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
  • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
• • 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
  • C08L23/0876—Salts thereof, i.e. ionomers
• • 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 fiexurai 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 fiexurai storage modulus ( ⁇ ') 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 poiyphenylene ether and molded articles comprising the composition useful as CVJ boots.
• WO201 1/043129 discloses a composition comprising a resin component comprising 5 - 75 wt % poiyphenylene ether, 5 - 40 wt % thermoplastic elastomer and 20 - 90 wt % polyoiefin resin; and a phosphorous and/or nitrogen containing flame retardant. Needed are thermoplastic elastomer compositions that have good low temperature flexibility, flex fatigue resistance at operating temperatures in the range of 23 °C to 140 °C, high stiffness at elevated temperature, and melt flow rates appropriate for rapid manufacturing of molded articles.
• composition comprising a melt mixed blend comprising: a) 58 to 96.8 weight percent one or more copoiyester 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
• ⁇ 2 ⁇ ( ⁇ )-0(0)- ⁇ 2
• R is H, CH 3 or C2H5, and R 2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X comprises 0 to 50 weight % of E/X/Y copolymer; and
• Y is a radical formed from giycidyi (meth)acrylate
• composition has a low temperature glass transition 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 to provide articles having high stiffness at elevated temperature and melt flow rate of about 1.0 or greater.
• composition comprising a melt mixed blend comprising: a) 58 to 98.8 weight percent one or more copoiyester thermoplastic elastomers; b) 3 to 40 weight percent polyphenylene ether;
• 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 is H, CH 3 or C2H5, and R 2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X comprises 0 to 50 weight % of E/X/Y copolymer; and
• Y is a radical formed from giycidyi (meth)acrylate
• composition has a low temperature glass transition between minus 100 and plus 150 °C.
• Copolyester thermoplastic elastomers (IPCs) useful in the invention include copolyesterester elastomers, copoiycarbonateester 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 terephthalates,
• soft polyester segments are aliphatic polyesters, including polybutylene adipate, po!ytetramethyladipate and poiycaprolactone.
• the copoiyesterester 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, Copoiyesterester elastomers comprising urethane groups may be prepared by reacting the different polyesters in the molten phase, after which the resulting copoiyesterester is reacted with a low
• molecular weight poiyisocyanate such as for example diphenyimethyiene 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 dicarboxy!ic 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 dicarboxylic 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. 0848712.
• 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-taii 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 poiy(alkylene oxide)glycols 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 carboxyi groups from a dicarboxyiic acid having a molecular weight of less than about 300;
• D is a divalent radical remaining after removal of hydroxy! 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 dicarboxyiic acid.
• Suitable long-chain glycols are po!y(a!ky!ene 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 800 to about 3000.
• Preferred po!y(a!ky!ene oxide) glycols include poiy(tetramethylene oxide) glycol, po!y(trimethy!ene oxide) glycol, po!y(propy!ene oxide) glycol, po!y(ethy!ene oxide) glycol, copolymer glycols of these a!ky!ene oxides, and block copolymers such as ethylene oxide-capped polyipropylene 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 copo!yetheresters refers to low molecular weight
• ester units represented b 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, alicyc!ic and aromatic di hydroxy compounds.
• Preferred compounds are diols with about 2-15 carbon atoms such as ethylene, propylene, isobutylene, tetramethy!ene, 1 ,4-pentamethylene, 2,2- dimethy!trimethylene, hexameihy!ene and decamethyiene glycols, dihydroxycyclohexane. cyclohexane dimethanoi, resorcinol, hydroquinone, 1 ,5- dihydroxynaphihalene, etc.
• Especially preferred diols are aliphatic diols containing 2-8 carbon atoms, and a more preferred diol is 1 ,4-butanedioL
• bisphenois which can be used are bis(p-hydroxy)diphenyi, bis(p-hydroxyphenyl)methane, and bis(p-hydroxypheny!propane.
• Equivalent ester-forming derivatives of diols are also useful.
