CN104592509B - A kind of low acid-base value polyamide moulding composition - Google Patents
A kind of low acid-base value polyamide moulding composition Download PDFInfo
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Abstract
The invention discloses a kind of low acid-base value polyamide moulding compositions, and including polyamide, reinforcing material and/or filler, additive and/or other polymer, the repetitive unit of the polyamide are formed：Account for the dicarboxylic acid units of 40 ~ 50mol% of repetitive unit of polyamide；The carbon number for accounting for 40 ~ 50mol% of repetitive unit of polyamide is 2 ~ 14 aliphatic diamine unit；The carbon number for accounting for 0 ~ 10mol% of repetitive unit of polyamide is 6 ~ 14 lactams or amino carboxylic acid unit；In the polyamide, the content of biology base carbon is more than 40%.The apparent carboxyl-content [m] and apparent amine groups content [n] that the polyamide moulding composition is obtained surely by automatic potential titrator tests meet following scope：[m]≤550mol/t；[n]≤800mol/t；Good dimensional stability and anti-ethylene glycol characteristic is presented in the molded product of polyamide moulding composition of the present invention.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of low acid-base value 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 coefficient of friction 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 the raw material from petroleum cracking product that existing polyamide mainly uses in the synthesis process.Oil
With non-renewable, and the refining of these raw materials needs to make the complicated chemical process of experience, consumes big energy and generates very much
Cause the by-product of environmental pollution.
In addition, during actual use polyamide, which will generally pass through modification, to be applied.Due in modifying process
High-temperature fusion is carried out, high-temperature fusion inherently polymer terminal group further reacts and the balance of degradation.It is each along with adding in
Kind additive, certain variation has occurred in property of polymer during this.The acid-base value of final product is equally applied to exist
Larger impact.
The present inventor by many experiments find, using the polyamide with particular organisms base content obtain with
The polyamide moulding composition of specific acid-base value can solve mechanical properties decrease after being impregnated in molded product warpage, ethylene glycol solution
The problems such as.
The content of the invention
The shortcomings that in order to overcome the prior art and deficiency, it is an object of the invention to provide a kind of steady with excellent size
The low acid-base value polyamide moulding composition of qualitative and anti-ethylene glycol solution characteristic.
The present invention is achieved by the following technical solutions：
A kind of low acid-base value polyamide moulding composition, including polyamide, reinforcing material and/or filler, additive
And/or other polymer.
The repetitive unit of the polyamide is made of following component：
Component A：Account for the dicarboxylic acid units of 40 ~ 50mol% of repetitive unit of polyamide；
Component B：The carbon number for accounting for 40 ~ 50mol% of repetitive unit of polyamide is 2 ~ 14 aliphatic diamine list
Member；
Component C：The carbon number for accounting for 0 ~ 10mol% of repetitive unit of polyamide is 6 ~ 14 lactams or aminocarboxylic
Acid unit；
Wherein, the component A is by accounting for the naphthalate units A1 of its 50 ~ 100mol% and accounting for the aliphatic of its 0 ~ 50mol%
Dicarboxylic acid units A2 is formed；
Wherein, the component B by account for its 50 ~ 100mol% 1,10- decamethylene diamines unit B 1, account for its 0 ~ 50mol% carbon it is former
Aliphatic diamine unit B 2 that subnumber is 2 ~ 9 and the aliphatic diamine unit B 3 that the carbon number for accounting for its 0 ~ 10mol% is 11 ~ 14
Composition；
And meet in component A or component B at least any one component, include two or more different units.
In the polyamide, the content of biology base carbon is in more than 40mol%；The content of the biology base carbon according to
ASTM standard D6866-12/Method-B is measured；
The apparent carboxyl-content [m] and apparent amine that the polyamide moulding composition is obtained surely by automatic potential titrator tests
Base content [n] meets following scope：
[m]≤550mol/t；
[n]≤800mol/t。
Preferably, the apparent carboxyl-content [m] meets following scope：5mol/t≤[m]≤450mol/t, preferably
10mol/t≤[m]≤110mol/t。
Preferably, the apparent amine groups content [n] meets following scope：50mol/t≤[n]≤550mol/t, preferably
80mol/t≤[n]≤300mol/t。
Preferably, in the polyamide, the molar content of biology base carbon is more than 40%；More preferably biology base carbon
Molar content be more than 50%.
