WO2018049807A1 - 一种半芳香族共聚酰胺树脂和由其组成的聚酰胺模塑组合物 - Google Patents

一种半芳香族共聚酰胺树脂和由其组成的聚酰胺模塑组合物 Download PDF

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WO2018049807A1
WO2018049807A1 PCT/CN2017/078640 CN2017078640W WO2018049807A1 WO 2018049807 A1 WO2018049807 A1 WO 2018049807A1 CN 2017078640 W CN2017078640 W CN 2017078640W WO 2018049807 A1 WO2018049807 A1 WO 2018049807A1
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acid
mol
semi
derived
aromatic copolyamide
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PCT/CN2017/078640
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English (en)
French (fr)
Inventor
张传辉
曹民
姜苏俊
史振国
孙学科
范利明
陈明钦
黄木军
黄险波
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金发科技股份有限公司
珠海万通特种工程塑料有限公司
上海金发科技发展有限公司
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Priority to KR1020187001759A priority Critical patent/KR101998532B1/ko
Priority to JP2017566015A priority patent/JP6492199B2/ja
Priority to US15/737,320 priority patent/US10731002B2/en
Priority to EP17809167.4A priority patent/EP3339351B1/en
Publication of WO2018049807A1 publication Critical patent/WO2018049807A1/zh

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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/12—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids with both amino and carboxylic groups aromatically bound
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Definitions

  • the present invention relates to the field of engineering plastics, and more particularly to a semi-aromatic copolyamide resin and a polyamide molding composition composed thereof.
  • Polyamide resin is widely used because of its good comprehensive properties, including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricating properties, low friction coefficient, and certain flame retardancy. Reinforced modification with glass fiber and other fillers to improve performance and expand application range. In recent years, semi-aromatic polyamides have been developed with emphasis on their heat resistance and mechanical properties.
  • PA66 generally has a high water absorption rate, resulting in poor dimensional stability and a serious deterioration of mechanical properties for long-term use. Moreover, PA66 has a low melting point and is difficult to use in applications such as electrical and electronic and SMT processes where heat resistance is highly demanded.
  • the general solution in the industry is to replace the adipic acid with terephthalic acid to obtain a semi-aromatic polyamide.
  • the introduction of the benzene ring increases the rigidity of the molecular chain, improves its crystallization property, decreases the water absorption rate, and increases the melting point.
  • Examples of the above semi-aromatic polyamides such as PA6T/66, PA9T and PA10T have been widely used in the industry.
  • MXD6 can also be called semi-aromatic polyamide in fact, but its melting point is low, only 240 ° C, which is generally not considered to be a semi-aromatic polyamide.
  • CN102159620 discloses a meta-xylene polyamide-based semi-aromatic polyamide, such as PXD10 having a melting point of up to 290 ° C, high heat resistance and low water absorption, and is a semi-aromatic polyamide in the field of "non-terephthalic acid" A breakthrough.
  • US2688011 proposes a method for synthesizing a polyamide based on para-amino benzoic acid (PABA), which comprises p-aminobenzoic acid with an aliphatic diamine containing up to 14 even methylene groups and containing up to 14 An even number of methylene aliphatic diacids are copolymerized, wherein the above diamine and diacid are equimolar, and p-aminobenzoic acid accounts for 5-25 mol% of all monomer units.
  • PABA para-amino benzoic acid
  • the embodiment has been obtained A copolymer of PABA and 66 salt, the content of PABA in all monomer units is 9.6 mol%.
  • the melting point of the copolymer is only 248-250 ° C, which is difficult to meet the requirements of high temperature polyamide.
  • CN103122063 proposes a preparation method of semi-aromatic polyamide resin based on amino undecanediacid (AUA) and PABA, which is prepared by mixing aminoundecanoic acid, p-aminobenzoic acid, distilled water and catalyst into salt. The polymerization was carried out to obtain a copolymer of AUA and PABA having a melting point of about 310 °C. It is required that AUA and PABA must have equal molar ratios, otherwise it will "destroy the polycondensation reaction of nylon and cannot be polymerized".
  • AUA amino undecanediacid
  • PABA amino undecanediacid
  • the primary object of the present invention is to provide a based on or based on "non-terephthalic acid" which has both high heat resistance, improved color properties, excellent fluidity and low water absorption.
  • Another object of the present invention is to provide a polyamide molding composition comprising the above semi-aromatic copolyamide resin.
  • a semi-aromatic copolyamide resin expressed as a percentage by mole, consisting of the following repeating units:
  • the semi-aromatic copolyamide resin as a percentage by mole, consists of the following repeating units:
  • the semi-aromatic copolyamide resin as a percentage by mole, consists of the following repeating units:
  • the molar ratio of the unit derived from p-aminobenzoic acid and the unit derived from 11-aminoundecanoic acid or 11-lactam is not equal. .
  • the melting point of the semi-aromatic copolyamide resin of the present invention is 270-360 ° C according to ASTM D3418-2003; the intrinsic viscosity is 0.80-1.0 dl / g with reference to GB12006.1-89; water absorption ⁇ 2.0%; b value ⁇ 1.0;
  • the test method for water absorption rate is as follows: the sample is injection molded into a piece of 20 mm ⁇ 20 mm ⁇ 2 mm, the weight of which is recorded as a0, and then placed in 95° C.
  • the test method of the b value is: using a swatch mold 50*30*2mm, taking 3000g sample particles for injection molding, and obtaining a smooth swatch, placing the swatch The b value is obtained on the Lippo Color-Eye7000A computer colorimeter.
  • the other diamine having 4 to 36 carbon atoms is one or more selected from the group consisting of a linear or branched aliphatic diamine, a cycloaliphatic diamine, and an araliphatic diamine;
  • a branched aliphatic diamine is selected from the group consisting of 1,4-butane Amine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine (MPMD), 1,8-octanediamine (OMDA), 1,9-nonanediamine (NMDA), 2- Methyl-1,8-octanediamine (MODA), 2,2,4-trimethylhexamethylenediamine (TMHMD), 2,4,4-trimethylhexamethylenediamine (TMHMD) ), 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecane
  • the other diacid having 6 to 36 carbon atoms is selected from the group consisting of naphthalene dicarboxylic acid (NDA), isophthalic acid (IPS), adipic acid, suberic acid, azelaic acid, sebacic acid, and ten Monoalkane, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid, octadecanedioic acid, dimer acid, cis and/ Or one or more of transcyclohexane-1,4-dicarboxylic acid, cis and/or trans cyclohexane-1,3-dicarboxylic acid (CHDA).
  • NDA naphthalene dicarboxylic acid
  • IPS isophthalic acid
  • adipic acid suberic acid
  • azelaic acid sebacic acid
  • the invention also discloses a polyamide molding composition
  • a polyamide molding composition comprising the above semi-aromatic copolyamide resin, which comprises the following components in parts by weight:
  • the content of the reinforcing filler is preferably from 10 to 50 parts, more preferably from 15 to 40 parts, based on the total weight of the polyamide molding composition;
  • the content of the reinforcing filler is too low, the mechanical properties of the polyamide molding composition are poor; the content of the reinforcing filler is too high, and the surface of the polyamide molding composition product is seriously suspended, which affects the appearance of the product.
  • the reinforcing filler has a fibrous shape and an average length of 0.01 mm to 20 mm, preferably 0.1 mm to 6 mm; and an aspect ratio of 5:1 to 2000:1, preferably 30:1 to 600:1.
  • the polyamide molding composition exhibits a high heat distortion temperature and an increased high temperature rigidity.
  • the reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler
  • the inorganic reinforcing filler is selected from the group consisting of glass fiber, potassium titanate fiber, metal clad glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal curable fiber, asbestos fiber, alumina fiber, One or more of silicon carbide fibers, gypsum fibers or boron fibers, preferably glass fibers;
  • glass fibers not only improves the moldability of the polyamide molding composition, but also improves mechanical properties such as tensile strength, flexural strength and flexural modulus, and improves heat resistance, for example, when the thermoplastic resin composition is molded. Heat distortion temperature.
  • the organic reinforcing filler is selected from the group consisting of aramid fibers and/or carbon fibers.
  • the reinforcing filler has a non-fibrous shape such as a powder, a granule, a plate, a needle, a woven fabric or a felt, and has an average particle diameter of from 0.001 ⁇ m to 100 ⁇ m, preferably from 0.01 ⁇ m to 50 ⁇ m.
  • the average particle diameter of the reinforcing filler is less than 0.001 ⁇ m, it will result in poor melt processability of the polyamide resin; when the average particle diameter of the reinforcing filler is more than 100 ⁇ m, it will result in poor surface appearance of the injection molded article.
  • the average particle diameter of the above reinforcing filler is determined by an adsorption method, which may be selected from potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, Pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate, alumina, silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, One or more of calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide.
  • an adsorption method which may be selected from potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, wollastonite, zeolite, sericite, kaolin, mica, tal
  • These reinforcing fillers may be hollow; in addition, for swellable layered silicates such as bentonite, montmorillonite, hectorite, and synthetic mica, organication by cation exchange of interlayer ions with an organic ammonium salt may be used. Montmorillonite.
  • the inorganic reinforcing filler may be functionally treated with a coupling agent.
  • the coupling agent is selected from the group consisting of an isocyanate compound, an organosilane compound, an organic titanate compound, an organoborane compound, and an epoxy compound; preferably an organosilane compound;
  • the organosilane compound is selected from the group consisting of an epoxy group-containing alkoxysilane compound, a mercapto group-containing alkoxysilane compound, a urea group-containing alkoxysilane compound, and an isocyanate group-containing alkoxysilane compound.
  • an alkoxysilane compound containing a terminal amino group an alkoxysilane compound containing a hydroxyl group, an alkoxysilane compound containing a carbon-carbon unsaturated group, and an alkoxysilane compound containing an acid anhydride group.
