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WO2014138031A1 - Composition polyphtalamide/poly(éther de phénylène) renforcée - Google Patents

Composition polyphtalamide/poly(éther de phénylène) renforcée Download PDF

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Publication number
WO2014138031A1
WO2014138031A1 PCT/US2014/020236 US2014020236W WO2014138031A1 WO 2014138031 A1 WO2014138031 A1 WO 2014138031A1 US 2014020236 W US2014020236 W US 2014020236W WO 2014138031 A1 WO2014138031 A1 WO 2014138031A1
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WIPO (PCT)
Prior art keywords
composition
weight percent
phenylene ether
poly
polyphthalamide
Prior art date
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PCT/US2014/020236
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English (en)
Inventor
Sai-Pei Ting
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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Filing date
Publication date
Priority claimed from US13/801,366 external-priority patent/US8865279B2/en
Application filed by SABIC Innovative Plastics IP BV filed Critical SABIC Innovative Plastics IP BV
Priority to JP2015561533A priority Critical patent/JP2016509121A/ja
Priority to CN201480010720.4A priority patent/CN105073896A/zh
Priority to KR1020157027363A priority patent/KR102083231B1/ko
Priority to EP14760073.8A priority patent/EP2964703A4/fr
Publication of WO2014138031A1 publication Critical patent/WO2014138031A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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

Definitions

  • This application relates to polyphthalamide/poly(phenylene ether) blends and more particularly to reinforced polyphthalamide/poly(phenylene ether) blends.
  • PPE/PA66 blends Glass filled poly(phenylene ether)/polyamide 66 (GF-PPE/PA66) blends have been used in applications such as water pumps and water meters for long time.
  • the morphology of PPE/PA66 blends can be defined as "islands-and-sea" where PPE particles are the dispersed phase (as islands) and PA66 is the continuous phase (as sea).
  • PPE/PA66 blends are commonly recognized in industry as modified nylons with superior performance such as higher heat resistance, better dimension stability, less warpage and sagging, and less moisture absorption.
  • PPE/PA66 blends are also susceptible to moisture induced property changes such as reduction of flexural modulus and tensile strength as the moisture content in the nylon matrix increases.
  • moisture induced property changes such as reduction of flexural modulus and tensile strength as the moisture content in the nylon matrix increases.
  • aggressive chemicals such as chlorine in order to purify water
  • neat GF PA66 and GF PPE/PA66 blends may result in earlier part failure caused by severe nylon hydrolysis.
  • composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • a reinforced composition comprises
  • Q 2 is a 1,4-butyl group and Q 3 is a 1,6-hexyl group, and a poly(phenylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units wherein said compatibilized blend is formed from a mixture of said polyphthalamide and poly(phenylene ether) in a ratio of between 1.5: 1 and 7.0:1, and 0.2 to 0.9 weight percent citric acid; and
  • composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • an article comprises a reinforced composition comprising
  • a compatibilized blend of a polyphthalamide and a poly(phenylene ether) wherein said compatibilized blend is formed from a mixture of polyphthalamide and poly(phenylene ether) in a ratio of between 1.5: 1 and 7.0:1, and a functionalizing agent in an amount sufficient to effect compatibilization;
  • composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • an article comprises 55 to 80 weight percent (wt ) of a compatibilized blend of a polyphthalamide comprising (a) 60-70 mol of units of formula (I)
  • Q 2 is a 1,4-butyl group and Q 3 is a 1,6-hexyl group, and a poly(phenylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units wherein said compatibilized blend is formed from a mixture of said polyphthalamide and poly(phenylene ether) in a ratio of between 1.5: 1 and 7.0:1, and 0.2 to 0.9 weight percent citric acid; and
  • composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • Polyphthalamides are semi-aromatic, high temperature nylons that typically have melting points higher than 290°C and glass transitions temperatures greater than 80°C.
  • PPAs are generally based on polyamide 6T.
  • polyamide 6T has a melting point of 370°C, and therefore is difficult to process and/or blend with other polymers, such as polyphenylene ether (PPE).
  • PPAs generally are copolymers that have various ratios of polyamide 6T, polyamide 61, and polyamide 6/6 to control properties such as melt flow, melting point, and glass transition temperature.
