WO2018049808A1 - Semi-aromatic copolyamide resin and polyamide molding composition consisting of semi-aromatic copolyamide resin - Google Patents

Abstract

Disclosed are a semi-aromatic copolyamide resin and a polyamide molding composition consisting of the semi-aromatic copolyamide resin. The semi-aromatic copolyamide resin consists of the following repeat units: (A) 26-80 mol% of units derived from para-aminobenzoic acid; (B) 0-37 mol% of units derived from diamine having 4-36 carbon atoms; (C) 0-37 mol% of units derived from diacid having 6-36 carbon atoms; and (D) 0-74 mol% of units derived from amino acid or lactam having 6-36 carbon atoms, wherein (A)+(B)+(C)+(D)=100 mol%, and the (D) units do not comprise units derived from 11-aminoundecanoic acid or 11-lactam. The semi-aromatic copolyamide resin of the present invention, obtained by replacing terephthalic acid with a para-aminobenzoic acid monomer and controlling the content of para-aminobenzoic acid units, has high heat resistance, high thermal stability, good fluidity, and low water absorption rate. The polyamide molding composition consisting of the semi-aromatic copolyamide resin also has obvious performance advantages in water absorption rate and thermal stability.

Description

Semi-aromatic copolyamide resin and polyamide molding composition composed thereof Technical field

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.

Background technique

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.

For the above problems of PA66, 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.

At present, it is generally believed that the "aromatic" units of semi-aromatic polyamides are mostly derived from terephthalic acid, and other sources for "aromatic" units are less involved.

Mitsubishi has developed the famous MXD6 product based on m-xylylenediamine and adipic acid. 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. However, due to The p-aminobenzoic acid content is low, and the obtained semi-aromatic polyamide has a low melting point. For example, the examples thereof give a copolymer of PABA and a salt of 66, which is contained in all monomer units in an amount of 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".

In view of the above, there is a need in the art for a semi-aromatic copolyamide resin based on or based on "non-terephthalic acid" monomers having high heat resistance, high thermal stability, low water absorption, and a polyamide composed thereof. Molding composition.

Summary of the invention

In order to overcome the shortcomings and deficiencies of the prior art, 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, high heat stability, excellent fluidity and low water absorption. A monomeric semi-aromatic copolyamide resin.

Another object of the present invention is to provide a polyamide molding composition comprising the above semi-aromatic copolyamide resin.

The invention is achieved by the following technical solutions:

A semi-aromatic copolyamide resin, expressed as a percentage by mole, comprising repeating units of the following components:

(A) 26-80 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

(B) from 0 to 37 mol%, based on the amount of all monomer units, derived from a diamine unit having from 4 to 36 carbon atoms;

(C) from 0 to 37 mol%, based on the amount of all monomer units, derived from a diacid unit having 6 to 36 carbon atoms;

(D) from 0 to 74 mol%, based on the total amount of monomer units, derived from an amino acid or lactam unit having from 6 to 36 carbon atoms;

Wherein (A) + (B) + (C) + (D) = 100 mol%, and the (D) unit does not contain a unit derived from 11-aminoundecanoic acid or undecanolactam.

As a further preferred embodiment of the present invention, the semi-aromatic copolyamide resin, in terms of percentage by mole, comprises repeating units of the following components:

(A) 26-80 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

(B) from 10 to 37 mol%, based on the total of the monomer units, derived from a diamine unit having from 4 to 36 carbon atoms;

(C) from 10 to 37 mol% based on the amount of all monomer units derived from a diacid unit having 6 to 36 carbon atoms;

Wherein (A) + (B) + (C) = 100 mol%.

As a further preferred embodiment of the present invention, the semi-aromatic copolyamide resin, in terms of percentage by mole, comprises repeating units of the following components:

(A) 26-80 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

(D) from 20 to 74 mol%, based on the amount of all monomer units, derived from an amino acid or lactam unit having from 6 to 36 carbon atoms;

Wherein (A) + (D) = 100 mol%, the (D) unit does not comprise a unit derived from 11-aminoundecanoic acid or undecanolactam.

