CN104804431B - A kind of polyamide moulding composition - Google Patents
A kind of polyamide moulding composition Download PDFInfo
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- CN104804431B CN104804431B CN201510135968.XA CN201510135968A CN104804431B CN 104804431 B CN104804431 B CN 104804431B CN 201510135968 A CN201510135968 A CN 201510135968A CN 104804431 B CN104804431 B CN 104804431B
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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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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 a kind of polyamide moulding composition, including consisting of：A, the polyamide with double fusing points of 30wt% 99.9wt%；B, the reinforcing filler of 0 70wt%；C, the additive of 0 70wt% and/or other polymer；Wherein, the sum of weight percent of tri- kinds of components of a, b, c is 100wt%；The polyamide has double fusing points, wherein the difference of the two fusing point is 5oC‑20oC；The carboxyl-content [m] and amino content [n] of the polyamide obtained surely by automatic potential titrator tests meet following range：Mole/ton of [m]≤300；Mole/ton of [n]≤200.Injecting products molding cycle can be shortened, and injection product surface glossiness is good using the polyamide moulding composition.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of polyamide moulding composition.
Background technology
Polyamide is because having good comprehensive performance, including mechanical property, heat resistance, wear resistance, chemical resistance
And self lubricity, and friction coefficient is low, there is certain anti-flammability etc., is generally applied and is filled with glass fibre and other fillers
Enhancing is modified, and is improved performance and is expanded application range etc..In recent years semiaromatic polyamide composition due to its heat resistance and
Mechanical property is more excellent and by focus development.
However, homopolymerization PA6T, since fusing point is higher than decomposition temperature, usually adding a certain amount of copolymerization component thereto reduces
Its fusing point obtains PA6T/66, PA6T/6 etc..But the addition of copolymerization component destroys the crystal structure of homopolymer, leads to above-mentioned 6T
Performance of copolymer declines, and molding cycle extends during injection, is unfavorable for mouldings production.
Another method for reducing semiaromatic polyamide composition fusing point is to increase the length of fatty amine carbochain, for example, by oneself
Diamines is changed to nonamethylene diamine, obtains PA9T, and fusing point is less than 320oC, far below decomposition temperature, thermal decomposition during melt-processed is asked
It inscribes to solve to a certain extent, can be used normally.However, for polyamide 9T, due to the diamines as its constituent
Carbon atom number is odd number, so the chemical constitution of polyamide is asymmetric, equally destroys its crystallinity, and then cause under performance
Drop.
At present, those skilled in the art generally carry out the molten condition of general description polymer with fusing point, but should for processing
With etc. for demands, this description still shows coarse.The melting process of polymer not occurs on one point, but in a segment limit
It carries out, this segment limit is commonly referred to as melting range, and the endothermic peak in melting range is defined as fusing point.The fusing point of polymer not only with monomer
Composition is related, polymerization process, the sequence length of monomeric unit, arrangement mode, intermolecular force, crystal habit and orientation texture
Deng equally having larger impact to fusing point.Even if the identical polyamide of component, monomer ratio, due to the collective effect of above-mentioned factor,
The all possible difference of its fusing point is huge, so as to cause polyamide or even the difference of its composition performance.
The end group test of amide resin has become one general means of the industry, and the number to characterize polyamide is divided equally
The information of the various aspects such as sub- amount, the extent of reaction.Although the end group of polyamide may influence the pH value of solution, this is not only
One key factor.Different polyamide molecule chain rigidity, amide groups concentration, the sharp coefficient of the second dimension, Huggins parameters, theta solvent row
To wait can all significant impact be caused to its endgroup value.Even if the identical polyamide of component, monomer ratio, due to being total to for above-mentioned factor
Same-action, all possible difference of endgroup value is huge, so as to cause polyamide or even the difference of its composition performance.
The present inventor is had found by many experiments, using with double fusing points and the polyamide resin of specific Amino End Group and end carboxyl
The polyamide moulding composition that fat is prepared can shorten the molding cycle of injecting products, while the surface light of injecting products
Damp degree gets a promotion.
Invention content
The shortcomings that in order to overcome the prior art, the purpose of the present invention is to provide one kind can shorten injecting products with insufficient
Molding cycle and the polyamide moulding composition with improvement surface property.
The present invention is achieved by the following technical solutions：
A kind of polyamide moulding composition, including consisting of：
A, the polyamide with double fusing points of 30wt%-99.9wt%；
B, the reinforcing filler of 0-70wt%；
C, the additive of 0-70wt% and/or other polymer；
Wherein, the total content of tri- kinds of components of a, b, c is 100wt%；
The polyamide for having double fusing points, it includes the repetitive units derived from following monomer mixture：Have
First monomer of two amido functional groups, referred to as monomer A；Have the second comonomer there are two carboxyl functional group or its precursor group,
Referred to as monomer B；And/or there are one amino and the Third monomer and/or lactams of a carboxyl functional group, referred to as monomer D for tool；
Wherein, monomer A at least contains a kind of monomer A with ten carbon atoms in the monomer mixture10；Monomer B is extremely
Contain a kind of non-fat race's monomer B with eight carbon atoms less8；
Wherein, based on the total molfraction of whole monomers, A10And B8Content meet the relationship of following α and β simultaneously：7.5
≤ α≤8.5, preferably 4.6≤β≤7,7.7≤α≤8,4.7≤β≤5；The definition of α and β is as shown in formula i and ii；
……………………（Formula i）
……………………（Formula ii）
Wherein, based on the total molfraction of whole monomers,
Represent the above-mentioned monomer A with ten carbon atoms10Molfraction；
Represent above-mentioned non-fat race's monomer B with eight carbon atoms8Molfraction；
Representing above-mentioned tool, there are one the monomer D's of the Third monomer and/or lactams of amino and carboxyl functional group
Molfraction；Its account for the total molfraction content of whole monomers for 0≤≤50mol%；
Represent the total moles number of above-mentioned monomer A, m represents monomer AmIn carbon atom number；
Represent the total moles number of above-mentioned monomer B, n represents monomer BnIn carbon atom number；
Using DSC instruments, by polyamide sample with 10oThe heating rate heating of C/min on DSC spectrograms until occur
First endothermic peak temperature will be denoted as T at this time；Another sample is taken with 10oThe heating rate of C/min rises to a certain temperature T+
40oC, constant temperature 3min, then with 10oThe rate of temperature fall of C/min is down to 50oC, constant temperature 3min, finally with 10oThe heating rate of C/min
Rise to T+40oC；Another sample second of being subject to heats up the DSC curve of record, which has double fusing points,
The difference of both middle fusing point is 5oC -20oC；
The carboxyl-content [m] and amino content [n] of the polyamide obtained surely by automatic potential titrator tests meet
Following range：
Mole/ton of [m]≤300；
Mole/ton of [n]≤200.