• diols includes equivalent ester-forming derivatives such as those mentioned. However, any molecular weight
• Dicarboxylic acids that can react with the foregoing long-chain glycols and low molecular weight diols to produce the copoiyetheresters are aliphatic, cycioaiiphatic 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 haiides 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 cycioaiiphatic. Aliphatic or cycioaiiphatic acids having conjugated unsaturaiion often cannot be used because of homopolymerizafion. However, some unsaturated acids, such as maieic 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 -SO 2 -.
• Representative useful aliphatic and cycioaliphatic acids that can be used include sebacic acid; 1 ,3-cyciohexane dicarboxylic acid; 1 ,4 ⁇ cyciohexane dicarboxylic acid; adipic acid; glutaric acid; 4- cyciohexane-1 ,2-dicarboxylic acid; 2-ethylsuberic acid; cyclopentanedicarboxylic acid decahydro-1 ,5-naphthy!ene dicarboxylic acid; 4,4' ⁇ bicyclohexyi dicarboxylic acid; decahydro-2,6-naphthy!ene dicarboxylic acid; 4,4'-methyienebis(cyclohexyl) carboxylic acid; and 3,4-furan dicarboxylic acid.
• Preferred acids are sebacic acid; 1 ,3-cyciohexane dicarbox
• aromatic dicarboxylic acids include phthalic, terephthaiic and isophthalic acids; bibenzoic acid; substituted dicarboxy compounds with two benzene nuclei such as bis(p-carboxyphenyl)methane; p-oxy-1 ,5-naphthalene dicarboxylic acid; 2,6-naphthalene dicarboxylic acid; 2,7-naphthalene
• substitution derivatives thereof such as halo, alkoxy, and aryl derivatives.
• Hydroxy! 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 terephthaiic 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-phenylene radicals and D groups that are not 1 ,4-buty!ene radicals does not exceed 30%.
• isophthalic acid is preferred and if a second low molecular weight diol is used, ethylene glycol, 1 ,3-propanedioL cyc!ohexanedimethanol, or hexamethylene 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 copoiyetheresters on a weighted average basis. For example, in a mixture that contains equal amounts of two
• 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 copolyetherester elastomers include, but are not limited to, copolyetherester elastomers prepared from monomers comprising (1 ) po!y(tetramethy!ene oxide) glycol; (2) a dicarboxyiic 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 ) poly(trimethylene oxide) glycol; (2) a dicarboxyiic acid selected from isophthalic acid, terephthalic acid and mixtures of these; and (3) a diol selected from 1 ,4-butanedio!, 1 ,3-propanediol and mixtures of these, or from monomers comprising (1 ) ethylene oxide-capped poiy(propylene oxide) glycol; (2) dicarboxyiic acid selected from isophthalic acid, terephthalic acid and mixtures of these; and (3) a dsol selected from 1 ,4-butanediol, 1 .3-propanediol and mixtures of these.
• the copolyetherester elastomers described herein are made from esters or mixtures of esters of terephthalic acid and/or isophthalic acid, 1 .4- butanedioi 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. dimethy!terephthalate, 1 ,4-butanediol and poly(ethylene oxide)glycol. More preferably, the copolyetheresters are prepared from esters of terephthalic acid, e.g. dimethyiterephthaiate, 1 ,4-butanedioi and
• the copo!yester thermoplastic elastomer can have a Durometer hardness of 55D or less and preferably SOD or less, and most preferably between 40D and 50D, as measured by ISO method 888.
• the composition comprises 3 to 40 weight percent poiyphenyiene ether (PPE).