As a further preferred embodiment of the present invention, the semi-aromatic copolyamide resin, in terms of percentage by mole, comprises repeating units of the following components:

(A) 35-60 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

(B) 5-25 mol% of diamine units derived from 4 to 36 carbon atoms, based on the total amount of monomer units;

(C) from 2 to 25 mol% based on the amount of all monomer units derived from a diacid unit having from 6 to 36 carbon atoms;

(D) 20-55 mol% of an amino acid or lactam unit derived from 6 to 36 carbon atoms, based on the total amount of monomer units;

Wherein (A) + (B) + (C) + (D) = 100 mol%, the (D) unit does not comprise a unit derived from 11-aminoundecanoic acid or undecanolactam.

The melting point of the above 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%; melt viscosity retention rate ≥ 85%; wherein the water absorption rate is tested by: injecting the sample into a 20 mm × 20 mm × 2 mm part, the weight of which is a0, and then placing it in 95 ° C water for 240 h, weighing it as a1, Water absorption rate = (a1 - a0) / a0 * 100%; the melt viscosity retention rate test method is: melt viscosity test on Dynisco LCR-7000 capillary rheometer, die mining With a CZ394-20 die, the shear rate is 1000 s-1 and the test temperature = (Tm + 15) °C. The melt viscosities at 5 min and 20 min of melting time were tested separately, and were recorded as MV 5 min and MV 20 min, and the melt viscosity retention ratio was MV 20 min / MV 5 min.

Wherein 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; Or a branched aliphatic diamine is selected from the group consisting of 1,4-butanediamine, 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-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1, One or more of 18-octadecanediamine; the cycloaliphatic diamine is selected from the group consisting of cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane (BAC), isophorone Diamine, norbornane dimethylamine, 4,4'-diaminodicyclohexylmethane (PACM), 2,2-(4,4'-diaminodicyclohexyl)propane (PACP), 3,3' One or more of dimethyl-4,4'-diaminodicyclohexylmethane (MACM); the araliphatic diamine is selected from the group consisting of Dimethylamine (MXDA).

Wherein, 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).

The invention also discloses a polyamide molding composition comprising the above semi-aromatic copolyamide resin, which comprises the following components in parts by weight:

Semi-aromatic copolyamide resin 30-100 parts;

Reinforcing filler 0-70 parts;

Additive 0-50 parts;

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;

If 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. Fibrous reinforcing filler When the content is within the above range, 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, silicon carbide fiber, One or more of gypsum fiber or boron fiber, preferably glass fiber;

The use of 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 μm to 100 μm, preferably from 0.01 μm to 50 μm.

When the average particle diameter of the reinforcing filler is less than 0.001 μm, it will result in poor melt processability of the polyamide resin; when the average particle diameter of the reinforcing filler is more than 100 μm, 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.

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.

In order to obtain a more excellent mechanical property of the polyamide molding composition, the inorganic reinforcing filler may be functionally treated with a coupling agent.

Wherein 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, One or more of 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 γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4- One or more of epoxycyclohexyl)ethyltrimethoxysilane;

The mercapto group-containing alkoxysilane compound is selected from the group consisting of γ-mercaptopropyltrimethoxysilane and/or γ-mercaptopropyltriethoxysilane;

The ureido group-containing alkoxysilane compound is selected from the group consisting of γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-(2-ureidoethyl)-terminated aminopropyl group One or more of a trimethoxysilane;

The isocyanate group-containing alkoxysilane compound is selected from the group consisting of γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-Isocyanatepropylmethyldiethoxysilane, γ-Isocyanatepropylethyldimethoxysilane, γ-Isocyanatepropylethyldiethoxysilane, γ-Isocyanatepropyltrichloride One or several of silanes;

The terminal amino group-containing alkoxysilane compound is selected from the group consisting of γ-(2-terminal aminoethyl)-terminated propylmethyldimethoxysilane and γ-(2-terminal aminoethyl) terminal One or more of aminopropyltrimethoxysilane and γ-terminal aminopropyltrimethoxysilane;