  • PPAs are distinct from high temperature nylons (HTN) in that PPAs comprise aromatic repeating units in an amount greater than or equal to 55 weight percent. The glass transitions temperature and the melting point are indicative of the aromatic content of the PPA.
  • Reinforced PPA has better hydrolytic stability than reinforced PA66.
  • reinforced PPE/PPA blends as described herein have better hydrolytic stability than reinforced PPA.
  • compositions described herein can be substantially free of added aliphatic polyamides.
  • Substantially free of added aliphatic polyamide is defined as containing less than or equal to 2 weight percent, or, more specifically less than or equal to 1 weight percent, or, more specifically, less than or equal to 0.5 weight percent of an added aliphatic polyamide, based on the total weight of the composition.
  • An added liphatic polyamides is defined as an aliphatic polyamide added in addition to the polyphthalamide. It is understood that polyphthalamides may contain residual aliphatic polyamides resulting from synthesis of the polyphthalamide. Aliphatic polyamides are distinguished from
  • Aliphatic polyamides in that aliphatic polyamides have no repeating units that comprise aromatic moieties.
  • Aliphatic polyamides include both homopolymers and copolymers.
  • Polyphthalamides comprise repeating units having formula (I)
  • C/ is independently at each occurrence a branched or unbranched alicyclic alkyl group having 4 to 8 carbons.
  • Q 1 is independently at each occurrence a 1,6-hexyl group.
  • Polyamide resins in general characterized by the presence of an amide group (-C(O)NH-) which is the condensation product of a carboxylic acid and an amine.
  • Polyphthalaimdes are the condensation product of terephthalic acid and an amine, isophthalic acid and an amine or a combination of terephthalic acid, isophthalic acid and an amine. When employing more than one diamine the ratio of the diamines can affect some of the physical properties of the resulting polymer such as the melt temperature.
  • the ratio of the acids can affect some of the physical properties of the resulting polymer as well.
  • the ratio of diamine to dicarboxylic acid is typically equimolar although excesses of one or the other may be used to determine the end group functionality.
  • the reaction can further include monoamines and monocarboxylic acids which function as chain stoppers and determine, at least in part, the end group functionality.
  • the polyphthalamide is a block copolymer or a random copolymer comprising the units of formula (I) and units of formula (II)
  • Q 2 and Q 3 are independently at each occurrence a branched or unbranched alicyclic alkyl group having 4 to 12 carbons.
  • Q 2 and Q 3 can be the same or different alicyclic alkyl group.
  • the polythalamide has a glass transition temperature (Tg) greater than or equal to 80°C, or, greater than or equal to 100°C, or, greater than or equal to 120°C.
  • the polythalamide also has melting temperature (Tm) of 290 to 330°C. Within this range the Tm may be greater than or equal to 300°C. Also within this range the Tm may be less than or equal to 325°C.
  • the polyphthalamide is present in an amount of 30 to 70 weight percent based on the total weight of the composition. Within this range the amount of polyphthalamide can be greater than or equal to 35 weight percent, or, more specifically, greater than or equal to 40 weight percent. Also within this range the amount of polyphthalamide can be less than or equal to 60 weight percent, or, more specifically, less than or equal to 55 weight percent.
  • the composition comprises a poly(phenylene ether).
  • Poly(phenylene ether) comprises re eating structural units of formula (III)
  • each Z is independently halogen, unsubstituted or substituted CrC 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, CrC 12 hydrocarbylthio, CrC 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Z is independently hydrogen, halogen, unsubstituted or substituted CrC 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, CrC 12 hydrocarbylthio, Cp C 12 hydrocarbyloxy, or C 2 -C 12 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 can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can 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", it can contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
  • the hydrocarbyl residue can 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 can contain heteroatoms within the backbone of the hydrocarbyl residue.
  • the poly(phenylene ether) can comprise molecules having aminoalkyl- containing end group(s), typically located in an ortho position to the hydroxy group. Also frequently present are tetramethyl diphenylquinone (TMDQ) end groups, typically obtained from reaction mixtures in which tetramethyl diphenylquinone by-product is present.
