaments, silicates, clays, calcined clays, asbestos, silica, titanium dioxide, titanate whiskers, glass flakes and fibers.
  • the preferred reinforcing fillers include any kind of glass fibers usually used for reinforcing thermoplastic resins and are relatively soda free glasses comprising lime-aluminum borosilicate glass such as types " C " and " E " glass.
  • the fibers may be in the form of filaments, or bundled into strands, ropes or rovings. They are conveniently used in the form of chopped strands of up to 5 cm in length and preferably in the range of 0.3 cm to 2.5 cm in length.
  • Other additives such as colorants, plasticizers, stabilizers and hardeners can be incorporated into the molding resins.
  • Blending of the polyarylene ester and the reinforcing filler is carried out in any convenient way, such as by dry mixing pellets or powder of polyarylene ester with the filler and mett blending and extrusion, or by adding filler to molten polyarylene ester, blending and extrusion.
  • the polyarylene ester, the reinforcing filler and any other additives are preferably as free as possible of water.
  • Mixing is preferably carried out in as short a time as possible to provide a sufficiently intimate and uniform blend and at a temperature selected for adequate melt viscosity but insufficient to cause thermal degradation of the resin.
  • the blend can be extruded and cut up into molding compounds such as granules and pellets by conventional techniques.
  • the molding resins can be molded in any equipment conveniently used for reinforced thermoplastic compositions e.g., a 14 gm. Arburg machine with temperature in the range of 250° to 350 °C and mold temperature of 100° to 150 °C can be used.
  • a 14 gm. Arburg machine with temperature in the range of 250° to 350 °C and mold temperature of 100° to 150 °C can be used.
  • the amount of reinforcing filler and the crystallization behavior of the polyarylene ester those skilled in the art will be able to make the conventional adjustments in molding cycles to accommodate the composition.
  • a charge consisting of 8.2 parts of isophthalic acid and 14.8 parts of 1,2-bis(4-acetoxyphenyl) ethane is placed in a reaction vessel equipped with a stirrer, condenser and receiver.
  • the vessel is evacuated and purged with nitrogen three times.
  • a nitrogen blanket is maintained in the reactor while it is heated to 250 °C, for about three hours during which period approximately 3.5 to 4.0 parts of acetic acid distills.
  • the vessel is evacuated to a pressure of 125 mm and heating at 275 °C is continued for one half hour during which period an additional 1 to 1.5 parts of acetic acid distills.
  • the vacuum is then increased to reduce the pressure to about 0.1 to 0.2 mm and the temperature is raised to 290 °C for an additional hour. At this point the reaction mixture becomes so viscous that further stirring is difficult. Heating is stopped, the reaction mixture is again blanketed with nitrogen and allowed to cool.
  • the resultant polymer is light yellow in color, crystalline and demonstrates an inherent viscosity of 0.57 in the phenol- tetrachloroethane solvent.
  • Example A A similar reaction is carried out under the same conditions and with the reactants and equipment described in Example A except that after the initial three hour period the temperature is raised to 275'C and the pressure is reduced to 125 mm for 30 minutes. Thereafter, the temperature is raised to 290 °C during the final period at high vacuum of 0.1 to 0.2 mm.
  • the resultant polymer demonstrates an inherent viscosity of 0.83 and is crystalline and a clear light yellow in color.
  • Examples C to U are carried out by reacting mixtures of diphenol diacetates and isophthalic acid by the melt method of Example A, with adjustment in the temperature and heating cycle appropriate for the rheology and morphology of the particular polyester or by melt polymerization to a prepolymer followed by solid state polymerization of the crystalline polyester.
  • Compositions and physical property data are set forth in Table 1.
  • Melt viscosities are det ⁇ mined at 316 °C with a Sieglaff-McKelvey Rheometer at a shear rate of 100 sec- 1 , using a capillary with a length to diameter ratio of 25 to 1.
  • polyester combinations containing high levels of 1,2-bis(hydroxyphenyl) ethane and acids such as isophthalic acid are opaque and exhibit crystalline melting points below 300 °C and crystallize rapidly while in contrast, polyester combinations containing substantial amounts of other diphenols and polyester combinations containing substantial amounts of substituted acids such as 5-t-butyl-isophthalic acid are amorphous.
  • Polyisophthalate of 1,2-bis(4-hydroxyphenyl) ethane prepared as in Example C is extruded and chopped to yield pellets of approximately 3 to 5 mm in length and 2 mm in diameter. 85 parts by weight of the pellets are blended in a tumble blender with 15 parts by weight of chopped glass strand, 4.8 mm length, containing 800 filaments of 13 micron diameter per strand supplied by Owens Corning Fiberglas Corporation under the trade name Owens-Corning Fiberglas 419.
  • the blend of polyester and glass fiber is force fed to the chopper of a single stage extruder heated to 320 °C and is slowly extruded through the strand die. The strand is cooled and chopped to provide pellets of molding resin.
  • the molding resin is injection molded in a 14 gm. Arburg machine at a temperature of 315°C and a mold temperature of 122°C to provide test bars.
  • the test bars are tested for tensile strength and elongation, ASTM D-638 ; flexural strength and modulus, ASTM D-790 ; impact strength ASTM D-256 ; heat distortion ASTM D-648.
  • the data are presented in Table 2.
  • Molding resins are prepared as in Example 1 with the polyisophthalate of 1,2-bis(4-hydroxyphenyl) ethane and respectively 22.5 and 30 parts by weight of glass fiber per 100 parts by weight of total composition.
  • the molding resins are injection molded into test bars and subjected to physical testing. The data are presented in Table 2.
  • Example 2 is subjected to the Underwriter's UL-94 test.
  • the rating for samples 1.58 mm in thickness is V-O (average flame out time within 5 seconds, no afterglow).
  • the polyester of Example 2 without glass fiber reinforcement in Example 3 (b) is rated V-O (average flame out time within 3 seconds with afterglow which causes within 30 seconds).
  • a test bar of Example 2 with a heat distortion temperature of 183 °C was subjected to a load in the range of 0.14 to 0.28 kg cm- 2 for 20 minutes at 210 °C. No flow or deformation occurs.
  • a test bar of a reinforced polytetramethylene terephthalate, containing 30 weight percent glass fiber, having a heat distortion temperature of 212 °C shows considerable flow and deformation under similar conditions and fails the UL-94 test.
  • Molding resins are prepared as in Example 1 by blending polyarylene ester Examples K, L, M, N, P and R with 30 weight percent of the total composition of Owens-Corning Fiberglas 419.
  • the molding resins are molded into test bars. Considerable enhancement of the tensile strength, modulus and heat distortion temperature is obtained in comparison with the unfilled polyesters.
  • Example 1 A polyarylene ester similar to Example U comprising the condensation product of bisphenol A and isophthalic acid, of inherent viscosity 0.8 is blended with glass fiber in the manner described in Example 1.
  • the molding resins thus obtained are molded into test bars and tested for physical properties.
  • Examples 10, 11 and 12 contain 15, 22.5 and 30 weight percent of glass fiber ;
  • Example 13 is the unreinforced polyester.
  • the data are presented in Table 3 and show that the heat distortion temperature of this polyester is relatively unaffected by the reinforcing filler in contrast to the pronounced effect obtained in Exemples 1-3 (a) comprising the polyisophthalate of 1,2-bis(4-hydroxyphenyl) ethane.
  • Molding resins containing 30 weight percent glass fiber are prepared in the manner of Example 1 from polyester Examples S and T.
  • the molding resins are molded into test bars.
  • the tensile strength and modulus of the polyesters are enhanced by the addition of glass fiber. However, little improvement in heat distortion temperature is obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Claims (13)

