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
• • 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
  • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
  • C08L23/0884—Epoxide-containing esters

Definitions

• the present invention relates to the field of thermoplastic polyester elastomer compositions and molded thermoplastic articles having improved performance at elevated temperatures.
• Thermoplastic polyester elastomers are used in applications that require a combination of high flexural modulus (stiffness) at elevated temperature (e.g. 100 °C), desirable low temperature properties including glass transitions below minus 25 °C, and flex fatigue resistance at normal operating temperatures.
• Elastomeric compositions having a dynamic mechanical analysis (DMA) curve as flat as possible, that is a flexural storage modulus (E ! ) change as low as possible between minus 40 and 130 °C are desirable. This measure implies that the stiffness of the composition changes little over the temperature range.
• Most polyester elastomer compositions show a significant drop-off in stiffness above about 50 °C.
• US 5,295,914 discloses a thermoplastic elastomer seal boot for a constant velocity universal joint, referred to as a CVJ boot.
• CVJ boot For advanced applications CVJ boots experiencing peak operating temperatures up to about 130 °C - 140 °C are required.
• EP 150454 A3 discloses a blend of polyetherester copolymers and polycarbonates with improved physical properties.
• JP 03505897 discloses a composition comprising a styrene/conjugated diene block copolymer, a thermoplastic elastomer, and a polyphenylene ether and molded articles comprising the composition useful as CVJ boots.
• WO201 1/043129 discloses a composition comprising a resin
• thermoplastic elastomer compositions that have good low temperature flexibility, flex fatigue resistance at operating temperatures in the range of 23 °C to 140 °C, and high stiffness at elevated temperature.
• composition comprising a melt mixed blend comprising: a) 52 to 96,9 weight percent one or more copolyester thermoplastic elastomers;
• polymeric toughener selected from the group consisting ethylene copolymers of the formula E/X/Y wherein:
• E is the radical formed from ethylene
• X is selected from the group consisting of radicals formed from
• R 1 is H, CH3 or C2H5, and R 2 is an alky! group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X
• Y is a radical formed from glycidyl (meth)acrylate
• composition has one or more low temperature glass transitions between minus 100 and plus 150 °C.
• molded articles comprising the composition as disclosed above including CVJ boots and air ducts for automotive applications.
• compositions as disclosed above are also disclosed.
• polymeric toughener selected from the group consisting ethylene copolymers of the formula E/X/Y wherein:
• E is the radical formed from ethylene
• X is selected from the group consisting of radicals formed from
• R 1 is H, CH3 or C2H5, and R 2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X
• Y is a radical formed from glycidyl (meth)acrylate and wherein the composition has one or more low temperature glass transitions between minus 100 and plus 150 °C.
• Copolyester thermoplastic elastomers (TPCs) useful in the invention include copolyesterester elastomers, copolycarbonateester elastomers, and copolyetherester elastomers, the latter being preferred.
• Copolyesteresters elastomers are block copolymers containing a) hard polyester segments and b) soft and flexible polyester segments.
• hard polyester segments are polyalkylene terephtha!ates,
• soft polyester segments are aliphatic polyesters, including polybutylene adipate, polytetramethyladipate and polycaprolactone.
• the copolyesterester elastomers contain blocks of ester units of a high melting polyester and blocks of ester units of a low melting polyester which are linked together through ester groups and/or urethane groups.
• Copolyesterester elastomers comprising urethane groups may be prepared by reacting the different polyesters in the molten phase, after which the resulting copolyesterester is reacted with a low molecular weight polyisocyanate such as for example diphenylmethylene diisocyanate.
• Copolycarbonateester elastomers are block copolymers containing a) hard segments consisting of blocks of an aromatic or semi-aromatic polyester and b)soft segments consisting of blocks of a polycarbonate containing polymeric component.
• the copolycarbonateester elastomer is made of hard polyester segments made up of repeating units derived from an aromatic dicarboxylic acid and an aliphatic diol, and of soft segments made up of repeating units of an aliphatic carbonate, and/or soft segments made up of randomly distributed repeating units of an aliphatic carbonate and either an aliphatic diol and an aliphatic dicarboxy!ic acid or a lactone, or a combination of these, wherein the hard segments and the soft segments can be connected with a urethane group.