Preferably, a kind of polyamide moulding composition, including consisting of：
A, the polyamide of 30wt%-97wt%；
B, the reinforcing filler of 1wt%-62wt%；
C, the additive of 0.1wt%-67wt% and/or other polymer；
Wherein, the total content of tri- kinds of components of a, b, c is 100wt%.
Preferably, the polyamide with double fusing points, based on the molar part all derived from diacid repetitive unit
Number, at least repetitive unit of 20mol% are derived from terephthalic acid (TPA) and/or Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.
Preferably, the polyamide with double fusing points, based on the molar part all derived from diamines repetitive unit
Number, at least repetitive unit of 20mol% are derived from 1,6- hexamethylene diamines and/or 1,10- decamethylene diamine.
The polyamide passes through the carboxyl-content [m] for the polyamide that automatic potential titrator tests obtain surely
With amino content [n] preferably following range：50 moles/ton≤mole/ton of [m]≤200；20 moles/ton≤[n]≤100 mole/
Ton.
The content of the component b is preferably 10wt%-50wt%, more preferably 15wt%-40wt%；
Reinforcing filler content is too low, causes polyamide moulding composition mechanical property poor；Reinforcing filler too high levels are gathered
Amide moulding compound product surface floats fibre seriously, influences product appearance.
The shape of the reinforcing filler is fibrous, average length 0.01mm-20mm, preferably 0.1mm-6mm；Its
Draw ratio is 5:1-2000:1, preferably 30:1-600:1, when threadiness reinforcing filler content within the above range when, polyamides
Amine moulding compound will show high heat distortion temperature and the high temperature rigid increased.
The reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers；
The inorganic reinforcing filler be selected from glass fibre, potassium titanate fibre, the glass fibre of clad, ceramic fibre,
Wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum are fine
The one or more of dimension or boron fibre, preferably glass fibre；
The mouldability of polyamide moulding composition can be not only improved using glass fibre, but also mechanical property example can be improved
Heat when for example thermoplastic resin composition is molded such as tensile strength, bending strength and bending modulus and raising heat resistance
Deformation temperature.
The organic reinforcing fillers are selected from aramid fibre and/or carbon fiber.
The shape of the reinforcing filler is Non-fibrous, such as powdered, graininess, plate, needle-shaped, fabric or felted,
Its average grain diameter is 0.001 μm -100 μm, preferably 0.01 μm -50 μm.
When the average grain diameter of reinforcing filler is less than 0.001 μm of melt processable that will lead to polyamide difference；Work as enhancing
The average grain diameter of filler is more than 100 μm, will lead to undesirable injection-molded article appearance.
The average grain diameter of above-mentioned reinforcing filler is measured by absorption method, may be selected from potassium titanate crystal whisker, ZnOw,
Aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophillite, bentonite, montmorillonite, lithium cover
De- soil, synthetic mica, asbestos, alumino-silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, iron oxide, calcium carbonate,
Magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride,
The one or more of silicon carbide or silica.
These reinforcing fillers can be hollow；It is in addition, molten for bentonite, montmorillonite, lithium montmorillonite, synthetic mica etc.
Swollen property phyllosilicate can use and interlayer ion is carried out to the organic montmorillonite after cation exchange using organic ammonium salt.
In order to which polyamide moulding composition is made to obtain more excellent mechanical performance, coupling agent can be used, inorganic enhancing is filled out
Material carries out functional processing.
Wherein coupling agent is selected from isocyanates based compound, organosilan based compound, organic titanate based compound, has
Machine borine based compound, epoxide；Preferably organosilan based compound；
Wherein, the organosilan based compound is selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group, contains sulfydryl
Alkoxysilane compound containing trialkylsilyl group in molecular structure, 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, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkane containing carbon-to-carbon unsaturated group containing end amido
Oxysilane compound, the one or more of alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group be selected from γ-glycidoxypropyltrime,hoxysilane, γ-
The one or more of glycidoxypropyl group triethoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-sulfydryl
Propyl-triethoxysilicane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups is selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl
Trimethoxy silane, γ-(2- urea groups ethyl) hold the one or more of aminocarbonyl propyl trimethoxy silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group is selected from γ-isocyanate group propyl-triethoxysilicane
Alkane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-isocyanic acid
Ester group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group propyl
The one or more of ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido is selected from γ-(2- ends amido ethyl) end aminocarbonyl propyl methyl two
Methoxy silane, γ-(2- ends amido ethyl) end aminocarbonyl propyl trimethoxy silane, γ-end aminocarbonyl propyl trimethoxy silane
One or more；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from γ-hydroxypropyl trimethoxy silane and/or γ-hydroxyl
Propyl-triethoxysilicane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group is selected from γ-methacryloxypropyl front three
Oxysilane, vinyltrimethoxysilane, N- β-(N- vinyl benzyl cardinal extremity amidos ethyl)-γ-end aminocarbonyl propyl trimethoxy
The one or more of base silane hydrochloride；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3- trimethoxy-silylpropyl succinic anhydrides；
The organosilan based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2- ends
Amido ethyl) end aminocarbonyl propyl methyl dimethoxysilane, γ-(2- ends amido ethyl) end aminocarbonyl propyl trimethoxy silane,
γ-end aminocarbonyl propyl trimethoxy silane or 3- trimethoxy-silylpropyl succinic anhydrides.
