Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• This invention relates to a toughened polyester composition
• a toughened polyester composition comprising a polyester and a functionalized elastomer.
• Polyesters have excellent mechanical properties, but are relatively brittle at low temperatures.
• U.S. Patent 4,657,971 5 discloses the use of modified, hydrogenated block copolymers of styrene and conjugated dienes as impact modifiers for polymer blends containing polyesters .
• the block copolymers may be modified with a variety of acid groups or derivatives of the acid groups.
• Blends of polyesters and modified elastomers were shown to
• polyesters are significantly and unexpectedly improved by blending the polyester with a modified elastomer comprising a hydrogenated conjugated diene having a star
• the blends of the invention comprise from 60% to 90% of the polyester and exhibit ductile failure at -20 °C.
• the present invention relates to a toughened polyester composition having an Izod impact strength at -20 °C of " at least 5.3 J/cm as determined by ASTM-D256 comprising:
• polyesters which may be used in the toughened polyester composition according to the present invention, are thermoplastic polyesters and include those polyesters described in European Patent Application No. 0,211,467. Accordingly, specific examples are polycaprolactones, polypivalolactones, cellulosics and polyalkylene terephthales, the latter being a preferred class of polyesters. Particularly preferred are the polybutylene terephthalate (PBT) polyesters. These PBT polyesters have the general formula: 0 0
• n is sufficient to provide an engineering thermoplastic polymer and X comprises one or more phenylene or substituted phenylene groups.
• X is non-substituted p-phenylene.
• the number average molecular weight of the PBT typically varies from 15,000 to 50,000, preferably from 25,000 to 50,000.
• 2v PBT is commercially available from e.g. General Electric
• VALOX thermoplastic polyester TYPET thermoplastic polyester
• CELANEX polyester Hoechst-Celanese
• the modified conjugated diene polymers are produced by free radical grafting of a hydrogenated conjugated diene polymer having
• grafting compound comprising alpha-beta ethylenic unsaturation and at least one epoxy group.
• the grafting compound is preferably glycidyl acrylate or glycidyl methacrylate, of which glycidyl acrylate is most preferred.
• Suitable polymers include selectively hydrogenated conjugated diene block copolymers of the general formula (A-B) (B) X n m wherein A is a polystyrene block having a peak molecular weight of less than 15,000, B is a polymer block of hydrogenated conjugated diene having a peak molecular weight in the range of from 15,000 to 50,000, X is a block of divinylbenzene and n and m are integers of 0 or higher, the sum of n and being at least 10. Most preferably n equals zero and m is at least 10.
• the block of the bisunsaturated coupling agent divinylbenzene generally constitutes less than 2% by weight of the polymer.
• the styrene blocks improve handling of the base polymer, if present, but do not enhance impact properties. Higher polystyrene content reduces the impact strength of the blends.
• the preferred conjugated diene blocks are hydrogenated polybutadiene or hydrogenated polyisoprene.
• the hydrogenated polybutadiene or polyisoprene blocks preferably have a residual unsaturation less than 2%. Hydrogenation may be effected by any known technique, e.g. by the process disclosed in U.S. Patent No. 27,145.
• the bisunsaturated coupling agent divinylbenzene is preferably added after polymerization of living polymers of the conjugated diene.
• a ratio of divinylbenzene to living polymer of 3:1 is preferred to accomplish an average of at least 10 polymeric arms per molecule as measured by gel permeation chromotagraphy in combination with a light scattering detector.
• the epoxy grafting compounds such as glycidyl acrylate or glycidyl methacrylate are grafted to the base block copolymer in an amount within the range from 1.0% to 10% by weight of the block copolymer, preferably from 1.5% to 5% by weight. Lower levels of functionality are ineffective in improving the low temperature toughness of the polyester.
• the base block copolymer may be functionalized using the known processes, such as those described in U.S. Patents Nos. 5,066,726; 4,033,888; 4,077,893; 4,670,173; 4,427,828; 4,578,429 and 4,628,072.
• the compositions prepared according to the present invention may incorporate other components known in the art to be useful in polyester compositions. These other components include, for example, fillers, pigments, antioxidants, stabilizers, processing oils, extenders and mold release agents.
• polyester compositions according to the present invention have an improved impact strength at -20 °C of at least 5.3 J/cm (10 ft-lb/in) and exhibit ductile failure during testing as shown in the following examples.
• Polyester compositions were prepared by blending VALOX 310 polyester, a commercially available polybutylene terephthalate (PBT) polyester having a number average molecular weight of 32,500, with several isoprene and butadiene polymers having grafted glycidyl acrylate or maleic anhydride for comparative purposes.
• PBT polybutylene terephthalate
• a star hydrogenated isoprene block copolymer was conventionally prepared by polymerizing living polymeric arms of isoprene having a peak molecular weight of 35,000, coupling the arms with divinylbenzene, and hydrogenating the polymerized isoprene.
• the residual unsaturation of the star polymer was reduced to less than 2% of the original aliphatic unsaturation.
• the star block copolymer was processed on a 25 mm Berstorff co-rotating twin screw extruder connected to a vacuum devolatilization unit. Prior to addition to the feed throat of the extruder, the polymer was tumbled with 3.0% by weight of glycidyl acrylate and 0.2% by weight of the peroxide (Luperox 101). The melt temperature of the extruder was 223 °C, and the extruder screw speed was 300 RPM (Rotations Per Minute) . To prepare the polymer for analysis, the modified block copolymer was dissolved in tetrahydrofuran, coagulated into isopropanol, and then washed with water.