• These elastomers and their preparation are described in, e.g. EP Pat. No. 0846712.
• Copolyetherester elastomers are the preferred thermoplastic polyesters in the resin compositions described herein and have a multiplicity of recurring long-chain ester units and short-chain ester units joined head-to-tail through ester linkages, said long-chain ester units being represented by formula (A):
• G is a divalent radical remaining after the removal of terminal hydroxy! groups from poly(alkylene oxide)g!yco!s having a number average molecular weight of between about 400 and about 6000, or preferably between about 400 and about 3000;
• R is a divalent radical remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300;
• D is a divalent radical remaining after removal of hydroxyl groups from a diol having a molecular weight less than about 250.
• long-chain ester units as applied to units in a polymer chain refers to the reaction product of a long-chain glycol with a dicarboxylic acid.
• Suitable long-chain glycols are poly ⁇ alkylene oxide) glycols having terminal (or as nearly terminal as possible) hydroxy groups and having a number average molecular weight of from about 400 to about 6000, and preferably from about 600 to about 3000.
• Preferred poly(alkylene oxide) glycols include poly(tetramethylene oxide) glycol, poly(trimeihylene oxide) glycol, poly(propylene oxide) glycol, poly ⁇ eihylene oxide) glycol, copolymer glycols of these alkylene oxides, and block copolymers such as ethylene oxide-capped poly(propylene oxide) glycol. Mixtures of two or more of these glycols can be used.
• short-chain ester units as applied to units in a polymer chain of the copolyetheresters refers to low molecular weight compounds or polymer chain units having molecular weights less than about 550.
• ester units represented by Formula (B) above.
• Included among the low molecular weight diols which react to form short-chain ester units suitable for use for preparing copolyetheresters are acyclic, alicyclic and aromatic dihydroxy compounds.
• Preferred compounds are diols with about 2-15 carbon atoms such as ethylene, propylene, isobutylene, tetramethylene, 1 ,4- pentamethylene, 2,2-dimethyitrimethylene, hexamethylene and
• decamethylene glycols dihydroxycyclohexane, cyclohexane dimethanol, resorcinol, hydroquinone, 1 ,5-dihydroxynaphthalene, etc.
• diols are aliphatic diols containing 2-8 carbon atoms, and a more preferred diol is 1 ,4-butanedio!.
• bisphenols which can be used are bis(p-hydroxy)diphenyi, bis(p-hydroxyphenyl)methane, and bis(p- hydroxyphenyl)propane. Equivalent ester-forming derivatives of diols are also useful.
• diols includes equivalent ester-forming derivatives such as those mentioned. However, any molecular weight requirements refer to the corresponding diols, not their derivatives.
• Dicarboxylic acids that can react with the foregoing long-chain glycols and low molecular weight diols to produce the copolyetheresters are aliphatic, cycloaliphatic or aromatic dicarboxylic acids of a low molecular weight, i.e., having a molecular weight of less than about 300.
• the term "dicarboxylic acids" as used herein includes functional equivalents of dicarboxylic acids that have two carboxyl functional groups that perform substantially like dicarboxylic acids in reaction with glycols and diols in forming copolyetherester polymers. These equivalents include esters and ester- forming derivatives such as acid balides and anhydrides. The molecular weight requirement pertains to the acid and not to its equivalent ester or ester- forming derivative.
• an ester of a dicarboxylic acid having a molecular weight greater than 300 or a functional equivalent of a dicarboxylic acid having a molecular weight greater than 300 are included provided the corresponding acid has a molecular weight below about 300.
• the dicarboxylic acids can contain any substituent groups or combinations that do not substantially interfere with the copolyetherester polymer formation and use of the polymer in the flame retardant compositions of the invention.
• aliphatic dicarboxylic acids refers to carboxylic acids having two carboxyl groups each attached to a saturated carbon atom. If the carbon atom to which the carboxyl group is attached is saturated and is in a ring, the acid is cycloaliphatic. Aliphatic or cycloaliphatic acids having conjugated unsaturation often cannot be used because of homopolymerization. However, some unsaturated acids, such as maleic acid, can be used.
