CN104804432B - A kind of polyamide moulding composition - Google Patents
A kind of polyamide moulding composition Download PDFInfo
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- CN104804432B CN104804432B CN201510135969.4A CN201510135969A CN104804432B CN 104804432 B CN104804432 B CN 104804432B CN 201510135969 A CN201510135969 A CN 201510135969A CN 104804432 B CN104804432 B CN 104804432B
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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
- 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 30wt% 99.9wt% polyamide with double fusing points；B, 0 70wt% reinforcer；C, 0 70wt% additive and/or other polymer；Wherein, the percetage by weight sum of tri- kinds of components of a, b, c is 100wt%；In the polyamide with double fusing points, based on the molar content of all carbon atoms in polyamide, the molar content of bio-based carbon is more than 40%.The present invention is by using the polyamide with double fusing points and the bio-based carbon of specific molar content, the polyamide moulding composition being prepared by it, can shorten the molding cycle of injecting products, while the surface gloss of injecting products gets a promotion.
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 combination property, including mechanical property, heat resistance, wear resistance, chemical proofing
And self lubricity, and coefficient of friction is low, there is certain anti-flammability etc., it is generally applied is filled with glass fibre and other fillers
Enhancing is modified, and is improved performance and is expanded application etc..In recent years semiaromatic polyamide composition due to its heat resistance and
Mechanical property is more excellent and by focus development.
But the raw material from petroleum cracking product that existing polyamide mainly uses in building-up process.Oil
With non-renewable, and the synthesis of these raw materials needs to make the complicated chemical process of experience, consumes big energy and produces
The accessory substances of environmental pollution are much caused, contains some volatile gas in this polyamide, can gradually dissipate in use
Issue, influence user's health.As polyamide is applied to the field that food contacts, volatile gas contains in daiamid composition
Amount is even more that needs are reasonably controlled.
At present, those skilled in the art typically carry out the molten condition of general description polymer with fusing point, but should for processing
With etc. for demand, this description still shows coarse.The melting process of polymer not occurs on one point, but in a segment limit
Carry 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 considerable influence to fusing point.Even if component, monomer ratio identical polyamide, due to the collective effect of above-mentioned factor,
The all possible difference of its fusing point is huge, so as to cause the difference of polyamide or even its composition performance.
The present inventor is had found by many experiments, using the polyamides with double fusing points and the bio-based carbon of specific molar content
Polyimide resin, the polyamide moulding composition being prepared by it, the molding cycles of injecting products, while injecting products can be shortened
Surface gloss get a promotion.
The content of the invention
The shortcomings that in order to overcome prior art and deficiency, it is an object of the invention to provide one kind can shorten injecting products
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 30wt%-99.9wt% polyamide with double fusing points；
B, 0-70wt% reinforcer；
C, 0-70wt% additive and/or other polymer；
Wherein, the total content of tri- kinds of components of a, b, c is 100wt%；
The polyamide with double fusing points, it includes the repeat unit derived from following monomer mixture：Have
First monomer of two amido functional groups, referred to as monomer A；Second comonomer with two carboxyl functional groups or its precursor group,
Referred to as monomer B；And/or Third monomer and/or lactams with an amino and a carboxyl functional group, referred to as monomer D；
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 following α and β relation simultaneously：7.5
≤ α≤8.5, preferably 4.6≤β≤7,7.7≤α≤8,4.7≤β≤5；α and β definition 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 the monomer D's of the above-mentioned Third monomer with an amino and carboxyl functional group and/or lactams
Molfraction；Its account for the total molfraction content of whole monomers for 0≤≤50mol%；
Above-mentioned monomer A total moles number is represented, m represents monomer AmIn carbon atom number；
Above-mentioned monomer B total moles number is represented, n represents monomer BnIn carbon atom number；
Using DSC instruments, by polyamide sample with 10oC/min heating rate heating on DSC spectrograms until occur
First endothermic peak, now temperature it will be designated as T；Another sample is taken with 10oC/min heating rate rises to a certain temperature T+
40oC, constant temperature 3min, then with 10oC/min rate of temperature fall is down to 50oC, constant temperature 3min, finally with 10oC/min heating rate
Rise to T+40oC；It is defined by the DSC curve of second of record that heats up of another sample, the polyamide has double fusing points, its
In the difference of the two fusing point be 5oC -20oC；
It is described to have in double melting point polyamide resins, based on the molar content of all carbon atoms in polyamide, biology
The molar content of base carbon is in more than 40mol%, preferably more than 50mol%.