Wherein, terephthalic acid units, the isophthalic of 0 ~ 20mol% two of the naphthalate units A1 by 80 ~ 100mol%
The O-phthalic acid unit of formic acid unit and 0 ~ 10mol% form；The aliphatic dicarboxylic acid unit is that carbon number is 2 ~ 14
Aliphatic dicarboxylic acid unit.
Wherein, the aliphatic dicarboxylic acid is ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pungent two
At least one in acid, 2- methyl suberic acid, azelaic acid, decanedioic acid, undecandioic acid, 12 diacid, 13 diacid or 14 diacid
Kind.
Wherein, the aliphatic diamine for containing 2 ~ 9 carbon atoms is ethylenediamine, propane diamine, slough amine, cadaverine, 2- first
Base pentanediamine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, 2- methyl octamethylenediamine, 2,2,4- trimethylhexamethylenediamines, 2,4,4- tri-
Any one or more in methyl hexamethylene diamine, 5- methyl-nonamethylene diamine or nonamethylene diamine；It is described to contain 11 ~ 14 carbon originals
The aliphatic diamine of son is any one or more in 11 diamines, 12 diamines, 13 diamines or 14 diamines.
Wherein, the lactams for containing 6 ~ 14 carbon atoms or amino carboxylic acid be 6-aminocaprolc acid, caprolactam, 10-
In aminocapric acid, 11- aminoundecanoic acids, 11 lactams, 12-aminolauric acid or lauric lactam any one or it is more
Kind.
The prior art does not specifically note the particular combination of pH-value in polyamide moulding composition, certainly in the prior art
In do not point out that above-mentioned particular combination can improve corrosion resistance and surface characteristic of polyamide moulding composition molded product etc. yet
The information of various problems.
Above-mentioned low acid-base value polyamide moulding composition, the content of the polyamide is 30~99.9wt%；The increasing
The content of strong material and/or filler is 0-70wt%；The content of the additive and/or other polymer is 0.1-70wt%.
The content of wherein reinforcing material and/or filler is preferably 10 ~ 50wt%, more preferably 15-40%.
Filer content is too low, causes daiamid composition mechanical property poor；Filer content is excessively high, daiamid composition system
Product surface floating fiber is serious, influences product appearance.
The shape of the reinforcing filler is threadiness, and average length 0.01-20mm is preferably 0.1 ~ 6mm；Its major diameter
Than for 5:1~2000:1, it is preferably 30:1~600:1, when threadiness reinforcing filler content within the above range when, polyamide group
High heat distortion temperature and the high temperature rigid increased will be shown by closing object.
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 are preferably glass fibre；
The mouldability of daiamid composition can be not only improved using glass fibre, but also mechanical property can be improved and for example drawn
It stretches intensity, bending strength and bending modulus and improves thermal deformation of heat resistance when for example thermoplastic resin composition is molded
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 0.001~100 μm, is preferably 0.01~50 μm.
When the average grain diameter of reinforcing filler 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 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 carborundum 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 daiamid composition is made to obtain more excellent mechanical performance, can be used coupling agent to inorganic reinforcing filler into
Row 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 daiamid 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 0.05 ~ 10wt% compared with inorganic reinforcing filler weight, preferably 0.1 ~
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 in polyamide disperse undesirable risk,
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 object；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 agent.
The fire retardant is fire retardant or fire retardant and the composition of fire-retardant assistance agent, and content is preferably 10 ~ 40wt%；
Flame retardant agent content is too low to cause flame retardant effect to be deteriorated, and flame retardant agent content is excessively high to cause material mechanical performance 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 are 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 with such as following formula（I）And/or（II）The compound of expression is representative.
In formula（Ⅰ）And formula（II）In, R1And R2It may be the same or different, represent the C1 of straight-chain or branch-like respectively
~C6- alkyl, aryl or phenyl；R3C1~C10- alkylidenes of expression straight-chain or branch-like, C6~C10- arlydene, C6~
C10- alkyl arylenes or C6~C10- aryl alkylenes；M represents calcium atom, magnesium atom, aluminium atom and/or zinc atom；M is 2
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
Closing the example of object includes Clariant Corporation（Clariant) manufacture EXOLIT OP1230, OP1311, OP1312, OP930,
OP935 etc..
The daiamid composition for including above-mentioned polyamide of the present invention, the additive component may also contain up to
One or more of impact modifying agents of 45wt%；Preferably 5~30wt%.