Conventionally inorganic reinforcing filler can be surface-treated using above-mentioned organosilan based compound,
Then itself and polyamide are subjected to melting mixing again, to prepare the polyamide moulding composition.
Organosilicon methane series chemical combination can also be added in directly while inorganic reinforcing filler and polyamide melting mixing
Object carries out in-situ blending.
Wherein, the dosage of the coupling agent is the 0.05wt%-10wt% relative to inorganic reinforcing filler weight, preferably
0.1wt%-5wt%。
When the dosage of coupling agent is less than 0.05wt%, the effect of apparent improved mechanical properties is not achieved；Work as coupling agent
Dosage be more than 10wt% when, inorganic reinforcing filler easily agglomerates, and disperses undesirable risk in polyamide,
Mechanical performance is eventually led to decline.
The additive is selected from the one or more of fire retardant, impact modifying agent, other polymer, processing aid；It is described
Other polymer are preferably fatty polyamide, polyolefin homopolymer, ethene-alpha-olefin copolymer, ethylene-acrylate copolymers
The one or more of object；The processing aid be selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, releasing agent, lubricant, pigment,
Dyestuff, plasticizer, antistatic agent one or more.
The fire retardant is fire retardant or fire retardant and the fire-retardant composition for assisting agent, based on polyamide moulding composition
Total weight, content are preferably 10wt%-40wt%；Flame retardant agent content is too low to cause flame retardant effect to be deteriorated, and flame retardant agent content is excessively high
Material mechanical performance is caused to decline.
The fire retardant is halogenated flame retardant or halogen-free flame retardants；
The halogenated flame retardant is selected from brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, bromination benzene
Ethylene maleic acid anhydride copolymer, brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, bromination are gathered
The one or more of carbonic ester, three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer, preferably preferred brominated polyphenylene second
Alkene；
The halogen-free flame retardants is selected from one kind or several of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus fire retardant
Kind；Preferably phosphonium flame retardant.
The phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, phosphorus
Triphenyl phosphate ester, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate, butylbenzene system phosphate or phosphinates
It is one or more of；Preferably phosphinates；
Phosphinate salt compound is using the compound that such as following formula I and/or II represent as representative.
In Formulas I and Formula II, R1And R2It may be the same or different, represent the C1-C6- of straight-chain or branch-like respectively
Alkyl, aryl or phenyl.R3Represent C1-C10- alkylidenes, C6-C10- arlydene, the C6-C10- alkyl of straight-chain or branch-like
Arlydene, C6-C10- aryl alkylenes.M represents calcium atom, magnesium atom, aluminium atom and/or zinc atom.M be 2 or 3, n be 1 or
3, x be 1 or 2.
The more specific example of phosphinate salt compound includes dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethyl time
Phosphonic acids aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethyl
Methyl-phosphinic acid zinc, diethyl phosphinic acids calcium, diethyl phosphinic acids magnesium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, methyl
N-propyl phosphinic acids calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc, first are burnt
Two (methyl-phosphinic acids）Calcium, methane two（Methyl-phosphinic acid）Magnesium, methane two（Methyl-phosphinic acid）Aluminium, methane two（Methyl time phosphine
Acid）Zinc, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Calcium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Magnesium, benzene-Isosorbide-5-Nitrae-(dimethyl time phosphine
Acid）Aluminium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, aminomethyl phenyl time phosphine
Sour aluminium, methylphenylphosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl time phosphine
Sour zinc etc., preferably dimethylphosphinic acid calcium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid I beggars, second
Ylmethyl phosphinic acids aluminium, ethylimethyphosphinic acid zinc, diethyl phosphinic acids calcium, aluminum diethylphosphinate, diethyl phosphinic acids zinc,
More preferable aluminum diethylphosphinate.
Phosphinate salt compound as fire retardant can be obtained easily from market.It can be from the phosphinic acids salinization that market obtains
The example for closing object includes Clariant Corporation（Clariant）EXOLIT OP1230 of manufacture, OP1311, OP1312, OP930,
OP935 etc..
The polyamide moulding composition for including above-mentioned polyamide of the present invention, based on the total of polyamide moulding composition
Weight, the additive component may also contain up to one or more of impact modifying agents of 45wt%；Preferably 5wt%-
30wt%。
Wherein, the impact modifying agent can be natural rubber, polybutadiene, polyisoprene, polyisobutene, butadiene
And/or isoprene and styrene or with styrene derivative and with the copolymer of other comonomers, hydrogenated copolymer and/
By grafting or with acid anhydride,（Methyl）Prepared by acrylic acid or its ester are copolymerized copolymer；The impact modifying agent can also be
Graft rubber with cross-linked elastomer core, the cross-linked elastomer core is by butadiene, isoprene or alkyl acrylate structure
Into, and with the graft shell that is made of polystyrene or can be nonpolarity or polar olefin homopolymer or copolymer, example
Such as EP rubbers, ethylene/propylene/diene rubber or Ethylene-octene rubber or ethylene-vinyl acetate rubber or pass through
Grafting or with acid anhydride,（Methyl）Nonpolarity or polar olefin homopolymer or copolymer obtained from acrylic acid or the copolymerization of its ester；It is described
Impact modifying agent can also be carboxylic acid functionalized copolymer, such as poly-（Ethylene -co-（Methyl）Acrylic acid）It is or poly-（Ethylene -1-
Alkene -co-（Methyl）Acrylic acid）, wherein 1- alkene is olefine or with the unsaturation more than 4 atoms（Methyl）Propylene
Acid esters, including those copolymers acid groups by metal ion neutralization to a certain extent.