  • TMDQ tetramethyl diphenylquinone
  • the poly(phenylene ether) can be in the form of a homopolymer; a copolymer; a graft copolymer; an ionomer; or a block copolymer; as well as combinations comprising two or more of the foregoing polymers.
  • Poly(phenylene ether) includes polyphenylene ether comprising 2,6-dimethyl-l,4-phenylene ether units optionally in combination with 2,3,6-trimethyl-l,4-phenylene ether units.
  • the poly(phenylene ether) can be prepared by the oxidative coupling of monohydroxyaromatic compound(s) such as 2,6-xylenol and/or 2,3,6-trimethylphenol.
  • Catalyst systems are generally employed for such coupling; they can contain heavy metal compound(s) such as a copper, manganese or cobalt compound, usually in combination with various other materials such as a secondary amine, tertiary amine, halide or combination of two or more of the foregoing.
  • a portion of the poly(phenylene ether) can be functionalized with a polyfunctional compound (functionalizing agent) as described below.
  • the poly(phenylene ether) can be functionalized prior to making the composition or can be functionalized as part of making the composition. Furthermore, prior to functionalization the poly(phenylene ether) can be extruded, for example to be formed into pellets. It is also possible for the poly(phenylene ether) to be melt mixed with other additives that do not interfere with functionalization. Exemplary additives of this type include s, flow promoters, and the like.
  • the poly(phenylene ether) can comprise 0.1 weight percent weight percent to 90 weight percent of structural units derived from a functionalizing agent, based on the total weight of the poly(phenylene ether). Within this range, the poly(phenylene ether) can comprise less than or equal to 80 weight percent, or, more specifically, less than or equal to 70 weight percent of structural units derived from functionalizing agent, based on the total weight of the poly(phenylene ether).
  • the poly(phenylene ether) can have a number average molecular weight of 3,000 to 40,000 grams per mole (g/mol) and a weight average molecular weight of 5,000 to 80,000 g/mol, as determined by gel permeation chromatography using monodisperse polystyrene standards, a styrene divinyl benzene gel at 40°C and samples having a concentration of 1 milligram per milliliter of chloroform.
  • the poly(phenylene ether) or combination of poly(phenylene ether)s has an initial intrinsic viscosity of 0.1 to 0.60 deciliters per gram (dl/g), as measured in chloroform at 25°C.
  • Initial intrinsic viscosity is defined as the intrinsic viscosity of the poly(phenylene ether) prior to melt mixing with the other components of the composition and final intrinsic viscosity is defined as the intrinsic viscosity of the poly(phenylene ether) after melt mixing with the other components of the composition.
  • final intrinsic viscosity is defined as the intrinsic viscosity of the poly(phenylene ether) after melt mixing with the other components of the composition.
  • poly(phenylene ether) may be up to 30% higher after melt mixing.
  • the percentage of increase can be calculated by (final intrinsic viscosity - initial intrinsic viscosity)/initial intrinsic viscosity. Determining an exact ratio, when two initial intrinsic viscosities are used, will depend somewhat on the exact intrinsic viscosities of the poly(phenylene ether) used and the ultimate physical properties that are desired.
  • the poly(phenylene ether) is present in an amount of 10 to 30 weight percent based on the total weight of the composition. Within this range the poly(phenylene ether) may be present in an amount greater than or equal to 15 weight percent, or, more specifically, greater than or equal to 18 weight percent. Also within this range the poly(phenylene ether) can be present in an amount of less than or equal to 25 weight percent, or, more specifically, less than or equal to 20 weight percent.
  • the compatibilized polyphthalamide/poly(phenylene ether) blend is formed using a functionalizing agent.
  • the expression “functionalizing agent” refers to polyfunctional compounds which interact with the poly(phenylene ether), the polyamide resin, or both. This interaction may be chemical (e.g., grafting) and/or physical (e.g., affecting the surface characteristics of the dispersed phases). In either instance the resulting compatibilized polyphthalamide/poly(phenylene ether) composition appears to exhibit improved compatibility, particularly as evidenced by enhanced impact strength, mold knit line strength and/or elongation.
  • the expression “compatibilized polyphthalamide/poly(phenylene ether) blend” refers to those compositions which have been physically and/or chemically compatibilized with a functionalizing agent.
  • the functionalizing agent comprises a polyfunctional compound that is one of two types.
