WO2007140070A2 - Composition de poly(éther d'arylène), procédé et article correspondants - Google Patents

Composition de poly(éther d'arylène), procédé et article correspondants Download PDF

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Publication number
WO2007140070A2
WO2007140070A2 PCT/US2007/067854 US2007067854W WO2007140070A2 WO 2007140070 A2 WO2007140070 A2 WO 2007140070A2 US 2007067854 W US2007067854 W US 2007067854W WO 2007140070 A2 WO2007140070 A2 WO 2007140070A2
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composition
poly
fibers
acid
block copolymer
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PCT/US2007/067854
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English (en)
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WO2007140070A3 (fr
Inventor
Kim Balfour
Vijay Mhetar
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General Electric Company
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Priority claimed from US11/420,088 external-priority patent/US20070276067A1/en
Priority claimed from US11/420,081 external-priority patent/US20070276082A1/en
Application filed by General Electric Company filed Critical General Electric Company
Priority to EP07782964A priority Critical patent/EP2035501A2/fr
Publication of WO2007140070A2 publication Critical patent/WO2007140070A2/fr
Publication of WO2007140070A3 publication Critical patent/WO2007140070A3/fr

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    • 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
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00

Definitions

  • Poly(arylene ether) resins and their blends with nonelastomeric polystyrene resins are highly valued for their balance of properties including stiffness, impact strength, heat resistance, and electrical resistivity.
  • poly(arylene ether) resins and resin blends with improved balance of ductility, stiffness, and heat resistance are highly valued for their balance of properties including stiffness, impact strength, heat resistance, and electrical resistivity.
  • One approach to improving ductility is to blend the poly(arylene ether) resin with styrenic impact modifiers such as polystyrene-polybutadiene-polystyrene triblock copolymers (SBS), polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers (SEBS), or rubber-modified polystyrenes (sometimes called "high impact polystyrenes” or "HIPS”).
  • SBS polystyrene-polybutadiene-polystyrene triblock copolymers
  • SEBS polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers
  • HIPS rubber-modified polystyrenes
  • addition of these impact modifiers generally reduces stiffness and heat resistance. Accordingly, there remains a need for poly(arylene ether) blends that offer improved balances of ductility, stiffness, and
  • one embodiment is a composition comprising the product obtained on melt-kneading a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and a crosslinking agent that is a polyamine compound, an aminosilane, or a combination thereof, wherein the aminosilane has the formula
  • each occurrence of R 1 is independently hydrogen, C 1 -C 12 hydrocarbyl, or Ci -C 12 hydrocarbylene covalently bound to Y; each occurrence of R 2 and R 3 is independently C 1 -C 12 hydrocarbyl; each occurrence of Y is independently C 1 -Cj 2 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4.
  • Another embodiment is a composition
  • a composition comprising the product obtained on melt- kneading a poly(arylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units, 2,3,6-trimethyl-l,4-phenylene ether units, or a combination thereof; a maleic- anhydride functionalized, hydrogenated block copolymer comprising at least one polystyrene block and at least one hydrogenated poly(conjugated diene) block, and having a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and a polyethyleneimine having a number average molecular weight of about 100 to about 10,000 atomic mass units.
  • Another embodiment is a composition
  • a composition comprising the product obtained on melt- kneading about 50 to about 95 parts by weight of a poly(arylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units, 2,3,6-trimethyl-l,4-phenylene ether units, or a combination thereof; about 5 to about 50 parts by weight of a maleic-anhydride functionalized block copolymer selected from the group consisting of polystyrene- poly(ethylene-butylene)-polystyrene triblock copolymer, polystyrene-poly(ethylene- propylene)-polystyrene triblock copolymer, and mixtures thereof; wherein the maleic- anhydride functionalized block copolymer has a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and about 0.02 to about 2 parts by weight of a polyethylene
  • compositions suitable for melt-kneading include compositions suitable for melt-kneading.
  • a composition comprising a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and a polyamine compound, an aminosilane having the formula
  • each occurrence of R 1 is independently hydrogen, Cj-Ci 2 hydrocarbyl, or C 1 -C 12 hydrocarbylene covalently bound to Y; each occurrence of R 2 and R 3 is independently C 1 -C12 hydrocarbyl; each occurrence of Y is independently C 1 -C 12 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4, or a combination of the polyamine compound and the aminosilane compound.
  • one embodiment is a method of preparing a composition, comprising melt-kneading a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and a polyamine compound, an aminosilane having the formula
  • each occurrence of R 1 is independently hydrogen, Ci-C 12 hydrocarbyl, or C 1 -C 12 hydrocarbylene covalently bound to Y; each occurrence of R and R 3 is independently Ci -C 12 hydrocarbyl; each occurrence of Y is independently Ci -C 12 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4, or a combination of the polyamine compound and the aminosilane compound.
  • FIG. 1 is a transmission electron micrograph of a composition obtained on melt- kneading a poly(arylene ether) and an acid-functionalized block copolymer, but no polyamine compound or aminosilane.
  • FIG. 2 is a transmission electron micrograph of a composition obtained on melt- kneading a poly(arylene ether), an acid-functionalized block copolymer, and a polyamine compound.
  • FIG. 3 is a transmission electron micrograph of a composition obtained on melt- kneading a poly(arylene ether), an acid-functionalized block copolymer, and an aminosilane compound.
  • One embodiment is a composition
  • a composition comprising the product obtained on melt-kneading a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and a rubber-crosslinking agent selected from a polyamine compound, an aminosilane, or a combination thereof, wherein the aminosilane has the formula
  • each occurrence of R 1 is independently hydrogen, Ci-C 12 hydrocarbyl, or C 1 -Cj 2 hydrocarbylene covalently bound to Y; each occurrence of R 2 and R 3 is independently C 1 -C 12 hydrocarbyl; each occurrence of Y is independently C 1 -C 12 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4.
  • One embodiment is a composition
  • a composition comprising the product obtained on melt-kneading a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and a polyamine compound.