The hydroxyl group-containing alkoxysilane compound is selected from the group consisting of γ-hydroxypropyltrimethoxysilane and/or γ-hydroxypropyltriethoxysilane;

The alkoxysilane compound containing a carbon-carbon unsaturated group is selected from the group consisting of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and N-β-(N-vinylbenzyl One or more of terminal aminoethyl)-γ-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 γ-methacryloxypropyltrimethoxysilane, γ-(2-terminal aminoethyl)-terminated propylmethyldimethoxysilane, γ-( 2-terminal aminoethyl)-terminated aminopropyltrimethoxysilane, γ-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.

It is also possible to directly add an organosilane system while melt-kneading the inorganic reinforcing filler and the polyamide resin. The compounds were blended in situ.

Wherein, 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.

When 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 is poorly dispersed in the polyamide resin. The risk eventually 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-α-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. One or more of a benzene phosphate, a butyl benzene phosphate or a phosphinate; preferably a phosphinate;

The phosphinate compound is represented by a compound represented by, for example, the following formula I and/or II.

In Formula I and Formula 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, and x is 1 or 2.

More specific examples of the phosphinate compound 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 Aluminum, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-propylphosphinate, zinc methyl-n-propylphosphinate, Calcined bis(methylphosphinic acid) calcium, methane bis(methylphosphinic acid) magnesium, methane bis(methylphosphinic acid) aluminum, methane bis(methylphosphinic acid) zinc, benzene-1,4 -(Dimethylphosphinic acid) calcium, benzene-1,4-(dimethylphosphinic acid) magnesium, benzene-1,4-(dimethylphosphinic acid) aluminum, benzene-1,4-( Zinc dimethylphosphinic acid, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, diphenylphosphinium Calcium acid, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate, etc., preferably calcium dimethyl phosphinate, aluminum dimethyl phosphinate, Zinc methylphosphinate, I methyl phosphinic acid, aluminum ethyl methylphosphinate, zinc ethyl methylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate Zinc diethylphosphinate, more preferably aluminum diethylphosphinate.

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.

Wherein, the impact modifier may be natural rubber, polybutadiene, polyisoprene, polyisobutylene, butadiene and/or isoprene and styrene or with styrene derivatives and copolymerization with others Monomeric copolymer, 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 be a graft rubber having a crosslinked elastomer core. The crosslinked elastomer core is composed of butadiene, isoprene or alkyl acrylate, and has a graft shell composed of polystyrene or may be a non-polar or polar olefin homopolymer or copolymer. For example, ethylene propylene rubber, ethylene-propylene-diene rubber, or ethylene-octene rubber, or ethylene-vinyl acetate rubber, or non-polar obtained by grafting or copolymerizing with an anhydride, (meth)acrylic acid or its ester. Or a polar olefin homopolymer or copolymer; the impact modifier may also be a carboxylic acid functionalized copolymer such as poly(ethylene-co-(meth)acrylic acid) or poly(ethylene-1-olefin) - co-(meth)acrylic acid), wherein the 1-olefin is an alkene or an unsaturated (meth) acrylate having more than 4 atoms, including those copolymers in which acid groups are neutralized to some extent by metal ions .

An impact modifier based on styrene monomer (styrene and styrene derivatives) and other vinyl aromatic monomers, 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 a combination of these types of impact modifiers. 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. In the case of 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.

Other alkenyl aromatic compounds which may be used together with styrene or in admixture with styrene are vinyl groups which are substituted by a C1-20 hydrocarbyl group or by a halogen atom at the aromatic ring and/or on the C=C double bond. Aromatic monomer.

Examples of alkenyl aromatic monomers are 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, α-methylstyrene, and vinylnaphthalene.

Preference is given to using styrene, α-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.

Examples of 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. Preference is given to 1,3-butadiene and isoprene, in particular 1,3-butadiene (hereinafter abbreviated form Diene)).