  • the first type has in the molecule both (a) a carbon-carbon double bond and (b) at least one carboxylic acid, anhydride, epoxy, imide, amide, ester group or functional equivalent thereof.
  • Examples of such polyfunctional compounds include maleic acid; maleic anhydride; fumaric acid; maleic hydrazide; dichloro maleic anhydride; and unsaturated dicarboxylic acids (e.g. acrylic acid, butenoic acid, methacrylic acid, t-ethylacrylic acid, pentenoic acid).
  • the functionalizing agent comprises maleic anhydride and/or fumaric acid.
  • the second type of polyfunctional functionalizing agent compounds are characterized as having both (a) a group represented by the formula (OR) wherein R is hydrogen or an alkyl, aryl, acyl or carbonyl dioxy group and (b) at least two groups each of which may be the same or different selected from carboxylic acid, acid halide, anhydride, acid halide anhydride, ester, orthoester, amide, imido, amino, and salts thereof.
  • R is hydrogen or an alkyl, aryl, acyl or carbonyl dioxy group
  • R is hydrogen or an alkyl, aryl, acyl or carbonyl dioxy group
  • at least two groups each of which may be the same or different selected from carboxylic acid, acid halide, anhydride, acid halide anhydride, ester, orthoester, amide, imido, amino, and salts thereof are the aliphatic polycarboxylic acids, acid esters and acid amides represented by the formula (IV):
  • R is a linear or branched chain saturated aliphatic hydrocarbon having 2 to 20, or, more specifically, 2 to 10 carbon atoms
  • R 1 is hydrogen or an alkyl, aryl, acyl or carbonyl dioxy group having 1 to 10, or, more specifically, 1 to 6, or, even more specifically, 1 to 4 carbon atoms
  • each R 11 is independently hydrogen or an alkyl or aryl group having 1 to 20, or, more specifically, 1 to 10 carbon atoms
  • each R 111 and R w are independently hydrogen or an alkyl or aryl group having 1 to 10, or, more specifically 1 to 6, or, even more specifically, 1 to 4, carbon atoms
  • m is equal to 1 and (n + s) is greater than or equal to 2, or, more specifically, equal to 2 or 3, and n and s are each greater than or equal to zero and wherein (OR 1 ) is alpha or beta to a carbonyl group and at least two carbonyl groups are separated by 2 to 6 carbon atoms.
  • R 1
  • Suitable polycarboxylic acids include, for example, citric acid, malic acid, agaricic acid; including the various commercial forms thereof, such as for example, the anhydrous and hydrated acids; and combinations comprising one or more of the foregoing.
  • the functionalizing agent comprises citric acid.
  • esters useful herein include, for example, acetyl citrate and mono- and/or distearyl citrates and the like.
  • Suitable amides useful herein include, for example, ⁇ , ⁇ '-diethyl citric acid amide; N- phenyl citric acid amide; N-dodecyl citric acid amide; ⁇ , ⁇ '-didodecyl citric acid amide and N-dodecyl malic acid.
  • Derivates include the salts thereof, including the salts with amines and the alkali and alkaline metal salts.
  • Exemplary suitable salts include calcium malate, calcium citrate, potassium malate, and potassium citrate.
  • the foregoing functionalizing agents may be added directly to the melt blend or pre-reacted with either or both the poly(phenylene ether) and polyamide.
  • at least a portion of the functionalizing agent is pre-reacted, either in the melt or in a solution of a suitable solvent, with all or a part of the poly(phenylene ether). It is believed that such pre-reacting may cause the functionalizing agent to react with the polymer and, consequently, functionalize the poly(phenylene ether).
  • the poly(phenylene ether) may be pre -reacted with maleic anhydride, fumaric acid and/or citric acid to form an anhydride and/or acid functionalized poly(phenylene ether) which has improved
  • the amount of the functionalizing agent used will be dependent upon the specific functionalizing agent chosen and the specific polymeric system to which it is added.
  • the functionalizing agent is employed in an amount of 0.05 to 2.0 weight percent, based on the total weight of the composition.