  • the epoxy group-containing alkoxysilane compound is selected from the group consisting of ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4- One or more of epoxycyclohexyl)ethyltrimethoxysilane;
  • the mercapto group-containing alkoxysilane compound is selected from the group consisting of ⁇ -mercaptopropyltrimethoxysilane and/or ⁇ -mercaptopropyltriethoxysilane;
  • the ureido group-containing alkoxysilane compound is selected from the group consisting of ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane, ⁇ -(2-ureidoethyl)-terminated aminopropyl group One or more of a trimethoxysilane;
  • the isocyanate group-containing alkoxysilane compound is selected from the group consisting of ⁇ -isocyanatepropyltriethoxysilane, ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, ⁇ -Isocyanatepropylmethyldiethoxysilane, ⁇ -Isocyanatepropylethyldimethoxysilane, ⁇ -Isocyanatepropylethyldiethoxysilane, ⁇ -Isocyanatepropyltrichloride One or several of silanes;
  • the terminal amino group-containing alkoxysilane compound is selected from the group consisting of ⁇ -(2-terminal aminoethyl)-terminated propylmethyldimethoxysilane and ⁇ -(2-terminal aminoethyl) terminal One or more of aminopropyltrimethoxysilane and ⁇ -terminal aminopropyltrimethoxysilane;
  • the hydroxyl group-containing alkoxysilane compound is selected from the group consisting of ⁇ -hydroxypropyltrimethoxysilane and/or ⁇ -hydroxypropyltriethoxysilane;
  • the alkoxysilane compound containing a carbon-carbon unsaturated group is selected from the group consisting of ⁇ -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and N- ⁇ -(N-vinylbenzyl One or more of terminal aminoethyl)- ⁇ -terminal aminopropyltrimethoxysilane hydrochloride;
  • the acid anhydride group-containing alkoxysilane compound is selected from the group consisting of 3-trimethoxysilylpropyl succinic anhydride;
  • the organosilane compound is preferably ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -(2-terminal aminoethyl)-terminated propylmethyldimethoxysilane, ⁇ -( 2-terminal aminoethyl)-terminated aminopropyltrimethoxysilane, ⁇ -terminal aminopropyltrimethoxysilane or 3-trimethoxysilylpropyl succinic anhydride.
  • the inorganic reinforcing filler may be surface-treated by a conventional method using the above organosilane-based compound, and then melt-kneaded with a polyamide resin to prepare the polyamide molding composition.
  • the coupling agent is used in an amount of 0.05% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight based on the weight of the inorganic reinforcing filler.
  • the amount of the coupling agent is less than 0.05% by weight, the effect of improving the mechanical properties is not obtained; when the amount of the coupling agent is more than 10% by weight, the inorganic reinforcing filler is liable to agglomerate, and in the polyamide resin The risk of poor dispersion ultimately leads to a decline in mechanical properties.
  • the additive is selected from one or more of a flame retardant, an impact modifier, other polymers, and a processing aid;
  • the other polymer is one or more of an aliphatic polyamide, a polyolefin homopolymer, an ethylene- ⁇ -olefin copolymer, and an ethylene-acrylate copolymer;
  • the processing aid is selected from one or more of an antioxidant, a heat resistant stabilizer, a weathering agent, a mold release agent, a lubricant, a pigment, a dye, a plasticizer, and an antistatic agent.
  • the flame retardant is a flame retardant or a combination of a flame retardant and a flame retardant assistant, and the content thereof is preferably 0-40 parts based on the total weight of the polyamide molding composition; the flame retardant content is too low to cause flame retardancy The effect is deteriorated, and the flame retardant content is too high, resulting in a decrease in mechanical properties of the material.
  • the flame retardant is a halogen flame retardant or a halogen free flame retardant
  • the halogen-based flame retardant is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, and brominated One or more of a phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, a brominated polycarbonate, a perbromotricyclopentadecane or a brominated aromatic crosslinked polymer, preferably a bromine Polystyrene
  • the halogen-free flame retardant is selected from one or more of a nitrogen-containing flame retardant, a phosphorus-containing flame retardant or a nitrogen and phosphorus-containing flame retardant; preferably a phosphorus-containing flame retardant.
  • the phosphorus-containing flame retardant is selected from the group consisting of aryl phosphate monophosphate, aryl phosphate bisphosphate, dimethyl alkylphosphonate, triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, and C.
  • aryl phosphate monophosphate aryl phosphate bisphosphate
  • dimethyl alkylphosphonate triphenyl phosphate
  • tricresyl phosphate tris(xylylene) phosphate
  • C C.
  • the phosphinate compound is represented by a compound represented by, for example, the following formula I and/or II.
  • R 1 and R 2 may be the same or different and each represents a linear or branched C1-C6-alkyl group, an aryl group or a phenyl group.
  • R 3 represents a linear or branched C1-C10-alkylene group, a C6-C10-arylene group, a C6-C10-alkylarylene group, or a C6-C10-arylalkylene group.
  • M represents a calcium atom, a magnesium atom, an aluminum atom and/or a zinc atom.
  • M is 2 or 3
  • n is 1 or 3
  • x is 1 or 2.
  • phosphinate compound examples include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate , magnesium ethyl methylphosphinate, aluminum ethyl methylphosphinate, zinc ethyl methylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, diethylphosphinic acid
  • a phosphinate compound as a flame retardant can be easily obtained from the market.
  • Examples of commercially available phosphinate compounds include EXOLIT OP1230, OP1311, OP1312, OP930, OP935, and the like, manufactured by Clariant.
  • the polyamide molding composition of the present invention comprising the above semi-aromatic copolyamide resin, the additive component may further comprise up to 45 wt% of one or more impact modifiers based on the total weight of the polyamide molding composition.
  • the agent is preferably from 5% by weight to 30% by weight.
  • the impact modifier may be natural rubber, polybutadiene, polyisoprene, polyisobutylene, butadiene and/or isoprene and styrene or with styrene derivatives and copolymerization with others a copolymer of a monomer, a hydrogenated copolymer, and/or a copolymer obtained by grafting or copolymerizing with an anhydride, (meth)acrylic acid or an ester thereof; the impact modifier may also have a crosslinked elastomer a graft rubber of a core composed of butadiene, isoprene or alkyl acrylate, and having a graft shell composed of polystyrene or may be a non-polar or polar olefin a polymer or copolymer, such as ethylene propylene rubber, ethylene-propylene-diene rubber, or ethylene-octene rubber, or ethylene-vinyl acetate
  • the agent is a block copolymer composed of an alkenyl aromatic compound and a conjugated diene, and a hydrogenated block copolymer composed of an alkenyl aromatic compound and a conjugated diene, and these types of impact modification Combination of agents.
  • the block copolymer comprises at least one block a derived from an alkenyl aromatic compound and at least one block b derived from a conjugated diene.
  • hydrogenated block copolymers the proportion of aliphatically unsaturated carbon-carbon double bonds is reduced by hydrogenation.
  • Suitable block copolymers are di-, tri-, tetra- and multi-block copolymers having a linear structure. However, branched and star structures can also be used in accordance with the present invention. Branched block copolymers are obtained in a known manner, for example by grafting of the polymer "side branches" to the polymer backbone.
  • alkenyl aromatic monomers examples include styrene, p-methyl styrene, alpha-methyl styrene, ethyl styrene, t-butyl styrene, vinyl toluene, 1,2-diphenylethylene, 1,1-diphenylethylene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, and chlorostyrene, and combinations thereof. Preference is given to styrene, p-methylstyrene, ⁇ -methylstyrene, and vinylnaphthalene.
  • styrene Preference is given to using styrene, ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinyltoluene, 1,2-diphenylethylene and 1,1-diphenylethylene. Or a mixture of these substances. It is particularly preferred to use styrene. However, alkenylnaphthalene can also be used.
  • diolefin monomers which may be used are 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3 - pentadiene, 1,3-hexadiene, isoprene, chloroprene and piperylene.
  • 1,3-butadiene and isoprene in particular 1,3-butadiene (hereinafter referred to as butadiene in the abbreviated form).
  • the alkenyl aromatic monomer used preferably comprises styrene
  • the diene monomer used preferably comprises butadiene, which means that a styrene-butadiene block copolymer is preferred.
  • the block copolymers are generally prepared by anionic polymerization in a manner known per se.
  • the proportion of the comonomer is preferably from 0 to 50% by weight, particularly preferably from 0 to 30% by weight, particularly preferably from 0 to 15% by weight, based on the total amount of the monomers used.
  • suitable comonomers are respectively acrylates, especially C1 to C12 alkyl acrylates, such as n-butyl acrylate or 2-ethylhexyl acrylate, and methacrylates, especially methacrylic acid C1 to C12.
  • Alkyl esters such as methyl methacrylate (MMA).
  • Other possible comonomers are (meth)acrylonitrile, glycidyl (meth)acrylate, vinyl methyl ether, glycols. Diallyl and divinyl ether, divinylbenzene and vinyl acetate.
  • the hydrogenated block copolymer further comprises, if appropriate, a lower hydrocarbon moiety such as ethylene, propylene, 1-butene, dicyclopentadiene or a non-conjugated diene.
  • a lower hydrocarbon moiety such as ethylene, propylene, 1-butene, dicyclopentadiene or a non-conjugated diene.
  • the proportion of unreduced aliphatic unsaturated bonds derived from block b in the hydrogenated block copolymer is less than 50%, preferably less than 25%, especially less than 10%.
  • the aromatic moiety derived from block a is reduced to an extent of up to 25%.
  • the block copolymer preferably comprises from 20% by weight to 90% by weight of block a, in particular from 50% by weight to 85% by weight, of block a.
  • the diolefin can be introduced into the block b in a 1,2-orientation or a 1,4-position.
  • the block copolymer has a molar mass of from 5000 g/mol to 500,000 g/mol, preferably from 20,000 g/mol to 300,000 g/mol, in particular from 40,000 g/mol to 200,000 g/mol.
  • Suitable hydrogenated block copolymers are commercially available products such as (Kraton polymers) G1650, G1651 and G1652, and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141 and H1272.
  • non-hydrogenated block copolymers are polystyrene-polybutadiene, polystyrene-poly(ethylene-propylene), polystyrene-polyisoprene, poly(?-methylstyrene)-poly Butadiene, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly(ethylene-propylene)-polystyrene, polystyrene-polyisoprene-polystyrene, and Poly( ⁇ -methylstyrene) polybutadiene-poly( ⁇ -methylstyrene), and combinations thereof.
  • Suitable non-hydrogenated block copolymers which are commercially available are available under the trade names (Phillips), (Shell), (Dexco) and (Kuraray).