Styrene-based monomer（Styrene and styrene derivative）With the impact modifying agent of other vi-ny l aromatic monomers,
It is the block copolymer that is made of alkenyl aromatic compounds and conjugated diene and by alkenyl aromatic compounds and conjugation two
The combination of hydrogenated block copolymer and these type impact modifying agents that alkene is formed.The block copolymer includes at least one
Block a and at least one block b derived from conjugated diene of the kind derived from alkenyl aromatic compounds.It is total in hydrogenated diblock
In the case of polymers, the ratio of aliphatic unsaturation carbon-to-carbon double bond is reduced by hydrogenating.Suitable block copolymer is that have
Two, three, the four of linear chain structure and segmented copolymer.But branched and star structure can also be used according to the present invention.With
Know that mode obtains branched block copolymer, such as passes through polymer " collateral chain " to the graft reaction of main polymer chain.
The other alkenyl aromatic chemical combination that can be used together with styrene or be used with the form of mixtures with styrene
Object be aromatic ring and/or in C=C double bonds by C1-20 alkyl or the vi-ny l aromatic monomers replaced by halogen atom.
The example of alkenyl aromatic monomer is styrene, p-methylstyrene, α-methylstyrene, ethyl styrene, uncle
Butylstyrene, vinyltoluene, 1,2- diphenylethlenes, 1,1- diphenylethlenes, vinyl-dimethyl benzene, vinyltoluene,
Vinyl naphthalene, divinylbenzene, bromostyrene and chlorostyrene, and combinations thereof.Optimization styrene, p-methylstyrene,
α-methylstyrene and vinyl naphthalene.
It is preferable to use styrene, α-methylstyrene, p-methylstyrene, ethyl styrene, t-butyl styrene, ethylene
Base toluene, 1,2- diphenylethlenes, 1,1- diphenylethlenes or these substances mixture.Particularly preferably use benzene second
Alkene.But it is also possible to use alkenyl naphthalene.
The example for the diolefinic monomer that can be used is 1,3-butadiene, 2- methyl-1s, 3- butadiene, 2,3- dimethyl-
1,3-butadiene, 1,3-pentadiene, 1,3- hexadienes, isoprene, chlorobutadiene and pentadiene.It is preferred that 1,3-butadiene and
Isoprene, especially 1,3-butadiene (are hereinafter represented) with abbreviated form butadiene.
Used alkenyl aromatic monomer preferably includes styrene, and used diolefinic monomer preferably includes fourth two
Alkene, it means that optimization styrene-butadiene block copolymer.The block copolymer is usually by anionic polymerisation with it
Known to body prepared by mode.
Other than styrene monomer and diolefinic monomer, other other monomers can also be used simultaneously.Based on being made
With the total amount of monomer, the ratio of comonomer is preferably 0-50wt%, particularly preferably 0-30wt%, particularly preferably 0-15wt%.
The example of suitable comonomer is acrylate respectively, especially acrylic acid C1~C12 Arrcostabs, such as n-butyl acrylate
Or 2-EHA and methacrylate, especially methacrylic acid C1~C12 Arrcostabs, such as metering system
Sour methyl esters（MMA）.Other possible comonomers are（Methyl）Acrylonitrile,（Methyl）Glycidyl acrylate, vinyl first
Base ether, the diallyl of dihydric alcohol and divinyl ether, divinylbenzene and vinyl acetate.
Other than conjugated diene, if applicable, hydrogenated block copolymer is also comprising lower hydrocarbon part, such as second
Alkene, propylene, 1- butylene, bicyclopentadiene or non-conjugated diene hydrocarbon.Unreduced aliphatic unsaturated bond derived from block b is in hydrogen
The ratio changed in block copolymer is less than 50%, preferably smaller than 25%, especially less than 10%.Aromatic fractions derived from block a are also
Original arrives at most 25% degree.Pass through the hydrogenation of styrene-butadiene copolymer and styrene-butadiene-styrene
Hydrogenation, obtains hydrogenated block copolymer, i.e., styrene-（Ethylene/Butylene）Diblock copolymer and styrene-（Ethylene/Butylene）-
Styrene triblock copolymer.
Block copolymer preferably comprises the block a of the block a, especially 50wt%-85wt% of 20wt%-90wt%.Alkadienes
It can be orientated with 1,2- or Isosorbide-5-Nitrae-orientation is introduced into block b.
The molal weight of block copolymer is 5000g/mol-500000g/mol, preferably 20000g/mol-300000g/
Mol, particularly 40000g/mol-200000g/mol.
Suitable hydrogenated block copolymer is the product that can be bought from the market, such as（Kraton polymer）G1650、
G1651 and G1652 and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141 and H1272.
The example of non-hydrogenated block copolymer is polystyrene-polybutadiene, polystyrene-poly（Ethylene-propylene）, polyphenyl
Ethylene-polyisoprene gathers（α-methylstyrene）Polybutadiene, polystyrene-polybutadiene-polystyrene（SBS）, it is poly-
Styrene-poly-（Ethylene-propylene）Polystyrene, polystyrene-polyisoprene-polystyrene and poly-（α-methylstyrene）
Polybutadiene-poly-（α-methylstyrene）, and combinations thereof.
The suitable non-hydrogenated block copolymer that can be bought from the market has the trade mark to be（Phillips）、（Shell）、
（Dexco）With（Kuraray）Multiple product.
The polyamide moulding composition for including above-mentioned polyamide of the present invention, the additive component can also include
Other polymer, other polymer are selected from fatty polyamide, polyolefin homopolymer or ethene-alpha-olefin copolymer, second
Alkene-acrylate copolymer.
The fatty polyamide includes but are not limited to be originated from the aliphatic diacid and aliphatic two of 4~20 carbon atoms
Amine either aliphatic diacid, aliphatic diamine and the lactams of the lactams of 4~20 carbon atoms or 4~20 carbon atoms
Polymer in it is one or more.It includes but are not limited to, polyhexamethylene adipamide（PA66）, polycaprolactam（PA6）, it is poly-
Hexamethylene sebacamide（PA610）, nylon 1010（PA1010）, adipic acid-hexamethylene diamine-caprolactam copolymer
（PA66/6）, poly- 11 lactams（PA11）, nylon 12（PA12）And its two or more of mixtures.