  • the amount of functionalizing agent may be greater than or equal to 0.1, or, more specifically, greater than or equal to 0.2, or, more specifically, greater than or equal to 0.5 weight percent. Also within this range the amount of functionalizing agent may be less than or equal to 1.75, or, more specifically, less than or equal to 1.5 weight percent, or, more specifically less than or equal to 0.9 weight percent.
  • the composition comprises a nylon glass fiber.
  • a nylon glass fiber is defined as a glass fiber surface treated with silanes to improve adhesion and dispersion with polyamide as are commonly known in the art.
  • the glass fiber may have an average length of 2.8 to 3.6 millimeters.
  • the glass fiber may have an average diameter of 8 to 16 micrometers.
  • the nylon glass fiber is incorporated in an amount of 20 to 45 weight percent based on the total weight of the composition.
  • the amount of reinforcing filler can be greater than or equal to 25 weight percent, or, more specifically, greater than or equal to 28 weight percent. Also within this range the amount of reinforcing filler can be less than or equal to 40, or, more specifically, less than or equal to 37 weight percent.
  • the composition can, optionally, further comprise one or more other additives known in the thermoplastics arts.
  • Useful additives include, for example, stabilizers, mold release agents, processing aids, drip retardants, nucleating agents, dyes, pigments, colorants, crystallization nucleators, metal salts, antioxidants, anti-static agents, plasticizers, lubricants, blowing agents, metal deactivators, antiblocking agents, nanoclays, fragrances (including fragrance-encapsulated polymers), and the like, and combinations thereof.
  • Additives can be added in amounts that do not unacceptably detract from the desired performance and physical properties of the composition. Such amounts can be determined by a skilled artisan without undue experimentation.
  • the total amount of additives will be less than or equal to 5 weight percent based on the total weight of the composition.
  • the composition comprises a black pigment.
  • the black pigment comprises carbon black in an amount up to 0.5 weight percent, based on the total weight of the composition.
  • composition can, optionally, exclude any polymer other than those taught herein as required.
  • the composition can be prepared using various techniques, including batch or continuous techniques that employ kneaders, extruders, mixers, and the like.
  • the composition can be formed as a melt blend employing a twin-screw extruder.
  • at least some of the components are added sequentially.
  • the poly(phenylene ether) and functionalizing agent may be added to the extruder at the feed throat or in feeding sections adjacent to the feed throat, while the polyphthalamide may be added to the extruder in a subsequent feeding section downstream.
  • the functionalized poly(phenylene ether) may be added to the extruder at the feed throat or in feeding sections adjacent to the feed throat, while the polyphthalamide may be added to the extruder in a subsequent feeding section downstream.
  • a vacuum system may be applied to the extruder, prior to the second sequential addition, to generate a sufficient vacuum to lower the residual levels of non-reacted functionalizing agent and any other volatile materials.
  • the sequential addition of the components may be accomplished through multiple extrusions.
  • a composition may be made by preextrusion of selected components, such as the poly(phenylene ether) and the
  • the extruder may be a two lobe or three lobe twin screw extruder.
  • composition can be used to make articles such as engine fluid handling components, engine cooling components such as hoses, pumps, manifolds, turbo outlets, and fluid meters.
  • Embodiment 1 A reinforced composition comprising 55 to 80 wt of a compatibilized blend of a polyphthalamide and a poly(phenylene ether) wherein said compatibilized blend is formed from a mixture of polyphthalamide and poly(phenylene ether) in a ratio of between 1.5: 1 and 7.0:1, and a functionalizing agent in an amount sufficient to effect compatibilization; and 20 to 45 wt of a nylon glass fiber, wherein the composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • Embodiment 2 The reinforced composition of Embodiment 1, wherein the polyphthalamide is present in an amount of 30 to 70 weight percent and the poly(phenylene ether) is present in an amount of 10 to 30 weight percent, and weight percent is based on the total weight of the composition.
  • Embodiment 3 The reinforced composition of Embodiment 1 or 2, wherein the polyphthalamide has a melting point greater than 290°C and a glass transition temperature greater than or equal to 80°C.
  • Embodiment 4 The reinforced composition of any of Embodiments 1-3, wherein the composition is substantially free of added aliphatic polyamides.
  • Embodiemnt 5 The reinforced composition of any of Embodiments 1-4, wherein the glass fiber has an average diameter of 8 to 16 micrometers.
