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CN107903390A - A kind of semiaromatic polyamide composition and preparation method thereof and the polyamide moulding composition being made from it - Google Patents

A kind of semiaromatic polyamide composition and preparation method thereof and the polyamide moulding composition being made from it Download PDF

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Publication number
CN107903390A
CN107903390A CN201710952545.6A CN201710952545A CN107903390A CN 107903390 A CN107903390 A CN 107903390A CN 201710952545 A CN201710952545 A CN 201710952545A CN 107903390 A CN107903390 A CN 107903390A
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China
Prior art keywords
acid
semi
aromatic polyamide
diamines
polyamide resin
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CN201710952545.6A
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Chinese (zh)
Inventor
张传辉
曹民
黄险波
叶南飚
史振国
王道波
卢伟光
阎昆
常欢
黄野
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Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials Co Ltd
Zhuhai Wantong Chemical Co Ltd
Original Assignee
Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials Co Ltd
Zhuhai Wantong Chemical Co Ltd
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Application filed by Kingfa Science and Technology Co Ltd, Tianjin Kingfa Advanced Materials Co Ltd, Zhuhai Wantong Chemical Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Priority to CN201710952545.6A priority Critical patent/CN107903390A/en
Publication of CN107903390A publication Critical patent/CN107903390A/en
Priority to PCT/CN2018/100323 priority patent/WO2019072013A1/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • 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

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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)

Abstract

The invention discloses a kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it.The content of free benzoic acid is less than 200ppm in Semi-aromatic polyamide resin.The Semi-aromatic polyamide resin is made of following repetitive unit：(a) terephthalic acid (TPA) either its derivative and optionally one or more other aromatics or aliphatic diacid；(b) one or more aliphatic diamines with 10 to 20 carbon atoms, and optionally one or more other diamines；(c) optionally one or more amino carboxylic acids and/or lactams；Wherein, terephthalic acid (TPA) accounts for 50 100mol% of (a), one or more have 50 100mol% that the aliphatic diamine of 10 to 20 carbon atoms accounts for (b), and one or more amino carboxylic acids and/or lactams account for 0 25mol% of the total amount of (a)+(b)+(c).The Semi-aromatic polyamide resin of the present invention improves the problems such as device in Gas and product pollution of melt-processed process.

Description

A kind of semiaromatic polyamide composition and preparation method thereof and the polyamide molding being made from it Composition
Technical field
The present invention relates to high molecular polymerization and engineering plastics technical field, more particularly, to a kind of semiaromatic polyamide composition and Its preparation method and the polyamide moulding composition being made from it.
Background technology
Polyamide（Polyamide, PA）, nylon is commonly called as, has had 80 since the 1930s realizes industrialization History for many years.Initial stage mainly as the raw material of spinning, could be used as engineering plastics to use, with vapour after the 1950s The application fields such as turner industry, electronics, communications and transportation, machinery, aerospace industry and various dairy industries develop rapidly, its produce and Demand has been positioned at the first place of five large-engineering plastics.Polyamide because it is with good comprehensive performance, including mechanical property, Heat resistance, wear resistance, chemical proofing and self lubricity, and friction coefficient is low, has certain anti-flammability etc., it is extensive For glass fibre and other filler filling enhancing modifieds, improve performance and expand application range etc..Half virtue in recent years Fragrant polyamide due to its heat resistance and mechanical property it is more excellent and by focus development.
Semiaromatic polyamide composition is usually either by with phenyl ring by the diamine with phenyl ring and aliphatic binary acid The monomer polymerization such as binary acid and aliphatic diamine obtains.Semiaromatic polyamide composition carrys out agent control point frequently with benzoic acid end-blocking Son amount.Since amidation process is reversible reaction, if cannot effectively control reaction process condition, always there is part in polymerizate Unreacted benzoic acid exists.Since benzoic acid melts, boiling point is higher, and the operation such as vacuumize in polymerization process is often difficult to it Extraction, causes it to there is the residual in the form of free state in final resin.This small molecule residual often causes subsequently molten The problems such as melting device in Gas in process, product pollution, directly affects injection efficiency and article surface performance.Chinese patent CN104530421A discloses a kind of preparation method of semiaromatic polyamide composition, is carried out using benzoic acid as molecular weight regulator End-blocking, but be not concerned with how remaining free benzoic acid in removing system.
The content of the invention
The purpose of the present invention, be to overcome the deficiencies of the prior art and provide it is a kind of with low free benzoic acid content half Aromatic polyamide with and preparation method thereof.It is a further object to provide one kind to include above-mentioned semiaromatic polyamide composition Semiaromatic polyamide composition composition.
The present invention is achieved by the following technical solutions：
The Semi-aromatic polyamide resin, the gross weight based on Semi-aromatic polyamide resin, the content for the benzoic acid that dissociates Less than 200ppm.
As further preferred embodiment of the present invention, the Semi-aromatic polyamide resin, based on semi-aromatic The gross weight of polyamide, the content of free benzoic acid are less than 100ppm.
As further preferred embodiment of the present invention, the Semi-aromatic polyamide resin, based on semi-aromatic The gross weight of polyamide, the small 50ppm of content for the benzoic acid that dissociates.
As further preferred embodiment of the present invention, the Semi-aromatic polyamide resin, based on semi-aromatic The gross weight of polyamide, the small 30ppm of content for the benzoic acid that dissociates.
The Semi-aromatic polyamide resin, it derived from following repetitive unit by forming：
(a) terephthalic acid (TPA) either its derivative and optionally one or more other aromatics or aliphatic diacid；
(b) one or more aliphatic diamines with 10 to 20 carbon atoms, and it is optionally one or more with 4 to 9 The aliphatic diamine of carbon atom；
(c) optionally one or more amino carboxylic acids and/or lactams；
Wherein, terephthalic acid (TPA) accounts for the 50-100mol% of (a), and one or more have the aliphatic diamine of 10 to 20 carbon atoms The 50-100mol% of (b) is accounted for, one or more amino carboxylic acids and/or lactams account for the 0-25mol% of the total amount of (a)+(b)+(c).
