CN104262952B - A kind of low potential of hydrogen polyamide moulding composition - Google Patents
A kind of low potential of hydrogen polyamide moulding composition Download PDFInfo
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- 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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- 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
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The invention discloses a kind of low potential of hydrogen polyamide moulding composition, apparent carboxyl-content [m] and the apparent amine groups content [n] of this polyamide moulding composition surely obtained by automatic potential titrator tests are presented: [m]≤550mol/t, [n]≤800mol/t; A kind of above-mentioned low potential of hydrogen polyamide moulding composition, comprises following composition: at least one semiaromatic polyamide composition 10T/PQ of A, 30 ~ 99.9wt%; B, content are strongthener and/or the filler of X, X=0-70wt%; C, content are additive and/or other polymkeric substance of Y, Y=0.1-70wt%; The polyamide moulding composition that the present invention prepares, specific apparent carboxyl and apparent amido is adopted to combine and specific content range, can avoid that the pH-value due to polyamide moulding composition is too high causes the problems such as the easy burn into surface irregularity of its products formed, its products formed presents good erosion resistance and excellent surface property.
Description
Technical field
The present invention relates to polymeric material field, particularly the low potential of hydrogen polyamide moulding composition of one.
Background technology
Polymeric amide is because having good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, there is certain flame retardant resistance etc., it is extensively suitable for, by glass fibre and other filler filling enhancing modified, improving the aspect such as performance and broadened application scope.In recent years semiaromatic polyamide composition due to its resistance toheat and mechanical property more excellent and by focus development.
CN101175791 provides a kind of heat retention stability, hot water resistance and the chemical-resistant with height, and with the binding property of other resin etc. or the Semi-aromatic polyamide resin of excellent compatibility.Terminal amine base unit weight [the NH of this this molecular chain of resin
2] be more than 60mol/t, below 120mol/t, and terminal amine base unit weight and terminal carboxyl(group) amount [COOH] meet [NH
2]/[COOH]>=6.
CN102149748 provides a kind of polyamide resin with improvement processing characteristics.It presents :-be more than or equal to the amine chain end content of 20 μ eq/g; Be less than or equal to the sour chain end content of 100 μ eq/g; With the non-reacted chain end content being more than or equal to 20 μ eq/g.
JP6032980 provides a kind of method improving polyamide moulding composition products formed surface property.That is, the amino or carboxyl end group value of use side carries out modification lower than the polyamide substrate resin of 50meq/kg, and the appearance of molded articles obtained is better.But it only gives the method that single enhancing modified product appearance is improved, that is, only add mineral filler if glass etc. is as additive.And fashionable surface condition is added for the fire retardant, fire retarding synergist etc. of chemical property complexity do not point out.
But above-mentioned patent only defines the specified end group content of polyamide resin, but in actual use procedure, polyamide resin generally all could will be applied through modification.Owing to having carried out high-temperature fusion in modifying process, high-temperature fusion is the polymer terminal group balance of reacting further and degrading inherently.Add and add various additive, in this process, the character of polymkeric substance there occurs certain change.Considerable influence is there is equally in the potential of hydrogen of final product to its application.
The present inventor finds, the polyamide moulding composition with specific acid basicity can solve the problems such as products formed surface is perishable, coarse.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, a kind of products formed surface corrosion-resistant is the object of the present invention is to provide to lose and smooth polyamide moulding composition.
The present invention is achieved by the following technical solutions.
A kind of low potential of hydrogen polyamide moulding composition, apparent carboxyl-content [m] and the apparent amine groups content [n] of this polyamide moulding composition surely obtained by automatic potential titrator tests meet following scope:
[m]≤550mol/t, preferred 30mol/t≤[m]≤450mol/t, most preferably 50mol/t≤[m]≤350mol/t.
[n]≤800mol/t, preferred 50mol/t≤[n]≤750mol/t, most preferably 100mol/t≤[n]≤700mol/t.
A kind of above-mentioned low potential of hydrogen polyamide moulding composition, it comprises following composition:
At least one semiaromatic polyamide composition 10T/PQ of A, 30 ~ 99.9wt%, it comprises derived from following repeating unit:
A1,10T represent the unit obtained by 1，10-diaminodecane and terephthalic acid, and its content is 2-98mo%;
The unit that A2, PQ select free amino acid to obtain, the unit obtained by lactan, the unit be made up of aliphatie diamine and/or cycloaliphatic diamine and dicarboxylic acid, its content is 2-50mol%;
B, content are strongthener and/or the filler of X; Wherein, X=0-70wt%;
C, content are additive and/or other polymkeric substance of Y; Wherein, Y=0.1-70wt%;
Component A, B and C weight ratio sum are 100wt%.
Wherein, based on whole diacid, the terephthalic acid of maximum 98mol% can be replaced by other diacid, and other diacid are selected from m-phthalic acid and other contains aliphatic diacid and/or the cycloaliphatic diacid of 4-36 carbon atom.
Wherein, 1，10-diaminodecane can be replaced by other aliphatic diamine containing 4-36 carbon atom;
Described semiaromatic polyamide composition 10T/PQ, in described component A1, aliphatic diacid and cycloaliphatic diacid are selected from: hexanodioic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, octadecane diacid, dimer acids, cis and/or trans cyclohexane-1,4-dicarboxylic acid, cis and/or trans cyclohexane-1,3-dicarboxylic acid (CHDA) and combination.
