CN104804427A - Low-PH (potential of hydrogen) polyamide molding composition - Google Patents
Low-PH (potential of hydrogen) polyamide molding composition Download PDFInfo
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- CN104804427A CN104804427A CN201510135947.8A CN201510135947A CN104804427A CN 104804427 A CN104804427 A CN 104804427A CN 201510135947 A CN201510135947 A CN 201510135947A CN 104804427 A CN104804427 A CN 104804427A
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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
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- 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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- C08L2201/02—Flame or fire retardant/resistant
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- 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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- 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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Abstract
The invention discloses low-PH (potential of hydrogen) polyamide molding composition. The composition comprises components as follows: A, 30wt%-99wt% of polyamide resin, B, 0wt%-70wt% of reinforcing filler and C, 0wt%-70wt% of an additive and/or other polymer, wherein the PH value of the polyamide resin in phenol is larger than or equal to 2 and smaller than or equal to 6; the sum of weight percent of A, B and C is 100wt%. According to the low-PH polyamide molding composition, the content [m] of an apparent carboxyl group obtained through measurement by an automatic potentiometric titrator is smaller than or equal to 550 mole/ton. The polyamide molding composition with specific PH is prepared from polyamide resin with a specific pH value, polyamide resin can be effectively prevented from being degraded and generating gas in an injection molding process, further, the technical problems of flow marks, local blanching and the like are solved, and the color of the polyamide molding composition is improved.
Description
Technical field
The present invention relates to polymeric material field, particularly the low potential of hydrogen polyamide moulding composition of one.
Background technology
Polymeric amide is because having good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, there is certain flame retardant resistance etc., it is extensively suitable for, by glass fibre and other filler filling enhancing modified, improving the aspect such as performance and broadened application scope.In recent years semiaromatic polyamide composition due to its resistance toheat and mechanical property more excellent and by focus development.
CN101175791 provides a kind of heat retention stability, hot water resistance and the chemical-resistant with height, and with the binding property of other resin etc. or the polyamide resin of excellent compatibility.Terminal amine base unit weight [the NH of this this molecular chain of resin
2] be more than 60mol/t, below 120mol/t, and terminal amine base unit weight and terminal carboxyl(group) amount [COOH] meet [NH
2]/[COOH]>=6.
CN102149748 provides a kind of polyamide resin with improvement processing characteristics.It presents :-be more than or equal to the amine chain end content of 20 μ eq/g; Be less than or equal to the sour chain end content of 100 μ eq/g; With the non-reacted chain end content being more than or equal to 20 μ eq/g.
JP6032980 provides a kind of method improving polyamide moulding composition products formed surface property.That is, the amino or carboxyl end group value of use side carries out modification lower than the polyamide substrate resin of 50meq/kg, and the appearance of molded articles obtained is better.But it only gives the method that single enhancing modified product appearance is improved, that is, only add mineral filler if glass etc. is as additive.And fashionable surface condition is added for the fire retardant, fire retarding synergist etc. of chemical property complexity do not point out.
But above-mentioned patent only defines the specified end group content of polyamide resin, but in actual use procedure, polyamide resin generally all could will be applied through modification.Owing to having carried out high-temperature fusion in modifying process, high-temperature fusion is the polymer terminal group balance of reacting further and degrading inherently.Add and add various additive, in this process, the character of polymkeric substance there occurs certain change.Considerable influence is there is equally in the potential of hydrogen of final product to its application.
As mentioned above, the end group test of current polyamide resin has become the general means of the industry one, in order to characterize the information of each side such as number-average molecular weight, level of response of polymeric amide.Although the end group of polymeric amide may affect the pH value of solution, this and not exclusive important factor.Different polyamide molecule chain rigidity, amide group concentration, the second dimension sharp coefficient, Huggins parameter, theta solvent behavior etc. all can cause great effect to its pH value.Even if the polymeric amide that component, monomer ratio are identical, due to the acting in conjunction of above-mentioned factor, all possibility difference is huge for its pH value, thus causes the difference of polymer performance.The structure of polymeric reaction condition or polymeric amide is adjusted, the polymeric amide of different end group or pH value can be obtained.
The present inventor finds through great many of experiments, pH value in phenol is selected to present the polyamide resin of 2≤pH≤6 and then prepare the polyamide moulding composition with specific acid basicity, not only effectively can prevent polyamide resin from degraded occurring in injection moulding process and produce gas, and then solve the technical problems such as goods current mark, White Patches.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the object of the present invention is to provide one in injection moulding process, produce less gas, and the improved low potential of hydrogen polyamide moulding composition of color.
The present invention is achieved by the following technical solutions.