• PPE poiyphenyiene 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, homopolymers or copolymers obtained by oxidative polymerization of at least one compound described by genera! formula (!) wherein each Ri , F3 ⁇ 4, !3 ⁇ 4, R 4 , and f3 ⁇ 4 is independently selected from among hydrogen atoms, halogen atoms,
• hydrocarbon groups or substituted hydrocarbon groups (for example,
• polymers include poly(2,8 ⁇ dimethyl-1 ,4 ⁇ phenylene) ether, poly(2,8-diethyl-1 ,4-phenylene) ether, poly(2-methyl-6 ⁇ ethyl ⁇ 1 ,4-phenyiene) ether, poiy(2 ⁇ methyi ⁇ 6-propyi ⁇ 1 ,4-phenylene) ether, poiy(2,8 ⁇ dipropyl-1 ,4-phenylene) ether, pGiy(2 ⁇ ethyl ⁇ 8 ⁇ propyl-1 ,4-phenylene) ether, poly(2,8-dimethoxy-1 ,4-phenylene) ether, poiy(2,6-dichioromethyl ⁇ 1 ,4-phenylene) ether, poiy(.sup.2, ,sup.8 -dibromomethyl-1 ,4-phenylene) ether, poly(2,6-diphenyi ⁇ 1 ,4-phenyiene)
• polyphenylene ether copolymer is a copolymer containing some amount of an aikyl-3-substituted phenol, for example, 2,3,6-frimethylphenol, in the above-described polyphenylene ether repeating unit Copolymers in which styrene is grafted to these polyphenylene ethers may also be used.
• polyphenylene ethers with grafted styrene compounds include copolymers obtained by graft-polymerizing styrene, aipha-methylstyrene, vinyltoiuene, 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 0.85 dL/g when measured at 30 °C in chloroform solvent, 0.30 to 0.80 dL/g being especially preferred.
• the composition comprises 0,1 to 8,0 weight percent, preferably 0.5 to 8 weight percent or 0,5 to 3,0 weight percent, of ionomer.
• ionomer refers to a polymer that comprises ionic groups that are aikali metal ion carboxylates, for example, sodium carboxylates. Such polymers are generally produced by partially or fully neutralizing the carboxyiic acid groups of precursor acid copolymers, as defined herein, for example by reaction with a base.
• an alkali metal ionomer is a sodium ionomer (or sodium neutralized ionomer), for example a copolymer of ethylene and methacry!ic acid wherein all or a portion of the carboxyiic acid groups of the copolymerized methacrylic acid units are in the form of sodium carboxylates.
• the ionomer polymer comprises an ionomer that is an ionic, neutralized, or partially neutralized, derivative of a precursor acid copolymer.
• the precursor acid copolymer comprises copolymerized units of an a-olefin having 2 to 10 carbons and about 5 to about 30 wt%, about 5 to 25 wt %, or about 10 to about 25 wt%, of copolymerized units of an a ⁇ -ethylenica!!y unsaturated carboxyiic acid having 3 to 8 carbons, based on the total weight of the precursor acid copolymer.
• Suitable a-olefin comonomers include, but are not limited to, ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 3 methyl-1 -butene, 4- methyl-1 -pentene, and the like and mixtures of two or more of these cs-o!efins.
• the cs-o!efin is ethylene.
• Suitable ⁇ , ⁇ -ethylenicaily unsaturated carboxyiic acid comonomers include, but are not limited to, acrylic acids, methacrylic acids, itaconic acids, maleic acids, maieic anhydrides, fumaric acids, monomethyi maieic acids, and mixtures of two or more of these acid comonomers.
• the ⁇ , ⁇ ethylenically unsaturated carboxyiic acid is selected from acrylic acids, methacrylic acids, and mixtures of two or more acrylic acids or methacrylic acids.
• the precursor acid copolymers may further comprise copolymerized units of other comonomer(s), such as unsaturated carboxyiic acids having 2 to 10, or preferably 3 to 8 carbons, or derivatives thereof.
• Suitable acid derivatives include acid anhydrides, amides, and esters. Esters are preferred.
• esters of unsaturated carboxy!ic acids include, but are not limited to, methyl acrylates, methyl methacrylates, ethyl acryiates, ethyl methacrylates, propyl acrylates, propyl methacrylates, isopropyi acrylates, isopropyl methacrylates, butyl acrylates, butyl methacrylates, isobutyl acrylates, isobutyl methacrylates, tert-buty! acrylates, tert-buty! methacrylates, octyi acrylates, octyl methacrylates, undecyi acrylates, undecy!
• Suitable comonomers include, but are not limited to, methyl acryiates, methyl methacrylates, butyl acryiates, butyl methacrylates, giycidyl methacrylates, vinyl acetates, and mixtures of two or more thereof.
• the precursor acid copolymer does not incorporate other comonomers in any significant amount
• precursor acid copolymers are also suitable, provided that the properties of the copolymers are within the ranges described herein.