Described semiaromatic polyamide composition 10T/PQ, in described component A1 and A2, aliphatie diamine and cycloaliphatic diamine are selected from: straight or branched aliphatic diamine, particularly 1, 4-butanediamine, 1, 5-pentamethylene diamine, 1, 6-hexanediamine, 1, 8-octamethylenediamine (OMDA), 1, 9-nonamethylene diamine (NMDA), 2-methyl isophthalic acid, 8-octamethylenediamine (MODA), 2, 2, 4-trimethylhexamethylenediamine (TMHMD), 2, 4, 4-trimethylhexamethylenediamine (TMHMD), 5-methyl isophthalic acid, 9-nonamethylene diamine, 1, 11-undecane diamines, 2-butyl-2-ethyl-1, 5-pentamethylene diamine, 1, 12-dodecamethylene diamine, 1, 13-tridecane diamine, 1, 14-tetradecane diamines, 1, 16-n-Hexadecane diamines, 1, 18-octadecamethylene diamine, alicyclic diamine, particularly cyclohexanediamine, 1,3-two (end aminomethyl) hexanaphthene (BAC), isophorone diamine, norcamphane dimethylamine, 4,4 '-two end amido dicyclohexyl methyl hydride (PACM), 2,2-(4,4 '-two end amido dicyclohexyl) propane (PACP) and 3,3 '-dimethyl-4,4 '-two end amido dicyclohexyl methyl hydride (MACM), and combination.
Described semiaromatic polyamide composition 10T/PQ, wherein said lactan or amino acid are selected from: hexanolactam (CL), α, omega-amino-caproic acid, α, omega-amino-n-nonanoic acid, α, omega-amino-undeeanoic acid (AUA), laurolactam (LL), omega-amino-laurostearic acid (ADA) and combination thereof.
The present invention is by controlling the content comprising each component in the polyamide moulding composition of above-mentioned polyamide resin, the pH-value of polyamide moulding composition (the present invention to represent the pH-value of polyamide moulding composition with apparent carboxyl-content and apparent amine groups content) is regulated and controled, makes its pH-value meet specific span of the present invention.
The present inventor is surprised to find, and under the pH-value in the specific span of the present invention, the products formed of polyamide moulding composition presents good erosion resistance and excellent surface property.
Prior art does not specifically note the particular combination of pH-value in polyamide moulding composition, does not certainly point out that above-mentioned particular combination can improve the information of the various problem such as erosion resistance and surface property of polyamide moulding composition products formed in the prior art yet.
Wherein, the content of described B component reinforcing filler is preferably 10 ~ 50wt%, is more preferably 15 ~ 40%; Filler content is too low, causes polyamide moulding composition mechanical property poor; Filler content is too high, and polyamide moulding composition product surface is floating fine serious, affects product appearance.
The shape of described reinforcing filler is threadiness, and its mean length is 0.01-20mm, is preferably 0.1 ~ 6mm; Its length-to-diameter ratio is 5:1 ~ 2000:1, is preferably 30:1 ~ 600:1, when fibrous reinforcing filler content is in above-mentioned scope, and the high temperature rigid that polyamide moulding composition will show high heat distortion temperature and increase.
Described reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers;
Described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Use glass fibre not only can improve the mouldability of polyamide moulding composition, and mechanical property such as tensile strength, flexural strength and modulus in flexure can be improved, and improve heat-drawn wire when thermotolerance such as thermoplastic resin composition carries out molding.
Described organic reinforcing fillers is selected from Kevlar and/or carbon fiber.
The shape of described reinforcing filler is Non-fibrous, such as Powdered, particulate state, tabular, needle-like, fabric or felted, its median size is 0.001 ~ 100 μm, be preferably 0.01 ~ 50 μm, will the melt processable of polyamide resin difference be caused when the median size of reinforcing filler is less than 0.001 μm; When the median size of reinforcing filler is greater than 100 μm, bad injection-molded article appearance will be caused.Above-mentioned reinforcing filler can be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.These reinforcing fillers can be hollow; In addition, for swelling property layered silicates such as wilkinite, polynite, lithium montmorillonite, synthetic micas, can use and adopt organic ammonium salt that interlayer ion is carried out the organic montmorillonoid after cationic exchange.
More excellent mechanical property is obtained in order to make polyamide moulding composition, coupling agent can be adopted to carry out functional processing to inorganic reinforcing filler, and wherein coupling agent is selected from isocyanic ester based compound, organosilane based compound, organic titanate based compound, organo-borane based compound, epoxy compounds; Be preferably organosilane based compound;
Wherein, described organosilane based compound be selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group(ing), the alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group, alkoxysilane compound containing trialkylsilyl group in molecular structure containing amino, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group, alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group one or more.
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group(ing) be selected from γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxyl silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-Mercaptopropyltriethoxysilane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups be selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, γ-(2-urea groups ethyl) TSL 8330 one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group be selected from γ-isocyanate group propyl-triethoxysilicane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-isocyanate group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan one or more;
Described containing amino alkoxysilane compound containing trialkylsilyl group in molecular structure be selected from γ-(2-amino-ethyl) amino propyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from γ-hydroxypropyl Trimethoxy silane and/or γ-hydroxypropyl triethoxyl silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group be selected from γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, N-β-(N-vinylbenzylaminoethyl)-gamma-amino propyl trimethoxy silicane hydrochloride one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3-trimethoxy-silylpropyl succinyl oxide;
Described organosilane based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2-amino-ethyl) amino propyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane or 3-trimethoxy-silylpropyl succinyl oxide.
Above-mentioned organosilane based compound conventionally can be adopted to carry out surface treatment to inorganic reinforcing filler, and then itself and polyamide resin are carried out melting mixing, to prepare described polyamide moulding composition; Also directly while inorganic reinforcing filler and polyamide resin melting mixing, organosilane based compound can be added and carries out in-situ blending;
Wherein, the consumption of described coupling agent is 0.05 ~ 10wt% relative to inorganic reinforcing filler weight, is preferably 0.1 ~ 5wt%; When the consumption of coupling agent is less than 0.05wt%, it does not reach the effect of obvious improved mechanical properties; When the consumption of coupling agent is greater than 10wt%, inorganic reinforcing filler easily condenses, and in polyamide resin, disperse bad risk, finally causes mechanical property to decline.
