CN104804427B - 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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- CN104804427B CN104804427B CN201510135947.8A CN201510135947A CN104804427B CN 104804427 B CN104804427 B CN 104804427B CN 201510135947 A CN201510135947 A CN 201510135947A CN 104804427 B CN104804427 B CN 104804427B
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- 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
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of low acid-base value polyamide moulding composition, including forming as follows：A, the polyamide of 2≤pH≤6 is presented in the pH value in phenol of 30wt% 99wt%；B, the reinforcing filler of 0 70wt%；C, the additive of 0 70wt% and/or other polymer；The sum of component A, B and C weight percent is 100wt%；Apparent carboxyl-content [m]≤550 mole/ton that the low acid-base value polyamide moulding composition is obtained surely by automatic potential titrator tests；The polyamide moulding composition with specific acid-base value is prepared using the polyamide with certain ph in the present invention, it not only can effectively prevent polyamide from degradation occurring in injection moulding process and generates gas, and then the technical problems such as product current mark, White Patches are solved, and the color of polyamide moulding composition can be made to be improved.
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.
CN101175791 provides a kind of heat retention stability, hot water resistance and chemical-resistant with height, and
Adhesiveness or polyamide excellent in compatibility with other resins etc..Terminal amine base unit weight [the NH of the resin strand2]
For more than 60mol/t, below 120mol/t, and terminal amine base unit weight and terminal carboxyl group amount [COOH] meet [NH2]/[COOH]≥6。
CN102149748 provides a kind of polyamide for having and improving processing performance.It is presented：- be greater than or equal to
The amine chain end content of 20 μ eq/g；Sour chain end content less than or equal to 100 μ eq/g；With more than or equal to 20 μ eq/g's
Non-reacted chain end content.
JP6032980 provides a kind of method for improving polyamide moulding composition surface of the molded article performance.That is, using end
The polyamide substrate resin of amino or carboxyl end group value less than 50meq/kg is modified, and obtained appearance of molded articles is preferable.However,
It only gives the method for single enhancing modified product appearance investigation, i.e. only adds inorganic filler such as glass etc. and is used as additive.And
The surface condition of fire retardant, fire retarding synergist when additions for chemical property complexity is not pointed out.
However, above-mentioned patent only defines the specified end group content of polyamide, but polyamide in actual use
Resin, which will generally pass through modification, to be applied.Due to having carried out high-temperature fusion in modifying process, high-temperature fusion is inherently poly-
Close the balance that object end group is further reacted and degraded.Along with various additives are added in, property of polymer occurs during this
Certain variation.The acid-base value of final product is equally applied to that there are larger impacts.
As described above, the end group test of polyamide has become one general means of the industry at present, to table
Levy the information of each side such as number-average molecular weight, the extent of reaction of polyamide.Although the end group of polyamide may influence molten
The pH value of liquid, this and not exclusive key factor.Different polyamide molecule chain rigidity, amide groups concentration, the sharp coefficient of the second dimension,
Huggins parameters, theta solvent behavior etc. all can cause significant impact to its pH value.Even if the identical polyamides of component, monomer ratio
Amine, due to the collective effect of above-mentioned factor, all possible difference of pH value is huge, so as to cause the difference of polymer performance.To poly-
The structure for closing reaction condition or polyamide is adjusted, and can obtain different end group or the polyamide of pH value.
The present inventor has found by many experiments, select in phenol pH value present 2≤pH≤6 polyamide and then
The polyamide moulding composition with specific acid-base value is prepared, not only can effectively prevent polyamide in injection moulding process
It is middle that degradation generation gas occurs, and then solve the technical problems such as product current mark, White Patches.
The content of the invention
The shortcomings that in order to overcome the prior art and deficiency, generate it is an object of the invention to provide one kind in injection moulding process
Less gas, and the low acid-base value polyamide moulding composition that color is improved.
The present invention is achieved by the following technical solutions.
