CN104211953A - Polyamide resin and polyamide composition containing same - Google Patents
Polyamide resin and polyamide composition containing same Download PDFInfo
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- CN104211953A CN104211953A CN201410381216.7A CN201410381216A CN104211953A CN 104211953 A CN104211953 A CN 104211953A CN 201410381216 A CN201410381216 A CN 201410381216A CN 104211953 A CN104211953 A CN 104211953A
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Abstract
The invention discloses a polyamide resin and a polyamide composition containing the same. The polyamide resin consists of following repeating unit components: 60-95 mol% of a 10T unit which is composed of a monomer 1,10-decamethylenediamine and terephthalic acid, and 5-40 mol% of a 5'T unit which is composed of a monomer 5' and terephthalic acid, wherein the monomer 5' is 2-methy-1,5-pentamethylenediamine and/or 1,3-pentamethylenediamine. The polyamide composition containing the polyamide resin includes: 30-99 wt% of the polyamide resin, 0-70 wt% of a reinforcing filling material, and 0.1-50 wt% of an additive. The polyamide resin is prepared from specific dicarboxylic acid and diamine monomer in a certain mole percentage so that problems of serious heat releasing, material caking, difficult stirring, high-temperature volatilization and even material clashing during a polymerization reaction of the dicarboxylic acid and the diamine monomer are avoided. In addition, a melting point of the polyamide resin is higher than 260 DEG C. The polyamide resin is strong in heat-resistance performance, is low in water absorption, and can be used in a situation that a reflux welding temperature is higher than 260 DEG C and a situation in which an oil tube of an engine requires the performances above to be higher.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of polyamide resin and consisting of daiamid composition.
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.
But, in the polymerization process of polymeric amide, due to diamines and the higher reactive behavior of aromatic diacid, in the process of feeding intake, local diamines contacts with aromatic diacid and will react very soon, heat release is serious, causes material caking, stirring difficulty, vaporization at high temperature that the security incidents such as punching material even occur.Further, because local reaction causes polyreaction uneven, and then the performance of final product is affected.Especially for some lower aliphatic diamines, as hexanediamine, pentamethylene diamine etc., its boiling point is lower, and volatility is very strong, and this problem is particularly serious.
Prior art does not specifically note 1,10-decamethylene diamine and monomer 5 ' (2-methyl isophthalic acid, 5-pentamethylene diamine or 1,3-pentamethylene diamine) particular combination, certainly do not point out the favourable specific molar percentage improving PA10T/5 ' T performance that the present invention can be provided to find in the prior art yet.Do not point out material caking when can improve polyreaction about PA10T/5 ' T combination in prior art, stir difficulty, the various problem information such as punching material even occur vaporization at high temperature yet.
Especially, described terephthalic acid, based on whole dicarboxylic acid, 20mol% is replaced by other araliphatic containing 6 ~ 36 carbon atoms, aliphatics or cycloaliphatic dicarboxylic acid at the most; Preferred 10mol% at the most; Be more preferably and be not substituted, namely substantially only based on, preferably completely only based on as dicarboxylic acid to benzene two Yue acid.
Described 1，10-diaminodecane and monomer 5 ', based on whole diamines, 20mol% is replaced by other aliphatics containing 4 ~ 36 carbon atoms, cyclic aliphatic, aryl aliphatic diamine at the most; Preferred 10mol% at the most; Be more preferably and be not substituted, namely substantially only based on, preferably completely only based on as the 1，10-diaminodecane of diamines and monomer 5 ' (2-methyl isophthalic acid, 5-pentamethylene diamine or 1,3-pentamethylene diamine).
Described polyamide resin, based on whole monomer, 20mol% is formed by lactan or amino acid at the most; Be preferably 10mol% at the most to be formed by lactan or amino acid; Be more preferably and do not formed by lactan or amino acid, namely substantially only by, preferably completely only formed by component 10T unit and 5 ' T unit.
Preferably, described other araliphatic, aliphatics or the cycloaliphatic dicarboxylic acid containing 6 ~ 36 carbon atoms is selected from 2,6-naphthalene dicarboxylic acids (NDA), m-phthalic acid, 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-one or more of dicarboxylic acid (CHDA).