  • the polyamide molding composition of the present invention comprising the above semi-aromatic copolyamide resin, the additive component may further comprise other polymers selected from the group consisting of aliphatic polyamides, polyolefin homopolymers, and ethylene. - ⁇ -olefin copolymer, ethylene-acrylate copolymer.
  • the aliphatic polyamides include, but are not limited to, aliphatic diacids and aliphatic diamines derived from 4 to 20 carbon atoms, or lactams of 4 to 20 carbon atoms, or aliphatic groups of 4 to 20 carbon atoms.
  • aliphatic diacids and aliphatic diamines derived from 4 to 20 carbon atoms, or lactams of 4 to 20 carbon atoms, or aliphatic groups of 4 to 20 carbon atoms.
  • lactams One or more of a polymer of a diacid, an aliphatic diamine, and a lactam.
  • PA66 polyhexamethylene adipamide
  • PA6 polycaprolactam
  • PA610 polysebacyldiamine
  • PA1010 polysebacic acid diamine
  • PA66/6 adipic acid-hexane Amine-caprolactam copolymer
  • PA11 polyundecanolactam
  • PA12 polydodelactam
  • the ethylene- ⁇ -olefin copolymer is preferably an EP elastomer and/or an EPDM elastomer (ethylene-propylene rubber and ethylene-propylene-diene rubber, respectively).
  • the elastomer may include an elastomer based on an ethylene-C3-C12- ⁇ -olefin copolymer containing 20% by weight to 96% by weight, preferably 25% by weight to 85% by weight of ethylene, wherein C3-C12- ⁇ - is particularly preferred herein.
  • the olefin includes an olefin selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and/or 1-dodecene, and particularly preferably other polymers including ethylene-propylene.
  • the further polymer may further comprise a terpolymer based on an ethylene-C3-C12- ⁇ -olefin and a non-conjugated diene, preferably containing 25 wt% to 85 wt% of ethylene and up to 10 wt% of a non-conjugated diene, and particularly preferably, the C3-C12- ⁇ -olefin includes a olefin, 1-butene, 1-pentene, 1-hexene An olefin of 1-octene, 1-decene and/or 1-dodecene, and/or wherein the non-conjugated diene is preferably selected from the group consisting of bicyclo [2.2.1] heptadiene, 1,4-hexyl Diene, dicyclopentadiene and/or especially 5-ethylidene norbornene.
  • Ethylene-acrylate copolymers can also be used as components of the other polymers.
  • the other polymer comprises a component having an anhydride group by thermal reaction of the backbone polymer with an unsaturated dianhydride, with an unsaturated dicarboxylic acid, or with a monoalkyl ester of an unsaturated dicarboxylic acid.
  • a free radical reaction introduced at a concentration sufficient to bind well to the polyamide, and it is preferred here to use an agent selected from the group consisting of:
  • maleic acid, maleic anhydride, monobutyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride Preferably, 0.1% by weight to 4.0% by weight of the unsaturated acid anhydride is grafted onto the impact-resistant component as a component of C, or the unsaturated dianhydride or its precursor is applied by grafting together with other unsaturated monomers. It is generally preferred that the degree of grafting is from 0.1% to 1.0%, particularly preferably from 0.3% to 0.7%.
  • Another possible component of other polymers is a mixture of an ethylene-propylene copolymer and an ethylene-butene copolymer, where the degree of grafting of the maleic anhydride (MA grafting degree) is from 0.3% to 0.7%.
  • the additive component may comprise a component having a functional group such as a carboxylic acid group, an ester group, an epoxy group, an oxazoline group, a carbodiimide group, an isocyanate group.
  • the silanol group, and the carboxylate group, or the additive component may comprise a combination of two or more of the above functional groups.
  • the monomer having the functional group can be copolymerized or grafted onto the elastomeric polyolefin to form a knot Hehe.
  • the impact modifier based on an olefin polymer can also be modified by grafting with an unsaturated silane compound such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triacetylsilane, methacryloxypropyltrimethoxysilane, or propylenetrimethoxysilane.
  • an unsaturated silane compound such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triacetylsilane, methacryloxypropyltrimethoxysilane, or propylenetrimethoxysilane.
  • An elastomeric polyolefin is a random, alternating or block copolymer having a linear, branched or core-shell structure and contains functional groups which are reactive with the terminal groups of the polyamide, thereby being used in polyamides and impact modifiers. Provide sufficient compatibility between the two.
  • the impact modifiers of the present invention include homopolymers or copolymers of olefins (e.g., ethylene, propylene, 1-butene) (e.g., polybutene-1), or olefins and copolymerizable monomers (e.g., vinyl acetate). a copolymer of (meth) acrylate, and methyl hexadiene).
  • olefins e.g., ethylene, propylene, 1-butene
  • olefins and copolymerizable monomers e.g., vinyl acetate
  • a copolymer of (meth) acrylate, and methyl hexadiene e.g., vinyl acetate
  • Examples of crystalline olefin polymers are low density, medium density and high density polyethylene, polypropylene, polybutadiene, poly-4-methylpentene, ethylene-propylene block copolymer, or ethylene-propylene random Copolymer, ethylene-methylhexadiene copolymer, propylene-methylhexadiene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-hexene copolymer, ethylene-propylene-methylhexadiene Copolymer, poly(ethylene-vinyl acetate) (EVA), poly(ethylene-ethyl acrylate) (EEA), ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene- A propylene-diene terpolymer, and a combination of the above polymers.
  • EVA ethylene-vinyl acetate
  • EAA
  • TAFMER MC201 Blend of g-MA (-0.6%) 67% EP copolymer (20 mol% propylene) + 33% EB copolymer (15 mol% 1-butene)): Mitsui Chemicals, Japan.
  • TAFMER MH5010 g-MA (-0.6%) ethylene-butene copolymer; Mitsui.
  • TAFMER MH7010 g-MA (-0.7%) ethylene-butene copolymer; Mitsui.
  • TAFMER MH7020 g-MA (-0.7%) EP copolymer; Mitsui.
  • EXXELOR VA1801 g-MA (-0.7%) EP copolymer; Exxon Mobile Chemicals, US.
  • EXXELOR VA1803 g-MA (0.5-0.9%) EP copolymer, amorphous, Exxon.
  • EXXELOR VA1810 g-MA (-0.5%) EP copolymer, Exxon.
  • EXXELOR MDEX 941l g-MA (0.7%) EPDM, Exxon.
  • FUSABOND MN493D g-MA (-0.5%) ethylene-octene copolymer, DuPont, US.
  • FUSABOND A EB560D (g-MA) ethylene-n-butyl acrylate copolymer, DuPont ELVALOY, DuPont.
  • copolymers of maleic anhydride graft functionalized butadiene and styrene non-polar or polar olefin homopolymers and copolymers prepared by grafting with maleic anhydride, and carboxylic acid functionalized a copolymer, such as poly(ethylene-co-(meth)acrylic acid) or poly(ethylene-co-1-olefin-co-(meth)acrylic acid), wherein the acid group has been to some extent by metal ions with.
  • processing aids such as an antioxidant and/or a heat-resistant stabilizer (hindered phenol type, hydroquinone type, etc.) may be added to the polyamide resin of the present invention at any time within the range not impairing the effects of the present invention.
  • Phosphite esters and their substituents copper halides, iodine compounds, etc., and weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.) , mold release agents and lubricants (aliphatic alcohols, aliphatic amides, aliphatic bisamides, diureas and polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, Aniline black, etc.), plasticizer (octyl p-hydroxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent) , non-ionic antistatic agents such as polyoxyethylene sorbitan monostearate, betained amphoteric antistatic agents, etc.).
  • the polyamide resin or the polyamide resin composition of the present invention may be molded by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, or film molding.
  • These molded articles can be molded into a desired shape, and can be used in resin molded articles such as automobile parts and machine parts.
  • radiator parts for automobile engines especially radiator tank components such as the top and bottom of radiator tanks, coolant reserve tanks, water pipes, water pump casings, pump impellers, valves, etc.
  • Components used in contact with cooling water in the engine room of a car such as switches, subminiature slide switches, DIP switches, housings for switches, lamp holders, straps, connectors, connector housings, connector housings , IC sockets, bobbins, spool covers, relays, relay boxes, capacitor housings, internal parts of motors, small motor housings, gear cams, equalizing wheels, gaskets, insulators, fasteners, buckles, clamps, Bicycle wheels, casters, helmets, terminal blocks, housings for power tools, insulation for starters, spoilers, tanks, radiator tanks, chamber tanks, liquid storage tanks, fuse boxes, air purifiers Housing, air conditioning fan, terminal housing, wheel cover, suction and exhaust pipe, bearing support, cylinder head cover, intake manifold, water pipe impeller Clutch release lever, speaker diaphragm, heat resistant container, microwave oven parts, rice cooker component, a printer ribbon guide, represented by electrical / electronic related parts, automobile / vehicle related parts, home / Office electrical components,
  • the polyamide molding composition of the invention has a water absorption rate of ⁇ 1.0%, and the heat distortion temperature is 280°C-320°C according to the national standard GB/T 1634.2-2004; b value ⁇ 3.0; wherein the water absorption rate is tested by: The sample was injection molded into a 20 mm ⁇ 20 mm ⁇ 2 mm piece, the weight of which was recorded as a0, and then placed in 95 ° C water for 240 h, the weight was weighed as a1, and the water absorption rate was (a1-a0)/a0*100.
  • the test method of the b value is: using a color plate mold 50*30*2mm, taking 3000g sample particles for injection molding, and obtaining a smooth swatch, the color plate is placed on the Lippo Color-Eye7000A computer color measurement The b value is obtained on the instrument.
  • the invention has the following beneficial effects:
  • the present invention prepares a semi-aromatic copolyamide by replacing the terephthalic acid with a p-aminobenzoic acid monomer and by controlling the molar content of the p-aminobenzoic acid unit and the 11-aminoundecanoic acid or 11-lactam unit.
  • the resin has both high heat resistance, improved color performance, excellent fluidity, and low water absorption.
  • the polyamide molding composition composed of the semi-aromatic copolyamide resin has heat resistance, water absorption, color, and the like. Performance also has significant advantages.
  • the raw materials used in the present invention are all derived from commercially available products.