• aromatic dicarboxylic acids refer to dicarboxylic acids having two carboxyl groups each attached to a carbon atom in a carbocyclic aromatic ring structure. It is not necessary that both functional carboxyl groups be attached to the same aromatic ring and where more than one ring is present, they can be joined by aliphatic or aromatic divalent radicals or divalent radicals such as -O- or --SO2-.
• Representative useful aliphatic and cycloaliphatic acids that can be used include sebacic acid; 1 ,3-cyclohexane dicarboxylic acid; 1 ,4-cycIohexane dicarboxylic acid; adipic acid; glutaric acid; 4-cyclohexane ⁇ 1 ,2-dicarboxylic acid; 2-ethylsuberic acid; cyclopentanedicarboxylic acid decahydro-1 ,5-naphthyiene dicarboxylic acid; 4,4'-bicyclohexyl dicarboxylic acid; decahydro-2,6-naphthylene dicarboxylic acid; 4,4 ! -methylenebis(cyclohexyl) carboxylic acid; and 3,4-furan dicarboxylic acid.
• Preferred acids are cyclohexane-dicarboxylic acids and adipic acid.
• aromatic dicarboxylic acids include phthalic,
• terephthalic and isophthalic acids terephthalic and isophthalic acids; bibenzoic acid; substituted dicarboxy compounds with two benzene nuclei such as bis(p ⁇ carboxypheny!methane; p-oxy-1 ,5-naphthalene dicarboxy!ic acid; 2,6-naphthalene dicarboxylic acid; 2,7-naphthalene dicarboxylic acid; 4,4'-sulfonyl dibenzoic acid and C1-C12 aikyl and ring substitution derivatives thereof, such as halo, aikoxy, and aryl derivatives.
• Hydroxyl acids such as p-(beta-hydroxyethoxy)benzoic acid can also be used provided an aromatic dicarboxylic acid is also used.
• Aromatic dicarboxylic acids are a preferred class for preparing the copolyetherester elastomer useful for this invention.
• aromatic acids those with 8-18 carbon atoms are preferred, particularly terephthalic acid alone or with a mixture of phthalic and/or isophthalic acids.
• the copolyetherester elastomer preferably comprises from at or about 15 to at or about 99 weight percent short-chain ester units corresponding to Formula (B) above, the remainder being long-chain ester units corresponding to Formula (A) above. More preferably, the copolyetherester elastomer comprise from at or about 20 to at or about 95 weight percent, and even more preferably from at or about 50 to at or about 90 weight percent short-chain ester units, where the remainder is long-chain ester units.
• At least about 70% of the groups represented by R in Formulae (A) and (B) above are 1 ,4-phenylene radicals and at least about 70% of the groups represented by D in Formula (B) above are 1 ,4-butyiene radicals and the sum of the percentages of R groups which are not 1 ,4-phenyIene radicals and D groups that are not 1 ,4-butylene radicals does not exceed 30%.
• isophthalic acid is preferred and if a second low molecular weight diol is used, ethylene glycol, 1 ,3-propanediol, cyclohexanedimethanol, or hexamethy!ene glycol are preferred.
• a blend or mixture of two or more copolyetherester elastomers can be used.
• the copolyetherester elastomers used in the mixture need not on an individual basis come within the values disclosed herein for the elastomers.
• the blend of two or more copolyetherester elastomers must conform to the values described herein for the copolyetheresters on a weighted average basis.
• one copolyetherester elastomer can contain 60 weight percent short-chain ester units and the other resin can contain 30 weight percent short-chain ester units for a weighted average of 45 weight percent short-chain ester units.