  • the compositions described herein may exhibit improved stiffness, and heat resistance, and may further exhibit improved ductility.
  • the composition may exhibit one or more of a flexural modulus of at least 1400 megapascals, more specifically about 1400 to about 2000 megapascals, measured at 23 0 C according ASTM D 790; a heat deflection temperature of at least 165°C, more specifically about 165 to about 180 0 C, measured according to ASTM D 648; and a dispersed phase having a number average particle diameter of about 0.1 to about 2 micrometers.
  • One embodiment is a composition
  • a composition comprising the product obtained on melt-kneading a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and an aminosilane having the formula
  • each occurrence of R is independently hydrogen, CpCi 2 hydrocarbyl, or Ci -C i 2 hydrocarbylene covalently bound to Y; each occurrence of R 2 and R 3 is independently C 1 -C 12 hydrocarbyl; each occurrence of Y is independently C 1 -Ci 2 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4.
  • the compositions described herein may exhibit an improved balance of stiffness, heat resistance, and ductility.
  • the composition may exhibit one or more of a flexural modulus of at least 1250 megapascals, more specifically about 1250 to about 1910 megapascals, measured at 23°C according ASTM D 790; and a heat deflection temperature of at least 155°C, more specifically about 155 to about 180 0 C, measured according to ASTM D 648; and a dispersed phase having a major axis of about 0.5 to 5 micrometers, and a minor axis of about 0.05 to about 2.0 micrometers.
  • poly(arylene ether) comprises repeating structural units having the formula
  • each Z 1 is independently halogen, unsubstituted or substituted Ci-Cj 2 hydrocarbyl with the proviso that that the hydrocarbyl group is not tertiary hydrocarbyl, Ci-Ci 2 hydrocarbylthio, C]-Ci 2 hydrocarbyloxy, or C 2 -Ci 2 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Z is independently hydrogen, halogen, unsubstituted or substituted Ci-C] 2 hydrocarbyl with the proviso that that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -Cj 2 hydrocarbylthio, Ci-C 12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
  • hydrocarbyl refers to a residue that contains only carbon and hydrogen.
  • the residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
  • hydrocarbyl residue when the hydrocarbyl residue is described as "substituted", may contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
  • the hydrocarbyl residue may also contain halogen atoms, nitro groups, cyano groups, carbonyl groups, carboxylic acid groups, ester groups, amino groups, amide groups, sulfonyl groups, sulfoxyl groups, sulfonamide groups, sulfamoyl groups, hydroxyl groups, alkoxyl groups, or the like, and it may contain heteroatoms within the backbone of the hydrocarbyl residue.
  • the poly(arylene ether) comprises 2,6-dimethyl-l,4-phenylene ether units, 2,3,6-trimethyl-l,4-phenylene ether units, or a combination thereof.
  • the poly(arylene ether) may comprise molecules having aminoalkyl-containing end group(s), typically located in a position ortho to the hydroxy group. Also frequently present are tetramethyldiphenoquinone (TMDQ) end groups, typically obtained from reaction mixtures in which tetramethyldiphenoquinone by-product is present.
  • TMDQ tetramethyldiphenoquinone
  • the poly(arylene ether) may be in the form of a homopolymer, a copolymer, a graft copolymer, an ionomer, or a block copolymer, as well as combinations thereof.
  • the composition is substantially free of acid- or anhydride- functionalized poly(arylene ether).
  • the term “substantially free” means that the composition comprises less than 0.5 weight percent of the specified component. More specifically, the composition may comprise less than 0.1 weight percent of the specified component, or none of the specified component may be intentionally added.
  • the composition comprises an acid- or anhydride- functionalized poly(arylene ether), such as maleic anhydride-functionalized poly(arylene ether), but the amount of the acid- or anhydride-functionalized poly(arylene ether) is small enough not to substantially interfere with the processability of the composition.
  • the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 1.0 deciliter per gram, measured at 25°C in chloroform. Intrinsic viscosity is defined as the intrinsic viscosity of the poly(arylene ether) prior to melt-kneading with the other components of the composition. Those skilled in the art will appreciate that the intrinsic viscosity of the poly(arylene ether) may increase up to 30% after melt-kneading.
  • the poly(arylene ether) may have an intrinsic viscosity of at least about 0.1 deciliter per gram, or at least about 0.2 deciliter per gram, or at least about 0.3 deciliter per gram. Also within this range, the poly(arylene ether) may have an intrinsic viscosity of up to about 0.8 deciliter per gram, or up to about 0.6 deciliter per gram.
  • the composition subjected to melt-kneading comprises an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene.
  • the acid-functionalized block copolymer is the product of functionalizing an unhydrogenated or hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene with a functionalizing agent that is an acid or an acid anhydride.
  • Suitable functionalizing agents include, for example, maleic acid, maleic anhydride, methyl maleic acid, methyl maleic anhydride, dimethyl maleic acid, dimethyl maleic anhydride, monochloro maleic acid, monochloro maleic anhydride, dichloro maleic acid, dichloro maleic anhydride, 5-norbornene-2,3-dicarboxylic acids, 5-norbornene-2,3- dicarboxylic acid anhydrides, tetrahydrophthalic acids, tetrahydrophthalic anhydrides, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, trimellitic acid, trimellitic acid anhydride, trimellitic anhydride acid chloride, and the like, and mixtures thereof.
  • the acid-functionalized block copolymer is prepared from an unfunctionalized block copolymer precursor.
  • block copolymer refers to a single block copolymer or a combination of block copolymers.
  • the block copolymer comprises at least one block (A) comprising repeating aryl alkylene units derived from an alkenyl aromatic monomer and at least one block (B) comprising repeating alkylene units derived from a conjugated diene monomer.
  • the arrangement of blocks (A) and (B) may be a linear structure (including so-called tapered block copolymers) or a radial teleblock structure having branched chains.
  • A-B-A triblock copolymers have two blocks A comprising repeating aryl alkylene units.