  • Test method for melting point of semi-aromatic copolyamide resin refer to ASTM D3418-2003; specific test method is: test the melting point of the sample using a Perkin Elmer Dimond DSC analyzer; nitrogen atmosphere, flow rate is 40 mL / min; test at 10 ° C first /min was heated to 340 ° C, held at 340 ° C for 2 min, then cooled to 50 ° C at 10 ° C / min, and then heated to 340 ° C at 10 ° C / min, the endothermic peak temperature at this time as the melting point T m ;
  • Test method for intrinsic viscosity of semi-aromatic copolyamide resin Refer to GB12006.1-89, method for determining the viscosity of polyamide; the specific test method is: measuring the intrinsic viscosity of polyamide in 98% concentrated sulfuric acid at 25 °C ⁇ 0.01 °C ;
  • Test method for color (b value) of semi-aromatic copolyamide resin (molding composition) Using a color plate mold 50*30*2 mm, 3000 g of sample particles were injection-molded to obtain a smooth swatch. The swatch was placed on a Lippo Color-Eye 7000A computer colorimeter to obtain a b value. This value reflects the color of the semi-aromatic copolyamide resin (molding composition) article, and the higher the value, the worse the color of the article.
  • the reaction raw materials were added in the proportions shown in Table 1 in an autoclave equipped with a magnetic coupling stirring, a condenser, a gas phase port, a feed port, and a pressure explosion port. Additional benzoic acid, sodium hypophosphite and deionized water were added. The amount of benzoic acid material was 2.5% of the molar amount of all monomers, the weight of sodium hypophosphite was 0.1% by weight of the other charge except ionized water, and the weight of deionized water was 30% of the total charge weight. The mixture was purged with high-purity nitrogen gas as a shielding gas, and the temperature was raised to 220 ° C over 2 hours with stirring.
  • the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2.2 MPa for 2 hours, and the pressure was kept constant by removing the formed water.
  • the prepolymer is dried under vacuum at 80 ° C for 24 hours to obtain a prepolymerized product which is solid-phase viscosified under a vacuum of 30-60 ° C and 50 Pa below the melting point to obtain a semi-aromatic Copolyamide resin.
  • the performance indexes such as intrinsic viscosity, melting point, water absorption, and color of the obtained semi-aromatic copolyamide resin are shown in Table 1.
  • the prepared semi-aromatic copolyamide resin has the advantages of high heat resistance, improved color performance, excellent fluidity, and low water absorption.
  • the content of p-aminobenzoic acid in the resin A' is too low, the melting point of the resin is low, and the heat resistance is poor; the content of p-aminobenzoic acid in the resin B' is too high, resulting in the melting point of the resin being higher than the decomposition temperature, and has no application value; C' and D' do not use 11-aminoundecanoic acid as a comonomer, resulting in poor color of the resin.
  • the semi-aromatic copolyamide resin, reinforcing filler, flame retardant, other additives, etc. are uniformly mixed in a high-mixer, and then added to the twin-screw extruder through the main feed port to enhance the filler passage side. Feed the side of the weighing scale.
  • the polyamide composition is obtained by extrusion, cooling with water, granulation and drying. The extrusion temperature was set to 20 ° C above the melting point, and the results of each performance are shown in Table 2.
  • the polyamide molding composition comprising the semi-aromatic copolyamide resin of the present invention has a significant advantage in heat resistance, water absorption and color under the same molding composition formulation.

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Abstract

本发明公开了一种半芳香族共聚酰胺树脂和由其组成的聚酰胺模塑组合物，由如下重复单元组成： (A)26-80mol％的衍生自对氨基苯甲酸的单元； (B)4-70mol％的衍生自11-氨基十一酸或11-内酰胺的单元，和0-70mol％的衍生自其它具有6-36个碳原子的氨基酸或内酰胺组成的单元； (C)0-37mol％的衍生自具有4-36个碳原子的二胺单元； (D)0-37mol％的衍生自具有6-36个碳原子的二酸单元；其中，(A)+(B)+(C)+(D)＝100mol％；且衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不同时等于50mol％。本发明半芳香族共聚酰胺树脂兼具高耐热性、改善的颜色性能、优异的流动性和低吸水率等性能优势，由其组成的模塑组合物在耐热性、吸水率和颜色等性能也具有明显优势。

Description

一种半芳香族共聚酰胺树脂和由其组成的聚酰胺模塑组合物 技术领域
本发明涉及工程塑料技术领域，特别涉及一种半芳香族共聚酰胺树脂和由其组成的聚酰胺模塑组合物。
背景技术
聚酰胺树脂因具有良好的综合性能，包括力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性，且摩擦系数低，有一定的阻燃性等，其被广泛适于用玻璃纤维和其它填料填充增强改性，提高性能和扩大应用范围等方面。近几年来半芳香族聚酰胺由于其耐热性能和力学性能更优而被重点开发。