Preferably, a kind of polyamide moulding composition, including consisting of：
A, 30wt%-95wt% polyamide；
B, 1wt%-68wt% reinforcer；
C, 0.1wt%-65wt% additive 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 repeat unit
Number, at least 20mol% repeat unit is 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 repeat unit
Number, at least 20mol% repeat unit is derived from 1,6- hexamethylene diamines and/or 1,10- decamethylene diamine.
The content of the component b is preferably 10wt%-50wt%, more preferably 15wt%-40wt%；
Reinforcer content is too low, causes polyamide moulding composition mechanical property poor；Reinforcer too high levels, gather
Acid amides moulding compound product surface is floating fine serious, influences product appearance.
The reinforcer is shaped as threadiness, and its average length is 0.01mm-20mm, preferably 0.1mm-6mm；Its
Draw ratio is 5:1-2000:1, preferably 30:1-600:1, when threadiness reinforcer content within the above range when, polyamides
Amine moulding compound will show high heat distortion temperature and the high temperature rigid increased.
The reinforcer 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, and mechanical property example can be improved
Such as tensile strength, bending strength and bending modulus, and heat when improving heat resistance for example thermoplastic resin composition being molded
Deformation temperature.
The organic reinforcing fillers are selected from aramid fibre and/or carbon fiber.
The reinforcer is shaped as Non-fibrous, such as powdered, graininess, tabular, needle-like, 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 reinforcer is less than 0.001 μm of melt processable that will cause polyamide difference；Work as enhancing
The average grain diameter of filler is more than 100 μm, will cause bad injection-molded article appearance.
The average grain diameter of above-mentioned reinforcer is determined by absorption method, its 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, aluminum 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 carborundum or silica.
These reinforcers can be hollow；It is in addition, molten for bentonite, montmorillonite, lithium montmorillonite, synthetic mica etc.
Swollen property phyllosilicate, it can use and interlayer ion is carried out to the organic montmorillonite after cation exchange using organic ammonium salt.
In order that polyamide moulding composition obtains more excellent mechanical performance, coupling agent can be used to fill out inorganic enhancing
Material carries out functional processing.
Wherein coupling agent is selected from isocyanates based compound, organosilan based compound, organic titanate based compound, had
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 radicals, 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 NCO,
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
TMOS 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 radicals 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 NCO is selected from γ-NCO propyl-triethoxysilicane
Alkane, γ-NCO propyl trimethoxy silicane, γ-NCO hydroxypropyl methyl dimethoxysilane, γ-isocyanic acid
Ester group hydroxypropyl methyl diethoxy silane, γ-NCO ethyl dimethoxysilane, γ-NCO propyl group
The one or more of ethyl diethoxy silane, γ-NCO 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
TMOS, vinyltrimethoxy silane, 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 directly while inorganic reinforcing filler and polyamide melting mixing
Thing carries out in-situ blending.
Wherein, the dosage of the coupling agent is the 0.05wt%-10wt% relative to inorganic reinforcing filler weight, is preferably
0.1wt%-5wt%。
When the dosage of coupling agent is less than 0.05wt%, it does not reach the effect of obvious improved mechanical properties；Work as coupling agent
Dosage when being more than 10wt%, inorganic reinforcing filler easily condenses, and disperses bad risk in polyamide,
Mechanical performance is ultimately resulted in decline.