The preferred EP elastomers of the ethene-alpha-olefin copolymer and/or EPDM elastomers（It is ethylene-propylene rubber respectively
With ethylene/propylene/diene rubber）.For example, elastomer can include being based on containing 20wt%-96wt%, preferably 25wt%-
The elastomer of the ethylene-C3 of 85wt% ethylene~C12- alpha olefin copolymers, wherein being particularly preferably C3~C12- α-alkene herein
Hydrocarbon includes the alkene selected from propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene and/or 1- laurylenes, particularly preferably
Other polymer include the one or more of ethylene-propylene rubber, LLDPE, VLDPE.
Alternatively or additionally（Such as in the mixture）, other polymer can also include based on ethylene-
The terpolymer of C3~C12- alpha-olefins and non-conjugated diene hydrocarbon, herein preferably its contain 25wt%-85wt% ethylene and
At most maximum is the non-conjugated diene hydrocarbon of 10wt%, and particularly preferred C3~C12- alpha-olefins are included selected from propylene, 1- fourths herein
Alkene, 1- amylenes, 1- hexenes, 1- octenes, the alkene of 1- decene and/or 1- laurylenes and/or wherein non-conjugated diene hydrocarbon is preferably
Selected from two rings [2.2.1] heptadiene, Isosorbide-5-Nitrae-hexadiene, especially dicyclopentadiene and/or 5- ethylidene norbornenes.
Vinyl-acrylate copolymer is also used as the ingredient of other polymer.
Other possible forms of other polymer are ethylene-butene copolymer and the mixing comprising these systems respectively
Object（Blend）.
Preferably, other polymer include the ingredient with anhydride group, these pass through trunk polymer and unsaturation
Dicarboxylic anhydride, with unsaturated dicarboxylic or thermal response or radical reaction with the monoalkyl ester of unsaturated dicarboxylic, be enough with
The concentration of polyamide good combination introduces, and herein preferably with selected from following reagent：
Maleic acid, maleic anhydride, butyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride.It is preferred that 0.1wt%-
The unsaturated acid anhydride of 4.0wt% is grafted in the shock resistance component of the ingredient as C or unsaturated dicarboxylic anhydride or its precursor lead to
It crosses together with other unsaturated monomers and is grafted to apply.Generally preferable grafting degree is 0.1%-1.0%, particularly preferably 0.3%-
0.7%.Another possible ingredient of other polymer is the mixing being made of ethylene-propylene copolymer and ethylene-butene copolymer
Object, herein maleic anhydride grafting degree（MA grafting degrees）For 0.3%-0.7%.
It can also be used as a mixture for the above-mentioned possible system of other polymer.
In addition, the additive component can include with functional group component, the functional group be, for example, carboxylic acid group,
Ester group, epoxy group, oxazoline group, carbodiimide group, isocyanate groups, silanol and carboxylate group,
Or the additive component can include the combination of two or more in above-mentioned functional group.List with the functional group
Body can be combined by being copolymerized or being grafted on elastomeric polyolefin.
In addition, the impact modifying agent based on olefin polymer can also change by using unsaturated silane compound grafting
Property, the unsaturated silane compound is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, three second of vinyl
Acyl silanes, methacryloxypropyl trimethoxy silane or acrylic trimethoxy silane.
Elastomeric polyolefin is have straight chain, branch or nucleocapsid random, alternately or block copolymer, and containing can
With the functional group that the end group with polyamide reacts, enough tolerabilities are thus provided between polyamide and impact modifying agent.
Therefore, impact modifying agent of the invention includes alkene（Such as ethylene, propylene, 1- butylene）Homopolymer or copolymerization
Object or alkene and copolymerisable monomer（Such as vinyl acetate,（Methyl）Acrylate and methyl hexadiene）Copolymer.
The example of crystalline olefin polymer be low-density, Midst density and high density polyethylene (HDPE), polypropylene, polybutadiene,
Poly- 4- methylpentenes, Ethylene-Propylene Block Copolymer or ethylene-propylene random copolymer, ethylene-methyl hexadiene copolymerization
Object, propylene-methyl hexadiene copolymer, ene-propylene-butene copolymer, Ethylene-propylene-hexene Copolymer, ethylene-propylene-
Methyl hexadiene copolymer gathers（Ethane-acetic acid ethyenyl ester）（EVA）, it is poly-（Ethylene-ethylacrylate）（EEA）, ethylene-octene
Copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, ethylene/propylene/diene terpolymer and above-mentioned poly-
Close the combination of object.
The commercially available impact modifying agent example that can be used for the additive component has：
TAFMER MC201：G-MA (- 0.6%) 67%EP copolymers (20mol% propylene)+33%EB copolymers (15mol%1-
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 copolymers；Mitsui.
EXXELOR VA1801：G-MA (- 0.7%) EP copolymers；Exxon Mobile Chemicals, US.
EXXELOR VA1803：G-MA (0.5-0.9%) EP copolymers, amorphous, Exxon.
EXXELOR VA1810：G-MA (- 0.5%) EP copolymers, Exxon.
EXXELOR MDEX 941l：G-MA (0.7%) EPDM, Exxon.
FUSABOND MN493D：G-MA (- 0.5%) ethylene-octene copolymer, DuPont, US.
FUSABOND A EB560D：(g-MA) ethylene/n-butyl acrylate copolymer, DuPont ELVALOY,
DuPont。
The carboxyl of also preferably ionomer, wherein polymer-bound is all mutually bonded or is bonded by metal ion
To a certain extent.