  • A-B diblock copolymers have one block A comprising repeating aryl alkylene units.
  • the pendant aryl moiety of the aryl alkylene units may be monocyclic or polycyclic and may have a substituent at any available position on the cyclic portion. Suitable substituents include C]-C 4 alkyl groups.
  • An exemplary aryl alkylene unit is a phenyl-substituted dimethylene unit (- CH(Ph)CH 2 -) derived from styrene.
  • Block A may further comprise C 2 -C] 5 alkylene units as long as the mole fraction of aryl alkylene units exceeds the mole fraction of alkylene units.
  • Block B comprises repeating C 2 -C] 5 alkylene units such as ethylene (dimethylene), propylene, butylene, or combinations of two or more of the foregoing.
  • Block B may further comprise aryl alkylene units as long as the mole fraction of alkylene units exceeds the mole fraction of aryl alkylene units.
  • Each occurrence of block A may have a molecular weight which is the same or different than other occurrences of block A.
  • each occurrence of block B may have a molecular weight which is the same or different than other occurrences of block B.
  • the B block comprises a copolymer of aryl alkylene units and C 2 - C 15 alkylene units such as ethylene, propylene, butylene, or combinations of two or more of the foregoing.
  • the B block may further comprise some unsaturated carbon- carbon bonds.
  • the B block may be a controlled distribution copolymer.
  • controlled distribution is defined as referring to a molecular structure lacking well-defined blocks of either monomer, with "runs" of any given single monomer attaining a maximum number average of 20 units as shown by either the presence of only a single glass transition temperature (T g ), intermediate between the Tg of either homopolymer, or as shown via proton nuclear magnetic resonance methods.
  • Each A block may have an average molecular weight of about 3,000 to about 60,000 g/mol and each B block may have an average molecular weight of about 30,000 to about 300,000 g/mol.
  • Each B block comprises at least one terminal region adjacent to an A block that is rich in alkylene units and a region not adjacent to the A block that is rich in aryl alkylene units.
  • the total amount of aryl alkylene units is 15 to 75 weight percent, based on the total weight of the block copolymer.
  • the weight ratio of alkylene units to aryl alkylene units in the B block may be 5:1 to 1:2.
  • Exemplary block copolymers are further disclosed in U.S. Patent Application No. US 2003/181584 Al of Handlin et al. International Patent Application No. WO 2003/66696 Al of Handlin et al. Suitable controlled distribution block copolymers are also commercially available from Kraton Polymers as KRATON® A-RP6936 and KRATON® A-RP
  • the repeating aryl alkylene units result from the polymerization of aryl alkylene monomers such as styrene, chlorostyrenes such as p-chlorostyrene, methylstyrenes such as alpha-methylstyrene and p-methylstyrene, and combinations thereof.
  • aryl alkylene monomers such as styrene, chlorostyrenes such as p-chlorostyrene, methylstyrenes such as alpha-methylstyrene and p-methylstyrene, and combinations thereof.
  • the repeating alkylene units result from the hydrogenation of repeating unsaturated units derived from a conjugated diene such as 1,3 -butadiene, 2-methyl- 1,3 -butadiene (isoprene), 2-chloro-l,3-butadiene (chloroprene), 2,3-dimethyl-l,3 ⁇ butadiene, 1,3- pentadiene, 1,3-hexadiene, and combinations thereof.
  • the conjugated diene may polymerize via 1,4 addition and/or 1,2 addition.
  • the B block when the conjugated diene polymerizes via 1,4 addition, may contain in-chain aliphatic carbon- carbon double bonds, and when the conjugated diene polymerizes via 1,2 addition, the B block may contain pendant aliphatic carbon-carbon double bonds.
  • Exemplary block copolymers include polystyrene-poly(ethylene/propylene), polystyrene-poly(ethylene/propylene)-polystyrene, polystyrene- poly(ethylene/butylene), and polystyrene-poly(ethylene/butylene)-polystyrene.
  • the acid-functionalized block copolymer may be prepared by graft-reacting an acid moiety or its derivative onto the hydrogenated block copolymer via a free radically initiated reaction.
  • Suitable monomers that may be grafted include unsaturated mono- and polycarboxylic acids and anhydrides containing from about 3 to about 20 carbon atoms.
  • the grafting monomer is maleic anhydride.
  • the grafted polymer will usually contain about 0.1 to about 10 weight percent of the grafted monomer, specifically about 0.2 to about 5 weight percent of the grafted monomer.
  • the grafting reaction can be carried out in solution or by melt-mixing the base block copolymer and the acid/anhydride monomer in the presence of a free radical initiator.
  • Solution processes are described, for example, in U.S. Pat. Nos. 4,033,888 and 4,077,893 to Kiovsky, and 4,670,173 to Hayashi et al.
  • Melt-mixing processes are described, for example, in U.S. Pat. Nos. 4,427,828 to Hergenrother et al., 4,578,429 to Gergen et al., and 4,628,072 and 4,657,971 to Shiraki et al.
  • Suitable acid- functionalized block polymers are also commercially available as, for example, KRATON® FG1901 and KRATON® FG1924 from Kraton Polymers.
  • the acid-functionalized block copolymer is a maleic anhydride- functionalized linear block copolymer or radial teleblock copolymer of styrene and a conjugated diene selected from the group consisting of butadiene, isoprene, and combinations thereof, wherein the an acid-functionalized block copolymer has a styrene content of about 10 to about 50 weight percent.
  • the acid-functionalized block copolymer is a maleic anhydride- functionalized polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a styrene content of about 10 to about 50 weight percent or a maleic anhydride- functionalized polystyrene-poly(ethylene-butylene) diblock copolymer having a styrene content of about 10 to about 50 weight percent.
  • the composition subjected to melt-kneading may comprise a polyamine compound.
  • a polyamine compound is a compound that comprises at least three amine groups that may be primary amine groups, secondary amine groups, or a combination thereof.
  • the polyamine compound may comprise, in addition to the at least three amine groups, alkylene groups that may optionally be substituted with catenary (in-chain) ether oxygen atoms.