The additive is selected from fire retardant, impact modifying agent, other polymer, the one or more of 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 thing；The processing aid be selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, releasing agent, lubricant, pigment,
Dyestuff, plasticizer, the one or more of antistatic additive.
The fire retardant is fire retardant or fire retardant and the composition of fire-retardant assistance agent, based on polyamide moulding composition
Gross weight, its 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 too 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, the cyclopentadecane of perbromo- three 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 R2Can be with identical, can also be different, the C1-C6- of straight-chain or branch-like is represented 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 preferably aluminum diethylphosphinate.
Phosphinate salt compound as fire retardant can be obtained easily from market.Can be from the phosphinic acids salinization that market obtains
The example of compound 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 45wt% one or more of impact modifying agents；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 up of polystyrene or can be nonpolar 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）Nonpolar 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-（Ethene -co-（Methyl）Acrylic acid）It is or poly-（Ethene -1-
Alkene -co-（Methyl）Acrylic acid）, wherein 1- alkene is olefine or the unsaturation with more than 4 atoms（Methyl）Propylene
Acid esters, including acid groups are neutralized those copolymers to a certain extent by metal ion.
Styrene-based monomer（Styrene and styrene derivative）With the impact modifying agent of other vi-ny l aromatic monomers,
It is the block copolymer being made up of alkenyl aromatic compounds and conjugated diene, and by alkenyl aromatic compounds and conjugation two
The hydrogenated block copolymer that alkene is formed, and the combination of these type impact modifying agents.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 hydrogenation.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 the graft reaction of main polymer chain is arrived by polymer " collateral chain ".
The other alkenyl aromatic chemical combination that can be used together with styrene or be used with the form of mixtures with styrene
Thing be aromatic ring and/or in C=C double bonds by C1-20 alkyl or the vi-ny l aromatic monomers substituted 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 preferred that use styrene, α-methylstyrene, p-methylstyrene, ethyl styrene, t-butyl styrene, ethene
Base toluene, 1,2- diphenylethlenes, the mixture of 1,1- diphenylethlenes or these materials.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 isophthalic acids, 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 generally by anionic polymerisation with it
Known to body prepared by mode.
In addition to 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.
In addition to conjugated diene, if appropriate, hydrogenated block copolymer also includes lower hydrocarbon part, such as second
Alkene, propylene, 1- butylene, bicyclopentadiene or non-conjugated diene hydrocarbon.Block b unreduced aliphatic unsaturated bond is come from 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 SB 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 20wt%-90wt% block a, especially 50wt%-85wt% block a.Alkadienes
It can be orientated with 1,2- or Isosorbide-5-Nitrae-orientation is incorporated 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
Ethene-polyisoprene, gather（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 derived 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 one or more.Include 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 mixture of two or more.
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 ethene-C3 of 85wt% ethene~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 ethylene-propylene rubber, LLDPE, VLDPE one or more.
Alternatively or additionally（Such as in the mixture）, other polymer can also include based on ethene-
The terpolymer of C3~C12- alpha-olefins and non-conjugated diene hydrocarbon, herein preferably its contain 25wt%-85wt% ethene and
At most maximum is 10wt% non-conjugated diene hydrocarbon, 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 composition of other polymer.
Other possible forms of other polymer are ethylene-butene copolymer and the mixing comprising these systems respectively
Thing（Blend）.
Preferably, other polymer include the composition with anhydride group, and 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%-
4.0wt% unsaturated acid anhydride is grafted in the shock resistance component of the composition as C, or unsaturated dicarboxylic anhydride or its precursor lead to
Cross together with other unsaturated monomers and be grafted to apply.Generally preferable grafting degree is 0.1%-1.0%, particularly preferably 0.3%-
0.7%.Another possible composition of other polymer is the mixing being made up of ethylene-propylene copolymer and ethylene-butene copolymer
Thing, herein maleic anhydride grafting degree（MA grafting degrees）For 0.3%-0.7%.