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 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-（Ethylene -co-（Methyl）Acrylic acid）It is or poly-（Ethylene -1-
Alkene -co-（Methyl）Acrylic acid）, wherein 1- alkene is olefine or the unsaturation with 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 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
Object be aromatic ring and/or in C=C double bonds by the alkyl of C1~20 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 preferable to use styrene, α-methylstyrene, p-methylstyrene, ethyl styrene, t-butyl styrene, ethylene
Base toluene, 1,2- diphenylethlenes, the mixture of 1,1- diphenylethlenes or these substances.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.
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 propylene
Sour N-butyl or 2-EHA and methacrylate, especially methacrylic acid C1~C12 Arrcostabs, such as
Methyl methacrylate（MMA）.Other possible comonomers are（Methyl）Acrylonitrile,（Methyl）Glycidyl acrylate,
Vinyl methyl ether, the diallyl of dihydric alcohol and divinyl ether, divinylbenzene and vinyl acetate.
In addition to 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.The unreduced aliphatic unsaturated bond of block b is come from hydrogen
Change the ratio in block copolymer and be 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 50~85wt% of 20~90wt%.Alkadienes can be with
It is introduced into 1,2- orientations or Isosorbide-5-Nitrae-orientation in block b.
The molal weight of block copolymer is 5000~500000g/mol, preferably 20000~300000g/mol, is particularly
40000~200000g/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 daiamid 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, ethylene-the third
Olefin(e) acid ester 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.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 20~96wt%, preferably 25~85wt% second
The elastomer of the ethylene-C3 of alkene~C12- alpha olefin copolymers, wherein being particularly preferably C3~C12- alpha-olefins herein includes
Alkene selected from propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene and/or 1- laurylenes, it is particularly preferably other poly-
Closing object includes ethylene-propylene rubber, the one or more of 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, preferably it contains 25~85wt% ethylene and extremely herein
More maximums be 10wt% non-conjugated diene hydrocarbon, herein particularly preferred C3~C12- alpha-olefins include selected from propylene, 1- butylene,
1- amylenes, 1- hexenes, 1- octenes, the alkene of 1- decene and/or 1- laurylenes and/or wherein non-conjugated diene hydrocarbon preferably select
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 0.1~
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, 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, 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 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 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
Obtained nonpolar or polar olefin homopolymer and copolymer 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 shaping 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
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
Monomer：Raw material monomer used in the present invention is all abiotic base monomer if not otherwise indicated.Biology base
Monomer is only limitted to the 1,6- hexamethylene diamines in 1,10- decamethylene diamines, adipic acid, 11- aminoundecanoic acids and table 1.
The content of the biology base carbon is measured according to ASTM standard D6866-12/Method-B.
The test method of the relative viscosity of gained polyamide：With reference to GB12006.1-89, polyamide viscosity number assay method；Tool
Body examination method for testing is：25 ± 0.01oThe relative viscosity for the polyamide that concentration is 0.25g/dl 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 are
40mL/min；340 DEG C first are warming up to 10 DEG C/min during test, 2min is kept at 340 DEG C, is then cooled to 50 with 10 DEG C/min
DEG C, then 340 DEG C are warming up to 10 DEG C/min, endotherm peak temperature at this time is set to fusing pointT m；
The test method of apparent carboxyl-content：Sample carboxyl-content is titrated with autopotentiometric titrator；Take 0.5g polyamides
Amine molding combination composition granule, adds o-cresol 50mL, and reflux dissolving is rapidly added 400 μ L formalins, with what is demarcated after letting cool
KOH- ethanol solutions titrate carboxyl-content.The content is the apparent carboxyl-content [m] of polyamide moulding composition.
The test method of apparent amine groups content：Sample amino content is titrated with autopotentiometric titrator；Take 0.5g polyamides
Amine molding combination composition granule adds phenol 45mL and absolute methanol 3mL, is heated to reflux, and after observation sample is completely dissolved, is cooled to room
Temperature titrates amino content with the hydrochloric acid standard solution demarcated.The content is apparent amine groups content [n].
The dimensional stability of polyamide moulding composition molded product：Injection obtains the batten of a 100*100*1mm, uses
Center point gate feeding.Place it in 190oIt places in the baking oven of C constant temperature for 24 hours, is had using Beijing coordinate measuring machine of sublimating
The NHC-Y443 type three-coordinates measuring machines of limit company production test the difference of the spline surfaces highs and lowsΔh, with this value
Characterization parameter as dimensional stability.ΔhIt is bigger, illustrate that dimensional stability is poorer；It is conversely, then better.