The alkenyl aromatic monomer used preferably comprises styrene, and 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.

In addition to the styrene monomer and the diene monomer, other additional monomers can be used simultaneously. 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. Examples of 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, diallyl and divinyl ethers of diols, divinylbenzene and vinyl acetate. ester.

In addition to the conjugated diene, the hydrogenated block copolymer further comprises, if appropriate, 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%. By hydrogenation of a styrene-butadiene copolymer and hydrogenation of a styrene-butadiene-styrene copolymer, a hydrogenated block copolymer, namely a styrene-(ethylene-butylene) diblock copolymer and benzene, is obtained. Ethylene-(ethylene-butylene)-styrene triblock copolymer.

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.

Examples of 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(α-methylstyrene) polybutadiene-poly(α-methylstyrene), and combinations thereof.

Suitable non-hydrogenated block copolymers which are commercially available under the trademarks (Phillips), (Shell), (Dexco) and (Kuraray) a variety of products.

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. -α-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. One or more of a polymer of a diacid, an aliphatic diamine, and a lactam. Including, but not limited to, polyhexamethylene adipamide (PA66), polycaprolactam (PA6), polysebacyldiamine (PA610), polysebacic acid diamine (PA1010), adipic acid-hexane Amine-caprolactam copolymer (PA66/6), polyundecanolactam (PA11), polydodelactam (PA12), and mixtures of two or more thereof.

The ethylene-α-olefin copolymer is preferably an EP elastomer and/or an EPDM elastomer (ethylene-propylene rubber and ethylene-propylene-diene rubber, respectively). For example, the elastomer may include an elastomer based on an ethylene-C3-C12-α-olefin copolymer containing 20% by weight to 96% by weight, preferably 25% by weight to 85% by weight of ethylene, wherein C3-C12-α- 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. One or several of rubber, LLDPE, VLDPE.

Alternatively or additionally (for example in a mixture), the further polymer may further comprise a terpolymer based on an ethylene-C3-C12-α-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-α-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.

Other possible forms of the other polymers are ethylene-butene copolymers and mixtures (blends) comprising these systems.

Preferably, 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. Or 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. Optimal 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 above possible systems for the other polymers can also be used in the form of a mixture.

Further, 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 may be bonded by copolymerization or grafting onto the elastomeric polyolefin.

Further, 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 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.

Thus, the impact modifiers of the present invention include homopolymers or copolymers of olefins (e.g., ethylene, propylene, 1-butene), such as polybutene-1, or olefins and copolymerizable monomers (e.g., vinyl acetate). a copolymer of (meth) acrylate, and methyl hexadiene).

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.

Examples of commercially available impact modifiers that can be used in the additive component are:

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.

Preference is also given to ionic polymers in which the polymer-bonded carboxyl groups are all bonded or bonded to each other by metal ions.

Particularly preferred are 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.

Further, various 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.).

In order to obtain the molded article of the present invention, 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. As a specific use, it is useful in the following applications: automotive engine cooling water system components, especially radiator tank components such as the top and bottom of the radiator tank, coolant storage Components such as spares, water pipes, water pump casings, pump impellers, valves, etc., which are used in contact with cooling water in the engine room of a car, with switches, ultra-small slide switches, DIP switches, switch housings, lamp holders, and strapping Belt, connector, connector housing, connector housing, IC socket type, bobbin, spool cover, relay, relay box, capacitor housing, internal parts of the motor, small motor housing, gear cam, equalization wheel, Gaskets, insulators, fasteners, buckles, clamps, bicycle wheels, casters, helmets, terminal blocks, housings for power tools, insulation for starters, spoilers, tanks, radiator tanks, chamber tanks ( Chamber tank), liquid storage tank, fuse box, air purifier housing, air conditioning fan, terminal housing, wheel cover, suction and exhaust pipe, bearing support, cylinder head cover, intake manifold, water pipe impeller, Clutch separation lever, speaker diaphragm, heat-resistant container, microwave oven parts, rice cooker parts, printer ribbon guides, etc. Representative electrical/electronic related parts, car/vehicle Related parts, home appliances/office electrical components, computer related components, fax/copier related components, mechanical related components, and other various uses.