Preferably, described other aliphatics containing 4 ~ 36 carbon atoms, cyclic aliphatic, aryl aliphatic diamine is selected from Putriscine, 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, cyclohexanediamine, two (amino methyl) hexanaphthene (BAC) of 1,3-, isophorone diamine, norcamphane dimethylamine, 4,4 '-diamino-dicyclohexyl methane (PACM), 2,2-(4,4 '-diaminocyclohexyl) propane (PACP), with 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane (MACM), one or more of m-xylene diamine (MXDA).
Preferably, described lactan or amino acid are selected oneself lactan (CL), α, omega-amino-caproic acid, α, omega-amino-n-nonanoic acid, α, one or more of omega-amino-undeeanoic acid (AUA), laurolactam (LL), omega-amino-laurostearic acid (ADA).
The fusing point of described polyamide resin is higher than 260
oc, is preferably 280
oc-320
oc; Melting point resin is too low, and under the pyroprocessing of reflow soldering, goods are easily out of shape; Melting point resin is too high, causes its processing characteristics to decline.Further, fusing point is too high close to decomposition temperature, easily makes goods various aspects of performance all decline.
Comprise a daiamid composition for above-mentioned polyamide resin, by weight percentage, comprise following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 70%;
Additive 0.1 ~ 50%.
Wherein, the content of described reinforcing filler is preferably 10 ~ 50wt%, is more preferably 15 ~ 40%; Filler content is too low, causes daiamid composition mechanical property poor; Filler content is too high, and daiamid 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 ~ 2000:1, is preferably 30 ~ 600:1, and when fibrous reinforcing filler content is in above-mentioned scope, the high temperature rigid that daiamid composition will show high heat distortion temperature and increase, above-mentioned size obtains fiber measurement by milscale.
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 daiamid 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 ~ 10 μm, is preferably 0.01 ~ 5 μm, will cause the melt processable of polyamide resin difference when the median size of reinforcing filler is less than 0.001 μm; When the median size of reinforcing filler is greater than 10 μm, bad injection-molded article appearance will be caused.The median size of above-mentioned reinforcing filler is measured by absorption method, it 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 daiamid 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 daiamid 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 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 nitrogenous flame ratardant, containing one or more of the fire retardant of phosphine fire retardant or nitrogenous and phosphine; Be preferably containing phosphine fire 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 the C1 C6-alkyl of straight-chain or branch-like, aryl or phenyl respectively.R
3represent the C1 C10-alkylidene group of straight-chain or branch-like, C6 C10-arylidene, C6 10-alkyl arylene or C6 10-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 EXOLIT 0P1230,0P1311,0P1312,0P930,0P935 etc. that Clariant Corporation (Clariant) manufactures.
The daiamid 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 ~ 20 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 ~ 12 alkyl ester, such as n-butyl acrylate or 2-EHA, and methacrylic ester, especially methacrylic acid C1 ~ 12 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 B block 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 B block 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 (Asahi Chemicals) 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 daiamid 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 polyolefin homopolymer or ethene-alpha-olefin copolymer, especially preferably EP elastomerics 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 ~ 12-alpha-olefin copolymer containing 20 ~ 96wt%, preferably 25 ~ 85wt% ethene, wherein particularly preferably be C3 ~ 12-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 ~ 12-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 ~ 12-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:
TAFMER MC201:g-MA (-0.6%) 67%EP multipolymer (20mol% propylene)+33%EB multipolymer (15mol%1-butylene)) blend: Mitsui Chemicals, Japan.
TAFMER MH5010:g-MA (-0.6%) ethylene-butene copolymer; Mitsui.
TAFMER MH7010:g-MA (-0.7%) ethylene-butene copolymer; Mitsui.
TAFMER MH7020:g-MA (-0.7%) EP multipolymer; Mitsui.
EXXELOR VA1801:g-MA (-0.7%) EP multipolymer; Exxon Mobile Chemicals, US.
EXXELOR VA1803:g-MA (0.5-0.9%) EP multipolymer, amorphous, Exxon.
