CN104804413A - Polyamide molding composition - Google Patents
Polyamide molding composition Download PDFInfo
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- CN104804413A CN104804413A CN201510135946.3A CN201510135946A CN104804413A CN 104804413 A CN104804413 A CN 104804413A CN 201510135946 A CN201510135946 A CN 201510135946A CN 104804413 A CN104804413 A CN 104804413A
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- polyamide
- fusing point
- reinforcing filler
- moulding composition
- polyamide resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses polyamide molding composition. The composition comprises components as follows: a, 30wt%-95wt% of polyamide resin with double melting points; b, 0-70wt% of reinforcing filler; c, 0-70wt% of an additive and/or other polymers, wherein the sum of weight percentages of the three components a, b and c is 100wt%; the polyamide resin has the double melting points, and the difference between the double melting points is in a range of 6 DEG C-22 DEG C. With the adoption of the polyamide molding composition prepared from the polyamide resin with the double melting points, the molding cycle of injection-molded products can be shortened, and the surface gloss of the injection-molded products is good.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of polyamide moulding 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 homopolymerization PA6T, because fusing point is higher than decomposition temperature, usually adds a certain amount of copolymerization component wherein and reduces its fusing point, obtain PA6T/66, PA6T/6 etc.But copolymerization component add the crystalline structure destroying homopolymer, cause above-mentioned 6T performance of copolymer to decline, during injection moulding shaping cycle extend, be unfavorable for that mouldings is produced.
Another method reducing semiaromatic polyamide composition fusing point is the length increasing aliphatic amide carbochain, and such as, hexanediamine is replaced by nonamethylene diamine, obtains PA9T, its fusing point is lower than 320
oc, far below decomposition temperature, thermolysis problem during melt-processed obtains and solves to a certain extent, can normally use.But for polyamide 9T, the carbonatoms due to the diamines as its constituent is odd number, so the chemical structure of polymeric amide is asymmetric, destroys its crystallinity equally, and then causes degradation.
At present, those skilled in the art generally carry out the molten state of general description polymkeric substance with fusing point, but for the demands such as processed and applied, this description is still aobvious coarse.The melting process of polymkeric substance not occurs on one point, but carries out in a segment limit, and this segment limit is commonly referred to melting range, and the endotherm(ic)peak in melting range is defined as fusing point.The fusing point of polymkeric substance not only forms relevant to monomer whose, and the sequence length of polymerization process, monomeric unit, arrangement mode, Intermolecular Forces, crystal habit and oriented structure etc. have considerable influence to fusing point equally.Even if the polymeric amide that component, monomer ratio are identical, due to the acting in conjunction of above-mentioned factor, all possibility difference is huge for its fusing point, thus causes the difference of polymeric amide and even its composition properties.
The present inventor is found by great many of experiments, adopt the polyamide moulding composition that the polyamide resin with two fusing point with special crystallization and melting behavior prepares, can shorten the shaping cycle of injecting products, the surface gloss of injecting products gets a promotion simultaneously.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the object of the present invention is to provide a kind of polyamide moulding composition that can shorten injecting products shaping cycle and there is improvement surface property.
The present invention is achieved by the following technical solutions:
A kind of polyamide moulding composition, comprises following composition:
The polyamide resin with two fusing point of a, 30wt%-95wt%;
The reinforcing filler of b, 0-70wt%;
The additive of c, 0-70wt% and/or other polymkeric substance;
Wherein, the weight percentage sum of a, b, c tri-kinds of components is 100wt%;
Adopt DSC instrument, by polyamide resin sample with 10
othere is first endotherm(ic)peak in the temperature rise rate heating direct of C/min, now temperature will be designated as T to DSC spectrogram.Get another sample with 10
othe temperature rise rate of C/min rises to a certain temperature T+40
oc, constant temperature 3min, then with 10
othe rate of temperature fall of C/min is down to 50
oc, constant temperature 3min, finally with 10
othe temperature rise rate of C/min rises to T+40
oc.Be as the criterion with the DSC curve of another sample second time intensification record, this polyamide resin has two fusing point, and wherein the difference of the two fusing point is 6
oc-22
oc.
Preferably, a kind of polyamide moulding composition, comprises following composition:
The polyamide resin of a, 30wt%-90wt%;
The reinforcing filler of b, 1wt%-69wt%;
The additive of c, 0.1wt%-62wt% and/or other polymkeric substance;
Wherein, the weight percentage sum of a, b, c tri-kinds of components is 100wt%.
Preferably, described in there is the polyamide resin of two fusing point, its fusing point presents: 270
oc≤fusing point≤330
oc.
Preferably, described in there is the polyamide resin of two fusing point, its cold crystallization temperature presents: 240
oc≤cold crystallization temperature≤300
oc.