The polyamide molding composition of the invention has a water absorption rate of ≤1.0% and a melt viscosity retention rate of ≥85%, wherein the water absorption rate is tested by: injecting the sample into a 20 mm×20 mm×2 mm part, the weight thereof After a0, and then placed in 95 ° C water for 240h, the weight is weighed as a1, water absorption = (a1-a0) / a0 * 100%; the melt viscosity retention rate is tested by: melt The viscosity test was carried out on a Dynisco LCR-7000 capillary rheometer using a CZ394-20 die with a shear rate of 1000 s-1 and a test temperature = (Tm + 15) °C. The melt viscosities at 5 min and 20 min of melting time were tested separately, and were recorded as MV 5 min and MV 20 min, and the melt viscosity retention ratio was MV 20 min / MV 5 min.

Compared with the prior art, the invention has the following beneficial effects:

The present invention prepares a semi-aromatic copolyamide resin which has high heat resistance, high heat stability and excellent flow by replacing terephthalic acid with p-aminobenzoic acid monomer and controlling the content of p-aminobenzoic acid unit. Properties such as properties and low water absorption, the polyamide molding composition composed of the semi-aromatic copolyamide resin also has obvious advantages in water absorption and thermal stability.

detailed description

The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.

The raw materials used in the present invention are all derived from commercially available products.

Performance test method:

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 water absorption: The sample was injection molded into a 20 mm × 20 mm × 2 mm part, and its weight was recorded as a ₀ . Then, after placing it in water at 95 ° C for 240 h, the weight was weighed as a1. Then, the water absorption rate = (a ₁ - a ₀ ) / a ₀ * 100%.

Test method for thermal stability (melt viscosity retention): The melt viscosity test was carried out on a Dynisco LCR-7000 capillary rheometer using a CZ394-20 die. Shear rate 1000 s ^-1 , test temperature = (T _m +15) °C. The melt viscosities at 5 min and 20 min of melting time were tested separately, and were recorded as MV _{5 min} and MV _{20 min} , and the melt viscosity retention rate was MV _{20 min} / MV _{5 min} .

Synthesis of semi-aromatic copolyamide resins A-H and A'-H'

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. After the reaction is completed, 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 melt viscosity retention of the obtained semi-aromatic copolyamide resin are shown in Table 1.

Table 1:

	Resin A	Resin B	Resin C	Resin D	Resin E	Resin F	Resin G	Resin H
Para-aminobenzoic acid/mol	30	36	40	50	60	36	60	80
1,6-hexanediamine/mol	35	32		25		7	10	4
Adipic acid/mol	35	32		25		7	10	4
Caprolactam/mol			60		40	50	20	12
Melting point / °C	279	315	327	332	344	313	342	355
Intrinsic viscosity / dl / g	0.88	0.89	0.91	0.89	0.93	0.90	0.92	0.95
Water absorption rate /%	1.6	1.8	1.7	1.3	1.2	1.5	1.3	1.9
Melt viscosity retention rate /%	95	91	92	98	97	93	91	85

Continued Table 1:

It can be seen from Table 1 that the content of p-aminobenzoic acid in the resin AG is controlled within the range of 26-80 mol, and the prepared semi-aromatic copolyamide resin has both high heat resistance, high heat stability, excellent fluidity and Low water absorption and other advantages. The content of p-aminobenzoic acid in the resins A' and B' 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 resins C' and D' is too high, resulting in the melting point of the resin being higher than the decomposition temperature. There is no application value; the resins E', F' and G' use 11-aminoundecanoic acid as a comonomer, resulting in a low viscosity retention of the resin and poor thermal stability.