EXXELOR VA1810:g-MA (-0.5%) EP multipolymer, 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 multipolymer, DuPont ELVALOY, 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.
Polyamide resin PA10T/5 ' T of the present invention can mix with polyphenylene oxide (PPE).Polyphenylene oxide itself is known.They through oxidative coupling, are prepared (see United States Patent (USP) 3661848,3378505,3306874,3306875 and 3639656) by ortho position by the dibasic phenol of alkyl by traditional method.Preparation method usually use based on other material (such as secondary amine, tertiary amine, halogen or its combine) catalyzer of heavy metal (such as copper, manganese or cobalt) that combines.The mixture of polymeric amide and polyphenylene oxide itself is also known, but does not propose the mixture of polyphenylene oxide and PA10T/5 ' T copolyamide.Such as, WO-A-2005/0170039, WO-A-2005/0170040, WO-A-2005/0170041 and WO-A-2005/0170042 disclose the mixture be made up of polymeric amide and PPE.
Suitable polyphenylene oxide is poly-(2,6-diethyl-1,4-phenylene) ether, poly-(2-methyl-6-ethyl-1,4-phenylene) ether, poly-(2-methyl-6-propyl group-Isosorbide-5-Nitrae-phenylene) ether, poly-(2,6-dipropyl-1,4-phenylene) ether, poly-(2-ethyl-6-propyl group-1,4-phenylene) ether or such as comprise the multipolymer of 2,3,6-trimethylammonium phenol and the mixture of polymkeric substance.Poly-(2, the 6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether preferably optionally combined with 2,3,6-trimethylammonium phenol unit.Polyphenylene oxide can be used with homopolymer, multipolymer, graft copolymer, segmented copolymer or ionomeric form.
Suitable polyphenylene oxide at 25 DEG C at CHCl
3in the intrinsic viscosity that records be generally 0.1 ~ 0.6dl/g.This correspond to 3000 ~ 40000 molecular weight Mn(number equal) and 5000 ~ 80000 weight-average molecular weight Mw.The combination of high-viscosity polyphenyl ether and low viscosity polyphenylene oxide can be used.The ratio of the polyphenylene oxide of two kinds of different viscosity depends on desired viscosity and physicals.
The blend of polyamide resin PA10T/5 ' T of the present invention can comprise the impact modifying agent of the polyphenylene oxide of 10 ~ 45wt% and optional 30wt% at the most, preferably 15wt% at the most.In order to better tolerability, use be in polyfunctional compound's form, with the expanding material of polyphenylene oxide, polymeric amide or two-way interaction.Described interaction can be chemical action (such as passing through grafting) and/or physical action (such as by the impact on the surface property of disperse phase).
Described expanding material can be the polyfunctional compound containing at least one hydroxy-acid group, carboxylic acid anhydride group, ester group, amide group or imide group.Can illustrate and mention such as toxilic acid, maleic anhydride, fumaric acid, vinylformic acid, methacrylic acid, methyl-maleic acid, methyl maleic anhydride, methylene-succinic acid, itaconic anhydride, butenylsuccinic acid, butenylsuccinic anhydride, tetrahydrophthalic acid, Tetra Hydro Phthalic Anhydride, N-phenylmaleimide, citric acid, oxysuccinic acid and 2-hydroxyl nonadecane-1, 2, 3-tricarboxylic acid, the monoesters of above-mentioned acid and C1 ~ C12 alcohol (such as methyl alcohol or ethanol) or diester, the monoamide of above-mentioned acid or diamide are (if suitable, the alkyl or aryl with 12 carbon atoms at the most can be replaced on N) and with the salt of basic metal or alkaline-earth metal (such as calcium and potassium).Particularly advantageous compound is toxilic acid, fumaric acid, maleic anhydride and citric acid.The expanding material of 0.05 ~ 2wt% can be added in the process preparing blend, or in a separate step by the functionalized described polyphenylene oxide of expanding material and/or polymeric amide.