The copolymer of the particularly preferred graft-functionalized butadiene of maleic anhydride and styrene, by being grafted with maleic anhydride
Nonpolarity or polar olefin homopolymer and copolymer obtained and carboxylic acid functionalized copolymer, such as poly- (ethylene-common (first
Base) acrylic acid) or it is poly-（Ethylene -co- 1- alkene -co-s（Methyl）Acrylic acid）, wherein the acid groups to a certain extent by
Metal ion neutralizes.
In addition, in the range of effect of the present invention is not destroyed, it can be at any time in the polyamide of the present invention
Add various processing aids, such as antioxidant and/or heat-resisting stabilizing agent（Hindered phenolic, quinhydrones system, phosphite ester system and it
Substitution body, copper halide, iodine compound etc.）, weather resisting agent（Resorcinol system, salicylate system, enumerate BTA system, hexichol first
Ketone system, amine system of being obstructed etc.）, releasing agent and lubricant（Aliphatic alcohol, aliphatic amide, aliphatic bisamide, two ureas and polyethylene
Wax etc.）, pigment（Cadmium sulfide, phthalocyanine, carbon black etc.）, dyestuff（Nigrosine, nigrosine etc.）, plasticizer（P-hydroxybenzoic acid is pungent
Ester, N-butylbenzenesulfonamide etc.）, antistatic agent（Alkyl sulphate type anionic system antistatic agent, quaternary ammonium salt cationic system resist
The nonionic systems antistatic agents such as electrostatic agent, polyoxyethylene sorbitan monostearate, glycine betaine system both sexes antistatic agent
Deng）.
In order to obtain the molded product of the present invention, the polyamide of the present invention or Amilan polyamide resin composition can be passed through
The random moldings methods such as injection moulding, extrusion molding, blow molding, vacuum forming, melt spinning, film molding are molded.It can be with
These molded products are molded into required shape, and can be used in synthetic resin of automobile component, mechanical part etc. etc..Make
It is useful in following purposes for specific purposes：The top of automobile engine cooling water component, particularly radiator tank
Pump parts such as the radiator waters box part such as portion and bottom, coolant reserve tank, water pipe, water pump shell, water pump vane, valve etc. are in vapour
The component used is contacted down in car engine room with cooling water, with Switch, microminiature slide switch, DIP switch, switch it is outer
Shell, lamp holder, strapping, connector, the shell of connector, the shell of connector, IC sockets class, roll, bobbin cover, relay,
Electrical relaybox, capacitor casing, the internal part of motor, small size motor shell, gear cam, dancing pulley, gasket, insulator,
Fastener is buckled, the insulation division of the shell of wire clamp, cycle wheel, Caster, safety cap, terminal board, electric tool, starter
Divide, spoiler, tank, radiator tank, chamber tank（Chamber tank）, receiver, fuse box, shell of air purifier, sky
Adjust fan, the shell of terminal, wheel cover, suction tracheae, bearing retainer, cylinder head cover, inlet manifold, water pipe impeller（waterpipe
impeller）, clutch lever, speaker diaphragm, heatproof container, microwave oven component, electric cooker component, printer color tape
The electrical/electronic associated components for representative such as guider, automobile/vehicle associated components, household electrical appliances/office electric component, computer
Associated components, facsimile machine/duplicator associated components, mechanical associated components, other various uses.
Compared with prior art, the present invention it has the advantages that：
Using the polyamide molding group being prepared with double fusing points and the polyamide of specific Amino End Group and end carboxyl
Object is closed, the molding cycle of injecting products can be shortened, while the surface gloss of injecting products gets a promotion.
Specific embodiment
The test method of gained polyamide relative viscosity：With reference to GB12006.1-89, polyamide viscosity number assay method；
Specifically test method is：25 ± 0.01oThe relative viscosity of the polyamide of a concentration of 10mg/ml is measured in 98% concentrated sulfuric acid of Cη r；
The test method of the fusing point of polyamide：With reference to ASTM D3418-2003, Standard Test Method
for Transition Temperatures of Polymers By Differential Scanning Calorimetry；
Specifically test method is：Using the fusing point of Perkin Elmer Diamond dsc analysis instrument test samples；Nitrogen atmosphere, flow velocity
For 40mL/min；First by polyamide sample with 10 during testoThe heating rate heating of C/min on DSC spectrograms until occur
First endothermic peak temperature will be denoted as T at this time；Another sample is taken with 10oThe heating rate of C/min rises to a certain temperature T+
40oC, constant temperature 3min, then with 10oThe rate of temperature fall of C/min is down to 50oC, constant temperature 3min, finally with 10oThe heating rate of C/min
Rise to T+40oC；Another sample of being subject to DSC curve that heating records for the second time, which has double fusing points, higher
Fusing point is denoted asT m1, it is denoted as compared with low melting pointT m2。
The test method of gained polyamide amino content：Sample amino content is titrated with autopotentiometric titrator；
0.5g polymer is taken, adds phenol 45mL and absolute methanol 3mL, is heated to reflux, after observation sample is completely dissolved, is cooled to room temperature, uses
The hydrochloric acid standard solution titration terminal amino group content demarcated.
The test method of the carboxyl-content of gained polyamide：Contained with autopotentiometric titrator titration sample carboxyl
Amount；0.5g polymer is taken, adds o-cresol 50mL, reflux dissolving is rapidly added 400 μ L formalins, with what is demarcated after letting cool
KOH- ethanol solutions titrate content of carboxyl end group.
The test method of surface gloss：
Surface gloss is according to GB8807-1988《Plastics bright luster test method》It is tested, test angle is
60o.It is 100mm × 100mm × 3.2mm to test product size.
The test method of molding cycle：
Molding cycle refers to that injection molding machine completes the All Time needed for a plastic.Injection temperature is higher than fusing point 30oC takes
The product of 5 test surfaces glossiness is molded, calculates the average value of injection molding time.