Above-mentioned possible system for other polymer can also use as a mixture.
In addition, the additive component can include with functional group component, the functional group be, for example, hydroxy-acid group,
Ester group, epoxide 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, vinyltrimethoxy silane, VTES, the second of vinyl three
Acyl silanes, methacryloxypropyl trimethoxy silane or acrylic trimethoxy silane.
Elastomeric polyolefin is have straight chain, side chain or core shell structure random, alternately or block copolymer, and containing can
With the functional group reacted with the end group of polyamide, enough tolerabilities are thus provided between polyamide and impact modifying agent.
Therefore, impact modifying agent of the invention includes alkene（Such as ethene, propylene, 1- butylene）Homopolymer or copolymerization
Thing, 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, ethene-methyl hexadiene copolymerization
Thing, propylene-methyl hexadiene copolymer, ene-propylene-butene copolymer, Ethylene-propylene-hexene Copolymer, ethylene-propylene-
Methyl hexadiene copolymer, gather（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-
The combination of compound.
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
Obtained nonpolar or polar olefin homopolymer and copolymer and carboxylic acid functionalized copolymer, such as poly- (ethene-common (first
Base) acrylic acid) or it is poly-（Ethene -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, 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 phenol series, 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 additive（Alkyl sulphate type anion system antistatic additive, quaternary ammonium salt cationic system resist
The nonionic system such as electrostatic agent, polyoxyethylene sorbitan monostearate antistatic additive, glycine betaine system both sexes antistatic additive
Deng）.
In order to obtain the products formed of the present invention, the polyamide of the present invention or Amilan polyamide resin composition can be passed through
The random molding methods such as injection moulding, extrusion molding, blow molding, vacuum forming, melt spinning, film shaping are molded.Can be with
These products formeds 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 based part, particularly radiator tank
Pump parts such as the radiator water box part such as portion and bottom, coolant reserve tank, water pipe, water pump shell, water pump vane, valve etc. are in vapour
The part used is contacted down in car engine room with cooling water, with Switch, microminiature slide switch, DIP switch, switch it is outer
Shell, lamp socket, 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, pad, insulator,
Fastener, buckle, 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 part, printer color tape
Guider etc. be representative electrical/electronic associated components, automobile/vehicle associated components, household electrical appliances/office electric component, computer
Associated components, facsimile machine/duplicator associated components, mechanical associated components, other various uses.
Embodiment
The molar content of the bio-based carbon measures according to ASTM standard D6866-12/Method-B.
The method of testing of gained polyamide relative viscosity：With reference to GB12006.1-89, polyamide viscosity number assay method；
Specifically method of testing is：25 ± 0.01oThe relative viscosity for the polyamide that concentration is 10mg/ml is measured in C 98% concentrated sulfuric acidη r；
The method of testing 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 method of testing 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 testoC/min heating rate heating on DSC spectrograms until occur
First endothermic peak, now temperature it will be designated as T；Another sample is taken with 10oC/min heating rate rises to a certain temperature T+
40oC, constant temperature 3min, then with 10oC/min rate of temperature fall is down to 50oC, constant temperature 3min, last 10oC/min heating rate liter
To T+40oC；The DSC curve recorded that heated up by second is defined, and the polyamide has double fusing points, and higher melt is designated asT m1,
It is designated as compared with low melting pointT m2。
The method of testing of surface gloss：
Surface gloss is according to GB8807-1988《Plastics bright luster test method》Tested, test angle is
60o.It is 100mm × 100mm × 3.2mm to test product size.