A kind of low acid-base value polyamide moulding composition, including forming as follows：
A, the polyamide of 2≤pH≤6 is presented in the pH value in phenol of 30wt%-99wt%；
B, the reinforcing filler of 0-70wt%；
C, the additive of 0-70wt% and/or other polymer；
The sum of component A, B and C weight percent is 100wt%；
The apparent carboxyl-content [m] that the low acid-base value polyamide moulding composition is obtained surely by automatic potential titrator tests
≤ 550 moles/ton.
Preferably, a kind of polyamide moulding composition, including consisting of：
A, the polyamide of 30wt%-95wt%；
B, the reinforcing filler of 1wt%-67wt%；
C, the additive of 0.1wt%-60wt% and/or other polymer；
The sum of component A, B and C weight percent is 100wt%；
The apparent carboxyl-content that the low acid-base value polyamide moulding composition is obtained surely by automatic potential titrator tests
Mole/ton of [m]≤550.
Preferably, polyamide pH value presentation in phenol of 2≤pH≤6 is presented in the pH value in phenol：3≤pH
≤5。
Preferably, the apparent carboxylic that the low acid-base value polyamide moulding composition is obtained surely by automatic potential titrator tests
Base content [m] meets following scope：50 moles/ton≤mole/ton of [m]≤450, preferably 100 moles/ton≤[m]≤300 are rubbed
That/ton.
The polyamide of 2≤pH≤6 is presented in the pH value in phenol, based on all derived from diacid repetitive unit
Molfraction, at least the repetitive unit of 20mol% is derived from terephthalic acid (TPA) and/or Isosorbide-5-Nitrae-hexamethylene in the polyamide
Alkane dioctyl phthalate.
The polyamide of 2≤pH≤6 is presented in the pH value in phenol, based on all derived from diamines repetitive unit
Molfraction, at least the repetitive unit of 20mol% is derived from 1,6- hexamethylene diamines and/or 1, the 10- last of the ten Heavenly stems two in the polyamide
Amine.
The content of the component B is preferably 10wt%-50wt%, more preferably 15wt%-40wt%；
Reinforcing filler content is too low, causes polyamide moulding composition mechanical property poor；Reinforcing filler too high levels are gathered
Amide moulding compound product surface floats fibre seriously, influences product appearance.
The shape of the reinforcing filler is threadiness, and average length 0.01mm-20mm is preferably 0.1mm-6mm；Its
Draw ratio is 5:1-2000:1, it is preferably 30:1-600:1, when threadiness reinforcing filler content within the above range when, polyamides
Amine moulding compound will show high heat distortion temperature and the high temperature rigid increased.
The reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers；
The inorganic reinforcing filler be selected from glass fibre, potassium titanate fibre, the glass fibre of clad, ceramic fibre,
Wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum are fine
The one or more of dimension or boron fibre are preferably glass fibre；
The mouldability of polyamide moulding composition can be not only improved using glass fibre, but also mechanical property example can be improved
Heat when for example thermoplastic resin composition is molded such as tensile strength, bending strength and bending modulus and raising heat resistance
Deformation temperature.
The organic reinforcing fillers are selected from aramid fibre and/or carbon fiber.
The shape of the reinforcing filler is Non-fibrous, such as powdered, graininess, plate, needle-shaped, fabric or felted,
Its average grain diameter is 0.001 μm -100 μm, is preferably 0.01 μm -50 μm.
When the average grain diameter of reinforcing filler is less than 0.001 μm of melt processable that will 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 which polyamide moulding composition is made to obtain more excellent mechanical performance, coupling agent can be used, inorganic enhancing is filled out
Material carries out functional processing.