  • Embodiment 6 The reinforced composition of Embodiments 1-5, wherein the glass fiber has an average length of 2.8 to 3.6 millimeters.
  • Embodiment 7 The reinforced composition of any of Embodiments 1-6, wherein the poly(phenylene ether) comprises 2,6-dimethyl-l,4-phenylene ether units.
  • Embodiment 8 The reinforced composition of any of Embodiments 1-7, wherein the polyphthalamide com rises (a) 60-70 mol of units of formula (I)
  • Q 2 is a 1,4-butyl group and Q 3 is a 1,6-hexyl group.
  • Embodiment 9 The reinforced composition of any of Embodiments 1-8, wherein the functionalizing agent comprises maleic anhydride, fumaric acid, or citric acid.
  • Embodiment 10 The reinforced composition of any of Embodiments 1-9, wherein the functionalizing agent is citric acid.
  • Embodiment 11 The reinforced composition of any of Embodiments 1-10, wherein the citric acid is used in an amount of 0.2 to 0.9 weight percent based on the total weight of the composition.
  • Embodiment 12 The reinforced composition of any of Embodiments 1-11, further comprising a black pigment.
  • Embodiment 13 The reinforced composition of Embodiment 12, wherein the black pigment is carbon black and is present in an amount up to 0.5 weight percent, based on the total weight of the composition..
  • Embodiment 14 A reinforced composition comprising 55 to 80 wt of a compatibilized blend of a poly hthalamide comprising (a) 60-70 mol of units of formula (I)
  • Q 2 is a 1,4-butyl group and Q 3 is a 1,6-hexyl group, and a poly(phenylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units wherein said compatibilized blend is formed from a mixture of said polyphthalamide and poly(phenylene ether) in a ratio of between 1.5: 1 and 7.0:1, and 0.2 to 0.9 weight percent citric acid; and 20 to 45 wt of a nylon glass fiber, wherein the composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • Embodiment 15 The composition of Embodiment 14, wherein the polyphthalamide is present in an amount of 30 to 70 weight percent, the poly(phenylene ether) is present in an amount of 10 to 30 weight percent, and weight percent is based on the total weight of the composition.
  • Embodiment 16 The reinforced composition of any of Embodiments 14-15, wherein the polyphthalamide has a melting point greater than 290°C and a glass transition temperature greater than or equal to 80°C.
  • Embodiment 17 The reinforced composition of any of Embodiments 14-16, wherein the composition is substantially free of added aliphatic polyamides.
  • Embodiment 18 The reinforced composition of any of Embodiments 14-17, wherein the glass fiber has an average diameter of 8 to 16 micrometers.
  • Embodiment 19 The reinforced composition of any of Embodiments 14-18, wherein the glass fiber has an an average length of 2.8 to 3.6 millimeters.
  • Embodiment 20 The reinforced composition of any of Embodiments 14-19, further comprising a black pigment.
  • Embodiment 21 The reinforced composition of Embodiment 20, wherein the black pigment is carbon black and is present in an amount up to 0.5 weight percent, based on the total weight of the composition.
  • Embodiment 22 An article comprises a reinforced composition comprising 55 to 80 wt of a compatibilized blend of a polyphthalamide and a poly(phenylene ether) wherein said compatibilized blend is formed from a mixture of polyphthalamide and poly(phenylene ether) in a ratio of between 1.5:1 and 7.0:1, and a functionalizing agent in an amount sufficient to effect compatibilization; and 20 to 45 wt of a nylon glass fiber, wherein the composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • Embodiment 23 The article of Embodiment 22, wherein the polyphthalamide is present in an amount of 30 to 70 weight percent and the poly(phenylene ether) is present in an amount of 10 to 30 weight percent, and weight percent is based on the total weight of the composition.
  • Embodiment 24 The article of any of Embodiments 22-23, wherein the polyphthalamide has a melting point greater than 290°C and a glass transition temperature greater than or equal to 80°C.
  • Embodiment 25 The article of any of Embodiments 22-24, wherein the composition is substantially free of added aliphatic polyamides.
  • Embodiment 26 The article of any of Embodiments 22-25, wherein the glass fiber has an average diameter of 8 to 16 micrometers.