  • the polyamine compound is free of carbonyl groups; in this embodiment, the polyamine is defined to exclude polyamides, polyamideimides, polyimides, and other carbonyl-containing compounds.
  • the polyamine may comprise at least four amine groups, or at least five amine groups, or at least six amine groups, or at least seven amine groups.
  • the polyamine compound comprises (a) at least three amine groups selected from the group consisting of primary amine groups, secondary amine groups, and combinations thereof, and (b) at least one C 2 -C 6 alkylene group optionally substituted with one or more ether oxygen atoms.
  • the polyamine compound has a boiling point of at least about 120 0 C, more specifically at least about 150 0 C, still more specifically at least about 180 0 C.
  • a boiling point facilitates efficient melt-kneading of the composition by reducing the amount of polyamine compound that is lost via volatilization before reacting with the acid-functionalized block copolymer.
  • the polyamine compound is chosen from polyetheramines, polyalkyleneimines, polyalkyleneamines, and mixtures thereof.
  • the polyamine compound is a polyetheramine.
  • Polyetheramines are oligomeric or polymeric molecules comprising repeating alkylene ether units and at least two primary amine termini. Suitable polyetheramines include those having the structure
  • R is C 2 -Ci 2 hydrocarbylene, more specifically C 2 -C 6 alkylene, still more specifically -CH 2 CH 2 - or -CH(CH 3 )CH?-; each occurrence of R is independently hydrogen or methyl; and q is 1 to about 100.
  • Commercially available examples of such polyetheramines include XTJ-505, XTJ-506, XTJ-507, JEFFAMINE® M-2070, JEFFAMINE® D-230, JEFFAMINE® D-400, JEFFAMINE® D-2000, XTJ-500, XTJ-501, XTJ-502, XTJ-510, and JEFFAMINE® EDR- 148, all from Huntsman.
  • Suitable polyetheramines further include those having the structure
  • R 3 is hydrogen or Ci-C 12 hydrocarbyl, more specifically Ci-C 6 alkyl; each occurrence of R 4 is independently hydrogen or methyl; and x and y and z are each independently 1 to about 100.
  • Commercially available examples of such polyetheramines include JEFFAMINE® T-403, JEFFAMINE® T-5000, and XTJ-509, all from Huntsman.
  • the polyamine compound is a polyalkyleneimine.
  • Polyalkyleneimines can be prepared by polymerizing an alkylene imine (e.g., ethyleneimine, also known as aziridine) in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, or the like. Specific methods for preparing polyalkyleneimines are described, for example, in U.S. Patent Nos. 2,182,306 to Ulrich et al., 3,033,746 to Mayle et al, 2,208,095 to Esselmann et al., 2,806,839 to Crowther, and 2,553,696 to Wilson.
  • the present invention also includes the cyclic amines that are typically formed as by-products of known synthetic methods. The presence of these materials may be increased or decreased depending on the reaction conditions.
  • Suitable polyalkyleneimines are commercially available as, for example, the polyethyleneimines EPOMIN® SP-003 (about 300 atomic mass units), EPOMIN® SP-006 (about 600 atomic mass units), EPOMIN® SP-012 (about 1200 atomic mass units), EPOMIN® SP-18 (about 1800 atomic mass units), EPOMIN® SP-200 (about 10,000 atomic mass units), EPOMIN® P-1000 (about 70,000 atomic mass units), and EPOMIN® P- 1050 (about 70,000 atomic mass units), all from Nippon Shokubai.
  • polyalkyleneimines further include the polyethyleneimines LUPASOL FG (about 800 atomic mass units), LUPASOL G20 (about 1,300 atomic mass units), and LUPASOL G35 (about 2,000 atomic mass units), all from BASF.
  • the polyamine compound is a polyalkyleneamine.
  • Polyalkyleneamines may be prepared by the reaction of an alkylene dichloride (e.g., ethylene- 1,2-dichloride) with ammonia, followed by fractional distillation. Examples of polyalkyleneamines are triethylene tetraamine, tetraethylenepentamine, and tetrabutylenepentamine, as well as the corresponding hexamines, heptamines, octamines, and nonamines. These compound or mixtures of compound may further comprise small amounts of reaction by-products, including cyclic amines, particularly piperazines, and cyclic amines with nitrogen-containing side chains. Mixtures of different polyalkyleneamines may be used. Preparation of polyalkyleneamines is described, for example, in U.S. Patent No. 2,792,372 to Dickson.
  • the polyamine compound may have a number average molecular weight of about 100 to about 1,000,000 atomic mass units. Within this range, the molecular weight may be at least about 200 atomic mass units, or at least about 300 atomic mass units. Also within this range, the molecular weight may be up to about 500,000 atomic mass units, or up to about 100,000 atomic mass units, or up to about 10,000 atomic mass units, or up to about 2,000 atomic mass units.
  • the poly(arylene ether), the acid-functionalized block copolymer, and the polyamine compound may be melt-kneading in proportions that provide the desired property balance.
  • the composition before melt-kneading comprises about 20 to about 99 parts by weight of the poly(arylene ether), about 1 to about 80 parts by weight of the acid-functionalized block copolymer, and about 0.01 to about 5 parts by weight of the polyamine compound, wherein all parts by weight are based on 100 parts by weight total of the poly(arylene ether) and the acid- functionalized block copolymer.
  • the poly(arylene ether) amount may be at least about 50 parts by weight, or at least about 80 parts by weight, or up to about 95 parts by weight, or up to about 90 parts by weight.
  • the amount of acid-functionalized block copolymer may be at least about 5 parts by weight, or at least about 10 parts by weight, or up to about 50 parts by weight, or up to about 20 parts by weight.
  • the polyamine compound amount may be at least about 0.1 part by weight, or at least about 0.2 part by weight, or up to about 3 parts by weight, or up to about 2 parts by weight, or up to about 1 part by weight.