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 (Chamber tank), 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 (waterpipe impeller), 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:
1) polyamide resin of the present invention adopts specific dicarboxylic acid and diamine monomer to combine and specific molar percentage, can avoid because the heat release in polymerization process of dicarboxylic acid and diamines is serious, material lumps, it is difficult to stir, the problems such as punching material even occur vaporization at high temperature.Further, due to steadily carrying out of polyreaction, the uneven first-class problem of the polyamide resin character that local reaction can be avoided acutely to cause;
2) polyamide resin of the present invention and the fusing point of daiamid composition that prepared by it are higher than 260
oc, thermotolerance is strong, and water-intake rate is low, can be applied to reflow soldering temperature more than 260
othe occasion that the occasion of C and engine oil tube etc. are higher to above-mentioned performance requriements.
Summary of the invention
In order to material caking when solving existing diamines and aromatic diacid polyreaction, stir difficulty, even there is the various technical problems such as punching material in vaporization at high temperature, primary and foremost purpose of the present invention is to provide one to have specific monomer composition, and has the polyamide resin of high heat resistance and low water absorption.
Another object of the present invention is to provide the daiamid composition comprising above-mentioned polyamide resin.
The present invention is achieved by the following technical solution:
A kind of polyamide resin, by mole% meter, is made up of following repeating unit component:
The 10T unit that component A:60 ~ 95mol% is formed by monomer 1，10-diaminodecane and terephthalic acid;
5 ' the T unit that B component: 5 ~ 40mol% is formed by monomer 5 ' and terephthalic acid;
Wherein, monomer 5 ' is 2-methyl isophthalic acid, 5-pentamethylene diamine and/or 1,3-pentamethylene diamine;
Based on whole dicarboxylic acid, the terephthalic acid of 30mol% is replaced by other araliphatic containing 6 ~ 36 carbon atoms, aliphatics or cycloaliphatic dicarboxylic acid at the most;
Based on whole diamines, the 1，10-diaminodecane of 30mol% and monomer 5 ' are replaced by other aliphatics containing 4 ~ 36 carbon atoms, cyclic aliphatic, aryl aliphatic diamine at the most;
And based on whole monomer, the polyamide resin of 30mol% is formed by lactan or amino acid at the most.
Especially, have been surprisingly found that, in polyamide resin PA10T/5 ' T, the above-mentioned molar percentage of each specific monomer can cause specific performance just.Such as, find when the concentration of 10T unit is lower than 60mol%, the fusing point of polyamide resin 10T/5 ' T can reduction fast, be therefore an impediment to the daiamid composition comprising this polyamide resin PA10T/5 ' T be applied to high temperature resistant, especially temperature is more than 260
othe reflow soldering field of C.
In addition, due to monomer in the present invention 5 ' (2-methyl isophthalic acid, 5-pentamethylene diamine or 1,3-pentamethylene diamine) the reactive behavior difference of two Amino End Group is larger, under the specific composition ratio of specific monomer of the present invention, this different reactive behavior have impact on the macroscopic property of reaction, avoids the problem that local reaction is violent, obtains highly homogeneous, stable performance, thermotolerance is high, water-intake rate is low polyamide resin PA10T/5 ' T in stable polymerization reaction under the prerequisite can carried out.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Polyamide resin PA10T/5 ' T copolyamide can be prepared by known method itself.Suitable method is described in many publications, some the possible methods discussed in patent documentation will be quoted hereinafter, and in the preparation method of PA10T/5 ' T copolyamide of the present invention, hereinafter described the disclosure of document is clearly by reference to being incorporated to herein:
US5708125 describes the method comprised the following steps, the method may be used for preparation PA10T/5 ' T copolyamide:
A) salt formation step, for being form the salt be made up of diamines and dicarboxylic acid in the aqueous solution of 5 ~ 50wt% in the concentration comprising each component, and, if properly, part pre-reaction is carried out, to obtain low-molecular-weight oligoamide under the pressure of at the temperature of 120 DEG C ~ 220 DEG C and at the most 23bar;
If b) properly, under the condition adopted at the end of its preparation process, the solution in step a) transferred in the second reaction vessel or transfer in the autoclave of stirring;
C) reactions steps is carried out, in this step, preset temperature is heated to along with by reactor content, and the preset value that control adjustment steam partial pressure arrives, react to obtain precondensate, wherein said preset value maintained by control discharge water vapour or, if properly, maintained by the introducing controlling the water vapour in the vapour generator that is communicated with autoclave;
D) stating step, keeps at least 10 minutes, and wherein the temperature of reactor content and steam partial pressure adjust separately in a controlled manner.