Wherein coupling agent is selected from isocyanates based compound, organosilan based compound, organic titanate based compound, has
Machine borine based compound, epoxide；Preferably organosilan based compound；
Wherein, the organosilan based compound is selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group, contains sulfydryl
Alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group,
Alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkane containing carbon-to-carbon unsaturated group containing end amido
Oxysilane compound, the one or more of alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group be selected from γ-glycidoxypropyltrime,hoxysilane, γ-
The one or more of glycidoxypropyl group triethoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-sulfydryl
Propyl-triethoxysilicane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups is selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl
Trimethoxy silane, γ-(2- urea groups ethyl) hold the one or more of aminocarbonyl propyl trimethoxy silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group is selected from γ-isocyanate group propyl-triethoxysilicane
Alkane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-isocyanic acid
Ester group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group propyl
The one or more of ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido is selected from γ-(2- ends amido ethyl) end aminocarbonyl propyl methyl two
Methoxy silane, γ-(2- ends amido ethyl) end aminocarbonyl propyl trimethoxy silane, γ-end aminocarbonyl propyl trimethoxy silane
One or more；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from γ-hydroxypropyl trimethoxy silane and/or γ-hydroxyl
Propyl-triethoxysilicane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group is selected from γ-methacryloxypropyl front three
Oxysilane, vinyltrimethoxysilane, N- β-(N- vinyl benzyl cardinal extremity amidos ethyl)-γ-end aminocarbonyl propyl trimethoxy
The one or more of base silane hydrochloride；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3- trimethoxy-silylpropyl succinic anhydrides；
The organosilan based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2- ends
Amido ethyl) end aminocarbonyl propyl methyl dimethoxysilane, γ-(2- ends amido ethyl) end aminocarbonyl propyl trimethoxy silane,
γ-end aminocarbonyl propyl trimethoxy silane or 3- trimethoxy-silylpropyl succinic anhydrides.
Conventionally inorganic reinforcing filler can be surface-treated using above-mentioned organosilan based compound,
Then itself and polyamide are subjected to melting mixing again, to prepare the polyamide moulding composition.
Organosilicon methane series chemical combination can also be added in directly while inorganic reinforcing filler and polyamide melting mixing
Object carries out in-situ blending.
Wherein, the dosage of the coupling agent is the 0.05wt%-10wt% compared with inorganic reinforcing filler weight, is preferably
0.1wt%-5wt%。
When the dosage of coupling agent is less than 0.05wt%, the effect of apparent improved mechanical properties is not achieved；Work as coupling agent
Dosage be more than 10wt% when, inorganic reinforcing filler easily agglomerates, and 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, based on polyamide moulding composition
Total weight, content are preferably 10wt%-40wt%；Flame retardant agent content is too low to cause flame retardant effect to be deteriorated, and flame retardant agent content is excessively high
Material mechanical performance is caused to decline.
The fire retardant is halogenated flame retardant or halogen-free flame retardants；
The halogenated flame retardant is selected from brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, bromination benzene
Ethylene maleic acid anhydride copolymer, brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, bromination are gathered
The one or more of carbonic ester, three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer 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 using the compound that such as following formula I and/or II represent as representative.
In Formulas I and Formula II, R1And R2It may be the same or different, represent the C1-C6- of straight-chain or branch-like respectively
Alkyl, aryl or phenyl.R3Represent C1-C10- alkylidenes, C6-C10- arlydene, the C6-C10- alkyl of straight-chain or branch-like
Arlydene, C6-C10- aryl alkylenes.M represents calcium atom, magnesium atom, aluminium atom and/or zinc atom.M be 2 or 3, n be 1 or
3, x be 1 or 2.
The more specific example of phosphinate salt compound includes dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethyl time
Phosphonic acids aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethyl
Methyl-phosphinic acid zinc, diethyl phosphinic acids calcium, diethyl phosphinic acids magnesium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, methyl
N-propyl phosphinic acids calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc, first are burnt
Two (methyl-phosphinic acids）Calcium, methane two（Methyl-phosphinic acid）Magnesium, methane two（Methyl-phosphinic acid）Aluminium, methane two（Methyl time phosphine
Acid）Zinc, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Calcium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Magnesium, benzene-Isosorbide-5-Nitrae-(dimethyl time phosphine
Acid）Aluminium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, aminomethyl phenyl time phosphine
Sour aluminium, methylphenylphosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl time phosphine
Sour zinc etc., preferably dimethylphosphinic acid calcium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid I beggars, second
Ylmethyl phosphinic acids aluminium, ethylimethyphosphinic acid zinc, diethyl phosphinic acids calcium, aluminum diethylphosphinate, diethyl phosphinic acids zinc,
More preferable aluminum diethylphosphinate.