  • composition before melt-kneading may comprise an aminosilane having the formula
  • each occurrence of R 1 is independently hydrogen, Ci-Ci 2 hydrocarbyl, or Ci -C i 2 hydrocarbylene covalently bound to Y; each occurrence of R 2 and R 3 is independently Ci -C 12 hydrocarbyl; each occurrence of Y is independently Ci -C 12 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4.
  • Suitable aminosilanes include, for example, 3- aminopropyltrimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-(aminopropyl)ethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylphenyldimethoxysilane, 2-aminoethyltriethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutyldimethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-(trimethoxysilyl)-2-butanamine, 3 - [diethoxy(hexyloxy)silyl] - 1 -propanamine, 3 - [tris(pentyloxy)silyl] - 1
  • the aminosilane is 3-aminopropyltriethoxysilane (Chemical Abstracts Registry No. 919-30-2). Methods for preparing aminosilanes are known in the art, and many aminosilanes are commercially available.
  • the poly(arylene ether), the acid-functionalized block copolymer, and the aminosilane may be melt-kneading in proportions that provide the desired property balance.
  • the composition before melt-kneading comprises about 20 to about 99 parts by weight of the poly(arylene ether), about 1 to about 80 parts by weight of the acid-functionalized block copolymer, and about 0.01 to about 5 parts by weight of the aminosilane, wherein all parts by weight are based on 100 parts by weight total of the poly(arylene ether) and the acid-functionalized block copolymer.
  • the poly(arylene ether) amount may be at least about 50 parts by weight, or at least about 80 parts by weight, or up to about 95 parts by weight, or up to about 90 parts by weight.
  • the acid-functionalized block copolymer amount may be at least about 5 parts by weight, or at least about 10 parts by weight, or up to about 50 parts by weight, or up to about 20 parts by weight.
  • the aminosilane amount may be at least about 0.1 part by weight, or at least about 0.2 part by weight, or up to about 2 parts by weight, or up to about 1 part by weight.
  • the composition before melt-kneading further comprises an atactic homopolystyrene, a rubber-modified polystyrene, or a mixture thereof.
  • the composition may, optionally, further comprise one or more fillers, including low- aspect ratio fillers, fibrous fillers, and polymeric fillers.
  • fillers including low- aspect ratio fillers, fibrous fillers, and polymeric fillers. Examples of such fillers well known to the art include those described in "Plastic Additives Handbook, 4 th Edition" R. Gachter and H. Muller (eds.), P.P. Klemchuck (assoc. ed.) Hansen Publishers, New York 1993.
  • Non-limiting examples of fillers include silica powder, such as fused silica, crystalline silica, natural silica sand, and various silane-coated silicas; boron- nitride powder and boron-silicate powders; alumina and magnesium oxide (or magnesia); wollastonite including surface-treated wollastonite; calcium sulfate (as, for example, its anhydride, dihydrate or trihydrate); calcium carbonates including chalk, limestone, marble and synthetic, precipitated calcium carbonates, generally in the form of a ground particulate which often comprises 98+% CaCO 3 with the remainder being other inorganics such as magnesium carbonate, iron oxide and alumino- silicates; surface-treated calcium carbonates; talc, including fibrous, modular, needle shaped, and lamellar talcs; glass spheres, both hollow and solid, and surface-treated glass spheres typically having coupling agents such as silane coupling agents and/or containing a
  • the above fillers may be used with various coatings, including, for example, metallic coatings and silane coating, to improve compatibility with and adhesion to the composition.
  • the composition may, optionally, further comprise various additives known in the thermoplastics art.
  • the composition may, optionally, further comprising an additive chosen from stabilizers, mold release agents, processing aids, flame retardants, drip retardants, nucleating agents, UV blockers, dyes, pigments, antioxidants, anti-static agents, blowing agents, mineral oil, metal deactivators, antiblocking agents, and the like, and combinations thereof.
  • Additives may be added in amounts that do not unacceptably detract from the desired physical properties of the composition.
  • the composition is substantially free of any thermoplastic or thermoset resin other than those described above.
  • the composition may be substantially free of an epoxy resin.
  • the composition may be substantially free of polyolefin, substantially free of polyamide, or substantially free of syndiotactic polystyrene.
  • One embodiment is a composition
  • a composition comprising the product obtained on melt-kneading a poly(arylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units, 2,3,6- trimethyl-l,4-phenylene ether units, or a combination thereof; a maleic-anhydride functionalized, hydrogenated block copolymer comprising at least one polystyrene block and at least one hydrogenated poly(conjugated diene) block, and having a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and a polyethyleneimine having a number average molecular weight of about 100 to about 10,000 atomic mass units.
  • One embodiment is a composition
  • a composition comprising the product obtained on melt-kneading about 50 to about 95 parts by weight of a poly(arylene ether) comprising 2,6-dimethyl- 1 ,4-phenylene ether units, 2,3,6-trimethyl-l,4- ⁇ henylene ether units, or a combination thereof; about 5 to about 50 parts by weight of a maleic-anhydride functionalized block copolymer selected from the group consisting of polystyrene-poly(ethylene- butylene)-polystyrene triblock copolymer, polystyrene-poly(ethylene-propylene)- polystyrene triblock copolymer, and mixtures thereof; wherein the maleic-anhydride functionalized block copolymer has a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and about 0.02 to about 2 parts by weight of a poly
  • the invention includes the compositions prior to melt-kneading.
  • one embodiment is a composition comprising a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and a polyamine compound.
  • Another embodiment is a composition, comprising a poly(arylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units, 2,3,6- trimethyl-l,4-phenylene ether units, or a combination thereof; a maleic-anhydride functionalized ⁇ olystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and a polyethyleneimine having a number average molecular weight of about 100 to about 10,000 atomic mass units.