• the modified polymer sample was analyzed for bound glycidyl acrylate content.
• the modified star polymer was found to contain 2.4% by weight glycidyl acrylate.
• the modified block copolymer was blended at 20% by weight loading with PBT polyester (VALOX 310 polyester) in a 25 mm Berstorff co-rotating twin screw extruder. The extruder screw speed was 300 RPM and the melt temperature reached was about 295 °C for the blend. Pellets from the resulting blend were injection molded into test specimens on a 0.59 ton/g (25 ton/1.5 oz) . Arburg injection molding machine.
• Example 1 of the present invention was tested for its impact strength (ASTM D-256) at room temperature (RT) and at low temperatures and tested for its flexural modulus (ASTM D-790). Table 1 gives the test results for comparing Example 1 of the present invention to the following comparison examples.
• the star hydrogenated isoprene base polymer of Example 1 was grafted with maleic anhydride in a 2" WEI counter-rotating twin screw extruder equipped with two injection ports and a vacuum devolatilization unit.
• maleic anhydride (2.5% by weight based on the polymer feed rate).
• second injection port was added a 50/50 mixture of mineral oil and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Luperox 101, 0.25% by weight based on polymer feed rate).
• the melt temperature of the polymer reached 280 °C and the extruder screw speed was 200 RPM.
• the modified block copolymer was dissolved in tetrahydrofuran, coagulated into isopropanol, and then washed with water.
• the modified polymer sample was analyzed for bound maleic anhydride content.
• the star polymer was found to contain 2.0% by weight maleic anhydride.
• the modified block copolymer was blended at 20% by weight loading with the PBT polyester of Example 1 in a 33 mm Werner-Pfleiderer twin screw extruder.
• the extruder screw speed was 300 RPM and the melt temperature reached was from 305-312 °C for the various blends.
• a linear block copolymer having 70% by weight styrene- butadiene-styrene (S-B-S) and 30% by weight styrene-butadiene - (S-EB) was conventionally prepared by polymerizing blocks of styrene having a peak molecular weight of 5,300 and blocks of butadiene having a peak molecular weight of 36,500, coupling 70% of the living polymers with methyl benzoate, and hydrogenating the polymerized butadiene. The residual unsaturation of the polymer was reduced to less than 2% of the original aliphatic unsaturation.
• the linear block copolymer was processed on a 25 mm Berstorff co-rotating twin screw extruder connected to a vacuum devolatilization unit. Prior to addition to the feed throat of the extruder, the polymer was tumbled with 3.0% by weight of glycidyl acrylate and 0.2% by weight of the peroxide Luperox 101. The melt temperature of the extruder was 232 °C, and the extruder screw speed was 300 RPM. The modified polymer was found to contain 2.4%w of glycidyl acrylate. ⁇ h e modified block copolymer was blended at 20% by weight loading with the PBT polyester of Example 1 in a 25mm Berstorff co-rotating twin screw extruder.
• a linear block copolymer having the structure butadiene- styrene (S-B-S) was conventionally prepared by polymerizing blocks of styrene having a peak molecular weight of 7,500, blocks of butadiene having a peak molecular weight of 35,000, and blocks of styrene having peak molecular weights of 7,500, and then hydrogenating the polymerized butadiene.
• the residual unsaturation of the polymer was reduced to less than 2% of the original aliphatic unsaturation.
• the linear block copolymer was processed on a 25mm Berstorff co-rotating twin screw extruder connected to a vacuum devolatilization unit.
• the polymer Prior to addition to the feed throat of the extruder, the polymer was tumbled with 3.0% by weight of glycidyl acrylate and 0.2% by weight of the peroxide Luperox 101.
• the melt temperature of the extruder was 241 °C, and the extruder screw speed was 300 RPM.
• the modified polymer was found to contain 2.2%w of glycidyl acrylate.
• the modified block copolymer was blended at 20% by weight loading with the PBT polyester of Example 1 in a 25mm Berstorff co-rotating twin screw extruder.
• the extruder screw speed was 300 RPM and the melt temperature reached was 298 °C for the blend.
• Pellets from the resulting blend were injection molded into test specimens on a 0.59 ton/g (25 ton/1.5 oz.) Arburg injection molding machine.
• Each of the blends was tested for its impact strength (ASTM D-256) at room temperature (RT) and at low temperatures and tested for its flexural modulus (ASTM D-790) .
• Table 1 gives the test results for comparing Comparative Example 3 to Example 1 of the present invention.

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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)
• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Epoxy Resins (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Graft Or Block Polymers (AREA)

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• 1992
  • 1992-12-30 US US07/998,206 patent/US5300567A/en not_active Expired - Lifetime
• 1993
  • 1993-12-09 TW TW082110447A patent/TW252139B/zh active
  • 1993-12-28 AU AU58157/94A patent/AU5815794A/en not_active Abandoned
  • 1993-12-28 WO PCT/EP1993/003728 patent/WO1994016013A1/en not_active Ceased
  • 1993-12-28 CN CN93121486A patent/CN1036276C/zh not_active Expired - Fee Related
  • 1993-12-28 AT AT94903887T patent/ATE163668T1/de not_active IP Right Cessation
  • 1993-12-28 JP JP6515660A patent/JPH08505179A/ja active Pending
  • 1993-12-28 ES ES94903887T patent/ES2113638T3/es not_active Expired - Lifetime
  • 1993-12-28 DE DE69317307T patent/DE69317307T2/de not_active Expired - Fee Related
  • 1993-12-28 EP EP94903887A patent/EP0677084B1/en not_active Expired - Lifetime

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