Phosphinate salt compound as fire retardant can be obtained easily from market.It can be from the phosphinic acids salinization that market obtains
Closing the example of object includes Clariant Corporation（Clariant）EXOLIT OP1230 of manufacture, OP1311, OP1312, OP930,
OP935 etc..
The polyamide moulding composition for including above-mentioned polyamide of the present invention, based on the total of polyamide moulding composition
Weight, the additive component may also contain up to one or more of impact modifying agents of 45wt%；Preferably 5wt%-
30wt%。
Wherein, the impact modifying agent can be natural rubber, polybutadiene, polyisoprene, polyisobutene, butadiene
And/or isoprene and styrene or with styrene derivative and with the copolymer of other comonomers, hydrogenated copolymer and/
By grafting or with acid anhydride,（Methyl）Prepared by acrylic acid or its ester are copolymerized copolymer；The impact modifying agent can also be
Graft rubber with cross-linked elastomer core, the cross-linked elastomer core is by butadiene, isoprene or alkyl acrylate structure
Into, and with the graft shell that is made of polystyrene or can be 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 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 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 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 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 50wt%-85wt% of 20wt%-90wt%.Alkadienes
It can be orientated with 1,2- or Isosorbide-5-Nitrae-orientation is introduced into block b.
The molal weight of block copolymer is 5000g/mol-500000g/mol, preferably 20000g/mol-300000g/
Mol, particularly 40000g/mol-200000g/mol.
Suitable hydrogenated block copolymer is the product that can be bought from the market, such as（Kraton polymer）G1650、
G1651 and G1652 and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141 and H1272.
The example of non-hydrogenated block copolymer is polystyrene-polybutadiene, polystyrene-poly（Ethylene-propylene）, polyphenyl
Ethylene-polyisoprene gathers（α-methylstyrene）- polybutadiene, polystyrene-polybutadiene-polystyrene（SBS）, it is poly-
Styrene-poly-（Ethylene-propylene）- polystyrene, polystyrene-polyisoprene-polystyrene and poly-（α-methylstyrene）
Polybutadiene-poly-（α-methylstyrene）, and combinations thereof.
The suitable non-hydrogenated block copolymer that can be bought from the market has the trade mark to be（Phillips）、（Shell）、
（Dexco）With（Kuraray）Multiple product.
The polyamide moulding composition for including above-mentioned polyamide of the present invention, the additive component can also include
Other polymer, other polymer are selected from fatty polyamide, polyolefin homopolymer or ethene-alpha-olefin copolymer, second
Alkene-acrylate copolymer.
The fatty polyamide includes but are not limited to be 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 20wt%-96wt%, preferably 25wt%-
The elastomer of the ethylene-C3 of 85wt% ethylene~C12- alpha olefin copolymers, wherein being particularly preferably C3~C12- α-alkene herein
Hydrocarbon includes the alkene selected from propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene and/or 1- laurylenes, particularly preferably
Other polymer include 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, herein preferably its contain 25wt%-85wt% ethylene and
At most maximum is the non-conjugated diene hydrocarbon of 10wt%, and particularly preferred C3~C12- alpha-olefins are included selected from propylene, 1- fourths herein
Alkene, 1- amylenes, 1- hexenes, 1- octenes, the alkene of 1- decene and/or 1- laurylenes and/or wherein non-conjugated diene hydrocarbon is preferably
Selected from two rings [2.2.1] heptadiene, Isosorbide-5-Nitrae-hexadiene, especially dicyclopentadiene and/or 5- ethylidene norbornenes.
Vinyl-acrylate copolymer is also used as the ingredient of other polymer.
Other possible forms of other polymer are ethylene-butene copolymer and the mixing comprising these systems respectively
Object（Blend）.