Described additive be selected from fire retardant, impact modifying agent, other polymkeric substance, processing aid one or more; Other polymkeric substance described be preferably fatty polyamide, polyolefin homopolymer, ethene-alpha-olefin copolymer, ethylene-acrylate copolymer one or more; Described processing aid be selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, releasing agent, lubricant, pigment, dyestuff, softening agent, static inhibitor one or more.
Wherein, described fire retardant is the composition of fire retardant or fire retardant and fire-retardant assistance agent, and its content is preferably 10 ~ 40wt%; The too low flame retardant effect that causes of flame retardant agent content is deteriorated, and the too high material mechanical performance that causes of flame retardant agent content declines.
Described fire retardant is halogenated flame retardant or halogen-free flame retardants;
Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecane or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene;
Described halogen-free flame retardants is selected from one or more of the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant.
Described phosphonium flame retardant is selected from one or more of monophosphate aryl phosphate ester, two banks aryl phosphate ester, alkyl phosphonic acid dimethyl ester, phosphonic acids triphenylmethyl methacrylate, phosphonic acids front three phenyl ester, phosphonic acids three (dimethylbenzene) ester, propyl benzene system phosphonic acid ester, butylbenzene system phosphonic acid ester or phosphinates; Be preferably phosphinates;
Phosphinates with the compound represented as shown in the formula (I) and/or (II) for representative.
In formula I and formula (II), R
1and R
2can be identical, also can be different, represent C1 ~ C6-alkyl of straight-chain or branch-like, aryl or phenyl respectively; R
3represent C1 ~ C10-alkylidene group of straight-chain or branch-like, C6 ~ C10-arylidene, C6 ~ C10-alkyl arylene or C6 ~ C10-aryl alkylene; 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 specifically example of phosphinate salt compound comprises dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethylimethyphosphinic acid zinc, diethyl phospho acid calcium, diethyl phospho acid magnesium, aluminum diethylphosphinate, diethyl phospho acid zinc, methyl-n-propylphosphinic acid calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc, first burns two (methyl-phosphinic acid) calcium, methane two (methyl-phosphinic acid) magnesium, methane two (methyl-phosphinic acid) aluminium, methane two (methyl-phosphinic acid) zinc, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) calcium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) magnesium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) aluminium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, methylphenylphosphinic acid aluminium, methylphenylphosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl phosphonic acid zinc etc., preferred dimethylphosphinic acid calcium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid I beggar, ethylimethyphosphinic acid aluminium, ethylimethyphosphinic acid zinc, diethyl phospho acid calcium, aluminum diethylphosphinate, diethyl phospho acid zinc, more preferably aluminum diethylphosphinate.
Phosphinate salt compound as fire retardant can easily obtain from market.The example of the phosphinate salt compound that can obtain from market comprises EXOLITOP1230, OP1311, OP1312, OP930, OP935 etc. that Clariant Corporation (Clariant) manufactures.
The polyamide moulding composition comprising above-mentioned polyamide resin of the present invention, described binder component can also comprise the one or more of impact modifying agents of 45wt% at the most; Be preferably 5 ~ 30wt%.
Wherein, described impact modifying agent can be natural rubber, polyhutadiene, polyisoprene, polyisobutene, divinyl and/or isoprene and vinylbenzene or with styrene derivatives and with the multipolymer of other comonomer, hydrogenated copolymer and/or by grafting or with acid anhydride, (methyl) vinylformic acid or its ester copolymerization and obtained multipolymer; Described impact modifying agent can also be the graft rubber with cross-linked elastomer core, described cross-linked elastomer core is made up of divinyl, isoprene or alkyl acrylate, and there is the graft shell that is made up of polystyrene or can be nonpolar or polar olefin homopolymer or multipolymer, such as ethylene-propylene rubber(EPR), ethylene/propylene/diene rubber, or Ethylene-octene rubber, or ethylene-vinyl acetate rubber, by grafting or with acid anhydride, (methyl) vinylformic acid or its ester copolymerization and the nonpolar or polar olefin homopolymer that obtains or multipolymer; Described impact modifying agent can also be carboxylic acid functionalized multipolymer, such as poly-(ethene-altogether-(methyl) vinylformic acid) or poly-(ethene-1-alkene-altogether-(methyl) vinylformic acid), wherein 1-alkene unsaturated (methyl) acrylate of being alkene or having more than 4 atoms, comprises acid groups and is neutralized those multipolymers to a certain extent by metal ion.
The impact modifying agent of styrene-based monomer (vinylbenzene and styrene derivatives) and other vi-ny l aromatic monomers, it is the segmented copolymer be made up of alkenyl aromatic compounds and conjugated diene, with the hydrogenated block copolymer be made up of alkenyl aromatic compounds and conjugated diene, and the combination of these type impact modifying agents.Described segmented copolymer comprises at least one derived from the block a of alkenyl aromatic compounds and at least one block b derived from conjugated diene.When hydrogenated block copolymer, the ratio of the unsaturated carbon-to-carbon double bond of aliphatics is reduced by hydrogenation.Suitable segmented copolymer is two, three, four and the segmented copolymer with linear chain structure.But, also can use branching and star structure according to the present invention.Obtain branched block copolymer in a known way, such as, by the graft reaction of polymkeric substance " collateral chain " to main polymer chain.
Can use together with vinylbenzene or with other alkenyl aromatic compounds used with cinnamic form of mixtures be aromatic ring and/or in C=C double bond by C1 ~ C20 alkyl or the vi-ny l aromatic monomers that replaced by halogen atom.