  • compositions comprising: about 50 to about 95 parts by weight of a poly(arylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units, 2,3,6-trimethyl-l,4-phenylene ether units, or a combination thereof; about 5 to about 50 parts by weight of a maleic-anhydride functionalized polystyrene-poly(ethylene- butylene)-polystyrene triblock copolymer having a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and about 0.02 to about 2 parts by weight of a polyethyleneimine having a number average molecular weight of about 100 to about 10,000 atomic mass units; wherein all parts by weight are based on 100 parts by weight total of the poly(arylene ether) and maleic-anhydride functionalized polystyrene-poly(ethylene- butylene)-polystyrene triblock
  • thermoplastic composition comprising melt-kneading a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and a polyamine compound.
  • the composition may be prepared by any method in which the poly(arylene ether), the acid-functionalized block copolymer, and the polyamine compound are ultimately melt-kneaded with each other.
  • the acid-functionalized block copolymer and polyamine compound are melt-kneaded with each other before being further melt-kneaded with the poly(arylene ether).
  • the polyamine compound and the poly(arylene ether) are melt-kneaded with each other before being further melt-kneaded with the acid-functionalized block copolymer.
  • the acid-functionalized block copolymer and the poly(arylene ether) are melt-kneaded with each other before being further melt- kneaded with the polyamine compound.
  • the acid- functionalized block copolymer, the polyamine compound, and the poly(arylene ether) are all melt-kneaded simultaneously (for example, the three components are all added at the feed throat of an extruder).
  • Apparatus suitable for preparing an intimate blend via melt-kneading includes, for example, a two-roll mill, a Banbury mixer, and a single-screw or twin-screw extruder.
  • melt-kneading comprises using a twin-screw extruder.
  • One embodiment is a composition
  • a composition comprising the product obtained on melt-kneading: a poly(arylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units, 2,3,6- trimethyl-l,4-phenylene ether units, or a combination thereof; a maleic- anhydride functionalized, hydrogenated block copolymer comprising at least one polystyrene block and at least one hydrogenated conjugated diene block, and having a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and 3-aminopropyltriethoxysilane.
  • One embodiment is a composition comprising the product obtained on melt-kneading: about 50 to about 95 parts by weight of a poly(arylene ether) comprising 2,6-dimethyl- 1 ,4-phenylene ether units, 2,3,6-trimethyl-l,4-phenylene ether units, or a combination thereof; about 5 to about 50 parts by weight of a maleic-anhydride functionalized block copolymer selected from the group consisting of polystyrene-poly(ethylene- butylene)-polystyrene triblock copolymer, polystyrene-poly(ethylene-propylene)- polystyrene triblock copolymer, and mixtures thereof; wherein the maleic-anhydride functionalized block copolymer has a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and about 0.1 to about 2 parts by weight of 3-aminopropyltri
  • One embodiment is a composition
  • a composition comprising the product obtained on melt-kneading a poly(arylene ether); and the reaction product of an aminosilane and an acid- functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene.
  • compositions prior to melt-kneading includes the compositions prior to melt-kneading.
  • one embodiment is a composition comprising a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and an aminosilane having the formula
  • each occurrence of R 1 is independently hydrogen, C 1 -C 12 hydrocarbyl, or Ci-Ci 2 hydrocarbylene covalently bound to Y; each occurrence of R 2 and R 3 is independently Ci-Ci 2 hydrocarbyl; each occurrence of Y is independently Ci-Cj 2 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4.
  • Another embodiment is a composition
  • a composition comprising a poly(arylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units, 2,3,6- trimethyl-l,4-phenylene ether units, or a combination thereof; a maleic-anhydride functionalized polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and 3- aminopropyltriethoxysilane.
  • Another embodiment is a composition
  • a composition comprising about 50 to about 95 parts by weight of a poly(arylene ether) comprising 2,6-dimethyl-l,4- phenylene ether units, 2,3,6-trimethyl-l,4-phenylene ether units, or a combination thereof; about 5 to about 50 parts by weight of a maleic-anhydride functionalized polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a styrene content of about 10 to about 50 weight percent and a bound maleic anhydride content of about 0.2 to about 5 weight percent; and about 0.1 to about 2 parts by weight of 3- aminopropyltriethoxysilane; wherein all parts by weight are based on 100 parts by weight total of the poly(arylene ether) and the maleic-anhydride functionalized polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.
  • one embodiment is a method of preparing a composition, comprising melt-kneading a poly(arylene ether), an acid-functionalized block copolymer of an alkenyl aromatic monomer and a conjugated diene, and an aminosilane having the formula
  • each occurrence of R 1 is independently hydrogen, Cj-Ci 2 hydrocarbyl, or Ci -C i 2 hydrocarbylene covalently bound to Y; each occurrence of R 2 and R 3 is independently Ci-C) 2 hydrocarbyl; each occurrence of Y is independently Ci-Cj 2 hydrocarbylene or hydrocarbyleneoxy wherein the hydrocarbylene or hydrocarbyleneoxy group may further comprise one or more catenary ether oxygen atoms; m is 1, 2, 3, or 4; n is 0, 1, 2, or 3; and p is 0, 1, 2, or 3; with the proviso that the sum of m and n and p is 4.
  • the composition may be prepared by any method in which the poly(arylene ether), the acid-functionalized block copolymer, and the aminosilane are ultimately melt-kneaded with each other.
  • the acid-functionalized block copolymer and aminosilane are melt-kneaded with each other before being further melt-kneaded with the poly(arylene ether).
  • the aminosilane and the poly(arylene ether) are melt-kneaded with each other before being further melt-kneaded with the acid-functionalized block copolymer.
  • the acid- functionalized block copolymer and the poly(arylene ether) are melt-kneaded with each other before being further melt-kneaded with the aminosilane.
  • the acid-functionalized block copolymer, the aminosilane, and the poly(arylene ether) are all melt-kneaded simultaneously (for example, the three components are all added at the feed throat of an extruder).
  • Apparatus suitable for preparing an intimate blend via melt-kneading includes, for example, a two-roll mill, a Banbury mixer, and a single-screw or twin-screw extruder.
  • melt- kneading comprises using a twin-screw extruder.