Preferably, other polymer include the ingredient with anhydride group, these pass through trunk polymer and unsaturation
Dicarboxylic anhydride, with unsaturated dicarboxylic or thermal response or radical reaction with the monoalkyl ester of unsaturated dicarboxylic, be enough with
The concentration of polyamide good combination introduces, and herein preferably with selected from following reagent：
Maleic acid, maleic anhydride, butyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride.It is preferred that 0.1wt%-
The unsaturated acid anhydride of 4.0wt% is grafted in the shock resistance component of the ingredient as C or unsaturated dicarboxylic anhydride or its precursor lead to
It crosses together with other unsaturated monomers and is grafted to apply.Generally preferable grafting degree is 0.1%-1.0%, particularly preferably 0.3%-
0.7%.Another possible ingredient of other polymer is the mixing being made of ethylene-propylene copolymer and ethylene-butene copolymer
Object, herein maleic anhydride grafting degree（MA grafting degrees）For 0.3%-0.7%.
It can also be used as a mixture for the above-mentioned possible system of other polymer.
In addition, the additive component can include with functional group component, the functional group be, for example, carboxylic acid group,
Ester group, 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.
Specific embodiment
The test method of gained polyamide relative viscosity：With reference to GB12006.1-89, polyamide viscosity number assay method；
Specifically test method is：The relatively viscous of the polyamide that concentration is 10mg/ml is measured in 25 DEG C ± 0.01 DEG C of 98% concentrated sulfuric acid
Spend η r；
The test method of the fusing point of polyamide：With reference to ASTM D3418-2003, Standard Test Method
for Transition Temperatures of Polymers By Differential Scanning Calorimetry；
Specifically test method is：Using the fusing point of Perkin Elmer Diamond dsc analysis instrument test samples；Nitrogen atmosphere, flow velocity
For 40mL/min；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 10 DEG C/min
50 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 pH of polyamide is measured：0.5000g polyamides are taken, add phenol 50mL, are cooled to room temperature after being heated to reflux,
Use its pH value of non-aqueous electrode test.
Polyamide（Moulding compound）Melting process weight-loss ratioτTest：
Test polyamide（Moulding compound）Melting weight-loss ratioτ, gas station is generated in injection moulding process to simulate.
Specific test method is as follows ---
By polyamide（Moulding compound）It is placed in 130oAfter keeping 4h in the baking oven of C, 50.0000g polymer is weighed,
It is put into a 250ml there-necked flasks, then inserts mechanical agitation paddle.The total weight of there-necked flask, polymer and mechanical agitation paddle is weighed,
It is denoted asm 0.Connect N2Pipe, condensing unit.Wherein, mechanical agitation paddle uses 20 type products of IKA EUROSTAR, sets stirring
Speed is 1500rpm.It is warming up to polyamide（Moulding compound）More than fusing point 30oAfter constant temperature, polyamides simultaneously is put by above-mentioned by C
Polyimide resin（Moulding compound）There-necked flask immerse oil bath in keep 30min.Then there-necked flask is taken out, wipes clean outer wall oil,
Cooling.The total weight of there-necked flask, polymer and mechanical agitation paddle is weighed, is denoted asm 1.Then polyamide（Moulding compound）It is molten
Melt weight-loss ratioτ= (m 0-m 1)/50.0000×100%。
Gained polyamide（Moulding compound）The test method of product color：Using colour table mold 50*30*2mm, take
After 3000g polymer particles are molded, the colour table of one-sided smooth is obtained.The colour table is placed in reason treasured Color-Eye7000A electricity
GanzWhiteness is obtained on brain colour photometerWValue.The value can reflect polyamide（Moulding compound）The color of product, the value are got over
Height illustrates that product color is better.
The test method of the apparent carboxyl-content of polyamide moulding composition：Sample carboxylic is titrated with autopotentiometric titrator
Base content；0.5g polyamide moulding composition particles are taken, add o-cresol 50mL, reflux dissolving is rapidly added 400 μ L first after letting cool
Aldehyde solution titrates carboxyl-content with the KOH- ethanol solutions demarcated.The content is the apparent carboxylic of polyamide moulding composition
Base content [m].
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 in reaction raw materials；Add sodium hypophosphite, benzoic acid and deionized water；Sodium hypophosphite weight is in addition to deionized water
The 0.1%-0.5% of other charged material weights, the amount of benzoic acid species are the 2%-8% of the amount of diacid total material, and deionized water weight is
The 20%-40% of total charged material weight.It vacuumizes and is filled with high-purity argon gas/carbon dioxide gas mixture as protection gas, start to react.It will
Reaction mixture be warming up to 220 DEG C of -230 DEG C of stirring 3-5 it is small when, then open valve slowly pressure release draining, while keep temperature
It is constant with pressure.Draining always to displacement reaches the 70% of input amount of deionized water.It starts to warm up at this time, the interior heating when 3 is small
To 250 DEG C -270 DEG C, when constant temperature 2 is small.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.