  • Embodiment 27 The article of any of Embodiments 22-26, wherein the glass fiber has an average length of 2.8 to 3.6 millimeters.
  • Embodiment 28 The article of any of Embodiments 22-27, wherein the poly(phenylene ether) comprises 2,6-dimethyl-l,4-phenylene ether units.
  • Embodiment 29 The article of any of Embodiments 22-28, wherein the polyphthalamide comprises (a) -70 mol of units of formula (I)
  • Q 2 is a 1,4-butyl group and Q 3 is a 1,6-hexyl group.
  • Embodiment 30 The article of any of Embodiments 22-29, wherein the functionalizing agent comprises maleic anhydride, fumaric acid, or citric acid.
  • Embodiment 31 The article of any of Embodiments 22-30, wherein the functionalizing agent is citric acid.
  • Embodiment 32 The article of any of Embodiments 22-31, wherein the citiric acid is used in an amount of 0.2 to 0.9 weight percent based on the total weight of the composition.
  • Embodiment 33 The article of any of Embodiments 22-32, wherein the composition further comprises a black pigment.
  • Embodiment 34 The article of Embodiment 33, wherein the black pigment is carbon black and is present in an amount up to 0.5 weight percent based on the total weight of the composition.
  • Embodiment 35 The article of any of Embodiments 22-34, wherein the article is selected from the group consisting of engine cooling components, engine fluid handling components, hoses, pumps, manifolds, turbo outlets, and fluid meters.
  • Embodiment 36 An article comprises 55 to 80 weight percent (wt%) of a compatibilized blend of a poly hthalamide comprising (a) 60-70 mol of units of formula (I)
  • Q 2 is a 1,4-butyl group and Q 3 is a 1,6-hexyl group, and a poly(phenylene ether) comprising 2,6-dimethyl-l,4-phenylene ether units wherein said compatibilized blend is formed from a mixture of said polyphthalamide and poly(phenylene ether) in a ratio of between 1.5: 1 and 7.0:1, and 0.2 to 0.9 weight percent citric acid; and 20 to 45 wt of a nylon glass fiber, wherein the composition contains less than 0.1 wt of phosphinates and less than 0.1 wt of impact modifiers and weight percent is based on the total weight of the composition.
  • Embodiment 37 The article of Embodiment 36, wherein the polyphthalamide is present in an amount of 30 to 70 weight percent, the poly(phenylene ether) is present in an amount of 10 to 30 weight percent, and weight percent is based on the total weight of the composition.
  • Embodiment 38 The article of any of Embodiments 36-37, wherein the polyphthalamide has a melting point greater than 290°C and a glass transition temperature greater than or equal to 80°C.
  • Embodiment 39 The article of any of Embodiments 36-38, wherein the composition is substantially free of added aliphatic polyamides.
  • Embodiment 40 The article of any of Embodiments 36-39, wherein the glass fiber has an average diameter of 8 to 16 micrometers.
  • Embodiment 41 The article of any of Embodiments 36-40, wherein the glass fiber has an average length of 2.8 to 3.6 millimeters.
  • Embodiment 42 The article of any of Embodiments 36-41, wherein the composition further comprises a black pigment.
  • Embodiment 43 The article of Embodiment 42, wherein the black pigment is carbon black and is present in an amount up to 0.5 weight percent, based on the total weight of the composition..
  • Embodiment 44 The article of any of Embodiments 36-43, wherein the article wherein is selected from the group consisting of engine cooling components, engine fluid handling components, hoses, pumps, manifolds, turbo outlets, and fluid meters
  • Polyphthalamide, Amodel A-1006C is a copolymer comprising three different repeating units in the following amounts: (a) 60-70 mol of units of formula (I) wherein Q 1 is a 1,6-hexyl group and the aromatic portion of the repeating unit is derived from
  • the Examples also contained 0.7 weight percent of a combination of additives (Irganox 1010, potassium iodide, copper iodide, and carbon black).
  • the examples were made by melt blending the poly(phenylene ether), citric acid, additives, polyphthalamide or polyamide to form a first melt mixture and melt mixing the masterbatch and glass fibers with the first melt mixture in a 30 millimeter Werner Pfleider twin screw extruder.