The Semi-aromatic polyamide resin, it derived from following repetitive unit by forming：
(a) terephthalic acid (TPA) either its derivative and optionally one or more other aromatics or aliphatic diacid；
(b) one or more aliphatic diamines with 4 to 9 carbon atoms, and it is optionally one or more with 10 to 20 The aliphatic diamine of carbon atom；
(c) optionally one or more amino carboxylic acids and/or lactams；
Wherein, terephthalic acid (TPA) accounts for the 30-100mol% of (a), and the aliphatic diamine that one or more have 4 to 9 carbon atoms accounts for (b) 50-100mol%, one or more amino carboxylic acids and/or lactams account for the 0-25mol% of the total amount of (a)+(b)+(c).
The Semi-aromatic polyamide resin, it derived from following repetitive unit by forming：
(a) terephthalic acid (TPA) either its derivative and optionally one or more other aromatics or aliphatic diacid；
(b) one or more aliphatic diamines with 4 to 9 carbon atoms, and it is optionally one or more with 10 to 20 The aliphatic diamine of carbon atom；
(c) optionally one or more amino carboxylic acids and/or lactams；
Wherein, terephthalic acid (TPA) accounts for the 5-30mol% of (a), and the aliphatic diamine that one or more have 4 to 9 carbon atoms accounts for (b) 50-100mol%, one or more amino carboxylic acids and/or lactams account for the 0-25mol% of the total amount of (a)+(b)+(c).
The Semi-aromatic polyamide resin is formed by 3 kinds or more than 3 kinds monomer polymerizations.
The other aromatics or aliphatic diacid are selected from M-phthalic acid, ethanedioic acid, malonic acid, succinic acid, penta Diacid, adipic acid, pimelic acid, suberic acid, 2- methyl suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, ten One or more in three docosandioic acids or tetracosandioic acid.
The aliphatic diamine of 10 to 20 carbon atoms is selected from decamethylene diamine, hendecane diamines, dodecamethylene diamine, 13 Alkane diamines, tetradecane diamines, pentadecane diamines, hexadecane diamines, heptadecane diamines, octadecamethylene diamine, nonadecane diamines, 20 One or more in alkane diamines.
The aliphatic diamine of 4 to 9 carbon atoms be selected from butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, One or more in nonamethylene diamine, 2- methyl octamethylenediamines.
The amino carboxylic acid or lactams are selected from 6-aminocaprolc acid, caprolactam, 10- aminocapric acids, 11- amino 11 One or more in acid, 11 lactams, 12-aminolauric acid or lauric lactam.
As the preferred embodiment of the present invention, the repetitive unit（b）Comprise only 1,10- decamethylene diamines.
As the preferred embodiment of the present invention, the repetitive unit（b）Comprise only 1,6- hexamethylene diamines.
As the preferred embodiment of the present invention, the repetitive unit（b）Comprise only 1,6- hexamethylene diamines and the 1,10- last of the ten Heavenly stems Diamines.
As the preferred embodiment of the present invention, the repetitive unit（c）Content is 0.
The Semi-aromatic polyamide resin, it is 10mg/ to measure concentration in 25 DEG C ± 0.01 DEG C of 98% concentrated sulfuric acid Ml, the relative viscosity of Semi-aromatic polyamide resin is 1.7-2.8, preferably 1.85-2.45, more preferably 2.0-2.3.
The relatively low Semi-aromatic polyamide resin poor-performing of relative viscosity, but the semiaromatic adoption that relative viscosity is too high Amide resin, processing fluidity are poor.
The Semi-aromatic polyamide resin, the fusing point with dystectic Semi-aromatic polyamide resin is 280- 340 DEG C, preferably 290-330 DEG C, more preferably 295-325 DEG C.
The Semi-aromatic polyamide resin, the fusing point with the Semi-aromatic polyamide resin of low melting point is 240- 279 DEG C, preferably 245-270 DEG C.
Preferably, the Semi-aromatic polyamide resin only has a fusing point.
The Semi-aromatic polyamide resin is amorphous, crystallite or undefined structure.
The Semi-aromatic polyamide resin polymerization：
Polymerization stage：Enter reaction raw materials in autoclave pressure, vacuumize and be filled with high-purity argon gas as protection gas, start to react.Will be anti- Answer mixture be warming up to 220 DEG C -230 DEG C stirring 3-5 it is small when, then open valve slowly pressure release draining, while keep temperature and Pressure is constant.Draining always to displacement reaches the 70% of input amount of deionized water.Start to warm up at this time to 250 DEG C -270 DEG C, it is permanent When temperature 2 is small.Valve discharging is opened after the completion of reaction, obtains prepolymer.The fusing point of prepolymer is tested, is set to T DEG C.Prepolymer is in 80 When vacuum drying 24 is small at DEG C.The increasing stick stage：Prepolymer obtains semiaromatic less than solid-phase tack producing is carried out at 40-70 DEG C of fusing point Polyamide resin.
Sodium hypophosphite can be selected in polymerization catalyst used.
The polymerization of the Semi-aromatic polyamide resin, with the total monomer weight to feed intake, polymerization stage to N,N-dimethylformamide, the N of 0.5-5wt%, one kind or several in N- diethylformamides, dimethyl sulfoxide (DMSO) are added in system Kind.
A kind of polyamide moulding composition for including the semiaromatic polyamide composition, by weight percentage, by following Component forms：
（A）Semiaromatic polyamide composition 30-95wt%；
（B）Reinforcing material 0-70wt%；
（C）Additive 0-50wt%；
Wherein,（A）+（B）+（C）=100%.
The preparation method of the semiaromatic polyamide composition composition：
By Semi-aromatic polyamide resin, reinforcing material, additive after high-speed mixer and mixing is uniform, added by main spout In double screw extruder.Extrusion, crosses water cooling, is granulated and the semiaromatic polyamide composition composition is obtained after drying.
Based on polyamide moulding composition gross weight, the content of the component B is preferably 10wt%-50wt%, more preferably 15wt%-40wt%。
Reinforcer content is too low, causes polyamide moulding composition mechanical property poor；Reinforcer too high levels, gather Acid amides moulding compound product surface floats fibre seriously, influences product appearance.