• two or more dipoiymers having differing amounts of copoiymerized carboxylic acid comonomer or differing melt indices may be used.
• a mixture of precursor acid copolymers including a dipolymer and a terpolymer may be suitable.
• the precursor acid copolymer may have a melt flow rate ( FR) of about 10 to about 1000 g/10 min, or about 20 to about 500 g/10 min, or about 40 to about 300 g/10 min, or about 50 to about 250 g/10 min, as determined in accordance with ASTM method D1238 at 190°C and 2.16 kg.
• the precursor acid copolymers are neutralized with a base so that the carboxylic acid groups in the precursor acid copolymer react to form carboxylate groups.
• the precursor acid copolymers groups are neutralized to a level of about 40% to about 90%, or about 40% to about 70%, or about 43% to about 80%, based on the total carboxylic acid content of the precursor acid copolymers as calculated or measured for the non-neutralized precursor acid copolymers.
• the base is a sodium ion-containing base, to provide a sodium ionomer wherein about 30% to about 90%, or about 40% to about 90%, or about 40% to about 70%, or about 43% to about 60% of the hydrogen atoms of the carboxylic acid groups of the precursor acid are replaced by sodium cations.
• the particular level of neutralization of the ionomer is referred to as the neutralization ratio.
• the ionomer comprises an ethylene/methacryiic acid copolymer having about 5 to 25 wt % methacry!ic acid repeat units based on the weight of the ethylene/methacryiic acid copolymer: and more particularly, the ethylene/methacryiic acid copolymer has a neutralization ratio of 0.40 to about 0.70.
• the precursor acid copolymers may be neutralized by any conventional procedure, such as those disclosed in U.S. Patent Nos. 3,404,134 and 6,518,385.
• Suitable ionomers for the invention are available from E.i. du Pont de Nemours and Co., Wilmington, DE, under the Surlyn® resin brand; or they can be prepared by synthesis.
• the as-neutra!ized ionomer may have a MFR of about 0.1 to about 50 g/10 min or less, or about 0.2 to about 30 g/10 min or less, or about 0.3 to about 25 g/10 min, or about 0.5 to about 10 g/10 min, or about 0.8 to about 5 g/10 min, as determined in accordance with ASTM method D1238 at 190°C and 2.18 kg.
• composition comprises 0.1 to 8.0 weight percent, preferably 0.5 to 8 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, CH 3 or C 2 H 5
• R 2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof;
• Y is a radical formed from giycidyl (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 rnethacrylate esters.
• the composition preferably has a weight ratio of ionomer to polymeric toughener of about 0.25 to 1 to 10 to 1 .
• Other embodiments include a weight ratio of ionomer to polymeric toughener of about 0.33 to 1 to about 5 to 1 , and 0.5 to 1 to about 5 to 1 .
• composition may optionally comprise additional additives such as thermal, oxidative, and/or light stabilizers; colorants; lubricants; moid release agents; and the like.
• additional additives such as thermal, oxidative, and/or light stabilizers; colorants; lubricants; moid 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-polymeric 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
• thermoplastic compositions disclosed herein are automotive parts or engine parts or
• 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 60 mm length, has a fiexurai storage modulus retention of at least 20 %, and preferably at least 25 %, at 140 °C iE' 140 ), as compared to the fiexurai storage modulus at 23 °C (E'23), as measured with dynamic mechanical analysis according to 1808721 -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.
• Another embodiment is a composition that has a flexural 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, E' UQI E'23 x 00 %, 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 8721 -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.
• Another embodiment is a composition, as disclosed above, having a melt flow rate of 1 .0 or greater, and preferably 1 .2 or greater, as measured with the method of International Standard ISO 1 133:1997(E) at a temperature of 230 ° C under a 10 kg weight. Melt flow rate of about 1 .0 or greater is particularly advantageous in manufacturing of blow-molded articles; where high throughput is necessary.