A kind of low potential of hydrogen polyamide moulding composition, comprises following composition:
The pH value in phenol of A, 30wt%-99wt% presents the polyamide resin of 2≤pH≤6;
The reinforcing filler of B, 0-70wt%;
The additive of C, 0-70wt% and/or other polymkeric substance;
Component A, B and C weight percentage sum are 100wt%;
The apparent carboxyl-content [m]≤550 mole/ton that this low potential of hydrogen polyamide moulding composition is obtained surely by automatic potential titrator tests.
Preferably, a kind of polyamide moulding composition, comprises following composition:
The polyamide resin of A, 30wt%-95wt%;
The reinforcing filler of B, 1wt%-67wt%;
The additive of C, 0.1wt%-60wt% and/or other polymkeric substance;
Component A, B and C weight percentage sum are 100wt%;
The apparent carboxyl-content [m]≤550 mole/ton that this low potential of hydrogen polyamide moulding composition is obtained surely by automatic potential titrator tests.
Preferably, described polyamide resin pH value in phenol that pH value presents 2≤pH≤6 in phenol presents: 3≤pH≤5.
Preferably, the apparent carboxyl-content [m] that described low potential of hydrogen polyamide moulding composition is obtained surely by automatic potential titrator tests meets following scope: 50 moles/ton≤[m]≤450 mole/ton, preferably 100 moles/ton≤[m]≤300 mole/ton.
Described in phenol pH value present the polyamide resin of 2≤pH≤6, based on all derived from the molfraction of diacid repeating unit, have the repeating unit of 20mol% in described polyamide resin at least derived from terephthalic acid and/or 1,4 cyclohexanedicarboxylic acid.
Described in phenol pH value present the polyamide resin of 2≤pH≤6, based on all derived from the molfraction of diamines repeating unit, have the repeating unit of 20mol% in described polyamide resin at least derived from 1,6-hexanediamine and/or 1，10-diaminodecane.
The content of described B component is preferably 10wt%-50wt%, is more preferably 15wt%-40wt%;
Reinforcing filler content is too low, causes polyamide moulding composition mechanical property poor; Reinforcing filler too high levels, polyamide moulding composition product surface is floating fine serious, affects product appearance.
The shape of described reinforcing filler is threadiness, and its mean length is 0.01mm-20mm, is preferably 0.1mm-6mm; Its length-to-diameter ratio is 5:1-2000:1, is preferably 30:1-600:1, when fibrous reinforcing filler content is in above-mentioned scope, and the high temperature rigid that polyamide moulding composition will show high heat distortion temperature and increase.
Described reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers;
Described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre;
Use glass fibre not only can improve the mouldability of polyamide moulding composition, and mechanical property such as tensile strength, flexural strength and modulus in flexure can be improved, and improve heat-drawn wire when thermotolerance such as thermoplastic resin composition carries out molding.
Described organic reinforcing fillers is selected from Kevlar and/or carbon fiber.
The shape of described reinforcing filler is Non-fibrous, such as Powdered, particulate state, tabular, needle-like, fabric or felted, and its median size is 0.001 μm-100 μm, is preferably 0.01 μm-50 μm.
The melt processable of polyamide resin difference will be caused when the median size of reinforcing filler is less than 0.001 μm; When the median size of reinforcing filler is greater than 100 μm, bad injection-molded article appearance will be caused.
The median size of above-mentioned reinforcing filler is measured by absorption method, it can be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.
These reinforcing fillers can be hollow; In addition, for swelling property layered silicates such as wilkinite, polynite, lithium montmorillonite, synthetic micas, can use and adopt organic ammonium salt that interlayer ion is carried out the organic montmorillonoid after cationic exchange.
In order to make polyamide moulding composition obtain more excellent mechanical property, coupling agent can be adopted to carry out functional processing to inorganic reinforcing filler.
Wherein coupling agent is selected from isocyanic ester based compound, organosilane based compound, organic titanate based compound, organo-borane based compound, epoxy compounds; Be preferably organosilane based compound;
Wherein, described organosilane based compound be selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group(ing), the alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group, containing the end alkoxysilane compound containing trialkylsilyl group in molecular structure of amido, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group, alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group one or more.
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group(ing) be selected from γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxyl silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-Mercaptopropyltriethoxysilane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups is selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, γ-(2-urea groups ethyl) hold aminocarbonyl propyl Trimethoxy silane one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group be selected from γ-isocyanate group propyl-triethoxysilicane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-isocyanate group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido is selected from γ-(2-hold amido ethyl) and holds aminocarbonyl propyl methyl dimethoxysilane, γ-(2-holds amido ethyl) to hold one or more of aminocarbonyl propyl Trimethoxy silane, γ-end aminocarbonyl propyl Trimethoxy silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from γ-hydroxypropyl Trimethoxy silane and/or γ-hydroxypropyl triethoxyl silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group be selected from γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, N-β-(N-vinyl benzyl cardinal extremity amido ethyl)-γ-end aminocarbonyl propyl Trimethoxy silane hydrochloride one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3-trimethoxy-silylpropyl succinyl oxide;
Described organosilane based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2-holds amido ethyl) holds aminocarbonyl propyl methyl dimethoxysilane, γ-(2-holds amido ethyl) to hold aminocarbonyl propyl Trimethoxy silane, γ-end aminocarbonyl propyl Trimethoxy silane or 3-trimethoxy-silylpropyl succinyl oxide.