The anti-ethylene glycol characteristic of polyamide moulding composition molded product：The batten of above-mentioned tensile strength experiment is existed
120o240h is impregnated in 50% aqueous solution of ethylene glycol of C, after being placed into room temperature, carries out above-mentioned tensile strength experiment.Calculate compared with
The conservation rate of tensile strength before dippingt。
t=（Tensile strength before dipping post-tensioning intensity/dipping）×100%.
T is higher, illustrates that anti-ethylene glycol characteristic is better.
Embodiment 1 ~ 9 and comparative example 1 ~ 8
Fusing point is less than 280oThe synthesis of the polyamide of C：
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 in reaction raw materials；Add sodium hypophosphite, benzoic acid and deionized water；Sodium hypophosphite weight is in addition to deionized water
The 0.1% of other charged material weights, the amount of benzoic acid species is the 4% of the amount of diacid total material, and deionized water weight is the weight that always feeds intake
The 30% of amount.It vacuumizes and is filled with high pure nitrogen as protection gas, start to react.It is small that reaction mixture is warming up to 290 DEG C of stirrings 3
When, valve slowly pressure release is then opened, while keeps temperature-resistant；Pressure is let out to normal pressure, starts to vacuumize；It is evacuated to
60Pa keeps reaction temperature；Reaction end is judged according to the variation of agitating paddle power；After reaction, stop vacuumizing, pour
Nitrogen is to 0.2MPa；Fused materials by die head are extruded, is cooled down, after air-cooled, pelletizing through sink, obtains polyamide.It is poly-
The performance indicators such as the fusing point of amide resin are listed in table 1 ~ 2.
The synthesis of polyamide of the fusing point higher than 280 DEG C：
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 in reaction raw materials；Add sodium hypophosphite, benzoic acid and deionized water.Sodium hypophosphite weight is in addition to deionized water
The 0.1% of other charged material weights, the amount of benzoic acid species is the 4% of the amount of diacid total material, and deionized water weight is the weight that always feeds intake
The 30% of amount.It vacuumizes and is filled with high pure nitrogen as protection gas, start to react.It is small that reaction mixture is warming up to 220 DEG C of stirrings 1
When, the temperature of reactant is then made to be increased to 230 DEG C under stiring；Reaction under 230 DEG C of constant temperature and the constant pressure of 2.2MPa after
It is continuous carry out 2 it is small when, keep pressure constant by removing formed water, valve discharging opened after the completion of reaction, obtains pre-polymerization
Object.Prepolymer be dried in vacuo at 80 DEG C 24 it is small when after, when solid-phase tack producing 10 is small under 250 DEG C, 50Pa vacuum conditions, gathered
Amide resin.The performance indicators such as the fusing point of polyamide are listed in table 1 ~ 2.
Table 1
Table 2
Embodiment 10 ~ 17 and comparative example 9-14：The preparation of polyamide moulding composition
By the formula of table 3-4 by polyamide, fire retardant, other auxiliary agents after high-speed mixer and mixing is uniform, pass through master
Spout is added in double screw extruder, and reinforcing filler is fed by side feeding scale side, is squeezed out, and water cooling is crossed, after being granulated and drying
Obtain the polyamide moulding composition.
Formula is parts by weight in 3 following table of table
Formula is parts by weight in 4 following table of table
It can be seen that from table 3-4 compared with comparative example, since the low acid-base value polyamide molding of the embodiment of the present invention combines
The apparent carboxyl and apparent amido of object are finally molded in the range of specific limit, and with specific Bio-based content
The good stability of the dimension of molded product, anti-ethylene glycol characteristic are good.