The content of described components b is preferably 10wt%-50wt%, is more preferably 15wt%-40wt%;
Reinforcing filler content is too low, causes polyamide moulding composition mechanical property poor; Reinforcing filler too high levels, 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 0.01mm-20mm, is preferably 0.1mm-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, and its median size is 0.001 μm-100 μm, is preferably 0.01 μm-50 μm.
The melt processable of polyamide resin difference will 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.
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.
In order to make polyamide moulding composition obtain more excellent mechanical property, coupling agent can be adopted to carry out functional processing to inorganic reinforcing filler.
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, containing the end alkoxysilane compound containing trialkylsilyl group in molecular structure of amido, 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 is selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, γ-(2-urea groups ethyl) hold aminocarbonyl propyl Trimethoxy silane 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;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido is selected from γ-(2-hold amido ethyl) and holds aminocarbonyl propyl methyl dimethoxysilane, γ-(2-holds amido ethyl) to hold one or more of aminocarbonyl propyl Trimethoxy silane, γ-end aminocarbonyl propyl Trimethoxy silane;
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-vinyl benzyl cardinal extremity amido ethyl)-γ-end aminocarbonyl propyl Trimethoxy silane 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-holds amido ethyl) holds aminocarbonyl propyl methyl dimethoxysilane, γ-(2-holds amido ethyl) to hold aminocarbonyl propyl Trimethoxy silane, γ-end aminocarbonyl propyl Trimethoxy silane 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 the 0.05wt%-10wt% relative to inorganic reinforcing filler weight, is preferably 0.1wt%-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.
Described fire retardant is the composition of fire retardant or fire retardant and fire-retardant assistance agent, and based on polyamide moulding composition gross weight, its content is preferably 10wt%-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, 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 or phosphinates; Be preferably phosphinates;
The compound that phosphinate salt compound represents with such as following formula I and/or II is 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 C1-C10-alkylidene group, C6-C10-arylidene, C6-C10-alkyl arylene, the C6-C10-aryl alkylene of straight-chain or branch-like.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 OP1230, OP1311, OP1312, OP930, OP935 etc. that Clariant Corporation (Clariant) manufactures.
The polyamide moulding composition comprising above-mentioned polyamide resin of the present invention, based on the gross weight of polyamide moulding composition, described binder component can also comprise the one or more of impact modifying agents of 45wt% at the most, is preferably 5wt%-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 ~ 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 50wt%-85wt% of 20wt%-90wt%.Diolefine can be incorporated in block b with 1,2-orientation or Isosorbide-5-Nitrae-orientation.
The molar mass of segmented copolymer is 5000g/mol-500000g/mol, preferred 20000g/mol-300000g/mol, particularly 40000g/mol-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 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 atom, or the lactan of 4-20 carbon atom, or one or more in the polymkeric substance of the aliphatic diacid of 4-20 carbon atom, 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 based on the elastomerics containing 20wt%-96wt%, the preferably ethene-C3-C12-alpha-olefin copolymer of 25wt%-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 25wt%-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.The unsaturated acid anhydride of preferred 0.1wt%-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.
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:
The polyamide moulding composition adopting the polyamide resin with two fusing point to prepare, can shorten the shaping cycle of injecting products, and the surface gloss of injecting products gets a promotion simultaneously.
Embodiment
The testing method of gained polyamide resin relative viscosity: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: 25
oc ± 0.01
oc 98% the vitriol oil in measure the relative viscosity that concentration is the polymeric amide of 10mg/ml
η r;
The testing method of the fusing point of polyamide resin: 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; During test first by polyamide resin sample with 10
othere is first endotherm(ic)peak in the temperature rise rate heating direct of C/min, now temperature will be designated as T to DSC spectrogram; Get another sample with 10
othe temperature rise rate of C/min rises to a certain temperature T+40
oc, constant temperature 3min, then with 10
othe rate of temperature fall of C/min is down to 50
oc, constant temperature 3min, finally with 10
othe temperature rise rate of C/min rises to T+40
oc; Be as the criterion with the DSC curve of another sample second time intensification record, this polyamide resin has two fusing point, and higher melt is designated as
t m1, comparatively low melting point is designated as
t m2.The exothermic peak temperature of process of cooling is set to cold crystallization temperature
t c.
The testing method of surface gloss
Surface gloss is tested according to GB8807-1988 " plastics specular gloss test method ", and test angle is 60
o.Test product is of a size of 100mm × 100mm × 3.2mm.
The testing method of shaping cycle
Shaping cycle, refers to that injection moulding machine completes the full time needed for a plastic.Injection temperature is higher than fusing point 30
oc, gets the product of injection moulding 5 test surfaces glossiness, calculates the mean value of injection moulding time.