1. Preßharz, enthaltend eine innige Mischung aus einem Polyarylenester und einem verstärkenden Füllstoff, dadurch gekennzeichnet, daß der Polyarylenester im wesentlichen aus Einheiten besteht, die sich von einer aromatischen Dicarbonsäure mit 8 bis 25 Kohlenstoffatomen ableiten, und gegebenenfalls einer kleineren Menge einer aliphatischen Dicarbonsäure mit 2 bis 20 Kohlenstoffatomen und einem Diphenol, enthaltend von 60 bis 100 Molprozent 1,2-Bis(4-hydroxyphenyl)-äthan und von 40 bis 0 Molprozent eines Diphenols mit 6 bis 25 Kohlenstoffatomen, wobei die inhärente Viskosität des Polyarylenesters bei 30 °C, bestimmt bei einer Konzentration von 0,5 g Polyester pro 100 ml Lösung in einem Lösungsmittelgemisch aus 60 Gewichtsteilen Phenol und 40 Gewichtsteilen sym-Tetrachloräthan, zumindest 0,5 beträgt.
2. Kristallines Preßharz nach Anspruch 1, in welchem die Schmelzviskosität des Polyarylenesters bei 350 °C, bestimmt bei einer Scherrate von 100 s-1 mit einem Kapillarrheometer, kleiner als 105 Poise ist.
3. Preßharz nach einem der Ansprüche 1 oder 2, in welchem der verstärkende Füllstoff ein körniger, plattenähnlicher, nadelförmiger oder faseriger Füllstoff ist und von 2 bis 60 Gewichtsprozent des Preßharzes ausmacht.
4. Preßharz nach einem der vorstehenden Ansprüche, in welchem der verstärkende Füllstoff ein faseriger, nichtmetallischer Füllstoff ist.
5. Preßharz nach einem der Ansprüche 1 bis 3, in welchem der verstärkende Füllstoff Glasfasern sind.
6. Preßharz nach einem der vorstehenden Ansprüche, in welchem die aromatische Dicarbonsäure Isophthalsäure, Terephthalsäure, 5-tert.-Butyl-isophthalsäure, 3,3'-, 3,4'- oder 4,4'-Bibenzoesäure oder einen Bis(carboxyphenyl)-äther, ein Bis(carboxyphenyl)-sulfid, ein Bis(carboxyphenyl)-sulfon, Bis(carboxyphenyl)-methan, 1,2-Bis(carboxyphenyl)-äthan, oder ein 2,2-Bis(4-carboxyphenyl)-propan, worin die Carboxygruppen in der 3- oder 4-Stellung stehen, umfaßt.
7. Preßharz nach einem der vorstehenden Ansprüche, in welchem das Diphenol mit 6 bis 25 Kohlenstoffatomen Resorcin, Hydrochinon, ein 3,3'-, 3,4'- oder 4,4-Diphenol oder ein Diphenol der nachfolgenden allgemeinen Formel
Figure imgb0008
umfaßt, in welcher die Hydroxylgruppen in den 3- oder 4-Stellungen stehen, Y die Bedeutung O, S, SOz, C = O, CH2, CH(CH3), C(CH3)2, (CH2)2 oder (CH2)3 hat, und R einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeutet und der Index m = 0 bis 4 ist.
8. Preßharz nach einem der vorstehenden Ansprüche, in welchem das Diphenol mit 6 bis 25 Kohlenstoffatomen Bis(4-hydroxyphenyl)-methan, 1,2-Bis(3-hydroxyphenyl)-äthan, 1-(3-hydroxyphenyl)-2-(4-hydroxyphenyl)-äthan, 2,2-Bis(4-hydroxyphenyl)-propan, Bis(4-hydroxyphenyl)-äther, Bis(4-hydroxyphenyl)-sulfid und Bis(4-hydroxyphenyl)-sulfon umfaßt.
9. Preßharz nach einem der vorstehenden Ansprüche, in welchem der Polyarylenester eine Kristallisationsgeschwindigkeit von zumindest 0,2 min-1 besitzt.
10. Kristallines Preßharz nach Anspruch 1, enthaltend von 2 bis 60 Gewichtsprozent der gesamten Zubereitung an verstärkendem Füllstoff, und worin der Polyarylenester im wesentlichen aus wiederkehrenden Einheiten der nachfolgenden allgemeinen Formel
Figure imgb0009
besteht und eine inhärente Viskosität bei 30 °C, wie sie bei einer Konzentration von 0,5 g Polyester pro 100 ml Lösung in einem Lösungsmittelgemisch aus 60 Gewichtsteilen Phenol und 40 Gewichtsteilen sym-Tetrachloräthan bestimmt wird, von zumindest 0,5 besitzt.
11. Preßharz nach Anspruch 10, in welchem der verstärkende Füllstoff ein körniger, plattenähnlicher, nadelförmiger oder faseriger Füllstoff ist.
12. Verfahren zur Herstellung eines Preßharzes nach Anspruch 1, dadurch gekennzeichnet, daß es das innige Mischen des Polyarylenesters mit dem verstärkenden Füllstoff umfaßt.
13. Geformter Harzartikel, gepreßt aus einem Preßharz gemäß Anspruch 1.
EP78300028A 1977-06-13 1978-06-09 Polyarylenester Formmassen, Verfahren zu ihrer Herstellung und so erhaltene Formkörper Expired EP0000097B1 (de)