The example of alkenyl aromatic monomer is vinylbenzene, p-methylstyrene, alpha-methyl styrene, ethyl styrene, t-butyl styrene, Vinyl toluene, 1,2-diphenylethlene, 1，1-diphenylethylene, vinyl-dimethyl benzene, Vinyl toluene, vinyl naphthalene, Vinylstyrene, bromostyrene and chlorostyrene and combination thereof.Optimization styrene, p-methylstyrene, alpha-methyl styrene and vinyl naphthalene.
The mixture of preferred use vinylbenzene, alpha-methyl styrene, p-methylstyrene, ethyl styrene, t-butyl styrene, Vinyl toluene, 1,2-diphenylethlene, 1，1-diphenylethylene or these materials.Particularly preferably be use vinylbenzene.But, also can usage chain thiazolinyl naphthalene.
The example of operable diolefinic monomer is 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, isoprene, chloroprene and m-pentadiene.Preferred 1,3-butadiene and isoprene, especially 1,3-butadiene (hereinafter representing with abbreviated form divinyl).
The alkenyl aromatic monomer used preferably includes vinylbenzene, and the diolefinic monomer used preferably includes divinyl, this means optimization styrene-butadiene block copolymer.Described segmented copolymer is prepared in a manner which is in itself known by anionoid polymerization usually.
Except styrene monomer and diolefinic monomer, the monomer that can also simultaneously use other other.Based on the total amount of used monomer, the ratio of comonomer is preferably 0 ~ 50wt%, is particularly preferably 0 ~ 30wt%, is particularly preferably 0 ~ 15wt%.The example of suitable comonomer is acrylate respectively, especially vinylformic acid C1 ~ C12 alkyl ester, such as n-butyl acrylate or 2-EHA, and methacrylic ester, especially methacrylic acid C1 ~ C12 alkyl ester, such as methyl methacrylate (MMA).Other possible comonomer is (methyl) vinyl cyanide, (methyl) glycidyl acrylate, vinyl methyl ether, the diallyl of dibasic alcohol and divinyl ether, Vinylstyrene and vinyl-acetic ester.
Except conjugated diene, if properly, hydrogenated block copolymer also comprises lower hydrocarbon part, such as ethene, propylene, 1-butylene, Dicyclopentadiene (DCPD) or non-conjugated diene hydrocarbon.The ratio of unreduced aliphatics unsaturated link(age) in hydrogenated block copolymer coming from block b is less than 50%, is preferably less than 25%, is especially less than 10%.Aromatic fractions derived from block a reverts to the degree of at the most 25%.By the hydrogenation of styrene-butadiene copolymer and the hydrogenation of styrene-butadiene-styrene, obtain hydrogenated block copolymer, i.e. vinylbenzene-(Ethylene/Butylene) diblock copolymer and vinylbenzene-(Ethylene/Butylene)-styrene triblock copolymer.
Segmented copolymer preferably comprises the block a of block a, the especially 50 ~ 85wt% of 20 ~ 90wt%.Diolefine can be incorporated in block b with 1,2-orientation or Isosorbide-5-Nitrae-orientation.
The molar mass of segmented copolymer is 5000 ~ 500000g/mol, preferably 20000 ~ 300000g/mol, particularly 40000 ~ 200000g/mol.
Suitable hydrogenated block copolymer is the product that can buy from the market, such as (Kraton polymkeric substance) G1650, G1651 and G1652, and (AsahiChemicals) H1041, H1043, H1052, H1062, H1141 and H1272.
The example of non-hydrogenated segmented copolymer is polystyrene-polybutadiene, polystyrene-poly (ethylene-propylene), polystyrene-poly isoprene, poly-(alpha-methyl styrene)-polyhutadiene, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly (ethylene-propylene)-polystyrene, polystyrene-poly isoprene-polystyrene and poly-(alpha-methyl styrene) polyhutadiene-poly-(alpha-methyl styrene) and combination thereof.
The suitable non-hydrogenated segmented copolymer that can buy from the market has trade mark to be the multiple product of (Phillips), (Shell), (Dexco) and (Kuraray).
The polyamide moulding composition comprising above-mentioned polyamide resin of the present invention, described binder component can also comprise other polymkeric substance, and other polymkeric substance described is selected from fatty polyamide, polyolefin homopolymer or ethene-alpha-olefin copolymer, ethylene-acrylate copolymer.
Described fatty polyamide includes but are not limited to the aliphatic diacid and aliphatie diamine that are derived from 4 ~ 20 carbon atoms, or the lactan of 4 ~ 20 carbon atoms, or one or more in the polymkeric substance of the aliphatic diacid of 4 ~ 20 carbon atoms, aliphatie diamine and lactan.Include but are not limited to, polyhexamethylene adipamide (PA66), polycaprolactam (PA6), polyhexamethylene sebacamide (PA610), nylon 1010 (PA1010), hexanodioic acid-hexanediamine-caprolactam copolymer (PA66/6), poly-11 lactan (PA11), nylon 12 (PA12), and two or more mixture.
The preferred EP elastomerics of described ethene-alpha-olefin copolymer and/or EPDM elastomerics (being ethylene-propylene rubber and ethylene/propylene/diene rubber respectively).Such as, elastomerics can comprise the elastomerics based on the ethene-C3 ~ C12-alpha-olefin copolymer containing 20 ~ 96wt%, preferably 25 ~ 85wt% ethene, wherein particularly preferably be C3 ~ C12-alpha-olefin herein and comprise the alkene being selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and/or 1-laurylene, particularly preferably other polymkeric substance comprise ethylene-propylene rubber, LLDPE, VLDPE one or more.