• a composition comprising a melt mixed blend comprising:
• 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, CH 3 or C 2 H 5
• R 2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X comprises 0 to 50 weight % of E/X/Y copolymer;
• Y is a radical formed from g!ycidyl (meth)acrylate
• composition has a low temperature glass transition between minus 100 and plus 150 °C; in an application requiring a combination of high-stiffness at elevated temperature and melt flow rate of 1.0 or greater; a combination of high- stiffness at elevated temperature, melt flow rate of 1.0 or greater, and flex fatigue resistance; or a combination of high-stiffness at elevated temperature, melt flow rate of 1.0 or greater, flex fatigue resistance and a fiexurai storage modulus of at least 50 MPa at 140 °C.
• 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 includedi g 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.
• Fiexurai Storage Modulus 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 285 °C.
• the test specimens were cut to a length of 80 mm. DMA measurements were made using a TA instruments mode! 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 damps.
• 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'i 40 ) was determined, and the ratio E'i 40 / 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 8721 -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 was determined with a De Mattia Flex Fatigue Machine Model D, from Getty Machine and Moid Inc., on compression molded test specimens, prepared as defined by ASTM D 813 on a hot press at 250 °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 888. Melt Flow Rate
• elt mix blending of components listed in Table 1 for Examples and Comparative Examples was performed according to the following procedure.
• PPE resin and heat stabilizers listed in the Table 1 were fed to the rear of a ZSK 26 mm twin screw extruder (Coperion Corporation).
• Polyether ester copolymer, ionomer and E/X/Y ethylene copolymer were combined and fed to the extruder through a side feeder.
• the temperature of the extruder was set at 300 °C from the rear feeder to the point of the side feeder.
• the temperature of the extruder from the side feeder to a die was set at 280 °C.
• a screw speed of 250 rpm and throughput of 1 1.34 kg /hour are typical conditions for the extrusion.
• Ingredient quantities shown in the Table are given in weight percent on the basis of the total weight of the thermoplastic composition.
• Polyether ester refers a polyether ester copolymer resin comprising about 52 weight percent of a short polyester repeat unit based on an ester of terephthaiic acid and 1 ,4-butanediol and about 48 weight percent of a long polyester repeat unit based on a ester of terephthaiic acid and
• po!y(tetramethy!ene oxide) glycol of molecular weight of 1400, having a SOD ⁇ urometer hardness.
• Hytrel® HTR8341 C BK is a polyether ester available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
• PPE refers Noryi® 640 polyphenylene ether resin available from GE Plastics.
• E/X/Y-1 refers to an ethy!ene/butylacry!ate/glycidy! methacrylate (68/22/12 weight ratio) terpolymer resin.
• E/X/Y-2 refers to an ethylene/butylacrylate/g!ycidyi methacrylate (66/25/9 weight ratio) terpolymer resin.
• lonomer -A resin is a neutralized ethylene-methacry!ic acid copolymer (1 1 wt % MAA, 58 mol % Na neutralized)
• I ganoxCg 1010 stabilizer was available from Ciba Specialty Chemicals !nc, Switzerland.
• I qanox® PS800 refers to dilauryl thiodipropionate available from Ciba Specialty Chemicals inc, Switzerland.
• Nauqard® 445 hindered amine refers to 4,4' di(.a,a- dimethy!benzyl)diphenylamine available commercially from Uniroyal Chemical Company, Middiebury, Conn.
• LDPE refers to low density polyethylene of 0.929 g/cm 3 and melting point of 115
• Examples 1 -6 and Comparative Examples C1 - C3 The components listed in Table 1 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 Table 1.
• Examples 1 -6 exhibit a melt flow rate of about 1.0 or greater while maintaining high stiffness at elevated temperature as evidenced by a E E' 23 of 23 % or higher.
• Comparative examples C1 -C3, comprising PPE but having no ionomer show an E E' 23 of about 28 - 30 %; but have a melt flow rate of 0.8 or less.
• Comparative Example C1 has a melt flow rate of 0.6 versus that of
• Example 1 or 1.2. This is surprising and unexpected because addition of 0.9 weight percent of ionomer, resulted in a doubling of the melt flow rate. One would not expect a small change in composition to have such a large effect on melt flow rate; yet still maintain high stiffness at elevated temperature. A 62 % improvement in melt flow rate is evident in comparing Comparative Example C3 with Example 3 at 20 wt % PPE.

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