The method of testing of molding cycle：
Molding cycle, refer to that injection machine completes the All Time needed for a plastic.Injection temperature is higher than fusing point 30oC, take
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 form
Ratio add 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.Vacuumize and be filled with high-purity argon gas as protection gas, start to react.Reactant mixture is warming up to
220 DEG C of -230 DEG C of stirring 3-5 hours, valve slowly pressure release draining is then opened, while keeping temperature and pressure are constant.One is in line
Water to displacement reaches the 70% of input amount of deionized water.Now start to warm up, 250 DEG C -270 DEG C were 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, T DEG C is set to.
After prepolymer is dried in vacuo 24 hours at 80 DEG C, protection is used as using the mixed gas of carbon dioxide/vapor
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, pass through sampling and testing viscosity and determine final polymerization terminal.During above-mentioned constantly heating and cooling, polymerizate
The change of solid-phase tack producing and crystal habit is carried out simultaneously, finally gives the polymerizate with different melting behaviors.
The heating and cooling program of monomer composition and solid-phase tack producing in reasonable adjusting said process, can obtain different bio-baseds
The polyamide of carbon content and fusing point.
Table 1 is the polyamide used in the present invention.Raw material monomer used in the present invention, such as non-specifically say
It is bright, it is all abiotic base monomer.Bio-based monomer is only limitted to the hexamethylene diamine in 1,10- decamethylene diamines and PA1, PA2.Polyamide
Property indices it is as follows：
Table 1
Embodiment 1-12 and comparative example 1-7：The preparation of polyamide moulding composition
By the formula of table 2 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 reinforcer is fed by side feeding scale side, extrusion, crosses water cooling, after being granulated and drying
To the polyamide moulding composition.
Formula is parts by weight in the following table of table 2
From table 2 it can be seen that as a result of the polyamide resin with double fusing points and the bio-based carbon of specific molar content
Fat, the surface gloss of the polyamide moulding composition that embodiment is prepared and molding cycle all have bright relative to comparative example
Aobvious advantage.
Claims (25)
1. a kind of polyamide moulding composition, form and be：
A, the 30wt%-99.9wt% polyamide with double fusing points；
B, 0-70wt% reinforcer；
C, 0-70wt% fire retardant and/or other polymer；
Wherein, the percetage by weight sum of tri- kinds of components of a, b, c is 100wt%；
The polyamide with double fusing points, it includes the repeat unit derived from following monomer mixture：With two
First monomer of amido functional group, referred to as monomer A；Second comonomer with two carboxyl functional groups or its precursor group, it is referred to as
Monomer B；And/or Third monomer and/or lactams with an amino and a carboxyl functional group, referred to as monomer D；
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 following α and β relation simultaneously： 7.7≤α
＜ 8,4.7≤β ＜ 5；α and β definition 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 the monomer D of the above-mentioned Third monomer with an amino and carboxyl functional group and/or lactams molar part
Number；It is 0 ＜ that it, which accounts for the total molfraction content of whole monomers,≤50mol%；
Above-mentioned monomer A total moles number is represented, m represents monomer AmIn carbon atom number；
Above-mentioned monomer B total moles number is represented, n represents monomer BnIn carbon atom number；
Using DSC instruments, by polyamide sample with 10oC/min heating rate heating on DSC spectrograms until occur first
Individual endothermic peak, now temperature it will be designated as T；Another sample is taken with 10oC/min heating rate rises to a certain temperature T+40oC, it is permanent
Warm 3min, then with 10oC/min rate of temperature fall is down to 50oC, constant temperature 3min, finally with 10oC/min heating rate rises to T+
40oC；Be defined by the heat up DSC curve of record of another sample second, the polyamide has double fusing points, wherein the two
The difference of fusing point is 5oC -20oC；
In the polyamide with double fusing points, based on the molar content of all carbon atoms in polyamide, bio-based
The molar content of carbon is in more than 40mol%.