PA66通常吸水率较高，导致其长时间使用的尺寸稳定性较差、力学性能下降较为严重。并且，PA66熔点较低，难以使用在对耐热性由较高要求的电子电气和SMT工艺等场合。
对于PA66的上述问题，业内一般的解决方案是采用对苯二甲酸取代己二酸，得到半芳香族聚酰胺。苯环的引入提高了分子链的刚性，提高了其结晶性能，吸水率下降，熔点提高。上述半芳香族聚酰胺的实例如PA6T/66、PA9T和PA10T等，都已经在工业界得到了广泛应用。
目前，一般认为半芳香族聚酰胺的“芳香”单元多来源于对苯二甲酸，对于“芳香”单元的其它来源较少涉及。
三菱公司开发出了著名的MXD6产品，是基于间苯二甲胺和己二酸的产物。MXD6实际上也可以称为半芳香族聚酰胺，不过其熔点较低，只有240℃，一般传统意义上并不认为其是半芳香族聚酰胺。
CN102159620公开了一种基于间苯二甲胺的半芳香族聚酰胺，如PXD10熔点高达290℃，具有高耐热性和低吸水率，是“非对苯二甲酸”领域半芳香族聚酰胺的一个突破。
US2688011提出了一种合成基于对氨基苯甲酸(para-amino benzoic acid，PABA)的聚酰胺的方法，将对氨基苯甲酸同含有最多14个偶数个亚甲基的脂肪族二胺和含有最多14个偶数个亚甲基的脂肪族二酸共聚合，其中上述二胺和二酸是等摩尔的，对氨基苯甲酸占所有单体单元的含量为5-25mol％。然而，由于对氨基苯甲酸含量较低，所得半芳香族聚酰胺的熔点较低。如，其实施例得到了 一种PABA和66盐的共聚物，PABA的在所有单体单元中的含量为9.6mol％。该共聚物熔点仅为248-250℃，难以达到耐高温聚酰胺的要求。
CN103122063提出了一种基于氨基十一酸(amino undecanediacid，AUA)和PABA的半芳香族聚酰胺树脂的制备方法，将氨基十一酸、对氨基苯甲酸、蒸馏水和催化剂混合成盐后，进行熔融聚合反应，得到AUA和PABA的共聚物，该共聚物熔点在310℃左右。其要求AUA和PABA必须具有相等的摩尔比，否则会“破坏尼龙的缩聚反应，无法进行聚合”。
鉴于此，本领域亟需一种具有高耐热性、改善颜色性能、低吸水率的基于或主要基于“非对苯二甲酸”单体的半芳香族共聚酰胺树脂及由其组成的聚酰胺模塑组合物。
发明内容
为了克服现有技术存在的缺点与不足，本发明的首要目的在于提供一种兼具高耐热性、改善颜色性能、优异的流动性和低吸水率的基于或主要基于“非对苯二甲酸”单体的半芳香族共聚酰胺树脂。
本发明的另一目的是提供包含上述半芳香族共聚酰胺树脂的聚酰胺模塑组合物。
本发明是通过以下技术方案实现的：
一种半芳香族共聚酰胺树脂，按摩尔百分比计，由如下重复单元组成：
(A)基于全部单体单元的量，26-80mol％的衍生自对氨基苯甲酸的单元；
(B)基于全部单体单元的量：4-70mol％的衍生自11-氨基十一酸或11-内酰胺的单元，和0-70mol％的衍生自其它具有6-36个碳原子的氨基酸或内酰胺组成的单元；
(C)基于全部单体单元的量，0-37mol％的衍生自具有4-36个碳原子的二胺单元；
(D)基于全部单体单元的量，0-37mol％的衍生自具有6-36个碳原子的二酸单元；
其中，(A)+(B)+(C)+(D)＝100mol％；且衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不同时等于50mol％。
作为本发明进一步优选的实施方案，所述的半芳香族共聚酰胺树脂，按摩尔百分比计，由如下重复单元组成：
(A)基于全部单体单元的量，26-80mol％的衍生自对氨基苯甲酸的单元；
(B)基于全部单体单元的量：4-70mol％的衍生自11-氨基十一酸或11-内酰胺的单元，和4-70mol％的衍生自其它具有6-36个碳原子的氨基酸或内酰胺组成的单元；
其中，(A)+(B)＝100mol％；且衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不同时等于50mol％。
作为本发明进一步优选的实施方案，所述的半芳香族共聚酰胺树脂，按摩尔百分比计，由如下重复单元组成：
(A)基于全部单体单元的量，40-60mol％的衍生自对氨基苯甲酸的单元；
(B)基于全部单体单元的量：10-40mol％的衍生自11-氨基十一酸或11-内酰胺的单元，和10-40mol％的衍生自其它具有6-36个碳原子的氨基酸或内酰胺组成的单元；
(C)基于全部单体单元的量，5-25mol％的衍生自具有4-36个碳原子的二胺单元；
(D)基于全部单体单元的量，5-25mol％的衍生自具有6-36个碳原子的二酸单元；
其中，(A)+(B)+(C)+(D)＝100mol％；且衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不同时等于50mol％。
作为本发明进一步优选的实施方案，上述的半芳香族共聚酰胺树脂中，所述衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不相等。
本发明所述半芳香族共聚酰胺树脂的熔点参照ASTM D3418-2003为270-360℃；特性粘度参照GB12006.1-89为0.80-1.0dl/g；吸水率≤2.0％；b值≤1.0；其中吸水率的测试方法为：将样品注塑成20mm×20mm×2mm的制件，其重量记为a0，然后将其置于95℃水中240h后，称量其重量记为a1，吸水率＝(a1-a0)/a0*100％；所述b值的测试方法为：使用色板模具50*30*2mm，取3000g样品粒子进行注塑后，得到一面光滑的色板，将该色板置于理宝Color-Eye7000A电脑测色仪上得到b值。
其中，所述具有4-36个碳原子的其它二胺选自直链或支链脂族二胺、环脂族二胺、芳脂族二胺中的一种或几种；所述直链或支链脂族二胺选自1，4-丁二 胺、1，5-戊二胺、2-甲基-1，5-戊二胺(MPMD)、1，8-辛二胺(OMDA)、1，9-壬二胺(NMDA)、2-甲基-1，8-辛二胺(MODA)、2，2，4-三甲基六亚甲基二胺(TMHMD)、2，4，4-三甲基六亚甲基二胺(TMHMD)、5-甲基-1，9-壬二胺、1，11-十一烷二胺、2-丁基-2-乙基-1，5-戊二胺、1，12-十二烷二胺、1，13-十三烷二胺、1，14-十四烷二胺、1，16-十六烷二胺、1，18-十八烷二胺中的一种或几种；所述环脂族二胺选自环己二胺、1，3-双(氨基甲基)环己烷(BAC)、异佛尔酮二胺、降莰烷二甲胺、4，4’-二氨基二环己基甲烷(PACM)、2，2-(4，4’-二氨基二环己基)丙烷(PACP)、3，3’-二甲基-4，4’-二氨基二环己基甲烷(MACM)中的一种或几种；所述芳脂族二胺选自间苯二甲胺(MXDA)。
其中，所述具有6-36个碳原子的其它二酸选自萘二羧酸(NDA)、间苯二酸(IPS)、己二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十八烷二酸、二聚体酸、顺式和/或反式环己烷-1，4-二羧酸、顺式和/或反式环己烷-1，3-二羧酸(CHDA)中的一种或几种。
本发明还公开了一种包含上述半芳香族共聚酰胺树脂的聚酰胺模塑组合物，按重量份数计，包括如下组分：
半芳香族共聚酰胺树脂                        30-100份；
增强填料                                    0-70份；
添加剂                                      0-50份；
基于聚酰胺模塑组合物总重量，所述增强填料的含量优选为10-50份，更优选为15-40份；
增强填料含量过低，导致聚酰胺模塑组合物力学性能较差；增强填料含量过高，聚酰胺模塑组合物制品表面浮纤严重，影响产品外观。
所述增强填料的形状为纤维状，其平均长度为0.01mm-20mm，优选为0.1mm-6mm；其长径比为5:1-2000:1，优选为30:1-600:1，当纤维状的增强填料含量在上述范围内时，聚酰胺模塑组合物就会表现出高热变形温度和增高的高温刚性。
所述增强填料为无机增强填料或有机增强填料；
所述无机增强填料选自玻璃纤维、钛酸钾纤维、金属包层的玻璃纤维、陶瓷纤维、硅灰石纤维、金属碳化物纤维、金属固化纤维、石棉纤维、氧化铝纤维、 碳化硅纤维、石膏纤维或硼纤维的一种或几种，优选为玻璃纤维；
使用玻璃纤维不仅可提高聚酰胺模塑组合物的可模塑性，而且可提高力学性能例如拉伸强度、弯曲强度和弯曲模量，及提高耐热性例如热塑性树脂组合物进行模塑时的热变形温度。
所述有机增强填料选自芳族聚酰胺纤维和/或碳纤维。
所述增强填料的形状为非纤维状，例如粉末状、颗粒状、板状、针状、织物或毡状，其平均粒径为0.001μm-100μm，优选为0.01μm-50μm。
当增强填料的平均粒径小于0.001μm将导致聚酰胺树脂差的熔融加工性；当增强填料的平均粒径大于100μm，将导致不良的注塑成型品表面外观。
上述增强填料的平均粒径通过吸附法来测定，其可选自钛酸钾晶须、氧化锌晶须、硼酸铝晶须、硅灰石、沸石、绢云母、高岭土、云母、滑石、粘土、叶腊石、膨润土、蒙脱土、锂蒙脱土、合成云母、石棉、硅铝酸盐、氧化铝、氧化硅、氧化镁、氧化锆、氧化钛、氧化铁、碳酸钙、碳酸镁、白云石、硫酸钙、硫酸钡、氢氧化镁、氢氧化钙、氢氧化铝、玻璃珠、陶瓷珠、氮化硼、碳化硅或二氧化硅的一种或几种。
这些增强填料可以是中空的；此外，对于膨润土、蒙脱土、锂蒙脱土、合成云母等溶胀性层状硅酸盐，可以使用采用有机铵盐将层间离子进行阳离子交换后的有机化蒙脱土。
为了使聚酰胺模塑组合物获得更为优良的机械性能，可采用偶联剂对无机增强填料进行功能性处理。
其中偶联剂选自异氰酸酯系化合物、有机硅烷系化合物、有机钛酸酯系化合物、有机硼烷系化合物、环氧化合物；优选为有机硅烷系化合物；
其中，所述有机硅烷系化合物选自含有环氧基的烷氧基硅烷化合物、含有巯基的烷氧基硅烷化合物、含有脲基的烷氧基硅烷化合物、含有异氰酸酯基的烷氧基硅烷化合物、含有端胺基的烷氧基硅烷化合物、含有羟基的烷氧基硅烷化合物、含有碳-碳不饱和基的烷氧基硅烷化合物、含有酸酐基的烷氧基硅烷化合物的一种或几种。
所述含有环氧基的烷氧基硅烷化合物选自γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基三乙氧基硅烷、β-(3，4-环氧环己基)乙基三甲氧基硅烷的一种或几种；