The shape of the reinforcer is threadiness, its average length is 0.01mm-20mm, is preferably 0.1mm-6mm；Its Draw ratio is 5:1-2000:1, it is preferably 30:1-600:1, when threadiness reinforcer content within the above range when, polyamides Amine moulding compound will show high heat distortion temperature and the high temperature rigid increased.
The reinforcer is inorganic reinforcing filler or organic reinforcing fillers.
The inorganic reinforcing filler be selected from glass fibre, potassium titanate fibre, the glass fibre of clad, ceramic fibre, Wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum are fine The one or more of dimension or boron fibre, are preferably glass fibre.
The mouldability of polyamide moulding composition can be not only improved using glass fibre, but also mechanical property example can be improved Such as tensile strength, bending strength and bending modulus, and heat when improving heat resistance for example thermoplastic resin composition being molded Deformation temperature.
The organic reinforcing fillers are selected from aramid fibre and/or carbon fiber.
The shape of the reinforcer is Non-fibrous, such as powdered, graininess, tabular, needle-shaped, fabric or felted, Its average grain diameter is 0.001 μm -100 μm, is preferably 0.01 μm -50 μm.
When reinforcer average grain diameter be less than 0.001 μm will cause polyamide moulding compound melt processable compared with Difference；When reinforcer average grain diameter be more than 100 μm, undesirable injection-molded article appearance will be caused.
The average grain diameter of above-mentioned reinforcer is measured by absorption method, its may be selected from potassium titanate crystal whisker, ZnOw, Aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophillite, bentonite, montmorillonite, stone Cotton, alumino-silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, sulphur Sour calcium, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride, carborundum or silica One or more.These reinforcers can be hollow；In addition, for swellabilities such as bentonite, montmorillonite, synthetic micas Phyllosilicate, can use and interlayer ion is carried out to the organic montmorillonite after cation exchange using organic ammonium salt.
In order to make polyamide moulding composition obtain more excellent mechanical performance, coupling agent can be used to fill out inorganic enhancing Material carries out functional processing.
Wherein coupling agent is selected from isocyanates based compound, organosilan based compound, organic titanate based compound, has Machine borine based compound, epoxide；Preferably organosilan based compound；
Wherein, the organosilan based compound is selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group, the alcoxyl containing sulfydryl Base silane compound, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group, contain Hold alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkoxy containing carbon-to-carbon unsaturated group of amido The one or more of silane compound, alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group be selected from γ-glycidoxypropyltrime,hoxysilane, γ- The one or more of glycidoxypropyl group triethoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-sulfydryl Propyl-triethoxysilicane.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups is selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, γ-(2- urea groups ethyl) hold the one or more of aminocarbonyl propyl trimethoxy silane.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group is selected from γ-isocyanate group propyl-triethoxysilicane Alkane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-isocyanic acid Ester group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group propyl group The one or more of ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido is selected from γ-(2- ends amido ethyl) end aminocarbonyl propyl methyl two Methoxy silane, γ-(2- ends amido ethyl) end aminocarbonyl propyl trimethoxy silane, γ-end aminocarbonyl propyl trimethoxy silane One or more.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from γ-hydroxypropyl trimethoxy silane and/or γ-hydroxyl Propyl-triethoxysilicane.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group is selected from γ-methacryloxypropyl front three Oxysilane, vinyltrimethoxysilane, N- β-(N- vinyl benzyl cardinal extremity amidos ethyl)-γ-end aminocarbonyl propyl trimethoxy The one or more of base silane hydrochloride.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3- trimethoxy-silylpropyl succinic anhydrides.
The organosilan based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2- ends Amido ethyl) end aminocarbonyl propyl methyl dimethoxysilane, γ-(2- ends amido ethyl) end aminocarbonyl propyl trimethoxy silane, γ-end aminocarbonyl propyl trimethoxy silane or 3- trimethoxy-silylpropyl succinic anhydrides.
Conventionally inorganic reinforcing filler can be surface-treated using above-mentioned organosilan based compound, Then itself and polyamide are subjected to melting mixing again, to prepare the polyamide moulding composition.
Organosilicon methane series chemical combination can also be added directly while inorganic reinforcing filler and polyamide melting mixing Thing carries out in-situ blending.
Wherein, the dosage of the coupling agent is the 0.05wt%-10wt% relative to inorganic reinforcing filler weight, is preferably 0.1wt%-5wt%。
When the dosage of coupling agent is less than 0.05wt%, it does not reach the effect of obvious improved mechanical properties；Work as coupling agent Dosage when being more than 10wt%, inorganic reinforcing filler easily agglomerates, and disperses undesirable risk in polyamide, Mechanical performance is ultimately resulted in decline.
The additive is selected from fire retardant, impact modifying agent, other polymers, the one or more of processing aid；It is described Other polymers are preferably fatty polyamide, polyolefin homopolymer, ethene-alpha-olefin copolymer, ethylene-acrylate copolymers The one or more of thing；The processing aid be selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, releasing agent, lubricant, pigment, Dyestuff, plasticizer, the one or more of antistatic additive.
The fire retardant is fire retardant or fire retardant and the composition of fire-retardant assistance agent, total based on polyamide moulding composition Weight, its content are preferably 0-40wt%；Flame retardant agent content is too low to cause flame retardant effect to be deteriorated, and flame retardant agent content is excessive to cause material Expect mechanical properties decrease.
The fire retardant is halogenated flame retardant or halogen-free flame retardants.
The halogenated flame retardant is selected from brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, bromination benzene Ethylene maleic acid anhydride copolymer, brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, bromination are gathered The one or more of carbonic ester, three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer, are preferably brominated Polystyrene；
The halogen-free flame retardants is selected from the one or more of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus fire retardant；It is excellent Elect phosphonium flame retardant as.
The phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, phosphorus Triphenyl phosphate ester, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate, butylbenzene system phosphate or phosphinates It is one or more of；Preferably phosphinates.
Phosphinate salt compound is using the compound that such as following formula I and/or II represent as representative.