The polyamide resin used in the present invention is as follows:
PA1: Chramid 3002 heat-resistant polyamide resin that Zhuhai Wantong Chemical Co., Ltd. produces, relative viscosity 2.114, fusing point
t m1=292
oc,
t m2=284
oc, cold crystallization temperature 255
oc;
PA2: Chramid 3004 heat-resistant polyamide resin that Zhuhai Wantong Chemical Co., Ltd. produces, relative viscosity 2.109, fusing point
t m1=312
oc,
t m2=304
oc, cold crystallization temperature 289
oc;
PA3: Chramid 3005 heat-resistant polyamide resin that Zhuhai Wantong Chemical Co., Ltd. produces, relative viscosity 1.998, fusing point
t m1=322
oc,
t m2=314
oc, cold crystallization temperature 293
oc;
PA4: the Vicnyl600 heat-resistant polyamide resin that JinFa Science Co., Ltd produces, relative viscosity 2.112, fusing point 313
oc, cold crystallization temperature 282
oc;
embodiment 1-11 and comparative example 1-3: the preparation of polyamide moulding composition
By table 1 formula by polyamide resin, fire retardant, other auxiliary agents 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.
In table 1 following table, formula is weight part
As can be seen from Table 1, owing to have employed the polyamide resin with two fusing point, surface gloss and the shaping cycle of embodiment polyamide moulding composition all have clear superiority relative to comparative example.
Claims (8)
1. a polyamide moulding composition, comprises following composition:
The polyamide resin with two fusing point of a, 30wt%-95wt%;
The reinforcing filler of b, 0-70wt%;
The additive of c, 0-70wt% and/or other polymkeric substance;
Wherein, the weight percentage sum of a, b, c tri-kinds of components is 100wt%;
Adopt DSC instrument, by polyamide resin sample with 10
othere is first endotherm(ic)peak in the temperature rise rate heating direct of C/min, now temperature will be designated as T to DSC spectrogram; Get another sample with 10
othe temperature rise rate of C/min rises to a certain temperature T+40
oc, constant temperature 3min, then with 10
othe rate of temperature fall of C/min is down to 50
oc, constant temperature 3min, finally with 10
othe temperature rise rate of C/min rises to T+40
oc; Be as the criterion with the DSC curve of another sample second time intensification record, this polyamide resin has two fusing point, and wherein the difference of the two fusing point is 6
oc-22
oc.
2. a polyamide moulding composition as claimed in claim 1, comprises following composition:
The polyamide resin of a, 30wt%-90wt%;
The reinforcing filler of b, 1wt%-69wt%;
The additive of c, 0.1wt%-62wt% and/or other polymkeric substance;
Wherein, the weight percentage sum of a, b, c tri-kinds of components is 100wt%.
3. polyamide moulding composition according to claim 1 and 2, is characterized in that, described in there is the polyamide resin of two fusing point, its fusing point presents: 270
oc≤fusing point≤330
oc.
4. polyamide moulding composition according to claim 1 and 2, is characterized in that, described in there is the polyamide resin of two fusing point, its cold crystallization temperature presents: 240
oc≤cold crystallization temperature≤300
oc.
5. polyamide moulding composition according to claim 1 and 2, is characterized in that, the shape of described reinforcing filler is threadiness, and its mean length is 0.01mm-20mm, is preferably 0.1mm-6mm; Its length-to-diameter ratio is 5:1-2000:1, is preferably 30:1-600:1; The content of described reinforcing filler is 10wt%-50wt%, is preferably 15wt%-40wt%; 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.
6. polyamide moulding composition according to claim 1 and 2, it is characterized in that, the shape of described reinforcing filler is Non-fibrous, its median size is 0.001 μm-100 μm, be preferably 0.01 μm-50 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.
7. polyamide moulding composition according to claim 1 and 2, is characterized in that, described additive contains fire retardant; Fire retardant is halogenated flame retardant or halogen-free flame retardants, preferred 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 brominated Polystyrene; Described halogen-free flame retardants is selected from one or more in the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus, is preferably phosphonium flame retardant; Based on the gross weight of polyamide moulding composition, the content of described fire retardant is 10wt%-40wt%.
8. polyamide moulding composition according to claim 7, 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, phosphinates one or more; Preferably there is the phosphinates of following structural formula I and/or II:
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 C1-C10-alkylidene group, C6-C10-arylidene, C6-C10-alkyl arylene, the C6-C10-aryl alkylene of straight-chain or branch-like; 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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| EP2813549A1 (en) * | 2012-01-09 | 2014-12-17 | Kingfa Sci Tech. Co., Ltd. | Halogen-free fire-retardant polyamide composition, and preparation method and application thereof |
| CN104262952A (en) * | 2014-09-19 | 2015-01-07 | 金发科技股份有限公司 | Low-pH-value polyamide molding composition |
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| EP2813549A1 (en) * | 2012-01-09 | 2014-12-17 | Kingfa Sci Tech. Co., Ltd. | Halogen-free fire-retardant polyamide composition, and preparation method and application thereof |
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