Alternatively or additionally (such as in the mixture), other polymkeric substance described can also comprise the terpolymer based on ethene-C3 ~ C12-alpha-olefin and non-conjugated diene hydrocarbon, herein preferably its contain 25 ~ 85wt% ethene and at the most maximum be the non-conjugated diene hydrocarbon of 10wt%, particularly preferably C3 ~ C12-alpha-olefin comprises and is selected from propylene herein, 1-butylene, 1-amylene, 1-hexene, 1-octene, the alkene of 1-decene and/or 1-laurylene, and/or wherein non-conjugated diene hydrocarbon is preferably selected from two rings [2.2.1] heptadiene, 1, 4-hexadiene, dicyclopentadiene and/or especially 5-ethylidene norbornene.
Ethylene-acrylate copolymer also can be used as the composition of other polymkeric substance described.
Other of other polymkeric substance described may form be ethylene-butene copolymer and the mixture (blend) comprising these systems respectively.
Preferably, other polymkeric substance described comprises the composition with anhydride group, these by trunk polymer and unsaturated dicarboxylic anhydride, with unsaturated dicarboxylic acid or with the thermal response of the mono alkyl ester of unsaturated dicarboxylic acid or free radical reaction, to be enough to introduce with the concentration of polymeric amide good combination, and herein preferably use be selected from following reagent:
Toxilic acid, maleic anhydride, butyl maleate, fumaric acid, equisetic acid and/or itaconic anhydride.Preferably the unsaturated acid anhydride of 0.1 ~ 4.0wt% is grafted in the shock resistance component as the composition of C, or unsaturated dicarboxylic anhydride or its precursor are applied by grafting together with other unsaturated monomer.Usually preferably graft(ing) degree is 0.1 ~ 1.0%, is particularly preferably 0.3 ~ 0.7%.Another of other polymkeric substance may composition be the mixture be made up of ethylene-propylene copolymer and ethylene-butene copolymer, and maleic anhydride graft degree (MA graft(ing) degree) is 0.3 ~ 0.7% herein.
May system can also use as a mixture for the above-mentioned of this other polymkeric substance.
In addition, described binder component can comprise the component with functional group, described functional group is such as hydroxy-acid group, ester group, epoxide group, oxazoline group, carbodiimide group, isocyanate groups, silanol and carboxylate group, or described binder component can comprise the combination of two or more in above-mentioned functional group.The monomer with described functional group can be combined by copolymerization or be grafted on elastomeric polyolefin.
In addition; impact modifying agent based on olefin polymer can also by carrying out modification with unsaturated silane compound grafting, and described unsaturated silane compound is such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetylsilane, methacryloxypropyl trimethoxy silane or propenyl Trimethoxy silane.
Elastomeric polyolefin is have straight chain, side chain or nucleocapsid structure random, alternately or segmented copolymer, and containing the functional group can reacted with the end group of polymeric amide, provides enough tolerability thus between polymeric amide and impact modifying agent.
Therefore, impact modifying agent of the present invention comprises homopolymer or the multipolymer of alkene (such as ethene, propylene, 1-butylene), or the multipolymer of alkene and copolymerisable monomer (such as vinyl-acetic ester, (methyl) acrylate and methyl hexadiene).
The example of crystalline olefin polymkeric substance is low density, Midst density and high density polyethylene(HDPE), polypropylene, polyhutadiene, poly-4-methylpentene, Ethylene-Propylene Block Copolymer, or ethylene-propylene random copolymer, ethene-methyl hexadiene multipolymer, propylene-methyl hexadiene multipolymer, ene-propylene-butene multipolymer, Ethylene-propylene-hexene Copolymer, ethylene-propylene-methyl hexadiene multipolymer, poly-(ethane-acetic acid ethyenyl ester) (EVA), poly-(ethylene-ethylacrylate) (EEA), ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, ethylene/propylene/diene terpolymer, and the combination of above-mentioned polymkeric substance.
The commercially available impact modifying agent example that may be used for described binder component has:
TAFMERMC201:g-MA (-0.6%) 67%EP multipolymer (20mol% propylene)+33%EB multipolymer (15mol%1-butylene)) blend: MitsuiChemicals, Japan.
TAFMERMH5010:g-MA (-0.6%) ethylene-butene copolymer; Mitsui.
TAFMERMH7010:g-MA (-0.7%) ethylene-butene copolymer; Mitsui.
TAFMERMH7020:g-MA (-0.7%) EP multipolymer; Mitsui.
EXXELORVA1801:g-MA (-0.7%) EP multipolymer; ExxonMobileChemicals, US.
EXXELORVA1803:g-MA (0.5-0.9%) EP multipolymer, amorphous, Exxon.
EXXELORVA1810:g-MA (-0.5%) EP multipolymer, Exxon.
EXXELORMDEX941l：g-MA(0.7%)EPDM，Exxon。
FUSABONDMN493D:g-MA (-0.5%) ethylene-octene copolymer, DuPont, US.
FUSABONDAEB560D:(g-MA) ethylene/n-butyl acrylate multipolymer, DuPontELVALOY, DuPont.
Also be preferably ionic polymer, wherein the carboxyl of polymer-bound is by metal ion all mutually bondings or be bonded to a certain degree.
The divinyl that particularly preferably maleic anhydride graft is functionalized and cinnamic multipolymer, by the nonpolar or polar olefin homopolymer that obtains with maleic anhydride graft and multipolymer and carboxylic acid functionalized multipolymer, such as poly-(ethene-(methyl) vinylformic acid altogether) or poly-(ethene--1-alkene altogether-altogether-(methyl) vinylformic acid), wherein said acid groups is neutralized by metal ion to a certain extent.