In Formulas I and Formula II, R1And R2It may be the same or different, represent the C1-C6- of straight-chain or branch-like respectively Alkyl, aryl or phenyl.R3Represent C1-C10- alkylidenes, C6-C10- arlydene, the C6-C10- alkyl of straight-chain or branch-like Arlydene, C6-C10- aryl alkylenes.M represents calcium atom, magnesium atom, aluminium atom and/or zinc atom.M be 2 or 3, n be 1 or 3, x be 1 or 2.
The more specific example of phosphinate salt compound includes dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethyl time Phosphonic acids aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethyl Methyl-phosphinic acid zinc, diethyl phosphinic acids calcium, diethyl phosphinic acids magnesium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, methyl N-propyl phosphinic acids calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc, first are burnt Two (methyl-phosphinic acid) calcium, methane two（Methyl-phosphinic acid）Magnesium, methane two（Methyl-phosphinic acid）Aluminium, methane two（Methyl time phosphine Acid）Zinc, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) calcium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) magnesium, benzene-Isosorbide-5-Nitrae-(dimethyl time phosphine Acid) aluminium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, aminomethyl phenyl time phosphine Sour aluminium, methylphenylphosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl time phosphine Sour zinc etc., preferably dimethylphosphinic acid calcium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethyl Methyl-phosphinic acid aluminium, ethylimethyphosphinic acid zinc, diethyl phosphinic acids calcium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, more It is preferred that aluminum diethylphosphinate.
Phosphinate salt compound as fire retardant can be obtained easily from market.Can be from the phosphinic acids salinization that market obtains The example of compound includes Clariant Corporation（Clariant）EXOLIT OP1230 of manufacture, OP1311, OP1312, OP930, OP935 etc..
The polyamide moulding composition for including above-mentioned Semi-aromatic polyamide resin of the present invention, based on polyamide molding group The gross weight of compound, the additive component may also contain up to one or more of impact modifying agents of 45wt%, be preferably 5wt%-30wt%。
Wherein, the impact modifying agent can be natural rubber, polybutadiene, polyisoprene, polyisobutene, butadiene And/or isoprene and styrene or with styrene derivative and with the copolymer of other comonomers, hydrogenated copolymer and/ By grafting or with acid anhydrides,（Methyl）Prepared by acrylic acid or its ester are copolymerized copolymer；The impact modifying agent can be with It is the graft rubber with cross-linked elastomer core, the cross-linked elastomer core is by butadiene, isoprene or alkyl acrylate Form, and with the graft shell that is made of polystyrene or can be nonpolar or polar olefin homopolymer or copolymer, Such as EP rubbers, ethylene/propylene/diene rubber, or Ethylene-octene rubber, or ethylene-vinyl acetate rubber, or it is logical Cross grafting or with acid anhydrides,（Methyl）Nonpolar or polar olefin homopolymer or copolymer obtained from acrylic acid or the copolymerization of its ester； The impact modifying agent can also be carboxylic acid functionalized copolymer, such as poly-（Ethene -co-（Methyl）Acrylic acid）It is or poly-（Second Alkene -1- alkene -co-s（Methyl）Acrylic acid）, wherein 1- alkene is olefine or the unsaturation with more than 4 atoms（First Base）Acrylate, including acid groups are neutralized those copolymers to a certain extent by metal ion.
Styrene-based monomer（Styrene and styrene derivative）With the impact modifying agent of other vi-ny l aromatic monomers, It is the block copolymer being made of alkenyl aromatic compounds and conjugated diene, and by alkenyl aromatic compounds and conjugation two The hydrogenated block copolymer that alkene is formed, and the combination of these type impact modifying agents.The block copolymer includes at least one Block a and at least one block b derived from conjugated diene of the kind derived from alkenyl aromatic compounds.It is total in hydrogenated diblock In the case of polymers, the ratio of aliphatic unsaturation carbon-to-carbon double bond is reduced by hydrogenation.Suitable block copolymer is that have Two, three, the four of linear chain structure and segmented copolymer.But branched and star structure can also be used according to the present invention.With Know that mode obtains branched block copolymer, such as " collateral chain " is grafted on main polymer chain by polymer graft reaction.
Other alkenyl aromatic chemical combination that can be used together with styrene or be used with the form of mixtures with styrene Thing be aromatic ring and/or in C=C double bonds by the alkyl of C1~20 or the vi-ny l aromatic monomers substituted by halogen atom.
The example of vi-ny l aromatic monomers is styrene, p-methylstyrene, α-methylstyrene, ethyl styrene, uncle Butylstyrene, vinyltoluene, 1,2- diphenylethlenes, 1,1- diphenylethlenes, vinyl-dimethyl benzene, vinyltoluene, One or several kinds in vinyl naphthalene, divinylbenzene, bromostyrene, chlorostyrene.Optimization styrene, to methylbenzene One or several kinds in ethene, α-methylstyrene and vinyl naphthalene.Preferably using styrene, α-methylstyrene, to first In base styrene, ethyl styrene, t-butyl styrene, vinyltoluene, 1,2- diphenylethlenes, 1,1- diphenylethlenes It is one or several kinds of.Particularly preferably use styrene.But it is also possible to use alkenyl naphthalene.
The example for the diolefinic monomer that can be used is 1,3-butadiene, 2- methyl isophthalic acids, 3- butadiene, 2,3- dimethyl- 1,3-butadiene, 1,3-pentadiene, 1,3- hexadienes, isoprene, chlorobutadiene and pentadiene.It is preferred that 1,3-butadiene or Isoprene, more preferably 1,3-butadiene (are hereinafter represented) with abbreviated form butadiene.
Used alkenyl aromatic monomer preferably includes styrene, and used diolefinic monomer preferably includes fourth two Alkene, it means that optimization styrene-butadiene block copolymer.The block copolymer is usually by anionic polymerisation with it Known to body prepared by mode.