  • an article may comprise a film, sheet, molded object, or composite, wherein the film, sheet, molded object or composite comprises at least one layer comprising the composition.
  • Articles may be prepared from the composition using fabrication methods known in the art, including, for example, single layer and multilayer foam extrusion, single layer and multilayer sheet extrusion, injection molding, blow molding, extrusion, film extrusion, profile extrusion, pultrusion, compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, foam molding, and the like. Combinations of the foregoing article fabrication methods may be used.
  • Specific articles for which the composition may be useful include, for example, fluid engineering articles such as pump impellers, pump housings, pump covers, water meters, hydroblocks, fittings, water treatment equipment, pool and spa components, manifolds, and valves.
  • poly(arylene ether) (“PPE”) was a poly(2,6-dimethyl-l,4-phenylene ether) having an intrinsic viscosity of about 0.33 deciliter per gram, obtained from GE Plastics.
  • the acid-functionalized block copolymer (“Acid-fxnd.
  • copolymer was a maleic anhydride-grafted, hydrogenated polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a styrene content of 30% and about 1.4-2.0% bound maleic anhydride, obtained as KRATON® FG 190 IX from Kraton Polymers.
  • the polyamine was a polyethyleneimine having a number average molecular weight of about 10,000 atomic mass units, obtained as EPOMIN® SP-200. Component amounts are presented in Table 1.
  • the crosslinking of the acid-functionalized block copolymer and blending of all components were conducted simultaneously in a melt-kneading process.
  • a dry blend containing the poly(arylene ether), the polyamine crosslinking agent, and the acid- functionalized block copolymer were added in the feed throat in a 30-millimeter, 10- zone twin-screw extruder operating at 350 rotations per minute with barrel temperatures from feed throat to die of 260 0 C, 29O 0 C, 300 0 C, and 300 0 C.
  • the twin- screw extruder uses a down stream feeder in zone 7 out of 10 zones. A vacuum vent is located in zone 10 with 20-25 inches of mercury vacuum being applied. The feed rate was about 16-18 kilograms per hour (35-40 pounds per hour).
  • the screw design employed had fairly intensive mixing in zones 2 to 4 with relatively mild mixing in zone 9.
  • the extrudate was cooled and pelletized. Test samples were injection molded using a barrel temperature of 300 0 C and a mold temperature of 95°C.
  • Flexural modulus was measured according to ASTM D 790 Method A at 23°C using samples having a depth of 3.2 millimeters and a width of 12.7 millimeters, a support span length of 5.08 centimeters (2 inches), and a crosshead motion rate of 1.27 millimeter/minute (0.05 inch/minute).
  • Notched Izod impact strength was measured according to ASTM D 256 Method A at 23°C using a 0.907 kilogram (2.00 pound) hammer, and specimens having a notch such that at least 1.02 centimeter (0.4 inch) of the original 1.27 centimeter (0.5 inch) depth remained under the notch; the specimens were conditioned for 24 hours at 23°C after notching.
  • Heat deflection temperature was measured according to ASTM D 648, Method B on injection molded specimens having a width of 3.20 millimeters and a depth of 12.80 millimeters. Specimens were conditioned for 24 hours at 23 0 C before testing. For heat deflection testing, samples were immersed in silicone oil, which was initially at less than 30 0 C. The standard deviation for each property value represents evaluation of three samples per test. Property values are given in Table 1. The results show that, relative to the corresponding comparative examples without polyamine, all of the inventive compositions exhibit unexpectedly improved stiffness (flexural modulus) and heat resistance (heat deflection temperature). Inventive samples with higher concentrations of acid-functionalized copolymer and polyamine (Exs.
  • FIGS. 1 and 2 are transmission electron micrographs corresponding to Comparative Example 1 and Example 1, respectively. Samples were prepared by cutting, blocking and facing a molded tensile bar on a Leica UCT ultramicrotome. Final microtomy of 100 nanometer sections was performed on the Leica UCT at room temperature.
  • compositions prepared from a poly(arylene ether), an acid-functionalized block copolymer, a polyamine crosslinker, and a filler exhibit surprisingly improved (reduced) shrinkage on molding and after further exposure to elevated temperature.
  • Component types and parts by weight are presented in Table 2.
  • the poly(arylene ether) and acid-functionalized block copolymer were the same as those used in Examples 1-9.
  • the polyamine was a polyethyleneimine having a number average molecular weight of about 600 atomic mass units, obtained as EPOMIN® SP-006.
  • An unfunctionalized poly(styrene-ethylene/butylene-styrene) triblock copolymer ("Unfxnd.
  • compositions were compounded and molded as described for Examples 1-9. Shrinkage values were determined at room temperature (23 0 C) on samples as-molded and after 5.5 and 39 hours in a 150 0 C oven.
  • Cross-flow shrinkage i.e., the degree of shrinkage in the dimension perpendicular to the dimension along which the composition flows into the mold
  • Percent cross-flow shrinkage was calculated as 10 6 *(mold diameter - sample diameter)/(mold diameter).
  • In-flow shrinkage i.e., the degree of shrinkage in the dimension along which the composition flows into the mold
  • Percent cross-flow shrinkage expressed in parts per million (ppm), was calculated as 10 6 *(mold length - sample length)/(mold length).
  • a knit line is a surface where two resin flows meet within a molded part. Knit lines are often unavoidable features of articles formed in molds with complex shapes, but the knit lines can be the weakest parts of those articles. It is therefore desirable to increase knit line strength in order to increase the physical strength of molded articles.
  • tensile bars were molded in a tool that allows resin to enter from both ends of the cavity. This results in two flow fronts that meet in a knit line at the center of the tensile bar.
  • the tensile bars corresponding to ASTM D 638-03 Type I, had cross-sectional dimensions of 13 millimeters by 3.2 millimeters at the knit line.
  • compositions were tested. All four compositions included a poly(2,6-dimethyl- 1 ,4-phenylene ether) having an intrinsic viscosity of 0.33 deciliter per gram obtained from General Electric Company and a maleic anhydride-grafted, hydrogenated polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a styrene content of 30% and about 1.4-2.0% bound maleic anhydride obtained as KRATON® FG1901X from Kraton Polymers.