2. a kind of polyamide moulding composition as claimed in claim 1, form and be：
A, 30wt%-95wt% polyamide；
B, 1wt%-68wt% reinforcer；
C, 0.1wt%-65wt% fire retardant 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, it is characterised in that the polyamides with double fusing points
Polyimide resin, based on the molfraction all derived from diacid repeat unit, at least 20mol% repeat unit is derived to benzene
Dioctyl phthalate and/or Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.
4. polyamide moulding composition according to claim 1 or 2, it is characterised in that the polyamides with double fusing points
Polyimide resin, the repetition list based on the molfraction all derived from diamines repeat 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, it is characterised in that the polyamides with double fusing points
In polyimide resin, based on the molar content of all carbon atoms in polyamide, the molar content of bio-based carbon is in more than 50mol%.
6. polyamide moulding composition according to claim 1 or 2, it is characterised in that the reinforcer is shaped as
Threadiness, its average length are 0.01mm-20mm；Its draw ratio is 5:1-2000:1；The content of the reinforcer is
10wt%-50wt%；The reinforcer 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, it is characterised in that the average length of the reinforcer is
0.1mm-6mm。
8. polyamide moulding composition according to claim 6, it is characterised in that the draw ratio of the reinforcer is
30:1-600:1。
9. polyamide moulding composition according to claim 6, it is characterised in that the content of the reinforcer is
15wt%-40wt%。
10. polyamide moulding composition according to claim 6, it is characterised in that the inorganic reinforcing filler is glass
Fiber.
11. polyamide moulding composition according to claim 10, it is characterised in that the glass fibre is clad
Glass fibre.
12. polyamide moulding composition according to claim 6, it is characterised in that the ceramic fibre is that carborundum is fine
Dimension.
13. polyamide moulding composition according to claim 1 or 2, it is characterised in that the reinforcer is shaped as
Non-fibrous, its 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, aluminum 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, the one or more of carborundum or silica.
14. polyamide moulding composition according to claim 13, it is characterised in that the average grain diameter of the reinforcer
For 0.01 μm -50 μm.
15. polyamide moulding composition according to claim 13, it is characterised in that the mica be selected from sericite and/
Or synthetic mica.
16. polyamide moulding composition according to claim 13, it is characterised in that the montmorillonite, which is selected from lithium and covered, to be taken off
Soil.
17. polyamide moulding composition according to claim 1 or 2, it is characterised in that the fire retardant is that halogen system is fire-retardant
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 in fire retardant or the nitrogenous and fire retardant of phosphorus；Gross 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, it is characterised in that the fire retardant is halogen-free flameproof
Agent.
19. polyamide moulding composition according to claim 17, it is characterised in that the halogenated flame retardant gathers for bromination
Styrene.
20. polyamide moulding composition according to claim 17, it is characterised in that the halogen-free flame retardants is phosphorous resistance
Fire agent.
21. polyamide moulding composition according to claim 17, it is characterised in that the brominated epoxy resin is selected from bromine
Change bisphenol A type epoxy resin.
22. polyamide moulding composition according to claim 20, it is characterised 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, the one or more of phosphinates.
23. polyamide moulding composition according to claim 22, it is characterised in that the phosphonium flame retardant is with such as
Lower structural formula I and/or II phosphinates：
In Formulas I and Formula II, R1And R2Can be with identical, can also be different, the C1-C6- alkane of straight-chain or branch-like is represented 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, it is characterised in that the aryl is phenyl.
25. polyamide moulding composition according to claim 23, it is characterised in that the C6-C10- arlydene is C6-
C10- alkyl arylenes.
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| CN103254422A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
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| CN101492534B (en) * | 2008-12-26 | 2011-04-13 | 金发科技股份有限公司 | Process for preparing semi-aromatic polyamides |
| FR2997089B1 (en) * | 2012-10-23 | 2015-11-13 | Arkema France | THERMOPLASTIC COMPOSITE MATERIAL BASED ON SEMI-CRYSTALLINE POLYAMIDE AND PROCESS FOR PRODUCING THE SAME |
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