In addition to styrene monomer and diolefinic monomer, other other monomers can also be used at the same time.Based on being made With the total amount of monomer, the ratio of comonomer is preferably 0-50wt%, particularly preferably 0-30wt%, particularly preferably 0-15wt%. The example of suitable comonomer is acrylate respectively, especially acrylic acid C1~C12 Arrcostabs, such as n-butyl acrylate Or 2-EHA, and methacrylate, especially methacrylic acid C1~C12 Arrcostabs, such as metering system Sour methyl esters（MMA）.Other possible comonomers are（Methyl）Acrylonitrile,（Methyl）Glycidyl acrylate, vinyl first Base ether, the diallyl of dihydric alcohol and divinyl ether, divinylbenzene and vinyl acetate.
In addition to conjugated diene, if applicable, hydrogenated block copolymer also includes lower hydrocarbon part, such as second Alkene, propylene, 1- butylene, bicyclopentadiene or non-conjugated diene hydrocarbon.The unreduced aliphatic unsaturated bond of block b is come from hydrogen Change the ratio in block copolymer and be less than 50%, preferably smaller than 25%, especially less than 10%.Aromatic fractions derived from block a are also Original arrives at most 25% degree.Pass through the hydrogenation of styrene-butadiene copolymer and styrene-butadiene-styrene Hydrogenation, obtains hydrogenated block copolymer, i.e., styrene-（Ethylene/Butylene）Diblock copolymer and styrene-（Ethylene/Butylene）- Styrene triblock copolymer.
Block copolymer preferably comprises the block a of the block a, especially 50wt%-85wt% of 20wt%-90wt%.Alkadienes It can be orientated with 1,2- or Isosorbide-5-Nitrae-orientation is incorporated into block b.
The molal weight of block copolymer is 5000g/mol-500000g/mol, preferably 20000g/mol-300000g/ Mol, particularly preferred 40000g/mol-200000g/mol.
Suitable hydrogenated block copolymer is the product that can be bought from the market, such as (Kraton polymer) G1650, G1651 and G1652, and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141 and H1272.
The example of non-hydrogenated block copolymer is polystyrene-polybutadiene, polystyrene-poly（Ethylene-propylene）, polyphenyl Ethene-polyisoprene, gather（α-methylstyrene）- polybutadiene, polystyrene-polybutadiene-polystyrene（SBS）, it is poly- Styrene-poly-（Ethylene-propylene）- polystyrene, polystyrene-polyisoprene-polystyrene, gather（α-methylstyrene）It is poly- Butadiene-poly-（α-methylstyrene）In one or several kinds.
The suitable non-hydrogenated block copolymer that can be bought from the market has the trade mark to be（Phillips）、（Shell）、 （Dexco）With（Kuraray）Multiple product.
Impact modifying agent based on olefin polymer can also be modified by using unsaturated silane compound grafting, described Unsaturated silane compound is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl triacetyl silicon Alkane, methacryloxypropyl trimethoxy silane or acrylic trimethoxy silane.
Elastomeric polyolefin is have straight chain, side chain or core shell structure random, alternately or block copolymer, and containing can With the functional group reacted with the end group of polyamide, enough tolerabilities are thus provided between polyamide and impact modifying agent.
Therefore, impact modifying agent of the invention includes alkene（Such as ethene, propylene, 1- butylene）Homopolymer or copolymerization Thing, or alkene and copolymerisable monomer（Such as vinyl acetate,（Methyl）Acrylate and methyl hexadiene）Copolymer.
The example of crystalline olefin polymer be low-density, Midst density and high density polyethylene (HDPE), polypropylene, polybutadiene, Poly- 4- methylpentenes, Ethylene-Propylene Block Copolymer or ethylene-propylene random copolymer, ethene-methyl hexadiene copolymerization Thing, propylene-methyl hexadiene copolymer, ene-propylene-butene copolymer, Ethylene-propylene-hexene Copolymer, ethylene-propylene- Methyl hexadiene copolymer, gather（Ethane-acetic acid ethyenyl ester）（EVA）, it is poly-（Ethylene-ethylacrylate）（EEA）, ethylene-octene Copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, one kind in ethylene/propylene/diene terpolymer or several Kind.
The commercially available impact modifying agent example that can be used for the additive component has：
TAFMER MC201：G-MA (- 0.6%) 67%EP copolymers (20mol% propylene)+33%EB copolymers (15mol%1- fourths Alkene)) blend：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 copolymers；Mitsui.
EXXELOR VA1801：G-MA (- 0.7%) EP copolymers；Exxon Mobile Chemicals, US.
EXXELOR VA1803：G-MA (0.5-0.9%) EP copolymers, amorphous, Exxon.
EXXELOR VA1810：G-MA (- 0.5%) EP copolymers, 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。
Commercially available impact modifying agent for the additive component is preferably ionomer, wherein polymer-bound Carboxyl be all mutually bonded or be bonded to a certain extent by metal ion.
The fourth graft-functionalized for the particularly preferred maleic anhydride of commercially available impact modifying agent of the additive component The copolymer of diene and styrene, by nonpolar or polar olefin homopolymer made from being grafted with maleic anhydride and copolymer, And carboxylic acid functionalized copolymer, such as it is poly- (ethene-common (methyl) acrylic acid) or poly-（Ethene -co- 1- alkene -co-s（First Base）Acrylic acid）, wherein the acid groups are neutralized by metal ion to a certain extent.
The polyamide moulding composition for including above-mentioned Semi-aromatic polyamide resin of the present invention, the additive component is also Other polymers can be included, the other polymers are total to selected from fatty polyamide, polyolefin homopolymer or ethene-alpha-olefin Polymers, vinyl-acrylate copolymer.
The fatty polyamide includes but are not limited to be derived from the aliphatic diacid and aliphatic two of 4-20 carbon atom Amine, the either aliphatic diacid of the lactams of 4-20 carbon atom or 4-20 carbon atom, aliphatic diamine and lactams One or more in polymer.Include but are not limited to, polyhexamethylene adipamide（PA66）, polycaprolactam（PA6）, poly- last of the ten Heavenly stems Two acyl hexamethylene diamines（PA610）, nylon 1010（PA1010）, adipic acid-hexamethylene diamine-caprolactam copolymer（PA66/ 6）, poly- 11 lactams（PA11）, nylon 12（PA12）, and its two or more of mixtures.