In addition, in the scope not destroying effect of the present invention, various processing aid can be added at any time in polyamide resin of the present invention, such as antioxidant and/or heat-resisting stabilizing agent (hindered phenol system, quinhydrones system, phosphorous acid ester system and their replacement body, copper halide, iodine compound etc.), weather resisting agent (Resorcinol system, salicylate system, benzotriazole system, benzophenone series, hindered amine system etc.), releasing agent and lubricant (fatty alcohol, aliphatic amide, aliphatics bisamide, two ureas and polyethylene wax etc.), pigment (Cadmium Sulfide, phthalocyanine, carbon black etc.), dyestuff (nigrosine, nigrosine etc.), softening agent (P-hydroxybenzoic acid monooctyl ester, N-butylbenzenesulfonamide etc.), static inhibitor (alkyl sulphate type negatively charged ion system static inhibitor, quaternary ammonium salt cationic system static inhibitor, the nonionic system static inhibitor such as polyoxyethylene sorbitan monostearate, trimethyl-glycine system both sexes static inhibitor etc.).
In order to obtain products formed of the present invention, can polyamide resin of the present invention or Amilan polyamide resin composition be come shaping by random molding methods such as injection molding, extrusion moulding, blow molding, vacuum forming, melt-spinning, film are shaping.These products formeds can be molded into desired shape, and can in middle uses such as the synthetic resins of trolley part, mechanical part etc.As concrete purposes, it is useful in following purposes: automobile engine cooling water based part, the particularly radiator water box part such as top and bottom of radiator tank, cooling fluid reserve tank, water pipe, water pump shell, water pump impeller, the parts used under the pump parts etc. such as valve contact with water coolant in car engine machine room, with Switch, subminiature slide switch, DIP switch, the shell of switch, lamp socket, strapping tape, junctor, the shell of junctor, the shell of junctor, IC socket class, roll, bobbin cover, rly., relay1 box, capacitor casing, the internal part of motor, small size motor shell, gear cam, dancing pulley, pad, isolator, fastening piece, button, wire clamp, cycle wheel, caster, safety helmet, terminal board, the shell of power tool, the insulated part of trigger, spoiler, tank, radiator tank, chamber tank (Chambertank), receiver, fuse unit, shell of air purifier, air-conditioning fan, the shell of terminal, wheel cover, suction tracheae, bearing retainer, cylinder head cover, intake manifold, water pipe impeller (waterpipeimpeller), clutch lever, speaker diaphragm, thermally resistant container, microwave oven component, electric cooker parts, the electrical/electronic associated components that printer color tape guider etc. are representative, automobile/vehicle associated components, household electrical appliances/office electrical component, computer associated components, facsimile recorder/duplicating machine associated components, machinery associated components, other various uses.
The present invention compared with prior art, has following beneficial effect:
The polyamide moulding composition that the present invention prepares, specific apparent carboxyl and apparent amido is adopted to combine and specific content range, can avoid that the pH-value due to polyamide moulding composition is too high causes the problems such as the easy burn into surface irregularity of its products formed, make the products formed of polyamide moulding composition present good erosion resistance and excellent surface property.
Embodiment
The testing method of the relative viscosity of gained prepolymer product and polymeric amide: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: in the vitriol oil of 25 ± 0.01 DEG C 98%, measure the relative viscosity η r that concentration is the polymeric amide of 0.25g/dl;
The testing method of the fusing point of polymeric amide: with reference to ASTMD3418-2003, StandardTestMethodforTransitionTemperaturesofPolymersByD ifferentialScanningCalorimetry; Concrete testing method is: the fusing point adopting PerkinElmerDimondDSC analyser test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First be warming up to 340 DEG C with 10 DEG C/min during test, keep 2min at 340 DEG C, be then cooled to 50 DEG C with 10 DEG C/min, then be warming up to 340 DEG C with 10 DEG C/min, endotherm peak temperature is now set to fusing point
t m;
The testing method of apparent carboxyl-content: with autopotentiometric titrator titration sample carboxyl-content; Get 0.5g polyamide moulding composition particle, add ortho-cresol 50mL, backflow is dissolved, and lets cool and adds rapidly 400 μ L formaldehyde solutions afterwards, with the KOH-ethanolic soln titration carboxyl-content demarcated.This content is the apparent carboxyl-content [m] of polyamide moulding composition.
The testing method of apparent amine groups content: with autopotentiometric titrator titration sample amino content; Get 0.5g polyamide moulding composition particle, add phenol 45mL and anhydrous methanol 3mL, reflux, after observation sample dissolves completely, be chilled to room temperature, with the hydrochloric acid standard solution titration amino content demarcated.This content is apparent amine groups content [n].
The surface property of polyamide moulding composition products formed is with surfaceness
r acharacterize, its test is carried out according to National Standard of the People's Republic of China GB10610-89 " rule and methodology of contact pin type apparatus measures surfaceness ".Concrete steps are: product sample being injection molded into 100mm × 100mm × 2mm.Use the JB-6C contact pin type roughmeter test surfaces roughness value that Guangzhou Guang Zhuo measuring instrument company limited produces
r a.
r alarger, surface is more coarse.
The erosion resistance of polyamide moulding composition products formed with 23 DEG C, soak in 5wt% aqueous ammonium chloride solution after stretching strength retentivity
trepresent; The test of tensile strength measures according to ISO527-2, and test condition is 23 DEG C and 10mm/min; Concrete steps are: injection-molded test specimens is immersed in 23 DEG C, in 5wt% aqueous ammonium chloride solution 1200 hours, then test tensile strength; Calculate the conservation rate relative to tensile strength before submergence
t.