The polyamide used in the present invention is prepared by the following method：
Stirred equipped with magnetic coupling, in the autoclave pressure of condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth by table
Ratio add in reaction raw materials；Add sodium hypophosphite, benzoic acid and deionized water；Sodium hypophosphite weight is in addition to deionized water
The 0.1%-0.5% of other charged material weights, the amount of benzoic acid species are the 2%-8% of the amount of diacid total material, and deionized water weight is
The 20%-40% of total charged material weight.It vacuumizes and is filled with high-purity argon gas as protection gas, start to react.Reaction mixture is warming up to
220 DEG C -230 DEG C are stirred 3-5 hours, then open valve slowly pressure release draining, while keep temperature and pressure constant.One is in line
Water to displacement reaches the 70% of input amount of deionized water.It starts to warm up at this time, 250 DEG C -270 DEG C was warming up in 3 hours, perseverance
Temperature 2 hours.Valve discharging is opened after the completion of reaction, obtains prepolymer.
According to the fusing point of the method test prepolymer of test polyamide fusing point, it is set as T DEG C.
After prepolymer is dried in vacuo 24 hours at 80 DEG C, using the mixed gas of carbon dioxide/vapor as protection
Gas carries out solid-phase tack producing.It is warming up to first（T-70）DEG C, constant temperature 1-5 hours.It is continuously heating to（T-50）DEG C, constant temperature 1-3 hours.
Then it is cooled to again（T-60）DEG C, constant temperature 1-5 hours.Finally it is warming up to（T-40）DEG C, constant temperature is until discharging.Last thermostatic process
In constantly sample, determine finally to polymerize terminal by sampling and testing viscosity.During above-mentioned continuous heating and cooling, polymerizate
The variation of solid-phase tack producing and crystal habit is carried out at the same time, finally obtains the polymerizate with different melting behaviors.
The rationally heating and cooling journey of the monomer composition in the adjusting above process, carbon dioxide/vapor ratio and solid-phase tack producing
Sequence can obtain different melting points and the polyamide of endgroup value.
The property indices of polyamide are as follows：
PA1：10T/4T=40/60, relative viscosity 2.185 have double fusing points：Tm1=323oC、Tm2=312oC, amino content
41 moles/ton, 105 mole/ton of carboxyl-content；
PA2：10T/10I/4T/4I=59.5/25.5/10.5/4.5, relative viscosity 2.153 have double fusing points：Tm1=
288oC、Tm2=272oC, 18 mole/ton of amino content, 73 mole/ton of carboxyl-content；
PA3：10T/10C/12=33/33/34, relative viscosity 2.209 have double fusing points：Tm1=275oC、Tm2=261oC, ammonia
73 mole/ton of base content, 288 mole/ton of carboxyl-content；
PA4：6T/6I=70/30, relative viscosity 2.171, fusing point 311oC, 43 mole/ton of amino content, carboxyl-content 98
Mole/ton；
PA5：10T/10C/12=33/33/34, relative viscosity 2.192, fusing point 269oC, 18 mole/ton of amino content, carboxylic
430 mole/ton of base content；
PA6：10T/12T=60/40, relative viscosity 2.144 have double fusing points：Tm1=266oC、Tm2=257oC, amino content
350 moles/ton, 20 mole/ton of carboxyl-content；
Wherein, C represents Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.
Embodiment 1-12 and comparative example 1-7：The preparation of polyamide moulding composition
By the formula of table 1 by polyamide, fire retardant, other auxiliary agents after high-speed mixer and mixing is uniform, fed by main
Material mouth is added in double screw extruder, and reinforcing filler is fed by side feeding scale side, is squeezed out, and crosses water cooling, after being granulated and drying
To the polyamide moulding composition.
Formula is parts by weight in 1 following table of table
It can be seen that from the comparison of the embodiment and comparative example of table 1 relative to comparative example, as a result of with double fusing points
And the polyamide with specific Amino End Group and content of carboxyl end group, the lustrous surface of the polyamide moulding composition of embodiment
Degree and molding cycle all have a clear superiority.
Claims (25)
1. a kind of polyamide moulding composition, form and be：
A, the polyamide with double fusing points of 30wt%-99.9wt%；
B, the reinforcing filler of 0-70wt%；
C, the fire retardant of 0-70wt% and/or other polymer；
Wherein, the sum of weight percent of tri- kinds of components of a, b, c is 100wt%；
The polyamide for having double fusing points, it includes the repetitive units derived from following monomer mixture：There are two tools
First monomer of amido functional group, referred to as monomer A；Has the second comonomer there are two carboxyl functional group or its precursor group, referred to as
Monomer B；And/or there are one amino and the Third monomer and/or lactams of a carboxyl functional group, referred to as monomer D for tool；
Wherein, monomer A at least contains a kind of monomer A with ten carbon atoms in the monomer mixture10；Monomer B at least contains
There is a kind of non-fat race's monomer B with eight carbon atoms8；
Wherein, based on the total molfraction of whole monomers, A10And B8Content meet the relationship of following α and β simultaneously：7.7≤α ＜
8,4.7≤β ＜ 5；The definition of α and β is as shown in formula i and ii；
……………………（Formula i）
……………………（Formula ii）
Wherein, based on the total molfraction of whole monomers,
Represent the above-mentioned monomer A with ten carbon atoms10Molfraction；
Represent above-mentioned non-fat race's monomer B with eight carbon atoms8Molfraction；
Represent molar part of the above-mentioned tool there are one the monomer D of the Third monomer and/or lactams of amino and carboxyl functional group
Number；Its account for the total molfraction content of whole monomers for 0≤≤50mol%；
Represent the total moles number of above-mentioned monomer A, m represents monomer AmIn carbon atom number；
Represent the total moles number of above-mentioned monomer B, n represents monomer BnIn carbon atom number；
Using DSC instruments, by polyamide sample with 10oThe heating rate heating of C/min on DSC spectrograms until occur first
A endothermic peak temperature will be denoted as T at this time；Another sample is taken with 10oThe heating rate of C/min rises to a certain temperature T+40oC, it is permanent
Warm 3min, then with 10oThe rate of temperature fall of C/min is down to 50oC, constant temperature 3min, finally with 10oThe heating rate of C/min rises to T+
40oC；Both another sample second of being subject to heats up the DSC curve of record, which has double fusing points, wherein
The difference of fusing point is 5oC -20oC；
The carboxyl-content [m] and amino content [n] of the polyamide obtained surely by automatic potential titrator tests meet following
Range：
Mole/ton of [m]≤300；
Mole/ton of [n]≤200.