The preferred EP elastomers of the ethene-alpha-olefin copolymer and/or EPDM elastomers（It is ethylene-propylene rubber respectively With ethylene/propylene/diene rubber）.For example, elastomer can include being based on containing 20wt%-96wt%, preferably 25wt%- The elastomer of the ethene-C3-C12- alpha olefin copolymers of 85wt% ethene, wherein being particularly preferably C3-C12- alpha-olefins herein Including the alkene selected from propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene and/or 1- laurylenes, particularly preferably its He includes ethylene-propylene rubber, the one or more of LLDPE, VLDPE by polymer.
As replacement or adding（Such as in the mixture）, the other polymers can also include based on ethene, C3-C12- alpha-olefins（Containing 3 carbon atoms to containing 12 carbon atoms-alpha-olefin）With the ternary polymerization of non-conjugated diene hydrocarbon Thing, the non-conjugated diene hydrocarbon that preferably it contains 25wt%-85wt% ethene herein and maximum level is 10wt%, herein especially It is preferred that C3-C12- alpha-olefins include being selected from propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene and/or 1- laurylenes Alkene, and/or wherein non-conjugated diene hydrocarbon；It is preferred that two rings [2.2.1] heptadiene, Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene and/or 5- ethylidene norbornenes.
Other possible forms of the other polymers are ethylene-butene copolymer and the mixing comprising these systems respectively Thing（Blend）.
Preferably, the other polymers include the component with anhydride group, these pass through trunk polymer and insatiable hunger Thermal response or radical reaction with dicarboxylic anhydride, with unsaturated dicarboxylic or with the monoalkyl ester of unsaturated dicarboxylic, to be enough Introduced with the concentration of polyamide good combination, and herein preferably with selected from following reagent：
Maleic acid, maleic anhydride, butyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride.It is preferred that 0.1wt%-4.0wt% Unsaturated acid anhydride be grafted in shock resistance component, or unsaturated dicarboxylic anhydride or its precursor by with other unsaturated monomers one Grafting applies.Generally preferable grafting degree is 0.1%-1.0%, particularly preferably 0.3%-0.7%.The another of other polymers can Energy component is the mixture being made of ethylene-propylene copolymer and ethylene-butene copolymer, herein maleic anhydride grafting degree（MA Grafting degree）For 0.3%-0.7%.
Above-mentioned possible system for the other polymers can also use as a mixture.
In addition, the additive component can include with functional group component, the functional group be, for example, carboxylic acid group, Ester group, epoxide group, oxazoline group, carbodiimide group, isocyanate groups, silanol and carboxylate group, Or the additive component can include the combination of two or more in above-mentioned functional group.List with the functional group Body can be obtained by being copolymerized or being grafted on elastomeric polyolefin.
In addition, in the range of effect of the present invention is not destroyed, can be at any time in the polyamide of the present invention Add various processing aids, such as antioxidant and/or heat-resisting stabilizing agent（Hindered phenol series, quinhydrones system, phosphite ester system and it Substitution body, copper halide, iodine compound etc.）, weather resisting agent（Resorcinol system, salicylate system, enumerate BTA system, hexichol first Ketone system, amine system of being obstructed etc.）, releasing agent and lubricant（Aliphatic alcohol, aliphatic amide, aliphatic bisamide, two ureas and polyethylene Wax etc.）, pigment（Cadmium sulfide, phthalocyanine, carbon black etc.）, dyestuff（Nigrosine, nigrosine etc.）, plasticizer（P-hydroxybenzoic acid is pungent Ester, N-butylbenzenesulfonamide etc.）, antistatic additive（Alkyl sulphate type anionic system antistatic additive, quaternary ammonium salt cationic system resist The nonionic system antistatic additive such as electrostatic agent, polyoxyethylene sorbitan monostearate, glycine betaine system both sexes antistatic additive Deng）.
In order to obtain the products formed of the present invention, the polyamide of the present invention or Amilan polyamide resin composition can be passed through The random molding methods such as injection moulding, extrusion molding, blow molding, vacuum forming, melt spinning, film shaping are molded.Can be with These products formeds are molded into required shape, and can be used in synthetic resin of automobile component, mechanical part etc. etc..Make It is useful in following purposes for specific purposes：The top of automobile engine cooling water based part, particularly radiator tank Pump parts such as the radiator water box part such as portion and bottom, coolant reserve tank, water pipe, water pump shell, water pump vane, valve etc. are in vapour The component used is contacted down in car engine room with cooling water, with Switch, microminiature slide switch, DIP switch, switch it is outer Shell, lamp holder, strapping, connector, the shell of connector, the shell of connector, IC sockets class, roll, bobbin cover, relay, Electrical relaybox, capacitor casing, the internal part of motor, small size motor shell, gear cam, dancing pulley, gasket, insulator, Fastener, buckle, the insulation division of the shell of wire clamp, cycle wheel, Caster, safety cap, terminal board, electric tool, starter Divide, spoiler, tank, radiator tank, chamber tank（Chamber tank）, receiver, fuse box, shell of air purifier, sky Adjust fan, the shell of terminal, wheel cover, suction tracheae, bearing retainer, cylinder head cover, inlet manifold, water pipe impeller（waterpipe impeller）, clutch lever, speaker diaphragm, heatproof container, microwave oven component, electric cooker component, printer color tape Guider etc. be representative electrical/electronic associated components, automobile/vehicle associated components, household electrical appliances/office electric component, computer Associated components, facsimile machine/duplicator associated components, mechanical associated components, other various uses.
The present invention has the advantages that：
1. the present invention adds a certain amount of intensive polar solvent, such as N, N- dimethyl methyls in the polymerization stage of semiaromatic polyamide composition Acid amides, N, N- diethylformamides, dimethyl sulfoxide (DMSO) etc., can significantly reduce the content for the benzoic acid that dissociates in resin, hence it is evident that change The problems such as device in Gas, product during kind melt-processed pollute, while the polymerization for not influencing Semi-aromatic polyamide resin is anti- Should.2. the intensive polar solvent of the present invention is cheap and dosage is seldom, solves mould in process with low-down cost The problems such as tool pollution and device in Gas, injection efficiency and article surface performance is set to be improved significantly.