• Preferred copo!yetherester eiastomers include, but are not limited to, copolyetherester elastomers prepared from monomers comprising (1 ) poly(tetramethylene oxide) glycol; (2) a dicarboxylic acid selected from isophthalic acid, terephthalic acid and mixtures of these; and (3) a diol selected from 1 ,4-butanediol, 1 ,3-propanedioI and mixtures of these, or from monomers comprising (1 ) po!y(trimethylene oxide) glycol; (2) a dicarboxylic acid selected from isophthalic acid, terephthalic acid and mixtures of these; and (3) a diol selected from 1 ,4-butanediol, 1 ,3-propanediol and mixtures of these, or from monomers comprising (1 ) ethylene oxide-capped
• poly(propylene oxide) glycol (2) dicarboxylic acid selected from isophthalic acid, terephthalic acid and mixtures of these; and (3) a diol selected from 1 ,4- butanediol, 1 ,3-propanediol and mixtures of these.
• the copolyetherester eiastomers described herein are made from esters or mixtures of esters of terephthalic acid and/or isophthalic acid, 1 ,4-butanediol and poly(tetramethylene ether)glycoi or po!y(trimethy!ene ether) glycol or ethylene oxide-capped polypropylene oxide glycol, or are prepared from esters of terephthalic acid, e.g. dimethylterephthalate, 1.4- butanediol and poly(ethylene oxide)glycol. More preferably, the
• copolyetheresters are prepared from esters of terephthalic acid, e.g.
• copolyetherester elastomers examples are commercially available under the trademark Hytrel ® from E. !. du Pont de Nemours and Company, Wilmington, Delaware.
• the copolyester thermoplastic elastomer can have a Durometer hardness of 55D or less and preferably 50D or less, and most preferably between 40D and SOD, as measured by ISO method 888.
• the composition comprises 3 to 40 weight percent polyphenylene ether (PPE).
• PPE polyphenylene ether
• Other embodiments include 3 to 30 weight percent, 5 to 25 weight percent, 6 to 25 weight percent, and 6 to 20 weight percent PPE.
• PPE resins known in the art may be used as the PPE resin (b), for example,
• , ⁇ 3 ⁇ 4, f3 ⁇ 4, f3 ⁇ 4, and R5 is independently selected from among hydrogen atoms, halogen atoms, hydrocarbon groups, or substituted hydrocarbon groups (for example, halogenohydrocarbon groups).
• polymers include poly(2,6-dimethy!-1 ,4- phenylene) ether, poly(2.6-diethyl-1 ,4-phenyiene) ether, poly(2-methyl-6- ethyl-1 ,4-phenyiene) ether, poly(2-methy!-6-propyi-1 ,4-phenylene) ether, poly(2,6-dipropyl-1 ,4-phenyiene) ether, poIy(2-ethyI-6-propyl-1 ,4-phenyIene) ether, poly(2,6-dimethoxy-1 ,4-phenylene) ether, poly(2,6-dich!oromethyl-1 ,4- phenylene) ether, poly(.sup.2,.sup.6 -dibromomethyi-1 ,4-phenylene) ether, poly(2,6-diphenyl-1 ,4-phenylene) ether, poly(2,6-diphenyl-1
• An especially preferred PPE resin is poly(2,6-dimethyl-1 ,4-phenylene) ether.
• the polyphenylene ether copolymer is a copolymer containing some amount of an a!kyi-3-substituted phenol, for example, 2,3,6-trimethylphenol, in the above- described polyphenylene ether repeating unit Copolymers in which styrene is grafted to these polyphenylene ethers may also be used.
• Examples of polyphenylene ethers with grafted styrene compounds include copolymers obtained by graft-polymerizing styrene, . alpha. -methylstyrene, vinyltoluene, chlorostyrene, or the like to the above-described polyphenylene ethers.
• the PPE resins used in the invention have an intrinsic viscosity of 0.15 to 0.65 dL/g when measured at 30 °C in chloroform solvent, 0.30 to 0.60 dL/g being especially preferred.
• the composition comprises 0.1 to 8.0 weight percent, preferably 0.5 to 6 weight percent, of polymeric toughener selected from the group consisting ethylene copolymers of the formula E/X/Y wherein:
• E is the radical formed from ethylene
• X is selected from the group consisting of radicals formed from
• R 1 is H, CH3 or C2H5, and R 2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof;
• Y is a radical formed from glycidyl (meth)acrylate
• X comprises 0 to 50 weight percent
• Y is about 2.0 to 15 weight percent
• E is the remainder weight percent of the E/X/Y copolymer.