所述含有巯基的烷氧基硅烷化合物选自γ-巯基丙基三甲氧基硅烷和/或γ-巯基丙基三乙氧基硅烷；
所述含有脲基的烷氧基硅烷化合物选自γ-脲基丙基三乙氧基硅烷、γ-脲基丙基三甲氧基硅烷、γ-(2-脲基乙基)端胺基丙基三甲氧基硅烷的一种或几种；
所述含有异氰酸酯基的烷氧基硅烷化合物选自γ-异氰酸酯基丙基三乙氧基硅烷、γ-异氰酸酯基丙基三甲氧基硅烷、γ-异氰酸酯基丙基甲基二甲氧基硅烷、γ-异氰酸酯基丙基甲基二乙氧基硅烷、γ-异氰酸酯基丙基乙基二甲氧基硅烷、γ-异氰酸酯基丙基乙基二乙氧基硅烷、γ-异氰酸酯基丙基三氯硅烷的一种或几种；
所述含有端胺基的烷氧基硅烷化合物选自γ-(2-端胺基乙基)端胺基丙基甲基二甲氧基硅烷、γ-(2-端胺基乙基)端胺基丙基三甲氧基硅烷、γ-端胺基丙基三甲氧基硅烷的一种或几种；
所述含有羟基的烷氧基硅烷化合物选自γ-羟基丙基三甲氧基硅烷和/或γ-羟基丙基三乙氧基硅烷；
所述含有碳-碳不饱和基的烷氧基硅烷化合物选自γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、N-β-(N-乙烯基苄基端胺基乙基)-γ-端胺基丙基三甲氧基硅烷·盐酸盐的一种或几种；
所述含有酸酐基的烷氧基硅烷化合物选自3-三甲氧基甲硅烷基丙基琥珀酸酐；
所述有机硅烷系化合物优选为γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-(2-端胺基乙基)端胺基丙基甲基二甲氧基硅烷、γ-(2-端胺基乙基)端胺基丙基三甲氧基硅烷、γ-端胺基丙基三甲氧基硅烷或3-三甲氧基甲硅烷基丙基琥珀酸酐。
可以按照常规的方法采用上述有机硅烷系化合物对无机增强填料进行表面处理，然后再将其与聚酰胺树脂进行熔融混炼，以制备所述聚酰胺模塑组合物。
也可以直接在无机增强填料与聚酰胺树脂熔融混炼的同时，加入有机硅烷系化合物进行原位共混。
其中，所述偶联剂的用量为相对于无机增强填料重量的0.05wt％-10wt％，优选为0.1wt％-5wt％。
当偶联剂的用量小于0.05wt％时，其达不到明显的改良机械性能的效果；当偶联剂的用量大于10wt％时，无机增强填料容易发生凝聚，并且在聚酰胺树脂中 分散不良的风险，最终导致机械性能发生下降。
所述添加剂选自阻燃剂、冲击改性剂、其它聚合物、加工助剂的一种或几种；
所述其它聚合物为脂肪族聚酰胺、聚烯烃均聚物、乙烯-α-烯烃共聚物、乙烯-丙烯酸酯共聚物的一种或几种；
所述加工助剂选自抗氧化剂、耐热稳定剂、耐候剂、脱模剂、润滑剂、颜料、染料、增塑剂、抗静电剂的一种或几种。
所述阻燃剂为阻燃剂或阻燃剂与阻燃协助剂的组合物，基于聚酰胺模塑组合物总重量，其含量优选为0-40份；阻燃剂含量过低导致阻燃效果变差，阻燃剂含量过高导致材料力学性能下降。
所述阻燃剂为卤系阻燃剂或无卤阻燃剂；
所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合物的一种或几种，优选为优选溴化聚苯乙烯；
所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂或含氮和磷的阻燃剂的一种或几种；优选为含磷阻燃剂。
所述含磷阻燃剂选自单磷酸芳基磷酸酯、双磷酸芳基磷酸酯、烷基膦酸二甲酯、磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、丙苯系磷酸酯、丁苯系磷酸酯或次膦酸盐的一种或几种；优选为次膦酸盐；
次膦酸盐化合物以例如下式I和/或II表示的化合物为代表。
Figure PCTCN2017078640-appb-000001
在式I及式II中，R1及R2可以相同，也可以不同，分别表示直链状或分支状的C1-C6-烷基、芳基或苯基。R3表示直链状或分支状的C1-C10-亚烷基、C6-C10-亚芳基、C6-C10-烷基亚芳基、C6-C10-芳基亚烷基。M表示钙原子、镁原子、铝原子和/或锌原子。M是2或3，n是1或3，x是1或2。
次膦酸盐化合物的更具体例子包括二甲基次膦酸钙、二甲基次膦酸镁、二甲基次膦酸铝、二甲基次膦酸锌、乙基甲基次膦酸钙、乙基甲基次膦酸镁、乙基甲基次膦酸铝、乙基甲基次膦酸锌、二乙基次膦酸钙、二乙基次膦酸镁、二乙基次膦酸铝、二乙基次膦酸锌、甲基正丙基次膦酸钙、甲基正丙基次膦酸镁、甲基正丙基次膦酸铝、甲基正丙基次膦酸锌、甲烧二(甲基次膦酸)钙、甲烷二(甲基次膦酸)镁、甲烷二(甲基次膦酸)铝、甲烷二(甲基次膦酸)锌、苯-1，4-(二甲基次膦酸)钙、苯-1，4-(二甲基次膦酸)镁、苯-1，4-(二甲基次膦酸)铝、苯-1，4-(二甲基次膦酸)锌、甲基苯基次膦酸钙、甲基苯基次膦酸镁、甲基苯基次膦酸铝、甲基苯基次膦酸锌、二苯基次膦酸钙、二苯基次膦酸镁、二苯基次膦酸铝、二苯基次膦酸锌等，优选二甲基次膦酸钙、二甲基次膦酸铝、二甲基次膦酸锌、乙基甲基次膦酸I丐、乙基甲基次膦酸铝、乙基甲基次膦酸锌、二乙基次膦酸钙、二乙基次膦酸铝、二乙基次膦酸锌，更优选二乙基次膦酸铝。
作为阻燃剂的次膦酸盐化合物可容易地从市场获得。可从市场获得的次膦酸盐化合物的例子包括科莱恩公司(Clariant)制造的EXOLIT OP1230、OP1311、OP1312、OP930、OP935等。
本发明的包含上述半芳香族共聚酰胺树脂的聚酰胺模塑组合物，基于聚酰胺模塑组合物的总重量，所述添加剂组分还可以包含至多45wt％的一种或更多种冲击改性剂，优选为5wt％-30wt％。
其中，所述冲击改性剂可以是天然橡胶、聚丁二烯、聚异戊二烯、聚异丁烯、丁二烯和/或异戊二烯与苯乙烯或与苯乙烯衍生物和与其它共聚单体的共聚物、氢化共聚物、和/或通过接枝或与酐、(甲基)丙烯酸或其酯共聚而制得的共聚物；所述冲击改性剂还可以是具有交联弹性体芯的接枝橡胶，所述交联弹性体芯由丁二烯、异戊二烯或烷基丙烯酸酯构成，并且具有由聚苯乙烯构成的接枝壳或者可以是非极性或极性烯烃均聚物或共聚物，例如乙丙橡胶，乙烯-丙烯-二烯烃橡胶，或乙烯-辛烯橡胶，或乙烯-乙酸乙烯酯橡胶，或通过接枝或与酐、(甲基)丙烯酸或其酯共聚而得到的非极性或极性烯烃均聚物或共聚物；所述冲击改性剂还可以是羧酸官能化的共聚物，例如聚(乙烯-共-(甲基)丙烯酸)或聚(乙烯-1-烯烃-共-(甲基)丙烯酸)，其中1-烯烃是链烯烃或者具有多于4个原子的不饱和(甲基)丙烯酸酯，包括酸基团被金属离子中和到一定程度的那些共聚物。
基于苯乙烯单体(苯乙烯和苯乙烯衍生物)和其它乙烯基芳族单体的冲击改 性剂，是由链烯基芳族化合物和共轭二烯烃构成的嵌段共聚物，和由链烯基芳族化合物和共轭二烯烃构成的氢化嵌段共聚物，和这些类型冲击改性剂的组合。所述嵌段共聚物包含至少一种衍生自链烯基芳族化合物的嵌段a和至少一种衍生自共轭二烯烃的嵌段b。在氢化嵌段共聚物的情况下，脂肪族不饱和碳-碳双键的比例通过氢化而降低。合适的嵌段共聚物是具有直链结构的二、三、四和多嵌段共聚物。但是，根据本发明也可以使用支化和星形结构。以已知方式获得支化嵌段共聚物，例如通过聚合物“侧支链”到聚合物主链的接枝反应。
可以与苯乙烯一起使用或以与苯乙烯的混合物形式使用的其它链烯基芳族化合物是在芳环和/或在C＝C双键上被C1～20烃基或被卤原子取代的乙烯基芳族单体。
链烯基芳族单体的实例是苯乙烯、对甲基苯乙烯、α-甲基苯乙烯、乙基苯乙烯、叔丁基苯乙烯、乙烯基甲苯、1，2-二苯基乙烯、1，1-二苯基乙烯、乙烯基二甲苯、乙烯基甲苯、乙烯基萘、二乙烯基苯、溴代苯乙烯、和氯代苯乙烯、及其组合。优选苯乙烯、对甲基苯乙烯、α-甲基苯乙烯、和乙烯基萘。
优选使用苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙基苯乙烯、叔丁基苯乙烯、乙烯基甲苯、1，2-二苯基乙烯、1，1-二苯基乙烯、或这些物质的混合物。特别优选的是使用苯乙烯。但是，也可以使用链烯基萘。
可以使用的二烯烃单体的实例是1，3-丁二烯、2-甲基-1，3-丁二烯、2，3-二甲基-1，3-丁二烯、1，3-戊二烯、1，3-己二烯、异戊二烯、氯丁二烯和间戊二烯。优选1，3-丁二烯和异戊二烯，尤其是1，3-丁二烯(下文中以缩写形式丁二烯表示)。
所使用的链烯基芳族单体优选包括苯乙烯，所使用的二烯烃单体优选包括丁二烯，这意味着优选苯乙烯-丁二烯嵌段共聚物。所述嵌段共聚物通常通过阴离子聚合以其本身已知的方式制备。
除了苯乙烯单体和二烯烃单体以外，还可以同时使用其它另外的单体。基于所使用单体的总量，共聚单体的比例优选为0-50wt％，特别优选为0-30wt％，特别优选为0-15wt％。合适的共聚单体的实例分别是丙烯酸酯，尤其是丙烯酸C1～C12烷基酯，例如丙烯酸正丁酯或丙烯酸2-乙基己酯，和甲基丙烯酸酯，尤其是甲基丙烯酸C1～C12烷基酯，例如甲基丙烯酸甲酯(MMA)。其它可能的共聚单体是(甲基)丙烯腈、(甲基)丙烯酸缩水甘油酯、乙烯基甲基醚、二元醇的 二烯丙基和二乙烯基醚、二乙烯基苯和乙酸乙烯酯。
除了共轭二烯烃之外，如果合适的话，氢化嵌段共聚物还包含低级烃部分，例如乙烯、丙烯、1-丁烯、二环戊二烯或非共轭二烯烃。源于嵌段b的未还原的脂肪族不饱和键在氢化嵌段共聚物中的比例小于50％，优选小于25％，尤其是小于10％。衍生自嵌段a的芳族部分还原到至多25％的程度。通过苯乙烯-丁二烯共聚物的氢化和苯乙烯-丁二烯-苯乙烯共聚物的氢化，得到氢化嵌段共聚物，即苯乙烯-(乙烯-丁烯)双嵌段共聚物和苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物。
嵌段共聚物优选包含20wt％-90wt％的嵌段a、尤其是50wt％-85wt％的嵌段a。二烯烃可以以1，2-取向或1，4-取向引入到嵌段b中。
嵌段共聚物的摩尔质量为5000g/mol-500000g/mol，优选20000g/mol-300000g/mol，特别是40000g/mol-200000g/mol。
合适的氢化嵌段共聚物是可以从市场上购得的产品，例如(Kraton聚合物)G1650、G1651和G1652，以及(Asahi Chemicals)H1041、H1043、H1052、H1062、H1141和H1272。
非氢化嵌段共聚物的实例是聚苯乙烯-聚丁二烯、聚苯乙烯-聚(乙烯-丙烯)、聚苯乙烯-聚异戊二烯、聚(α-甲基苯乙烯)-聚丁二烯、聚苯乙烯-聚丁二烯-聚苯乙烯(SBS)、聚苯乙烯-聚(乙烯-丙烯)-聚苯乙烯、聚苯乙烯-聚异戊二烯-聚苯乙烯、和聚(α-甲基苯乙烯)聚丁二烯-聚(α-甲基苯乙烯)、及其组合。