Brief description of the drawings
Fig. 1 is the extraction of lipid device used in benzoic acid content test method that dissociates in Semi-aromatic polyamide resin of the present invention Schematic diagram.
Embodiment
The present invention is further illustrated below by embodiment, and following embodiments are the preferable embodiment party of the present invention
Formula, but embodiments of the present invention and from the limitation of following embodiments.
Raw material of the present invention derives from commercial products；
Embodiment 1-17, comparative example 1-7：
The preparation of semiaromatic polyamide composition：
Reaction raw materials are added by the formula of table 1 in autoclave pressure, vacuumizes and is filled with high-purity argon gas as protection gas, start to react.Will Reaction mixture be warming up to 220 DEG C of -230 DEG C of stirring 3-5 it is small when, then open valve slowly pressure release draining, while keep temperature It is constant with pressure.Draining always to displacement reaches the 70% of input amount of deionized water.Start to warm up at this time to 250 DEG C -270 DEG C, When constant temperature 2 is small.Valve discharging is opened after the completion of reaction, obtains prepolymer.The fusing point of prepolymer is tested, is set to T DEG C.Prepolymer in After when vacuum drying 24 is small at 80 DEG C, prepolymer obtains semi-aromatic polyamides less than solid-phase tack producing is carried out at 40-70 DEG C of fusing point Polyimide resin.
The preparation of semiaromatic polyamide composition composition：
The Semi-aromatic polyamide resin that is prepared into table 1 by the formula of table 2, reinforcing material, additive etc. mix in high mixer After closing uniformly, added by main spout in double screw extruder.Extrusion, crosses water cooling, is granulated and obtains described half after drying Aromatic polyamide composition.
Each performance test methods：
The test method of the fusing point of Semi-aromatic polyamide resin and its prepolymer：
With reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry；Specifically test method is：Using Perkin Elmer The fusing point of Diamond dsc analysis instrument test samples；10 DEG C/min of heating rate；
The test method of Semi-aromatic polyamide resin relative viscosity：
Semiaromatic polyamide composition relative viscosity assay method, with reference to GB12006.1-89；Specifically test method is：25 DEG C ± The relative viscosity η for the semiaromatic polyamide composition that concentration is 10mg/ml is measured in 0.01 DEG C of 98% concentrated sulfuric acidr；
Free benzoic acid content test method in Semi-aromatic polyamide resin：
The free benzoic acid of extraction：Semi-aromatic polyamide resin 10.0g is weighed, free benzene is carried out using device as shown below Formic acid extracts.Resin is placed in fat extractor（See Fig. 1）, 250.0ml ethanol is added thereto, is heated to alcohol reflux, is returned Flow 5 drops/sec of condensate liquid drop frequency.24h is extracted, extract is then concentrated into 5.0ml afterwards；The free benzoic acid content of detection is pressed Free benzoic acid content is tested according to following document test methods：Niu Bo, Zou Qinghua Sorbicacid In Soy By Gas Chromatographies With content [J] Chinese Medicine guides of benzoic acid, 2011,9 (12):218-219.
Mold fouling situation test method：
Set injection temperature be higher than Semi-aromatic polyamide resin 15 DEG C of fusing point, then 40 DEG C colour table mould 50 × 30 × Semiaromatic polyamide composition moulding compound is injected in 2mm, and is kept for 25 seconds in the mould.Then demould, observe mould table Face pollution condition：Zero represents pollution condition, pollution more serious more than zero.
Table 1：The preparation of Semi-aromatic polyamide resin and each the performance test results
Continued 1
Table 2：The preparation of semiaromatic polyamide composition composition and mold fouling test case（Percentage by weight）
As it can be seen from table 1 by controlling the dosage of n,N-Dimethylformamide in polymerization process effectively to control finished product In dissociate benzoic acid content.When the dosage of n,N-Dimethylformamide is in the range of 0.5 ~ 5.0wt%, its usage amount is bigger, into The benzoic acid to dissociate in product is fewer.
From table 2 it can be seen that the moulding compound done using the relatively low Semi-aromatic polyamide resin containing free benzoic acid, Mold fouling is more slight；And, direct shadow serious using the moulding compound mold fouling that the higher resin of benzoic acid content is done Ring injection efficiency and article surface performance.

Claims (21)

1. a kind of Semi-aromatic polyamide resin, it is characterised in that the gross weight based on Semi-aromatic polyamide resin, dissociate benzene The content of formic acid is less than 200ppm.
2. Semi-aromatic polyamide resin according to claim 1, it is characterised in that the content of free benzoic acid is less than 100ppm, is preferably less than 50ppm, more preferably less than 30ppm.
3. Semi-aromatic polyamide resin according to claim 1, it is characterised in that it is by derived from following repetition list Member is formed：
(a) terephthalic acid (TPA) either its derivative and optionally one or more other aromatics or aliphatic diacid；
(b) one or more aliphatic diamines with 10 to 20 carbon atoms, and it is optionally one or more with 4 to 9 The aliphatic diamine of carbon atom；
(c) optionally one or more amino carboxylic acids and/or lactams；
Wherein, terephthalic acid (TPA) accounts for the 50-100mol% of (a), and one or more have the aliphatic diamine of 10 to 20 carbon atoms The 50-100mol% of (b) is accounted for, one or more amino carboxylic acids and/or lactams account for the 0-25mol% of the total amount of (a)+(b)+(c).
4. Semi-aromatic polyamide resin according to claim 1, it is characterised in that it is by derived from following repetition list Member is formed：
(a) terephthalic acid (TPA) either its derivative and optionally one or more other aromatics or aliphatic diacid；
(b) one or more aliphatic diamines with 4 to 9 carbon atoms, and it is optionally one or more with 10 to 20 The aliphatic diamine of carbon atom；
(c) optionally one or more amino carboxylic acids and/or lactams；
Wherein, terephthalic acid (TPA) accounts for the 30-100mol% of (a), and the aliphatic diamine that one or more have 4 to 9 carbon atoms accounts for (b) 50-100mol%, one or more amino carboxylic acids and/or lactams account for the 0-25mol% of the total amount of (a)+(b)+(c).