Test polyamide resin PA66 used and be purchased from tafelberg Shen Ma nylon company, model EPR277;
Test polyamide resin PA6 used and be purchased from BASF AG, model UltramidB4;
Test polyamide resin PA12 used and be purchased from Ying Chuan company, model VESTAMIDX7293;
embodiment 1 ~ 51
fusing point is lower than 280
o
the synthesis of the polyamide resin of C:
Reaction raw materials is added in the ratio in form in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth; Add sodium hypophosphite, phenylformic acid and deionized water again; Sodium hypophosphite weight is 0.1% of deionizing water other charged material weight outer, and the amount of benzoic acid species is 4% of the total amount of substance of diacid, and deionized water weight is 30% of total charged material weight.Vacuumize and be filled with high pure nitrogen as protection gas, start reaction.Reaction mixture is warming up to 290 DEG C to stir 3 hours, then opens valve slowly pressure release, keep temperature-resistant simultaneously; Pressure is let out to normal pressure, starts to vacuumize; Be evacuated to 60Pa, keep temperature of reaction; Change according to stirring rake power judges reaction end; After reaction terminates, stop vacuumizing, pour nitrogen to 0.2MPa; Molten materials is extruded by die head, after tank cooling, air-cooled, pelletizing, obtains polyamide resin.The performance index such as the fusing point of polyamide resin and relative viscosity are listed in table 1 ~ 4.
fusing point is higher than 280dEG C
the synthesis of polyamide resin:
Reaction raw materials is added in the ratio in form in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth; Add sodium hypophosphite, phenylformic acid and deionized water again.Sodium hypophosphite weight is 0.1% of deionizing water other charged material weight outer, and the amount of benzoic acid species is 4% of the total amount of substance of diacid, and deionized water weight is 30% of total charged material weight.Vacuumize and be filled with high pure nitrogen as protection gas, start reaction.Reaction mixture is warming up to 220 DEG C to stir 1 hour, then under agitation makes the temperature of reactant be elevated to 230 DEG C; React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure by removing formed water, opening valve discharging after having reacted, obtaining prepolymer.Prepolymer vacuum-drying after 24 hours at 80 DEG C, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.The performance index such as the fusing point of polyamide resin and relative viscosity are listed in table 1 ~ 4.
comparative example 1-5
fusing point is lower than 280
o
the synthesis of the polyamide resin of C:
Reaction raw materials is added in the ratio in form in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth; Add sodium hypophosphite, phenylformic acid and deionized water again; Sodium hypophosphite weight is 0.1% of deionizing water other charged material weight outer, and the amount of benzoic acid species is 4% of the total amount of substance of diacid, and deionized water weight is 30% of total charged material weight.Vacuumize and be filled with high pure nitrogen as protection gas, start reaction.Reaction mixture is warming up to 290 DEG C to stir 3 hours, then opens valve slowly pressure release, keep temperature-resistant simultaneously; Pressure is let out to normal pressure, starts to vacuumize; Be evacuated to 60Pa, keep temperature of reaction; Change according to stirring rake power judges reaction end; After reaction terminates, stop vacuumizing, pour nitrogen to 0.2MPa; Molten materials is extruded by die head, after tank cooling, air-cooled, pelletizing, obtains polyamide resin.The performance index such as the fusing point of polyamide resin and relative viscosity are listed in table 5.
fusing point is higher than 280dEG C
the synthesis of polyamide resin:
Reaction raw materials is added in the ratio in form in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth; Add sodium hypophosphite, phenylformic acid and deionized water again.Sodium hypophosphite weight is 0.1% of deionizing water other charged material weight outer, and the amount of benzoic acid species is 4% of the total amount of substance of diacid, and deionized water weight is 30% of total charged material weight.Vacuumize and be filled with high pure nitrogen as protection gas, start reaction.Reaction mixture is warming up to 220 DEG C to stir 1 hour, then under agitation makes the temperature of reactant be elevated to 230 DEG C; React and proceed 2 hours under the constant voltage of the constant temperature of 230 DEG C and 2.2MPa, keeping constant pressure by removing formed water, opening valve discharging after having reacted, obtaining prepolymer.Prepolymer vacuum-drying after 24 hours at 80 DEG C, at 250 DEG C, solid-phase tack producing 10 hours under 50Pa vacuum condition, obtains polyamide resin.The performance index such as the fusing point of polyamide resin and relative viscosity are listed in table 5.
embodiment 52 ~ 86 and comparative example 6 ~ 10: the preparation of polyamide moulding composition
By table 6 formula by polyamide resin, additive high-speed mixer and mixing evenly after, add in twin screw extruder by main spout, reinforcing filler is fed by feeding scale side, side, extrudes, cross water cooling, granulation also obtains described polyamide moulding composition after drying.
As can be seen from Table 6, relative to comparative example, because the apparent carboxyl of the low potential of hydrogen polyamide moulding composition of the embodiment of the present invention and apparent amido are in specific limited range, the surface of its final injection-molded article is comparatively smooth, and stretching strength retentivity is higher, good corrosion resistance.
Claims (17)
1. a low potential of hydrogen polyamide moulding composition, is characterized in that:
The apparent carboxyl-content [m] that this low potential of hydrogen polyamide moulding composition is obtained surely by automatic potential titrator tests and apparent amine groups content [n] meet following scope:
[m]≤550mol/t；
[n]≤800mol/t；
Described low potential of hydrogen polyamide moulding composition comprises following composition:
At least one semiaromatic polyamide composition 10T/PQ of A, 30 ~ 99.9wt%, it comprises derived from following repeating unit:
A1,10T are selected from the unit obtained by 1，10-diaminodecane and terephthalic acid, and its content is 2-98mo%;
A2, PQ are selected from the unit be made up of aliphatie diamine and dicarboxylic acid, and its content is 2-50mol%;
Described aliphatie diamine is 1,6-hexanediamine, and described dicarboxylic acid is terephthalic acid;
B, content are strongthener and/or the filler of X, wherein, and X=0-70wt%;
C, content are additive and/or other polymkeric substance of Y, wherein, and Y=0.1-70wt%;
Component A, B and C weight ratio sum are 100wt%.