可以从市场上购得的合适的非氢化嵌段共聚物有商标为(Phillips)、(Shell)、(Dexco)和(Kuraray)的多种产品。
本发明的包含上述半芳香族共聚酰胺树脂的聚酰胺模塑组合物，所述添加剂组分还可以包含其它聚合物，所述其它聚合物选自脂肪族聚酰胺、聚烯烃均聚物、乙烯-α-烯烃共聚物、乙烯-丙烯酸酯共聚物。
所述脂肪族聚酰胺包括但不仅限于源自4-20个碳原子的脂肪族二酸和脂肪族二胺，或者4-20个碳原子的内酰胺，或者4-20个碳原子的脂肪族二酸、脂肪族二胺和内酰胺的聚合物中的一种或多种。包括但不仅限于，聚己二酰己二胺(PA66)、聚己内酰胺(PA6)、聚癸二酰己二胺(PA610)、聚癸二酰癸二胺(PA1010)、己二酸－己二胺－己内酰胺共聚物(PA66/6)、聚十一内酰胺(PA11)、聚十二内酰胺(PA12)，及其两种或多种的混合物。
所述乙烯-α-烯烃共聚物优选EP弹性体和/或EPDM弹性体(分别是乙烯-丙烯橡胶和乙烯-丙烯-二烯烃橡胶)。例如，弹性体可以包括基于含有20wt％-96wt％、优选25wt％-85wt％乙烯的乙烯-C3-C12-α-烯烃共聚物的弹性体，其中此处特别优选的是C3-C12-α-烯烃包括选自丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯和/或1-十二烯的烯烃，特别优选其它聚合物包括乙烯-丙烯橡胶、LLDPE、VLDPE的一种或几种。
作为替代地或附加地(例如在混合物中)，所述其它聚合物还可以包含基于乙烯-C3-C12-α-烯烃和非共轭二烯烃的三元共聚物，此处优选的是其含有25wt％-85wt％乙烯和至多最大量为10wt％的非共轭二烯烃，此处特别优选C3-C12-α-烯烃包括选自丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯和/或1-十二烯的烯烃，和/或其中非共轭二烯烃优选地选自二环[2.2.1]庚二烯、1，4-己二烯、双环戊二烯和/或尤其是5-亚乙基降冰片烯。
乙烯-丙烯酸酯共聚物也可以用作所述其它聚合物的成分。
所述其它聚合物的其它可能形式分别是乙烯-丁烯共聚物和包含这些体系的混合物(共混物)。
优选地，所述其它聚合物包含具有酐基团的成分，这些通过主链聚合物与不饱和二酸酐、与不饱和二羧酸、或与不饱和二羧酸的单烷基酯的热反应或自由基反应，以足以与聚酰胺良好结合的浓度引入，并且此处优选的是使用选自以下的试剂：
马来酸、马来酸酐、马来酸单丁酯、富马酸、乌头酸和/或衣康酸酐。优选0.1wt％-4.0wt％的不饱和酸酐接枝到作为C的成分的抗冲击组分上，或者不饱和二酸酐或其前体通过与其它不饱和单体一起接枝来施加。通常优选接枝度为0.1％-1.0％，特别优选为0.3％-0.7％。其它聚合物的另一可能成分是由乙烯-丙烯共聚物和乙烯-丁烯共聚物构成的混合物，此处马来酸酐接枝度(MA接枝度)为0.3％-0.7％。
用于该其它聚合物的上述可能体系还可以以混合物的形式使用。
此外，所述添加剂组分可以包含具有官能团的组分，所述官能团例如为羧酸基团、酯基团、环氧基团、噁唑啉基团、碳二亚胺基团、异氰酸酯基团、硅烷醇基团、和羧酸酯基团，或者所述添加剂组分可以包含上述官能团中的两种或更多种的组合。具有所述官能团的单体可以通过共聚或接枝到弹性体聚烯烃上来结 合。
此外，基于烯烃聚合物的冲击改性剂还可以通过用不饱和硅烷化合物接枝来改性，所述不饱和硅烷化合物例如为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三乙酰基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、或丙烯基三甲氧基硅烷。
弹性体聚烯烃是具有直链、支链或核壳结构的无规、交替或嵌段共聚物，并含有可以与聚酰胺的端基反应的官能团，由此在聚酰胺和冲击改性剂之间提供足够的可相容性。
因此，本发明的冲击改性剂包括烯烃(例如乙烯、丙烯、1-丁烯)的均聚物或共聚物(如聚丁烯-1)，或者烯烃和可共聚单体(例如乙酸乙烯酯、(甲基)丙烯酸酯、和甲基己二烯)的共聚物。
结晶性烯烃聚合物的实例是低密度、中密度和高密度聚乙烯、聚丙烯、聚丁二烯、聚-4-甲基戊烯、乙烯-丙烯嵌段共聚物、或乙烯-丙烯无规共聚物、乙烯-甲基己二烯共聚物、丙烯-甲基己二烯共聚物、乙烯-丙烯-丁烯共聚物、乙烯-丙烯-己烯共聚物、乙烯-丙烯-甲基己二烯共聚物、聚(乙烯-乙酸乙烯酯)(EVA)、聚(乙烯-丙烯酸乙酯)(EEA)、乙烯-辛烯共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、乙烯-丙烯-二烯烃三元共聚物、以及上述聚合物的组合。
可以用于所述添加剂组分的可市购的冲击改性剂实例有：
TAFMER MC201：g-MA(-0.6％)67％EP共聚物(20mol％丙烯)+33％EB共聚物(15mol％1-丁烯))的共混物：Mitsui Chemicals，日本。
TAFMER MH5010：g-MA(-0.6％)乙烯-丁烯共聚物；Mitsui。
TAFMER MH7010：g-MA(-0.7％)乙烯-丁烯共聚物；Mitsui。
TAFMER MH7020：g-MA(-0.7％)EP共聚物；Mitsui。
EXXELOR VA1801：g-MA(-0.7％)EP共聚物；Exxon Mobile Chemicals，US。
EXXELOR VA1803：g-MA(0.5-0.9％)EP共聚物，无定形，Exxon。
EXXELOR VA1810：g-MA(-0.5％)EP共聚物，Exxon。
EXXELOR MDEX 941l：g-MA(0.7％)EPDM，Exxon。
FUSABOND MN493D：g-MA(-0.5％)乙烯-辛烯共聚物，DuPont，US。
FUSABOND A EB560D：(g-MA)乙烯-丙烯酸正丁酯共聚物，DuPont ELVALOY，DuPont。
还优选为离子聚合物，其中聚合物键合的羧基通过金属离子全部相互键合或键合到一定程度。
特别优选马来酸酐接枝官能化的丁二烯与苯乙烯的共聚物、通过与马来酸酐接枝制得的非极性或极性烯烃均聚物和共聚物、以及羧酸官能化的共聚物，例如聚(乙烯-共(甲基)丙烯酸)或聚(乙烯-共-1-烯烃-共-(甲基)丙烯酸)，其中所述酸基团已在一定程度上被金属离子中和。
此外，在不破坏本发明效果的范围内，可以在任意时刻在本发明的聚酰胺树脂中添加各种加工助剂，例如抗氧化剂和/或耐热稳定剂(受阻酚系、氢醌系、亚磷酸酯系以及它们的取代体、卤化铜、碘化合物等)、耐候剂(间苯二酚系、水杨酸酯系、苯并三唑系、二苯甲酮系、受阻胺系等)、脱模剂和润滑剂(脂肪族醇、脂肪族酰胺、脂肪族双酰胺、二脲和聚乙烯蜡等)、颜料(硫化镉、酞菁、炭黑等)、染料(尼格洛辛、苯胺黑等)、增塑剂(对羟基苯甲酸辛酯、N-丁基苯磺酰胺等)、抗静电剂(烷基硫酸盐型阴离子系抗静电剂、季铵盐型阳离子系抗静电剂、聚氧乙烯失水山梨糖醇单硬脂酸酯等非离子系抗静电剂、甜菜碱系两性抗静电剂等)。
为了获得本发明的成型品，可以将本发明的聚酰胺树脂或聚酰胺树脂组合物通过注射成型、挤出成型、吹塑成型、真空成型、熔融纺丝、膜成型等任意成型方法来成型。可以将这些成型品成型成所需形状，并可以在汽车部件、机械部件等的树脂成型品等中使用。作为具体的用途，在下列用途中是有用的：汽车发动机冷却水系部件、特别是散热器水箱的顶部和底部等散热器水箱部件、冷却液储备箱、水管、水泵壳、水泵叶轮、阀等水泵部件等在汽车发动机房内与冷却水接触下使用的部件，以开关类、超小型滑动开关、DIP开关、开关的外壳、灯座、捆扎带、连接器、连接器的外壳、连接器的壳、IC插座类、绕线轴、线轴罩、继电器、继电器箱、电容器壳体、马达的内部部件、小型马达壳体、齿轮凸轮、均衡轮、垫片、绝缘体、紧固件、扣、线夹、自行车车轮、小脚轮、安全帽、端子台、电动工具的外壳、起动器的绝缘部分、阻流板、罐、散热器水箱、腔罐(Chamber tank)、贮液罐、保险丝盒、空气净化器壳体、空调风扇、端子的外壳、轮罩、吸排气管、轴承承托、气缸头盖、进气歧管、水管叶轮(waterpipe impeller)、离合器分离杆、扬声器振动板、耐热容器、微波炉部件、电饭煲部件、打印机色带导向器等为代表的电气/电子相关部件，汽车/车辆相关部件、家电/ 办公电器部件、计算机相关部件、传真机/复印机相关部件、机械相关部件、其它各种用途。
本发明所述聚酰胺模塑组合物的吸水率≤1.0％，热变形温度按照国家标准GB/T 1634.2-2004测试为280℃-320℃；b值≤3.0；其中吸水率的测试方法为：将样品注塑成20mm×20mm×2mm的制件，其重量记为a0，然后将其置于95℃水中240h后，称量其重量记为a1，吸水率＝(a1-a0)/a0*100％；所述b值的测试方法为：使用色板模具50*30*2mm，取3000g样品粒子进行注塑后，得到一面光滑的色板，将该色板置于理宝Color-Eye7000A电脑测色仪上得到b值。
本发明与现有技术相比，具有如下有益效果：
本发明通过用对氨基苯甲酸单体代替对苯二甲酸，并通过控制对氨基苯甲酸单元与11-氨基十一酸或11-内酰胺的单元的摩尔含量，制备得到的半芳香族共聚酰胺树脂兼具高耐热性、改善颜色性能、优异的流动性和低吸水率等性能优势，由该半芳香族共聚酰胺树脂组成的聚酰胺模塑组合物在耐热性、吸水率和颜色等性能也具有明显优势。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
本发明所采用的原料均来源于市购产品。
性能测试方法：
半芳香族共聚酰胺树脂的熔点的测试方法：参照ASTM D3418-2003；具体测试方法是：采用Perkin Elmer Dimond DSC分析仪测试样品的熔点；氮气气氛，流速为40mL/min；测试时先以10℃/min升温至340℃，在340℃保持2min，然后以10℃/min冷却到50℃，再以10℃/min升温至340℃，将此时的吸热峰温度设为熔点Tm；
半芳香族共聚酰胺树脂特性粘度的测试方法：参照GB12006.1-89，聚酰胺粘数测定方法；具体测试方法为：在25℃±0.01℃的98％的浓硫酸中测量聚酰胺的特性粘度；
吸水率的测试方法：将样品注塑成20mm×20mm×2mm的制件，其重量记为a0。然后将其置于95℃水中240h后，称量其重量记为a1。则吸水率＝(a1-a0) /a0*100％。