2. a kind of polyamide moulding composition as described in claim 1, form and be：
A, the polyamide of 30wt%-97wt%；
B, the reinforcing filler of 1wt%-62wt%；
C, the fire retardant of 0.1wt%-67wt% and/or other polymer；
Wherein, the total content of tri- kinds of components of a, b, c is 100wt%.
3. polyamide moulding composition according to claim 1 or 2, which is characterized in that the polyamides with double fusing points
Polyimide resin, based on the molfraction all derived from diacid repetitive unit, at least repetitive unit of 20mol% is derived to benzene
Dioctyl phthalate and/or Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.
4. polyamide moulding composition according to claim 1 or 2, which is characterized in that the polyamides with double fusing points
Polyimide resin, the repetition list based on the molfraction all derived from diamines repetitive unit, at least 20mol% and less than 100mol%
Member is derived from 1,6- hexamethylene diamines and/or 1,10- decamethylene diamine.
5. polyamide moulding composition according to claim 1 or 2, which is characterized in that pass through automatic potential titrator tests
Surely the carboxyl-content [m] and amino content [n] of the polyamide obtained meet following range：
50 moles/ton≤mole/ton of [m]≤200；
20 moles/ton≤mole/ton of [n]≤100.
6. polyamide moulding composition according to claim 1 or 2, which is characterized in that the shape of the reinforcing filler is
Threadiness, average length 0.01mm-20mm；Its draw ratio is 5:1-2000:1；The content of the reinforcing filler is
10wt%-50wt%；The reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers, and the inorganic reinforcing filler is selected from glass
Fiber, potassium titanate fibre, ceramic fibre, wollastonite fibre, metallic carbide fibres, asbestos fibre, alumina fibre, gypsum are fine
The one or more of dimension, carbon fiber or boron fibre；The organic reinforcing fillers are selected from aramid fibre.
7. polyamide moulding composition according to claim 6, which is characterized in that the average length of the reinforcing filler is
0.1mm-6mm。
8. polyamide moulding composition according to claim 6, which is characterized in that the draw ratio of the reinforcing filler is
30:1-600:1。
9. polyamide moulding composition according to claim 6, which is characterized in that the content of the reinforcing filler is
15wt%-40wt%。
10. polyamide moulding composition according to claim 6, which is characterized in that the inorganic reinforcing filler is glass
Fiber.
11. polyamide moulding composition according to claim 10, which is characterized in that the glass fibre is clad
Glass fibre.
12. polyamide moulding composition according to claim 6, which is characterized in that the ceramic fibre is fine for silicon carbide
Dimension.
13. polyamide moulding composition according to claim 1 or 2, which is characterized in that the shape of the reinforcing filler is
Non-fibrous, average grain diameter is 0.001 μm -100 μm, selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, silicon ash
Stone, zeolite, kaolin, mica, talcum, clay, pyrophillite, bentonite, montmorillonite, asbestos, alumino-silicate, aluminium oxide, oxidation
Magnesium, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide,
Aluminium hydroxide, bead, ceramic bead, boron nitride, silicon carbide or silica one or more.
14. polyamide moulding composition according to claim 13, which is characterized in that the average grain diameter of the reinforcing filler
It is 0.01 μm -50 μm.
15. polyamide moulding composition according to claim 13, which is characterized in that the mica be selected from sericite and/
Or synthetic mica.
16. polyamide moulding composition according to claim 13, which is characterized in that the montmorillonite, which is selected from lithium and covers, to be taken off
Soil.
17. polyamide moulding composition according to claim 1 or 2, which is characterized in that the fire retardant is fire-retardant for halogen system
Agent or halogen-free flame retardants；The halogenated flame retardant is selected from brominated Polystyrene, brominated polyphenylether, brominated styrene-maleic anhydride
Copolymer, brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, brominated polycarbonate, perbromo- three
The one or more of cyclopentadecane or brominated aromatic cross-linked polymer；The halogen-free flame retardants is selected from nitrogenous flame ratardant, phosphorous
One or more of fire retardant or nitrogenous and phosphorus fire retardant；Total weight based on polyamide moulding composition, it is described fire-retardant
The content of agent is 10wt%-40wt%.
18. polyamide moulding composition according to claim 17, which is characterized in that the fire retardant is halogen-free flameproof
Agent.
19. polyamide moulding composition according to claim 17, which is characterized in that the halogenated flame retardant gathers for bromination
Styrene.
20. polyamide moulding composition according to claim 17, which is characterized in that the halogen-free flame retardants is phosphorous resistance
Fire agent.
21. polyamide moulding composition according to claim 17, which is characterized in that the brominated epoxy resin is selected from bromine
Change bisphenol A type epoxy resin.
22. polyamide moulding composition according to claim 20, which is characterized in that the phosphonium flame retardant is selected from single phosphorus
Sour aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate
(dimethylbenzene) ester, propyl benzene system phosphate, butylbenzene system phosphate, phosphinates one or more.
23. polyamide moulding composition according to claim 22, which is characterized in that the phosphonium flame retardant is with such as
The phosphinates of lower structure Formulas I and/or II：
In Formulas I and Formula II, R1And R2It may be the same or different, represent the C1-C6- alkane of straight-chain or branch-like respectively
Base, aryl；R3Represent C1-C10- alkylidenes, C6-C10- arlydene, the C6-C10- aryl alkylenes of straight-chain or branch-like；M
Represent 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.
24. polyamide moulding composition according to claim 23, which is characterized in that the aryl is phenyl.
25. polyamide moulding composition according to claim 23, which is characterized in that the C6-C10- arlydene is C6-
C10- alkyl arylenes.
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