Claims (24)
1. a kind of low acid-base value polyamide moulding composition, including polyamide, reinforcing material and/or filler, additive and/
Or other polymer；
The repetitive unit of the polyamide is made of following component：
Component A：Account for the dicarboxylic acid units of 40 ~ 50mol% of repetitive unit of polyamide；
Component B：The carbon number for accounting for 40 ~ 50mol% of repetitive unit of polyamide is 2 ~ 14 aliphatic diamine unit；
Component C：The carbon number for accounting for 0 ~ 10mol% of repetitive unit of polyamide is 6 ~ 14 lactams or amino carboxylic acid list
Member；
Wherein, the component A is by accounting for the naphthalate units A1 of its 50 ~ 100mol% and accounting for the aliphatic dicarboxyl of its 0 ~ 50mol%
Acid unit A2 is formed；
Wherein, the component B is by accounting for 1, the 10- decamethylene diamines unit B 1 of its 50 ~ 100mol%, accounting for the carbon number of its 0 ~ 50mol%
For 2 ~ 9 aliphatic diamine unit B 2 and account for the aliphatic diamine unit B 3 that the carbon number of its 0 ~ 50mol% is 11 ~ 14 and form；
And meet in component A or component B at least any one component, include two or more different units；
In the polyamide, the content of biology base carbon is in more than 40mol%；The content of the biology base carbon is marked according to ASTM
Quasi- D6866-12/Method-B is measured；
It is characterized in that, the apparent carboxyl-content [m] that the polyamide moulding composition is obtained surely by automatic potential titrator tests
Meet following scope with apparent amine groups content [n]：
[m]≤550mol/t；
[n]≤800mol/t；
The naphthalate units A1 by the terephthalic acid units of 80 ~ 100mol%, the isophthalic acid units of 0 ~ 20mol% and
The O-phthalic acid unit composition of 0 ~ 10mol%；
The aliphatic dicarboxylic acid unit is the aliphatic dicarboxylic acid unit that carbon number is 2 ~ 14；The aliphatic dicarboxylic acid choosing
From ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, 2- methyl suberic acid, azelaic acid, the last of the ten Heavenly stems two
At least one of acid, undecandioic acid, 12 diacid, 13 diacid or 14 diacid；
The aliphatic diamine containing 2 ~ 9 carbon atoms is selected from ethylenediamine, propane diamine, slough amine, cadaverine, 2- methylpents two
Amine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, 2- methyl octamethylenediamine, 2,2,4- trimethylhexamethylenediamines, 2,4,4- trimethyls six
Any one or more in methylene diamine or nonamethylene diamine；The aliphatic diamine containing 11 ~ 14 carbon atoms is 11
Any one or more in diamines, 12 diamines, 13 diamines or 14 diamines；
The lactams containing 6 ~ 14 carbon atoms or amino carboxylic acid are selected from 6-aminocaprolc acid, caprolactam, the 10- amino last of the ten Heavenly stems
Any one or more in acid, 11- aminoundecanoic acids, 11 lactams, 12-aminolauric acid or lauric lactam.
2. low acid-base value polyamide moulding composition according to claim 1, which is characterized in that the apparent carboxyl-content
[m] meets following scope：5mol/t≤[m]≤450mol/t.
3. low acid-base value polyamide moulding composition according to claim 2, which is characterized in that the apparent carboxyl-content
[m] meets following scope：10mol/t≤[m]≤110mol/t.
4. low acid-base value polyamide moulding composition according to claim 1, which is characterized in that the apparent amine groups content
[n] meets following scope：50mol/t≤[n]≤550mol/t.
5. low acid-base value polyamide moulding composition according to claim 4, which is characterized in that the apparent amine groups content
[n] meets following scope：80mol/t≤[n]≤300mol/t.
6. low acid-base value polyamide moulding composition according to claim 1, which is characterized in that the polyamide
In, the molar content of biology base carbon is more than 45%.
7. low acid-base value polyamide moulding composition according to claim 1, which is characterized in that the polyamide
Content is 30~99.9wt%；The content of the reinforcing material and/or filler is 0-69wt%；The additive and/or other poly-
The content for closing object is 0.1-70wt%；The content of the reinforcing material and/or filler is not 0.
8. the low acid-base value polyamide moulding composition according to claim 1 or 7, which is characterized in that the reinforcing filler
Shape for threadiness, average length 0.01-20mm；Its draw ratio is 5 ~ 2000:1；The content of the reinforcing filler is
10~50wt%；The reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers, and the inorganic reinforcing filler is selected from glass fibers
It is dimension, 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, the one or more of gypsum fiber or boron fibre；Organic enhancing
Filler is selected from aramid fibre.
9. low acid-base value polyamide moulding composition according to claim 8, which is characterized in that the reinforcing filler is put down
Equal length is 0.1 ~ 6mm.
10. low acid-base value polyamide moulding composition according to claim 8, which is characterized in that the reinforcing filler
Draw ratio is 30 ~ 600:1.
11. low acid-base value polyamide moulding composition according to claim 8, which is characterized in that the inorganic enhancing is filled out
Expect for glass fibre.