Examples 1-9 and Comparative Examples 1-5: Preparation of Polyamide Molding Compositions

According to the formulation of Table 2, the semi-aromatic copolyamide resin, flame retardant, processing aid, etc. are uniformly mixed in a high-mixer, and then added to the twin-screw extruder through the main feed port to reinforce the filler through the side feed scale. Side feeding. 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.

Table 2 Component and performance test results of polyamide molding composition (parts by weight)

Continued Table 2:

As can be seen from Table 2, the polyamide molding composition comprising the semi-aromatic copolyamide resin of the present invention has a significant advantage in terms of water absorption and thermal stability under the same molding composition formulation.

Claims (12)

1. A semi-aromatic copolyamide resin characterized by a percentage by mole, consisting of the following repeating units:

   (A) 26-80 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

   (B) from 0 to 37 mol%, based on the amount of all monomer units, derived from a diamine unit having from 4 to 36 carbon atoms;

   (C) from 0 to 37 mol%, based on the amount of all monomer units, derived from a diacid unit having 6 to 36 carbon atoms;

   (D) from 0 to 74 mol%, based on the total amount of monomer units, derived from an amino acid or lactam unit having from 6 to 36 carbon atoms;

   Wherein (A) + (B) + (C) + (D) = 100 mol%, and the (D) unit does not contain a unit derived from 11-aminoundecanoic acid or undecanolactam.
2. The semi-aromatic copolyamide resin according to claim 1, wherein the molar percentage is composed of the following repeating units:

   (A) 26-80 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

   (B) from 10 to 37 mol%, based on the total of the monomer units, derived from a diamine unit having from 4 to 36 carbon atoms;

   (C) from 10 to 37 mol% based on the amount of all monomer units derived from a diacid unit having 6 to 36 carbon atoms;

   Wherein (A) + (B) + (C) = 100 mol%.
3. The semi-aromatic copolyamide resin according to claim 1, wherein the molar percentage is composed of the following repeating units:

   (A) 35-60 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

   (B) 5-25 mol% of diamine units derived from 4 to 36 carbon atoms, based on the total amount of monomer units;

   (C) from 2 to 25 mol% based on the amount of all monomer units derived from a diacid unit having from 6 to 36 carbon atoms;

   (D) 20-55 mol% of an amino acid or lactam unit derived from 6 to 36 carbon atoms, based on the total amount of monomer units;

   Wherein (A) + (B) + (C) + (D) = 100 mol%, the (D) unit does not contain derivatives Units from 11-aminoundecanoic acid or undecanolactam.
4. The semi-aromatic copolyamide resin according to claim 1, wherein the molar percentage is composed of the following repeating units:

   (A) 26-80 mol% of units derived from p-aminobenzoic acid based on the total amount of monomer units;

   (D) from 20 to 74 mol%, based on the amount of all monomer units, derived from an amino acid or lactam unit having from 6 to 36 carbon atoms;