• Y may be in the range of about 2.0 to 12 weight percent, about 2.0 to 10 weight percent and 2.0 to about 8 weight percent in the E/X/Y copolymer.
• (meth)acryiate is meant to include acrylate esters and methacrylate esters.
• composition may optionally comprise additional additives such as thermal, oxidative, and/or light stabilizers; colorants; lubricants; mold release agents; and the like.
• additional additives such as thermal, oxidative, and/or light stabilizers; colorants; lubricants; mold release agents; and the like.
• additives can be added according to the desired properties of the resulting material, and the control of these amounts versus the desired properties is within the knowledge of the skilled artisan.
• composition is a mixture by melt-blending, in which all polymeric ingredients are adequately mixed, and all non-po!ymeric ingredients are adequately dispersed in a polymer matrix.
• Any melt-blending method may be used for mixing polymeric ingredients and non-polymeric ingredients of the present invention.
• polymeric ingredients and non-polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader. or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches.
• the present invention relates to a method for manufacturing an article by shaping the thermoplastic compositions disclosed herein.
• articles are automotive parts or engine parts or electrical/electronics parts.
• shaping it is meant any shaping technique, such as for example extrusion, injection molding, thermoform molding, compression molding or blow molding.
• the article is shaped by injection molding or blow molding.
• Another embodiment is a composition, as disclosed above, wherein an injection molded test specimen, molded in a mold cavity having a length of 135.35 mm, width of 12.89 mm and depth of 3.23 mm and cut to a 80 mm length, has a flexura! storage modulus retention of at least 20 %, and preferably at least 25 %, at 140 °C (E'uo), as compared to the flexura! storage modulus at 23 °C (E'23), as measured with dynamic mechanical analysis according to IS06721 -5, over a frequency range selected from 1 to 20 Hz. In various embodiments a 1 Hz, 5 Hz, 10 Hz, 15 Hz, and 20 Hz frequency can be used in the measurement, respectively.
• compositions that have a f!exura! storage modulus retention as stated above, and a flexural storage modulus of at least 50 MPa at 140 °C.
• high stiffness at elevated temperature means the composition has a flexural storage modulus retention, ⁇ ' 140 / E'23 x 100 %, of at least 20 %, and preferably at least 25 %.
• Another embodiment is a composition, as disclosed above, wherein compression molded test specimens prepared as defined by ASTM D 813 except having no 2 mm pierce, exhibits a total crack length of 20 mm or less on averaging three specimens after 200,000 cycles of bending according to ASTM D 813, at a test temperature of 100 °C.
• flex fatigue resistance means the composition exhibits a total crack length of 20 mm or less under the above stated conditions.
• compositions disclosed herein have one or more low temperature glass transition(s), defined as a glass transition between minus 100 and plus 150 °C. and optionally a high temperature glass transition above 200 °C due to the presence of PPE.
• One embodiment is a composition, as disclosed above, wherein the largest of the one or more low temperature glass
• transition(s) is minus 25 °C or less, and preferably minus 30 °C or less; as measured with dynamic mechanical analysis according to ISO method 6721 -5, at a frequency of 1 Hz, and a temperature scan rate of 2 °C/min.
• the largest of the one or more low temperature glass transition(s) is defined as the glass transition of the largest tan delta peak in the DMA scan.
• toughener selected from the group consisting ethylene copolymers of the formula E/X/Y wherein:
• E is the radical formed from ethylene
• X is selected from the group consisting of radicals formed from
• R 1 is H, CH3 or C2H5, and R 2 is an a!kyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X
• Y is a radical formed from glycidyl (meth)acrylate
• Another embodiment is a molded article comprising the compositions disclosed above.
• Specific molded articles are selected from the group consisting boots for auto drive shaft axle applications including CVJ (constant velocity joint) boots, propeller shaft joint boots, and other convoluted boots used to seal joint, linkages, or gears, in automotive vehicles; air ducts for automotive applications including fresh air ducts and pressurized inlet and outlet ducts used in turbocharged engines; and extruded tubes and pipes requiring high-stiffness at elevated temperature including air brake tubes.