E) drain steps, in this step, described precondensate can be introduced directly in end reaction equipment with molten state by snubber assembly or to be utilized is incorporated in end reaction equipment by solid-state separator and passage, remain on steps d simultaneously) at the end of adopt temperature-resistant, and at least maintain by introducing water vapour in autoclave and all discharge pipe/devices of being communicated with it from described vapour generator the steam partial pressure that this moment adopts, optionally carry out drying and/or pulverizing subsequently, and if properly, carry out other step of the method.
CN1246490 describes a kind of method preparing polymeric amide, substitutes corresponding composition and if comprise the following steps successively according to the present invention, may be used for preparation PA10T/5 ' T copolyamide equally:
(i) under the existence of 15 ~ 35wt% water, under the temperature of reaction of 250 DEG C ~ 280 DEG C, and meeting following formula P
0>=P>=0.7P
0(wherein P
0fit saturated vapor pressure under temperature of reaction) reaction pressure (P) under, polycondensation contains dicarboxylic acid component and the diamine components of terephthalic acid, to form the step of primary polycondensate thing;
By abovementioned steps (i) in the gained polycondensate that formed from reactor, move on to step under atmospheric environment, wherein the temperature of gained prepolymer is 250 DEG C ~ 280 DEG C, and water-content is 15 ~ 35wt%;
(iii) to the step deriving from abovementioned steps elementary prepolymer (ii) and carry out solid state polymerization or melt polymerization, to provide superpolyamide.
US5252661 describes the method for continuous production polymeric amide, the mode that described method is also suitable for suitably improving is for the production of PA10T/5 ' T copolyamide, the method comprises the following steps: the salt concn be first made up of dicarboxylic acid and diamines at the heated under pressure of 1 ~ 10bar is the aqueous solution of 30 ~ 70%, vaporize water simultaneously, the residence time is less than 60 seconds, is 250 ~ 300 DEG C, is then continuously separated prepolymer and steam to temperature, purified steam, and the diamines reclaiming entrained with.Finally, prepolymer is transferred to polycondensation district, and polycondensation under the gauge pressure of 1 ~ 10bar, at the temperature of 250 ~ 300 DEG C.When leaving condenser zone, transforming degree is advantageously at least 93%, and the water-content of prepolymer is 7wt% at the most.Because these short residence time substantially avoid the formation of secondary amine, thus it is crosslinked to avoid final product to produce.
For the preparation of the most familiar method of high-melting point polyamide, and for the preparation of the appropriate method of PA10T/5 ' T copolyamide, be two-step preparation: the first step is preparation low viscosity, low-molecular-weight precondensate.Solve the difficulty existed in polyreaction described in the present invention and mainly refer to this partial content.Aftercondensated (such as in an extruder) in solid phase or in the melt subsequently.Three-step approach is also fine, and comprises 1, precondensation, 2, solid state polymerization, and 3, be polymerized in the melt, as described in JP8311198.
For the product of fusing point lower than 300 DEG C, another kind of suitable method is intermittent type single stage method, as described in US3843611 and US3839296, wherein the mixture of monomer or its salt is heated to the temperature 1 ~ 16 hour of 250 ~ 320 DEG C, pressure is reduced to the minimal pressure of 1mmHg at the most from maximum value, gaseous matter evaporation simultaneously, if properly, by means of rare gas element.