   Wherein (A) + (D) = 100 mol%, and the (D) unit does not contain a unit derived from 11-aminoundecanoic acid or undecanolactam.
5. The semi-aromatic copolyamide resin according to any one of claims 1 to 4, wherein the melting point of the semi-aromatic copolyamide resin is 270-360 ° C according to the ASTM D3418-2003 standard; and the intrinsic viscosity is referred to GB12006. 1-89 is 0.80-1.0 dl / g; water absorption rate ≤ 2.0%; melt viscosity retention rate ≥ 85%; wherein the water absorption rate is tested by: injection molding the sample into a 20 mm × 20 mm × 2 mm part, the weight of which After a0, and then placed in 95 ° C water for 240h, the weight is weighed as a1, water absorption = (a1-a0) / a0 * 100%; the melt viscosity retention rate is tested by: melt The viscosity test was carried out on a Dynisco LCR-7000 capillary rheometer. The die was a CZ394-20 die with a shear rate of 1000 s-1 and a test temperature = (Tm + 15) ° C. The melting time was tested for 5 min and 20 min, respectively. The melt viscosity at the time, denoted as MV5min and MV20min, then the melt viscosity retention rate = MV20min/MV5min.
6. The semi-aromatic copolyamide resin according to any one of claims 1 to 3, wherein the diamine unit having 4 to 36 carbon atoms is selected from a linear or branched aliphatic diamine or a cycloaliphatic One or more of a group of diamines, arylaliphatic diamines; the linear or branched aliphatic diamines being selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine, 2-methyl -1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylene Diamine, 2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 2-butyl-2- Ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine One or more of 1,18-octadecanediamine; the cycloaliphatic diamine is selected from the group consisting of cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, isophorone Diamine, norbornane dimethylamine, 4,4'-diaminodicyclohexylmethane, 2,2-(4,4'-diaminodicyclohexyl)propane, 3,3'-dimethyl-4 One or more of 4'-diaminodicyclohexylmethane; Between the aromatic diamine is selected from m-xylylenediamine.
7. The semi-aromatic copolyamide resin according to any one of claims 1 to 3, wherein the diacid unit having 6 to 36 carbon atoms is selected from the group consisting of naphthalene dicarboxylic acid, isophthalic acid, and dimethic acid. Acid, suberic acid, bismuth Diacid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid, octadecanedioic acid, two One or more of a polymeric acid, cis and/or trans cyclohexane-1,4-dicarboxylic acid, cis and/or trans cyclohexane-1,3-dicarboxylic acid.
8. A polyamide molding composition comprising the semi-aromatic copolyamide resin according to any one of claims 1 to 7, in parts by weight, comprising the following components:

   Semi-aromatic copolyamide resin 30-100 parts;

   Reinforcing filler 0-70 parts;

   Additive 0-50 parts.
9. The polyamide molding composition according to claim 8, wherein the reinforcing filler has a fibrous shape having an average length of from 0.01 mm to 20 mm, preferably from 0.1 mm to 6 mm; and an aspect ratio of 5 : 1-2000:1, preferably 30:1-6-00:1; the reinforcing filler is contained in an amount of 10 to 50 parts, preferably 15 parts to 40 parts, based on the total weight of the polyamide molding composition; The reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler 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, One or more of asbestos fibers, alumina fibers, silicon carbide fibers, gypsum fibers or boron fibers, preferably glass fibers; the organic reinforcing filler is selected from the group consisting of aramid fibers and/or carbon fibers.
10. The polyamide molding composition according to claim 8, wherein the reinforcing filler has a non-fibrous shape and has an average particle diameter of from 0.001 μm to 100 μm, preferably from 0.01 μm to 50 μm, selected from the group consisting of titanic acid. Potassium whiskers, zinc oxide whiskers, aluminum borate whiskers, wollastonite, zeolites, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, silicon Aluminate, alumina, silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass One or more of beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide.
11. The polyamide molding composition according to claim 8, wherein the additive is selected from one or more of a flame retardant, an impact modifier, other polymers, and a processing aid; The flammable agent is a halogen-based flame retardant or a halogen-free flame retardant, preferably a halogen-free flame retardant; the other polymer is an aliphatic polyamide, a polyolefin homopolymer, an ethylene-α-olefin copolymer or an ethylene-acrylic acid. One or more of the ester copolymers.
12. The polyamide molding composition according to any one of claims 8 to 11, wherein the polyamide molding composition has a water absorption rate of ≤ 1.0% and a melt viscosity retention ratio of ≥ 85%, wherein water absorption rate The test method is: injection molding the sample into a 20 mm × 20 mm × 2 mm part, the weight of which is recorded as a0, and then After being placed in water at 95 ° C for 240 h, the weight was weighed as a1, water absorption = (a1 - a0) / a0 * 100%; the melt viscosity retention rate was tested by: melt viscosity test at Dynisco LCR - 7000 capillary rheometer, the die adopts CZ394-20 die, shear rate 1000s-1, test temperature = (Tm+15) °C, test the melt viscosity at 5min and 20min respectively. Recorded as MV5min and MV20min, the melt viscosity retention rate = MV20min/MV5min.