• Flexural storage modulus was determined with DMA measurements on injection molded test specimens.
• the test specimen mold cavity had a length of 135.35 mm, width of 12.89 mm and depth of 3.23 mm. Mold temperature was 45-55 °C; and melt temperature of the compositions were in the range of 245 to 265 °C.
• the test specimens were cut to a length of 60 mm. DMA measurements were made using a TA Instruments model DMA Q800. The test specimens were clamped on a 35 mm dual cantilever clamp to provide a 17.5 mm distance between the center and end clamps.
• the measurement was made with a frequency selected from a range of 1 to 20 Hz, over a temperature range of minus 145 °C to +170 °C with a 2.0 °C / minute ramp rate.
• Storage module at 23 °C (E'23) and 140 °C (E'140) was determined, and the ratio E'UQI E'23 x 100 % gave the retention of storage modulus.
• Glass transition temperature was determined with DMA measurements on injection molded test specimens as described above.
• the test specimens were as measured with dynamic mechanical analysis according to ISO method 6721 -5, at a frequency of 1 Hz, and a temperature scan rate of 2 °C/min.
• the glass transition was considered the apex of the tan delta peak.
• Table 1 list two glass transitions for some comparative examples that exhibit two low temperature glass transitions.
• Flex Fatigue resistance F!ex fatigue resistance was determined with a De Mattia Flex Fatigue Machine Mode! D, from Getty Machine and Mold Inc., on compression molded test specimens, prepared as defined by ASTM D 813 on a hot press at 250 '3 C, with the exception that no 2 mm pierce of the test specimen was performed. A 5 Hz flex frequency was used. The average of total crack length of three test specimens was determined after 200,000 cycles of bending according to ASTM D 813, at a test temperature of 100 °C. The maximum crack length in this test is the width of sample (25 mm).
• Durometer hardness was measured by ISO method 868.
• Polyether ester refers a polyether ester copolymer resin comprising about 52 weight percent of a short polyester repeat unit based on an ester of terephthalic acid and 1 ,4-butanedio! and about 48 weight percent of a long polyester repeat unit based on a ester of terephthalic acid and po!y(teirameihy!ene oxide) glycol of molecular weight of 1400, having a SOD ⁇ urometer hardness.
• Hytrel® HTR8341 C B K is a polyether ester available from E.L DuPont de Nemours and Company, Wilmington, Delaware, USA.
• PPE refers Noryl® 640 polyphenylene ether resin available from GE
• PBT refers to Crastin® 6130 polybutylene terephthalate resin available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
• E/X/Y-1 refers to an ethylene/butyiacrylate/giycidyi methacrylate (66/22/12 weight ratio) terpolymer resin.
• E/X/Y-2 refers to an ethylene/butylacry!ate/glycidyl methacrylate (66/25/9 weight ratio) terpolymer resin.
• Irganox® 1010 stabilizer was available from Ciba Specialty Chemicals inc, Switzerland.
• Irganox® PS800 refers to dilauryl thiodipropionate available from Ciba
• Weston 619F refers to distearyl pentaerythrito! diphosphite antioxidant from Chemtura Corporation.
• Naugard® 445 hindered amine refers to 4,4' di(.a,a- dimethylbenzyl)diphenylamine available commercially from Uniroyal Chemical Company, Middlebury, Conn.
• Examples 1 -5 and Comparative Examples C1 - C5 The components listed in Tables 1 and 2 for each composition were melt blended in an extruder as disclosed in the Methods section. Test specimens were prepared according to the methods disclosed in the Methods section and the results of physical testing are also listed in Tables 1 and 2.
• Examples 1-5 exhibit a combination high stiffness at elevated temperature as evidenced by a EW E' 2 3 of 28 % or higher.
• Comparative Examples C3 and C4 comprising E/X/Y polymeric toughener and either PBT or PC as a additive to improve stiffness, exhibit E' 140 / E 23 of 18.1 % or lower, significantly less Examples 1 -5.
• Compositions including PPE and E/X/Y polymeric toughener exhibit surprising and unexpected properties as compared to similar compositions comprising PBT or PC thermoplastic polymers.

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