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US05/806,388 US4127557A (en) 1976-07-28 1977-06-13 Reinforced polyarylene esters
US806388 1977-06-13

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EP0000097B1 true EP0000097B1 (de) 1981-02-11

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EP (1) EP0000097B1 (de)
JP (1) JPS5413552A (de)
AR (1) AR217302A1 (de)
AU (1) AU518000B2 (de)
BR (1) BR7803761A (de)
CA (1) CA1121081A (de)
DE (1) DE2860458D1 (de)
IT (1) IT1096718B (de)

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Publication number Priority date Publication date Assignee Title
JPS5710641A (en) * 1980-06-24 1982-01-20 Sumitomo Chem Co Ltd Wholly aromatic copolyester resin composition
JPS5820636A (ja) * 1981-07-30 1983-02-07 帝人株式会社 プラスチツク容器
DE3639428C1 (de) * 1986-11-18 1987-08-27 Rasselstein Ag Verfahren zum Herstellen eines mit einem eindrueckbaren OEffnungslappen versehenen Dosendeckels aus Blech

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US3511809A (en) * 1968-07-26 1970-05-12 Du Pont Polyesters from p-arylene-bis (dimethyl acetic acid)
JPS5641657B2 (de) * 1972-08-03 1981-09-29
JPS5518743B2 (de) * 1972-08-03 1980-05-21
US4102864A (en) * 1976-02-02 1978-07-25 Monsanto Company Polyesters of 1,2-bis(hydroxyphenyl) ethanes and aromatic dicarboxylic acids

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AR217302A1 (es) 1980-03-14
CA1121081A (en) 1982-03-30
IT1096718B (it) 1985-08-26
IT7824474A0 (it) 1978-06-12
JPS5413552A (en) 1979-02-01
BR7803761A (pt) 1979-04-17
EP0000097A1 (de) 1978-12-20
AU518000B2 (en) 1981-09-10
AU3703178A (en) 1979-12-20

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