2. low potential of hydrogen polyamide moulding composition according to claim 1, is characterized in that, described apparent carboxyl-content [m] meets following scope: 5mol/t≤[m]≤450mol/t.
3. low potential of hydrogen polyamide moulding composition according to claim 2, is characterized in that, described apparent carboxyl-content [m] meets following scope: 10mol/t≤[m]≤110mol/t.
4. low potential of hydrogen polyamide moulding composition according to claim 1, is characterized in that, described apparent amine groups content [n] meets following scope: 50mol/t≤[n]≤550mol/t.
5. low potential of hydrogen polyamide moulding composition according to claim 4, is characterized in that, described apparent amine groups content [n] meets following scope: 80mol/t≤[n]≤300mol/t.
6. low potential of hydrogen polyamide moulding composition according to claim 1, is characterized in that, the shape of described reinforcing filler is threadiness, and its mean length is 0.01-20mm; Its length-to-diameter ratio is 5:1 ~ 2000:1; The content of described reinforcing filler is 10 ~ 50wt%; Described reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers, and described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre; Described organic reinforcing fillers is selected from Kevlar and/or carbon fiber.
7. low potential of hydrogen polyamide moulding composition according to claim 6, is characterized in that, the mean length of described reinforcing filler is 0.1 ~ 6mm.
8. low potential of hydrogen polyamide moulding composition according to claim 6, is characterized in that, the length-to-diameter ratio of described reinforcing filler is 30:1 ~ 600:1.
9. low potential of hydrogen polyamide moulding composition according to claim 6, is characterized in that, described inorganic reinforcing filler is glass fibre.
10. low potential of hydrogen polyamide moulding composition according to claim 1, it is characterized in that, the shape of described reinforcing filler is Non-fibrous, its median size is 0.001 ~ 100 μm, be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.
11. low potential of hydrogen polyamide moulding compositions according to claim 10, is characterized in that, the median size of described reinforcing filler is 0.01 ~ 50 μm.
12. low potential of hydrogen polyamide moulding compositions according to claim 1, it is characterized in that, described additive contains fire retardant; Fire retardant is halogenated flame retardant or halogen-free flame retardants; Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecane or brominated aromatic cross-linked polymer; Described halogen-free flame retardants is selected from one or more of the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus; The content of described fire retardant is 10 ~ 40wt%.
13. low potential of hydrogen polyamide moulding compositions according to claim 12, it is characterized in that, described fire retardant is halogen-free flame retardants.
14. low potential of hydrogen polyamide moulding compositions according to claim 12, it is characterized in that, described halogenated flame retardant is brominated Polystyrene.
15. low potential of hydrogen polyamide moulding compositions according to claim 12, it is characterized in that, described halogen-free flame retardants is phosphonium flame retardant.
16. low potential of hydrogen polyamide moulding compositions according to claim 15, it is characterized in that, described phosphonium flame retardant be selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphoric acid ester, butylbenzene system phosphoric acid ester, hypophosphite one or more.
17. low potential of hydrogen polyamide moulding compositions according to claim 16, is characterized in that, described phosphonium flame retardant is for having the hypophosphite of following structure formula I and/or (II):
In formula I and formula (II), R
1and R
2can be identical, also can be different, represent C1 ~ C6-alkyl of straight-chain or branch-like, aryl or phenyl respectively; R
3represent C1 ~ C10-alkylidene group of straight-chain or branch-like, C6 ~ C10-arylidene, C6 ~ C10-alkyl arylene or C6 ~ C10-aryl alkylene; 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.
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| CN104804426B (en) * | 2015-03-26 | 2018-11-06 | 珠海万通特种工程塑料有限公司 | A kind of polyamide moulding composition |
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| CN104804413B (en) * | 2015-03-26 | 2018-11-06 | 珠海万通特种工程塑料有限公司 | A kind of polyamide moulding composition |
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| CN104788943A (en) * | 2015-03-26 | 2015-07-22 | 金发科技股份有限公司 | Polyamide molding composition |
| CN104672444B (en) * | 2015-03-26 | 2016-08-24 | 珠海万通特种工程塑料有限公司 | A kind of polyamide and consisting of daiamid composition |
| CN104804429B (en) * | 2015-03-26 | 2017-11-03 | 珠海万通特种工程塑料有限公司 | A kind of polyamide and the daiamid composition being made from it |
| CN105602010A (en) * | 2015-12-28 | 2016-05-25 | 宁波卡利特新材料有限公司 | Method for preparing modified rubber strengthening agent for relieving die wear |
| CN112724400A (en) * | 2020-12-29 | 2021-04-30 | 南京开创新材料科技有限公司 | Semi-aromatic polyamide resin with high CTI value and preparation method and application thereof |
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| JP2004315606A (en) * | 2003-04-14 | 2004-11-11 | Asahi Kasei Chemicals Corp | Polyamide resin molded article |
| JP2007277391A (en) * | 2006-04-06 | 2007-10-25 | Asahi Kasei Chemicals Corp | Glass filament reinforced polyamide resin composition and molded product |
| CN103254424A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
| CN103254422A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
| CN103254423A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
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| JP2004315606A (en) * | 2003-04-14 | 2004-11-11 | Asahi Kasei Chemicals Corp | Polyamide resin molded article |
| JP2007277391A (en) * | 2006-04-06 | 2007-10-25 | Asahi Kasei Chemicals Corp | Glass filament reinforced polyamide resin composition and molded product |
| CN103254424A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
| CN103254422A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
| CN103254423A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
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| CN104262952A (en) | 2015-01-07 |
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