5. Semi-aromatic polyamide resin according to claim 1, it is characterised in that it is by derived from following repetition list Member is formed：
(a) terephthalic acid (TPA) either its derivative and optionally one or more other aromatics or aliphatic diacid；
(b) one or more aliphatic diamines with 4 to 9 carbon atoms, and it is optionally one or more with 10 to 20 The aliphatic diamine of carbon atom；
(c) optionally one or more amino carboxylic acids and/or lactams；
Wherein, terephthalic acid (TPA) accounts for the 5-30mol% of (a), and the aliphatic diamine that one or more have 4 to 9 carbon atoms accounts for (b) 50-100mol%, one or more amino carboxylic acids and/or lactams account for the 0-25mol% of the total amount of (a)+(b)+(c).
6. according to claim 1-5 any one of them Semi-aromatic polyamide resins, it is characterised in that the semi-aromatic Polyamide is formed by 3 kinds or more than 3 kinds monomer polymerizations.
7. according to claim 1-5 any one of them Semi-aromatic polyamide resins, it is characterised in that the other virtue Race or aliphatic diacid are selected from M-phthalic acid, ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pungent two In acid, 2- methyl suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid or tetracosandioic acid One or more；The aliphatic diamine of 10 to 20 carbon atoms is selected from decamethylene diamine, hendecane diamines, dodecane two Amine, tridecane diamine, tetradecane diamines, pentadecane diamines, hexadecane diamines, heptadecane diamines, octadecamethylene diamine, nonadecane two One or more in amine, eicosane diamines；The aliphatic diamine of 4 to 9 carbon atoms be selected from butanediamine, pentanediamine, One or more in hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 2- methyl octamethylenediamines；The amino carboxylic acid or lactams Selected from 6-aminocaprolc acid, caprolactam, 10- aminocapric acids, 11- aminoundecanoic acids, 11 lactams, 12-aminolauric acid or One or more in lauric lactam.
8. Semi-aromatic polyamide resin according to claim 3, it is characterised in that the repetitive unit（b）Comprise only 1,10- decamethylene diamines.
9. Semi-aromatic polyamide resin according to claim 4 or 5, it is characterised in that the repetitive unit（b）Containing only There are 1,6- hexamethylene diamines.
10. according to claim 3-5 any one of them Semi-aromatic polyamide resins, it is characterised in that the repetitive unit （b）Comprise only 1,6- hexamethylene diamines and 1,10- decamethylene diamines.
11. according to claim 3-5 any one of them Semi-aromatic polyamide resins, it is characterised in that the repetitive unit （c）Content is 0.
12. according to claim 1-5 any one of them Semi-aromatic polyamide resins, it is characterised in that at 25 DEG C ± 0.01 DEG C 98% concentrated sulfuric acid in measure concentration be 10mg/ml, the relative viscosity of Semi-aromatic polyamide resin is 1.7-2.8, preferably 1.85-2.45, more preferably 2.0-2.3.
13. according to claim 1-5 any one of them Semi-aromatic polyamide resins, it is characterised in that the semi-aromatic Polyamide fusing point is 280-340 DEG C, preferably 290-330 DEG C, more preferably 295-325 DEG C.
14. according to claim 1-5 any one of them Semi-aromatic polyamide resins, it is characterised in that the semi-aromatic Polyamide fusing point is 240-279 DEG C, preferably 245-270 DEG C.
15. according to the Semi-aromatic polyamide resin any one of claim 1,2,3,4,5 or 13 or 14, its feature exists In the Semi-aromatic polyamide resin only has a fusing point.
16. according to claim 1-5 any one of them Semi-aromatic polyamide resins, it is characterised in that the semi-aromatic Polyamide is amorphous, crystallite or undefined structure.
17. the polymerization of claim 1-16 any one of them Semi-aromatic polyamide resins, it is characterised in that to feed intake Total monomer weight, n,N-Dimethylformamide, the N of 0.5-5wt%, N- diethyl first are added into system in polymerization stage One or more in acid amides, dimethyl sulfoxide (DMSO).
18. a kind of polyamide moulding composition for including claim 1-17 any one of them semiaromatic polyamide compositions, it is special Sign is, by weight percentage, composed of the following components：
（A）Semiaromatic polyamide composition 30-95wt%；
（B）Reinforcing material 0-70wt%；
（C）Additive 0-50wt%；
Wherein,（A）+（B）+（C）=100%.
19. polyamide moulding composition according to claim 18, it is characterised in that the shape of the reinforcer is fibre Shape is tieed up, its average length is 0.01mm-20mm, is preferably 0.1mm-6mm；Its draw ratio is 5:1-2000:1, it is preferably 30:1- 600:1；Gross weight based on polyamide moulding composition, the content of the reinforcer is 10-50 parts, is preferably 15 part -40 Part；The reinforcer is inorganic reinforcing filler or organic reinforcing fillers, and the inorganic reinforcing filler is selected from glass fibre, metatitanic acid Potassium fiber, the glass fibre of clad, ceramic fibre, wollastonite fibre, metallic carbide fibres, metal-cured fiber, stone Cotton fiber, alumina fibre, silicon carbide fibre, the one or more of gypsum fiber or boron fibre, are preferably glass fibre；It is described Organic reinforcing fillers are selected from aramid fibre and/or carbon fiber.
20. polyamide moulding composition according to claim 18, it is characterised in that the shape of the reinforcer is non- Threadiness, its average grain diameter be 0.001 μm -100 μm, be preferably 0.01 μm -50 μm, selected from potassium titanate crystal whisker, ZnOw, Aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophillite, bentonite, montmorillonite, lithium cover De- soil, synthetic mica, asbestos, alumino-silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, Magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride, The one or more of carborundum or silica.
21. polyamide moulding composition according to claim 18, it is characterised in that the additive be selected from fire retardant, Impact modifying agent, other polymers, the one or more of processing aid；The fire retardant is halogen-system fire retardant or halogen-free resistance Fire agent, preferably halogen-free flame-retardant；The other polymers are preferably fatty polyamide, polyolefin homopolymer, ethene-α-alkene The one or more of hydrocarbon copolymer, vinyl-acrylate copolymer.
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