  • compositions are detailed in Table 3.
  • tensile strengths at yield were measured at 25°C according to ASTM D 638-03 using five samples per composition and a testing speed of 5.08 centimeters/minute (2 inches/minute).
  • the results, presented in Table 3, show that addition of the polyamine crosslinker dramatically and unexpectedly increased the tensile strength at yield, which is a measure of the knit line strength because of the way the samples were molded.
  • addition of polyamine to a sample containing about 80 weight percent poly(arylene ether) and about 20 weight percent acid-functionalized block copolymer increased the tensile strength at yield from 2.19 megapascals to 24.2 megapascals; and addition of polyamine to a sample containing about 90 weight percent poly(arylene ether) and about 10 weight percent acid-functionalized block copolymer increased the tensile strength at yield from 8.24 megapascals to 23.6 megapascals.
  • copolymer was a maleic anhydride-grafted, hydrogenated polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a styrene content of 30% and about 1.4-2.0% bound maleic anhydride, obtained as KRATON® FG 190 IX from Kraton Polymers.
  • the aminosilane crosslinker was 3-aminopro ⁇ yltriethoxysilane obtained as SILQUEST® Al 100 from OSi Corporation. Component amounts are presented in Table 1.
  • the crosslinking of the acid-functionalized block copolymer and blending of all components were conducted simultaneously in a melt-kneading process.
  • a dry blend containing the poly(arylene ether), the aminosilane crosslinking agent, and the acid- functionalized block copolymer were added in the feed throat in a 30-millimeter, 10- zone twin-screw extruder operating at 350 rotations per minute with barrel temperatures from feed throat to die of 260 0 C, 290 0 C, 300 0 C, and 300 0 C.
  • the twin- screw extruder uses a down stream feeder in zone 7 out of 10 zones.
  • a vacuum vent is located in zone 10 with 20-25 inches of mercury vacuum being applied.
  • the feed rate was about 16-18 kilograms per hour (35-40 pounds per hour).
  • the screw design employed had fairly intensive mixing in zone 2 to 4 with relatively mild mixing in zone 9.
  • the extrudate was cooled and pelletized.
  • Flexural modulus was measured according to ASTM D 790 Method A at 23°C using samples having a depth of 3.2 millimeters and a width of 12.7 millimeters, a support span length of 5.08 centimeters (2 inches), and a crosshead motion rate of 0.127 centimeter/minute (0.05 inch/minute).
  • Notched Izod impact strength was measured according to ASTM D 256 Method A at 23°C using a 0.907 kilogram (2.00 pound) hammer, and specimens having a notch such that at least 1.02 centimeter (0.4 inch) of the original 1.27 centimeter (0.5 inch) depth remained under the notch; the specimens were conditioned for 24 hours at 23 0 C after notching.
  • Heat deflection temperature was measured according to ASTM D 648, Method B on injection molded specimens having a width of 3.20 millimeters and a depth of 12.80 millimeters. Specimens were conditioned for 24 hours at 23 0 C before testing. For heat deflection testing, samples were immersed in silicone oil, which was initially at less than 30 0 C. The standard deviation for each property value represents evaluation of three samples per test. Property values are given in Table 4. The results show that, relative to the corresponding comparative examples without aminosilane, all of the inventive compositions with aminosilane exhibit unexpectedly improved stiffness (flexural modulus) and heat resistance (heat deflection temperature). The inventive sample with higher concentrations of acid-functionalized copolymer and aminosilane (Ex. 22) also exhibited unexpectedly improved impact strength (notched Izod).
  • Figures 1 and 3 are transmission electron micrographs corresponding to Comparative Example 9 (identical to Comparative Example 1, above) and Example 22, respectively.
  • Figure 1 shows that the Comparative Example 9 composition had a lamellar morphology.
  • Figure 2 shows that the Example 22 composition had a morphology in which discrete rubber domains were dispersed in a poly(arylene ether) matrix.

Abstract

La présente invention concerne une composition de poly(éther d'arylène) présentant un équilibre amélioré entre la rigidité, la ductilité et la résistance thermique qui est préparée par un malaxage à l'état fondu d'un poly(éther d'arylène), d'un copolymère séquencé à fonctionnalité acide et d'un agent de réticulation qui est un composé polyamine, un composé aminosilane ou une combinaison de ceux-ci.
PCT/US2007/067854 2006-05-24 2007-05-01 Composition de poly(éther d'arylène), procédé et article correspondants WO2007140070A2 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0382548A2 (fr) * 1989-02-09 1990-08-16 Sumitomo Chemical Company, Limited Composition de résine thermoplastique
WO2001057137A1 (fr) * 2000-02-02 2001-08-09 General Electric Company Melanges thermoplastiques a adherence et stabilite thermique ameliorees
WO2004094530A1 (fr) * 2003-04-22 2004-11-04 General Electric Company Composition et procede destines a ameliorer l'adhesion en surface de compositions de resine a de la mousse de polyurethane
WO2005014719A1 (fr) * 2003-04-22 2005-02-17 General Electric Company Composition et methode pour ameliorer la resistance d'une soudure de compositions de polyphenylene ether

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0382548A2 (fr) * 1989-02-09 1990-08-16 Sumitomo Chemical Company, Limited Composition de résine thermoplastique
WO2001057137A1 (fr) * 2000-02-02 2001-08-09 General Electric Company Melanges thermoplastiques a adherence et stabilite thermique ameliorees
WO2004094530A1 (fr) * 2003-04-22 2004-11-04 General Electric Company Composition et procede destines a ameliorer l'adhesion en surface de compositions de resine a de la mousse de polyurethane
WO2005014719A1 (fr) * 2003-04-22 2005-02-17 General Electric Company Composition et methode pour ameliorer la resistance d'une soudure de compositions de polyphenylene ether

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