12. the low acid-base value polyamide moulding composition according to claim 1 or 7, which is characterized in that the reinforcing filler
Shape for Non-fibrous, average grain diameter is 0.001~10 μm, selected from potassium titanate crystal whisker, ZnOw, aluminum borate crystal whisker
Palpus, wollastonite, zeolite, mica, talcum, clay, synthetic mica, asbestos, alumino-silicate, aluminium oxide, silica, magnesia, oxygen
Change zirconium, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, hydrogen-oxygen
Change aluminium, bead, ceramic bead, boron nitride, the one or more of carborundum.
13. low acid-base value polyamide moulding composition according to claim 12, which is characterized in that the silica is two
Silica.
14. low acid-base value polyamide moulding composition according to claim 12, which is characterized in that the reinforcing filler
Average grain diameter is 0.01~5 μm.
15. low acid-base value polyamide moulding composition according to claim 12, which is characterized in that the clay is selected from height
Ridge soil, pyrophillite, bentonite, montmorillonite, the one or more of lithium montmorillonite.
16. low acid-base value polyamide moulding composition according to claim 12, which is characterized in that the mica is selected from thin,tough silk
Mica.
17. the low acid-base value polyamide moulding composition according to claim 1 or 7, which is characterized in that the additive contains
There is fire retardant；Fire retardant is halogenated flame retardant or halogen-free flame retardants；The halogenated flame retardant is selected from brominated Polystyrene, bromination is gathered
Phenylate, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy group tree
Fat, deca-BDE, decabromodiphenyl, brominated polycarbonate, three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer
It is one or more of；The halogen-free flame retardants be selected from nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus fire retardant one kind or
It is several；The content of the fire retardant is 10 ~ 40wt%.
18. low acid-base value polyamide moulding composition according to claim 17, which is characterized in that the fire retardant is nothing
Halogen fire retardant.
19. low acid-base value polyamide moulding composition according to claim 17, which is characterized in that the halogenated flame retardant
For brominated Polystyrene.
20. low acid-base value polyamide moulding composition according to claim 17, which is characterized in that the halogen-free flame retardants
For phosphonium flame retardant.
21. low acid-base value polyamide moulding composition according to claim 20, which is characterized in that the phosphonium flame retardant
Selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, propyl benzene system phosphate, butylbenzene system phosphoric acid
The one or more of ester, phosphinates.
22. low acid-base value polyamide moulding composition according to claim 21, which is characterized in that the phosphonium flame retardant
To have following structural formula（Ⅰ）And/or（II）Phosphinates：
In formula（Ⅰ）And formula（II）In, R1And R2May be the same or different, represent respectively the C1 of straight-chain or branch-like~
C6- alkyl, aryl；R3Represent C1~C10- alkylidenes, C6~C10- arlydene, the C6~C10- alkyl of straight-chain or branch-like
Arlydene or C6~C10- aryl alkylenes；M represents calcium atom, magnesium atom, aluminium atom and/or zinc atom；M is 2 or 3, n are 1
Or 3, x are 1 or 2.
23. low acid-base value polyamide moulding composition according to claim 22, which is characterized in that the aryl is selected from benzene
Base.
24. low acid-base value polyamide moulding composition according to claim 21, which is characterized in that the monophosphate aryl
Phosphate is selected from one or more of in triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester.
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| US5424104A (en) * | 1990-11-30 | 1995-06-13 | Mitsui Petrochemical Industries, Ltd. | Thermoplastic resin composition and use thereof |
| CN102070902A (en) * | 2009-11-23 | 2011-05-25 | Ems专利股份公司 | Semi-aromatic moulding masses and their applications |
| CN103087310A (en) * | 2013-01-14 | 2013-05-08 | 金发科技股份有限公司 | Polyamide resin and application thereof as well as polyamide composition consisting of same |
| CN104211953A (en) * | 2014-08-05 | 2014-12-17 | 金发科技股份有限公司 | Polyamide resin and polyamide composition containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5424104A (en) * | 1990-11-30 | 1995-06-13 | Mitsui Petrochemical Industries, Ltd. | Thermoplastic resin composition and use thereof |
| CN102070902A (en) * | 2009-11-23 | 2011-05-25 | Ems专利股份公司 | Semi-aromatic moulding masses and their applications |
| CN103087310A (en) * | 2013-01-14 | 2013-05-08 | 金发科技股份有限公司 | Polyamide resin and application thereof as well as polyamide composition consisting of same |
| CN104211953A (en) * | 2014-08-05 | 2014-12-17 | 金发科技股份有限公司 | Polyamide resin and polyamide composition containing same |
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