Prepolymer be dried in vacuo at 80 DEG C 24 it is small when after, using high-purity argon gas/carbon dioxide mixed gas as protect
It protects gas and carries out solid-phase tack producing, solid-phase tack producing temperature is（T-50）℃.Constantly sampling, is glued by sampling and testing during solid-phase tack producing
Degree determines final polymerization terminal.
Rationally adjust the monomer composition in the above process and high-purity argon gas/carbon dioxide gas mixture ratio as protection gas
Example can obtain the resin of different pH value.
The property indices of polyamide are as follows：
PA1：6T/66/6C=50/40/10, relative viscosity 2.152, fusing point 312oC, pH=2.7；
PA2：6T/66=50/50, relative viscosity 2.175, fusing point 315oC, pH=5.1；
PA3：6T/66/10T/106=48/32/12/8, relative viscosity 2.173, fusing point 310 oC, pH=3.3；
PA4：10T/6=50/50, relative viscosity 2.099, fusing point 257 oC, pH=4.2；
PA5：6T/66=13/87, relative viscosity 2.143, fusing point 278 oC, pH=1.5；
PA6：6T/66/10T/106=48/32/12/8, relative viscosity 2.221, fusing point 309 oC, pH=9.3；
Wherein, C represents Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.
Embodiment 1-15 and comparative example 1-4：The preparation of polyamide moulding composition
By the formula of table 1 by polyamide, fire retardant, other auxiliary agents after high-speed mixer and mixing is uniform, fed by main
Material mouth is added in double screw extruder, and reinforcing filler is fed by side feeding scale side, is squeezed out, and crosses water cooling, after being granulated and drying
To the polyamide moulding composition.
Formula is parts by weight in 1 following table of table
As it can be seen from table 1 compared with comparative example, as a result of the polyamide with certain ph, embodiment
The melting weight-loss ratio for the polyamide moulding composition with specific acid-base value being preparedτIt is relatively low, it is meant that it discharges gas
Less, product surface is good during for being molded.Meanwhile the GanzWhiteness of embodiment productWHigher, color is preferable.
Claims (24)
1. a kind of low acid-base value polyamide moulding composition, including forming as follows：
A, the polyamide of 2≤pH≤6 is presented in the pH value in phenol of 30wt%-99wt%；
B, the reinforcing filler of 0-70wt%；
C, the additive of 0-70wt% and/or other polymer；
The sum of component A, B and C weight percent is 100wt%；
The apparent carboxyl-content [m] that the low acid-base value polyamide moulding composition is obtained surely by automatic potential titrator tests is full
It is enough lower scope：100 moles/ton≤mole/ton of [m]≤300；
Based on the molfraction all derived from diacid repetitive unit, the repetition list of at least 20mol% in the polyamide
Member is derived from terephthalic acid (TPA) and/or Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic；
Based on the molfraction all derived from diamines repetitive unit, the repetition list of at least 20mol% in the polyamide
Member is derived from 1,6- hexamethylene diamines and/or 1,10- decamethylene diamine.
2. a kind of polyamide moulding composition as described in claim 1, including consisting of：
A, the polyamide of 30wt%-95wt%；
B, the reinforcing filler of 1wt%-67wt%；
C, the additive of 0.1wt%-60wt% and/or other polymer；
The sum of component A, B and C weight percent is 100wt%.
3. low acid-base value polyamide moulding composition according to claim 1 or 2, which is characterized in that the polyamide resin
Fat pH value in phenol is presented：3≤pH≤5.