半芳香族共聚酰胺树脂(模塑组合物)制品颜色(b值)的测试方法：使用色板模具50*30*2mm，取3000g样品粒子进行注塑后，得到一面光滑的色板。将该色板置于理宝Color-Eye7000A电脑测色仪上得到b值。该值即可反映半芳香族共聚酰胺树脂(模塑组合物)制品的颜色，该值越高，说明制品颜色越差。
热变形温度的测试：按照国家标准GB/T 1634.2-2004测试。
半芳香族共聚酰胺树脂A-J和A’-F’的合成
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的压力釜中按表1中的比例加入反应原料。再加入苯甲酸、次磷酸钠和去离子水。苯甲酸物质的量为所有单体摩尔量的2.5％，次磷酸钠重量为除去离子水外其他投料重量的0.1％，去离子水重量为总投料重量的30％。抽真空充入高纯氮气作为保护气，在搅拌下2个小时内升温到220℃，将反应混合物在220℃搅拌1小时，然后在搅拌下使反应物的温度升高到230℃。反应在230℃的恒温和2.2MPa的恒压下继续进行2小时，通过移去所形成的水而保持压力恒定。反应完成后出料，预聚物于80℃下真空干燥24小时，得到预聚产物，所述预聚产物在低于熔点30-60℃、50Pa真空条件下固相增粘，得到半芳香族共聚酰胺树脂。所得半芳香族共聚酰胺树脂的特性粘度、熔点、吸水率、颜色等性能指标列于表1中。
表1：
Figure PCTCN2017078640-appb-000002
续表1：
Figure PCTCN2017078640-appb-000003
从表1可以看出，树脂A-J中通过用对氨基苯甲酸单体代替对苯二甲酸，并通过控制对氨基苯甲酸单元与11-氨基十一酸或11-内酰胺的单元的摩尔含量，所制备得到的半芳香族共聚酰胺树脂兼具高耐热性、改善的颜色性能、优异的流动性和低吸水率等优点。树脂A’中的对氨基苯甲酸含量过低，树脂熔点较低，耐热性很差；树脂B’中的对氨基苯甲酸含量过高，导致树脂熔点高于分解温度，没有应用价值；树脂C’和D’没有使用11-氨基十一酸作为共聚单体，导致树脂颜色较差，树脂E’和树脂F’中对氨基苯甲酸与11-氨基十一酸或11-内酰胺同时为50mol％，二者摩尔比相同，导致树脂的分子量难以控制，特性粘度很高，流动性很差，不利于后期注塑加工。
实施例1-8及对比例1-6：聚酰胺模塑组合物的制备
按表2的配方将半芳香族共聚酰胺树脂、增强填料、阻燃剂、其他助剂等在高混机中混合均匀后，通过主喂料口加入双螺杆挤出机中，增强填料通过侧喂料秤侧喂。挤出，过水冷却，造粒并干燥后得到所述聚酰胺组合物。其中，挤出温度设定为熔点以上20℃，各性能结果如表2所示。
表2聚酰胺模塑组合物的组分及性能测试结果(重量份)
Figure PCTCN2017078640-appb-000004
续表2：
Figure PCTCN2017078640-appb-000005
从表2可以看出，在同样的模塑组合物配方下，包含本发明半芳香族共聚酰胺树脂的聚酰胺模塑组合物在耐热性、吸水率和颜色等性能具有明显优势。

Claims (12)

  1. 一种半芳香族共聚酰胺树脂，其特征在于，按摩尔百分比计，由如下重复单元组成：
    (A)基于全部单体单元的量，26-80mol％的衍生自对氨基苯甲酸的单元；
    (B)基于全部单体单元的量：4-70mol％的衍生自11-氨基十一酸或11-内酰胺的单元，和0-70mol％的衍生自其它具有6-36个碳原子的氨基酸或内酰胺组成的单元；
    (C)基于全部单体单元的量，0-37mol％的衍生自具有4-36个碳原子的二胺单元；
    (D)基于全部单体单元的量，0-37mol％的衍生自具有6-36个碳原子的二酸单元；
    其中，(A)+(B)+(C)+(D)＝100mol％；且衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不同时等于50mol％。
  2. 根据权利要求1所述的半芳香族共聚酰胺树脂，其特征在于，按摩尔百分比计，由如下重复单元组成：
    (A)基于全部单体单元的量，26-80mol％的衍生自对氨基苯甲酸的单元；
    (B)基于全部单体单元的量：4-70mol％的衍生自11-氨基十一酸或11-内酰胺的单元，和4-70mol％的衍生自其它具有6-36个碳原子的氨基酸或内酰胺组成的单元；
    其中，(A)+(B)＝100mol％；且衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不同时等于50mol％。
  3. 根据权利要求1所述的半芳香族共聚酰胺树脂，其特征在于，按摩尔百分比计，由如下重复单元组成：
    (A)基于全部单体单元的量，40-60mol％的衍生自对氨基苯甲酸的单元；
    (B)基于全部单体单元的量：10-40mol％的衍生自11-氨基十一酸或11-内酰胺的单元，和10-40mol％的衍生自其它具有6-36个碳原子的氨基酸或内酰胺组成的单元；
    (C)基于全部单体单元的量，5-25mol％的衍生自具有4-36个碳原子的二胺单元；
    (D)基于全部单体单元的量，5-25mol％的衍生自具有6-36个碳原子的二 酸单元；
    其中，(A)+(B)+(C)+(D)＝100mol％；且衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不同时等于50mol％。
  4. 根据权利要求1-3任一项所述的半芳香族共聚酰胺树脂，其特征在于，所述衍生自对氨基苯甲酸的单元和衍生自11-氨基十一酸或11-内酰胺的单元的摩尔含量不相等。
  5. 根据权利要求1-3任一项所述的半芳香族共聚酰胺树脂，其特征在于，所述半芳香族共聚酰胺树脂的熔点参照ASTM D3418-2003为270-360℃；特性粘度参照GB12006.1-89为0.80-1.0dl/g；吸水率≤2.0％；b值≤1.0；其中吸水率的测试方法为：将样品注塑成20mm×20mm×2mm的制件，其重量记为a0，然后将其置于95℃水中240h后，称量其重量记为a1，吸水率＝(a1-a0)/a0*100％；所述b值的测试方法为：使用色板模具50*30*2mm，取3000g样品粒子进行注塑后，得到一面光滑的色板，将该色板置于理宝Color-Eye7000A电脑测色仪上得到b值。
  6. 根据权利要求1-3任一项所述的半芳香族共聚酰胺树脂，其特征在于，所述具有4-36个碳原子的二胺单元选自直链或支链脂族二胺、环脂族二胺、芳脂族二胺中的一种或几种；所述直链或支链脂族二胺选自1，4-丁二胺、1，5-戊二胺、2-甲基-1，5-戊二胺、1，8-辛二胺、1，9-壬二胺、2-甲基-1，8-辛二胺、2，2，4-三甲基六亚甲基二胺、2，4，4-三甲基六亚甲基二胺、5-甲基-1，9-壬二胺、1，11-十一烷二胺、2-丁基-2-乙基-1，5-戊二胺、1，12-十二烷二胺、1，13-十三烷二胺、1，14-十四烷二胺、1，16-十六烷二胺、1，18-十八烷二胺中的一种或几种；所述环脂族二胺选自环己二胺、1，3-双(氨基甲基)环己烷、异佛尔酮二胺、降莰烷二甲胺、4，4’-二氨基二环己基甲烷、2，2-(4，4’-二氨基二环己基)丙烷、3，3’-二甲基-4，4’-二氨基二环己基甲烷中的一种或几种；所述芳脂族二胺选自间苯二甲胺。
  7. 根据权利要求1-3任一项所述的半芳香族共聚酰胺树脂，其特征在于，所述具有6-36个碳原子的二酸单元选自萘二羧酸、间苯二酸、己二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十八烷二酸、二聚体酸、顺式和/或反式环己烷-1，4-二羧酸、顺式和/或反式环己烷-1，3-二羧酸中的一种或几种。
  8. 一种包含权利要求1-7任一项所述的半芳香族共聚酰胺树脂的聚酰胺模塑组合物，按重量份数计，包括如下组分：
    半芳香族共聚酰胺树脂  30-100份；
    增强填料              0-70份；
    添加剂                0-50份。
  9. 根据权利要求8所述的聚酰胺模塑组合物，其特征在于，所述增强填料的形状为纤维状，其平均长度为0.01mm-20mm，优选为0.1mm-6mm；其长径比为5:1-2000:1，优选为30:1-600:1；基于聚酰胺模塑组合物的总重量，所述增强填料的含量为10-50份，优选为15份-40份；所述增强填料为无机增强填料或有机增强填料，所述无机增强填料选自玻璃纤维、钛酸钾纤维、金属包层的玻璃纤维、陶瓷纤维、硅灰石纤维、金属碳化物纤维、金属固化纤维、石棉纤维、氧化铝纤维、碳化硅纤维、石膏纤维或硼纤维的一种或几种，优选为玻璃纤维；所述有机增强填料选自芳族聚酰胺纤维和/或碳纤维。
  10. 根据权利要求8所述的聚酰胺模塑组合物，其特征在于，所述增强填料的形状为非纤维状，其平均粒径为0.001μm-100μm，优选为0.01μm-50μm，选自钛酸钾晶须、氧化锌晶须、硼酸铝晶须、硅灰石、沸石、绢云母、高岭土、云母、滑石、粘土、叶腊石、膨润土、蒙脱土、锂蒙脱土、合成云母、石棉、硅铝酸盐、氧化铝、氧化硅、氧化镁、氧化锆、氧化钛、氧化铁、碳酸钙、碳酸镁、白云石、硫酸钙、硫酸钡、氢氧化镁、氢氧化钙、氢氧化铝、玻璃珠、陶瓷珠、氮化硼、碳化硅或二氧化硅的一种或几种。
  11. 根据权利要求8所述的聚酰胺模塑组合物，其特征在于，所述添加剂选自阻燃剂、冲击改性剂、其它聚合物、加工助剂中的一种或几种；所述阻燃剂为卤系阻燃剂或无卤阻燃剂，优选无卤阻燃剂；所述其它聚合物为脂肪族聚酰胺、聚烯烃均聚物、乙烯-α-烯烃共聚物或乙烯-丙烯酸酯共聚物的一种或几种。
  12. 根据权利要求8-11任一项所述的聚酰胺模塑组合物，其特征在于，所述聚酰胺模塑组合物的吸水率≤1.0％，热变形温度按照国家标准GB/T 1634.2-2004测试为280℃-320℃；b值≤3.0；其中吸水率的测试方法为：将样品注塑成20mm×20mm×2mm的制件，其重量记为a0，然后将其置于95℃水中240h后，称量其重量记为a1，吸水率＝(a1-a0)/a0*100％；所述b值的测试方法为：使用色板模具50*30*2mm，取3000g样品粒子进行注塑后，得到一面光滑的色板， 将该色板置于理宝Color-Eye7000A电脑测色仪上得到b值。
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