  • the extruder for the polyamide 66 examples was set with barrel temperatures of 249-288°C and a die temperature of 288°C, with the screw rotating at 240 rotations per minute (rpm) and a rate of about 18 kilograms per hour.
  • the extruder for the polyphthalamide examples was set with barrel temperatures of 260-307°C and a die temperature of 343 °C, with the screw rotating at 240 rotations per minute (rpm) and a rate of about 18 kilograms per hour.
  • the amounts of the components of the compositions are shown in Table 3. Amounts are in weight percent based on the total weight of the compositions.
  • compositions were molded and tested. Testing methods are shown in Table 4. The compositions were tested after three time period/condition combinations - after molding, after immersion in 23C water for 13 and 31 days. The change is physical properties after immersion in 23C water is shown in Table 5. Table 4
  • the reinforced PPE/PPA examples (Examples 5 & 6) showed remarkable retention of stress @ break after immersion in water, especially when compared to reinforced PPA (Example 4), reinforced PA 6/6 (Example 1), and reinforced PPE/PA66 (Examples 2 &3)
  • compositions were also tested for stress ⁇ break both initially and after immersion in 80 °C water for 20 weeks. Results (in MPa) are shown in Table 6.
  • the reinforced PPE/PPA composition (Example 6) showed much better retention of tensile strength compared to the reinforced PPE/PA 66 (Example 3) and reinforced PPA (example 4).
  • Examples 7-11 were made as described above. The compositions are shown in Table 7. Similar to Examples 1-6 the Examples also contained 0.7 weight percent of a combination of additives (Irganox 1010, potassium iodide, copper iodide, and carbon black).
  • a combination of additives Irganox 1010, potassium iodide, copper iodide, and carbon black.
  • compositions were molded and tested for notched Izod (see Table 4 for the testing method).
  • the compositions were tested after molding and after exposure to heat aging for the time periods shown in Table 8.

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

Abstract

L'invention concerne une composition renforcée comprenant : 55 à 80 % en poids d'un mélange compatibilisé d'un polyphtalamide et d'un poly(éther de phénylène), ledit mélange compatibilisé étant formé à partir d'un mélange de polyphtalamide et de poly(éther de phénylène) dans un rapport d'entre 1,5:1 et 7,0:1 et d'un agent de fonctionnalisation dans une quantité suffisante pour effectuer une compatibilisation ; et 20 à 45 % en poids d'une fibre de verre de nylon, la composition contenant moins de 0,1 % en poids de phosphinates et moins de 0,1 % en poids d'agents antichoc et le pourcentage en poids étant basé sur le poids total de la composition.
PCT/US2014/020236 2013-03-04 2014-03-04 Composition polyphtalamide/poly(éther de phénylène) renforcée Ceased WO2014138031A1 (fr)

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JP2015561533A JP2016509121A (ja) 2013-03-04 2014-03-04 強化ポリフタルアミド／ポリ（フェニレンエーテル）組成物
CN201480010720.4A CN105073896A (zh) 2013-03-04 2014-03-04 增强的聚邻苯二甲酰胺/聚(亚苯基醚)组合物
KR1020157027363A KR102083231B1 (ko) 2013-03-04 2014-03-04 보강된 폴리프탈아미드/폴리(페닐렌 에테르) 조성물
EP14760073.8A EP2964703A4 (fr) 2013-03-04 2014-03-04 Composition polyphtalamide/poly(éther de phénylène) renforcée

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US13/801,366 US8865279B2 (en) 2013-03-04 2013-03-13 Reinforced polyphthalamide/poly(phenylene ether) composition

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WO2015049635A1 (fr) * 2013-10-02 2015-04-09 Sabic Global Technologies B.V. Composition renforcée de polyphtalamide/éther de poly(phénylène)

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CN114207035B (zh) 2019-10-21 2024-09-06 旭化成株式会社 增强树脂组合物、成型品以及高温时拉伸强度的提高方法
JP7655800B2 (ja) 2021-06-29 2025-04-02 旭化成株式会社 樹脂組成物及び成形品

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KR20150126011A (ko) 2015-11-10
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CN105073896A (zh) 2015-11-18
JP2016509121A (ja) 2016-03-24

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