4. low acid-base value polyamide moulding composition according to claim 1 or 2, which is characterized in that the reinforcing filler
Shape for threadiness, average length 0.01mm-20mm；Its draw ratio is 5:1-2000:1；The reinforcing filler contains
It measures as 10wt%-50wt%；The reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers, and the inorganic reinforcing filler is selected from
Glass fibre, potassium titanate fibre, ceramic fibre, wollastonite fibre, metallic carbide fibres, asbestos fibre, gypsum fiber or boron
The one or more of fiber；The organic reinforcing fillers are selected from aramid fibre and/or carbon fiber.
5. low acid-base value polyamide moulding composition according to claim 4, which is characterized in that the reinforcing filler is put down
Equal length is 0.1mm-6mm.
6. low acid-base value polyamide moulding composition according to claim 4, which is characterized in that the length of the reinforcing filler
Footpath ratio is 30:1-600:1.
7. low acid-base value polyamide moulding composition according to claim 4, which is characterized in that the reinforcing filler contains
It measures as 15wt%-40wt%.
8. low acid-base value polyamide moulding composition according to claim 4, which is characterized in that the inorganic reinforcing filler
For glass fibre.
9. low acid-base value polyamide moulding composition according to claim 8, which is characterized in that the glass fibre is gold
Belong to the glass fibre of covering.
10. low acid-base value polyamide moulding composition according to claim 4, which is characterized in that the ceramic fibre is
Silicon carbide fibre or alumina fibre.
11. low acid-base value polyamide moulding composition according to claim 1 or 2, which is characterized in that the reinforcing filler
Shape for Non-fibrous, average grain diameter is 0.001 μm -100 μm, selected from potassium titanate crystal whisker, ZnOw, aluminum borate crystal whisker
Palpus, wollastonite, zeolite, mica, talcum, clay, pyrophillite, synthetic mica, asbestos, alumino-silicate, aluminium oxide, magnesia, oxygen
Change zirconium, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, hydrogen-oxygen
Change the one or more of aluminium, bead, ceramic bead, boron nitride, carborundum or silica.
12. low acid-base value polyamide moulding composition according to claim 11, which is characterized in that the reinforcing filler
Average grain diameter is 0.01 μm -50 μm.
13. low acid-base value polyamide moulding composition according to claim 11, which is characterized in that the clay is swelling
Soil or kaolin.
14. low acid-base value polyamide moulding composition according to claim 11, which is characterized in that the mica is thin,tough silk cloud
It is female.
15. low acid-base value polyamide moulding composition according to claim 1 or 2, 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 styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, deca-BDE, ten bromos
Biphenyl, brominated polycarbonate, the one or more of three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer；The Halogen resistance
It fires agent and is selected from one or more of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus fire retardant；Based on polyamide molding
The total weight of composition, the content of the fire retardant is 10wt%-40wt%.
16. low acid-base value polyamide moulding composition according to claim 15, which is characterized in that the fire retardant is nothing
Halogen fire retardant.
17. low acid-base value polyamide moulding composition according to claim 15, which is characterized in that the halogenated flame retardant
For brominated Polystyrene.
18. low acid-base value polyamide moulding composition according to claim 16, which is characterized in that the halogen-free flame retardants
For phosphonium flame retardant.
19. low acid-base value polyamide moulding composition according to claim 15, which is characterized in that the brominated epoxy tree
Fat is brominated bisphenol a type epoxy resin.
20. low acid-base value polyamide moulding composition according to claim 18, 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, triphenyl phosphate, tricresyl phosphate,
Tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate, butylbenzene system phosphate, the one or more of phosphinates.
21. low acid-base value polyamide moulding composition according to claim 20, which is characterized in that the phosphonium flame retardant
To have the phosphinates of following structural formula I and/or II：
In Formulas I and Formula II, R1And R2It may be the same or different, represent the C1-C6- alkane of straight-chain or branch-like respectively
Base, aryl；R3Represent C1-C10- alkylidenes, the C6-C10- arlydene 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.
22. low acid-base value polyamide moulding composition according to claim 21, which is characterized in that the R3For C6-C10-
Alkyl arylene.
23. low acid-base value polyamide moulding composition according to claim 21, which is characterized in that the aryl is benzene
Base.
24. low acid-base value polyamide moulding composition according to claim 21, which is characterized in that the R3For C6-C10-
Aryl alkylene.
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