According to following standard following test sample measured:
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: 25 ± 0.01
oc 98% the vitriol oil in 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 ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; Concrete testing method is: the fusing point adopting Perkin Elmer Dimond dsc analysis instrument test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First with 10 during test
oc/min is warming up to 340
oc, 340
oc keeps 2min, then with 10
oc/min is cooled to 50
oc, then with 10
oc/min is warming up to 340
oc, is set to fusing point by endotherm peak temperature now
t m;
The testing method of gained polymeric amide terminal amino group content: with autopotentiometric titrator titration sample end amino content; Get 0.5g polymkeric substance, 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 terminal amino group content demarcated;
The testing method of gained polymeric amide content of carboxyl end group: with autopotentiometric titrator titration sample end carboxyl-content; Get 0.5g polymkeric substance, 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 content of carboxyl end group demarcated;
Water-intake rate test is carried out according to ISO62.Be specially product sample being injection molded into 64mm × 64mm × 2mm, its weight is designated as a0.Then to be placed in 23 DEG C of water after 24h, to weigh its weight and be designated as a1.Then water-intake rate=(a1-a0)/a0*100%.
Tensile strength: measure according to ISO 527-2, test condition is 23 DEG C and 10mm/min.
Tensile strength relative average debiation: measure 5 tensile strengths, the value obtained is TS
i, i=1-5.Its mean value is TS
0.Then relative average debiation be [| Σ (TS
i-TS
0)/5|/TS
0] × 100%.
IZOD notched Izod impact strength: measure according to ISO 180/1A, test condition is 23 DEG C, and breach type is A type.
embodiment 1 ~ 32 and comparative example 1 ~ 4
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 again sodium hypophosphite and deionized water (for the reaction that monomer 1,3-pentamethylene diamine participates in, also need to add phenylformic acid, its amount of substance be diamines, the total amount of substance of dicarboxylic acid 4%); Sodium hypophosphite weight is 0.1% of deionizing water other charged material weight outer, and deionized water weight is 30% of total charged material weight; Vacuumize and be filled with high pure nitrogen as protection gas, start reaction; Heat up according to predetermined heating schedule; Meanwhile, record from the end that feeds intake to the stirring time opening
t x; Reaction mixture is warming up to 220
oc stirs 1 hour, then under agitation makes the temperature of reactant be elevated to 230
oc; Reaction is 230
oproceeding 2 hours under the constant temperature of C and the constant voltage of 2.2MPa, keeping constant pressure by removing formed water, after having reacted, open valve discharging, record discharging time
t y; Prepolymer is in 80
ounder C, vacuum-drying 24 hours, obtains prepolymer product, and described prepolymer product is 250
ounder C, 50Pa vacuum condition, solid-phase tack producing 10 hours, obtains polyamide resin.The relative viscosity of polyamide resin, fusing point, water-intake rate and relevant mechanical performance index are listed in table 1 ~ 4.
Table 1
Table 2
Table 3
Table 4
As can be seen from embodiment 1 ~ 32 and comparative example 1 ~ 4 relatively, embodiment of the present invention, in prepolymerization process, due to specific reactive behavior and the specific molar percentage of monomer 5 ', its reaction mitigation is homogeneous, raw material is not easy caking, terminates to be significantly shorter than comparative example to opening churning time from feeding intake.Further, prepolymerization product is also comparatively homogeneous, stable, and the blowing time is also shorter relative to comparative example.More can find out advantage of the present invention from the performance of thickening product, because prepolymerization is steady, heat release is less, and make diamines be not easy to run off, the end group of polymkeric substance comparatively balances, and relative viscosity is higher simultaneously.And comparative example due to the heat release of polyreaction initial stage serious, diamines loss is comparatively large, and polymer terminal group is unbalance, and molecular weight is difficult to improve, and relative viscosity is lower, and mechanical property is poor.Further, because polyreaction fluctuation is comparatively large, cause polymerisate unstable properties, tensile strength average deviation is larger.
embodiment 33 ~ 49 and contrast 5 ~ 9
By table 5 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, and cross water cooling, granulation also obtains described daiamid composition after drying.Wherein, extrusion temperature is 330
oc.
In table 5 following table, formula is weight part
Continued 4
As can be seen from embodiment 33 ~ 49 and the contrast 5 ~ 9 of table 5, relative to comparative example 5 ~ 9, the daiamid composition that the present invention is obtained by embodiment 33 ~ 49, due to the polymerization process stable homogeneous of polyamide resin comprised, the performance of the daiamid composition therefore prepared by this polyamide resin is also homogeneous, water-intake rate is also lower, and mechanical property is also comparatively stable.
Claims (10)
1. a polyamide resin, is characterized in that, by mole% meter, is made up of following repeating unit component:
The 10T unit that component A:60 ~ 95mol% is formed by monomer 1，10-diaminodecane and terephthalic acid;
5 ' the T unit formed by monomer 5 ' and terephthalic acid of B component: 5 ~ 40mol%;
Wherein, monomer 5 ' is 2-methyl isophthalic acid, 5-pentamethylene diamine and/or 1,3-pentamethylene diamine;
Based on whole dicarboxylic acid, the terephthalic acid of 30mol% is replaced by other araliphatic containing 6 ~ 36 carbon atoms, aliphatics or cycloaliphatic dicarboxylic acid at the most;
Based on whole diamines, the 1，10-diaminodecane of 30mol% and monomer 5 ' are replaced by other aliphatics containing 4 ~ 36 carbon atoms, cyclic aliphatic, aryl aliphatic diamine at the most;
And based on whole monomer, the polyamide resin of 30mol% is formed by lactan or amino acid at the most.
2. polyamide resin according to claim 1, is characterized in that, described terephthalic acid, and based on whole dicarboxylic acid, 20mol% is replaced by other araliphatic containing 6 ~ 36 carbon atoms, aliphatics or cycloaliphatic dicarboxylic acid at the most; Preferred 10mol% at the most; Be more preferably and be not substituted.
3. polyamide resin according to claim 1, is characterized in that, described 1，10-diaminodecane and monomer 5 ', and based on whole diamines, 20mol% is replaced by other aliphatics containing 4 ~ 36 carbon atoms, cyclic aliphatic, aryl aliphatic diamine at the most; Preferred 10mol% at the most; Be more preferably and be not substituted.
4. polyamide resin according to claim 1, is characterized in that, described polyamide resin, and based on whole monomer, 20mol% is formed by lactan or amino acid at the most; Be preferably 10mol% at the most to be formed by lactan or amino acid; Be more preferably and do not formed by lactan or amino acid.
5. polyamide resin according to claim 1 and 2, it is characterized in that, described other araliphatic containing 6 ~ 36 carbon atoms, aliphatics or cycloaliphatic dicarboxylic acid are selected from 2, 6-naphthalene dicarboxylic acids (NDA), m-phthalic acid, 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, one or more of 3-dicarboxylic acid (CHDA).
6. the polyamide resin according to claim 1 or 3, is characterized in that, described other aliphatics containing 4 ~ 36 carbon atoms, cyclic aliphatic, aryl aliphatic diamine is selected from Putriscine, 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, cyclohexanediamine, two (amino methyl) hexanaphthene (BAC) of 1,3-, isophorone diamine, norcamphane dimethylamine, 4,4 '-diamino-dicyclohexyl methane (PACM), 2,2-(4,4 '-diaminocyclohexyl) propane (PACP), with 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane (MACM), one or more of m-xylene diamine (MXDA).
7. the polyamide resin according to claim 1 or 4, it is characterized in that, described lactan or amino acid are selected oneself lactan (CL), α, omega-amino-caproic acid, α, omega-amino-n-nonanoic acid, α, one or more of omega-amino-undeeanoic acid (AUA), laurolactam (LL), omega-amino-laurostearic acid (ADA).
8. comprise a daiamid composition for the polyamide resin described in any one of claim 1 ~ 4, by weight percentage, comprise following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 70%;
Additive 0.1 ~ 50%.
9. daiamid composition according to claim 8, is characterized in that, the content of described reinforcing filler is 10 ~ 50wt%; 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; Described organic reinforcing fillers is selected from Kevlar and/or carbon fiber.
10. daiamid composition according to claim 8, is characterized in that, described additive be selected from fire retardant, impact modifying agent, other polymkeric substance, processing aid one or more; Other polymkeric substance described be preferably 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.
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