Above-mentioned organosilane based compound conventionally can be adopted to carry out surface treatment to inorganic reinforcing filler, and then itself and polyamide resin are carried out melting mixing, to prepare described polyamide moulding composition.
Also directly while inorganic reinforcing filler and polyamide resin melting mixing, organosilane based compound can be added and carries out in-situ blending.
Wherein, the consumption of described coupling agent is the 0.05wt%-10wt% relative to inorganic reinforcing filler weight, is preferably 0.1wt%-5wt%.
When the consumption of coupling agent is less than 0.05wt%, it does not reach the effect of obvious improved mechanical properties; When the consumption of coupling agent is greater than 10wt%, inorganic reinforcing filler easily condenses, and in polyamide resin, disperse bad risk, finally causes mechanical property to decline.
Described additive be selected from fire retardant, impact modifying agent, other polymkeric substance, processing aid one or more; Other polymkeric substance described be preferably fatty polyamide, polyolefin homopolymer, ethene-alpha-olefin copolymer, ethylene-acrylate copolymer one or more; Described processing aid be selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, releasing agent, lubricant, pigment, dyestuff, softening agent, static inhibitor one or more.
Described fire retardant is the composition of fire retardant or fire retardant and fire-retardant assistance agent, and based on the gross weight of polyamide moulding composition, its content is preferably 10wt%-40wt%; The too low flame retardant effect that causes of flame retardant agent content is deteriorated, and the too high material mechanical performance that causes of flame retardant agent content declines.
Described fire retardant is halogenated flame retardant or halogen-free flame retardants;
Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecane or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene;
Described halogen-free flame retardants is selected from one or more of the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant.
Described phosphonium flame retardant is selected from one or more of monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphoric acid ester, butylbenzene system phosphoric acid ester or phosphinates; Be preferably phosphinates;
The compound that phosphinate salt compound represents with such as following formula I and/or II is for representative.
In formula I and formula II, R
1and R
2can be identical, also can be different, represent the C1-C6-alkyl of straight-chain or branch-like, aryl or phenyl respectively.R
3represent C1-C10-alkylidene group, C6-C10-arylidene, C6-C10-alkyl arylene, the C6-C10-aryl alkylene of straight-chain or branch-like.M represents calcium atom, magnesium atom, aluminium atom and/or zinc atom.M be 2 or 3, n be 1 or 3, x be 1 or 2.
The more specifically example of phosphinate salt compound comprises dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethylimethyphosphinic acid zinc, diethyl phospho acid calcium, diethyl phospho acid magnesium, aluminum diethylphosphinate, diethyl phospho acid zinc, methyl-n-propylphosphinic acid calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc, first burns two (methyl-phosphinic acid) calcium, methane two (methyl-phosphinic acid) magnesium, methane two (methyl-phosphinic acid) aluminium, methane two (methyl-phosphinic acid) zinc, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) calcium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) magnesium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) aluminium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, methylphenylphosphinic acid aluminium, methylphenylphosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl phosphonic acid zinc etc., preferred dimethylphosphinic acid calcium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid I beggar, ethylimethyphosphinic acid aluminium, ethylimethyphosphinic acid zinc, diethyl phospho acid calcium, aluminum diethylphosphinate, diethyl phospho acid zinc, more preferably aluminum diethylphosphinate.
Phosphinate salt compound as fire retardant can easily obtain from market.The example of the phosphinate salt compound that can obtain from market comprises EXOLIT OP1230, OP1311, OP1312, OP930, OP935 etc. that Clariant Corporation (Clariant) manufactures.
The polyamide moulding composition comprising above-mentioned polyamide resin of the present invention, based on the gross weight of polyamide moulding composition, described binder component can also comprise the one or more of impact modifying agents of 45wt% at the most; Be preferably 5wt%-30wt%.
Wherein, described impact modifying agent can be natural rubber, polyhutadiene, polyisoprene, polyisobutene, divinyl and/or isoprene and vinylbenzene or with styrene derivatives and with the multipolymer of other comonomer, hydrogenated copolymer and/or by grafting or with acid anhydride, (methyl) vinylformic acid or its ester copolymerization and obtained multipolymer; Described impact modifying agent can also be the graft rubber with cross-linked elastomer core, described cross-linked elastomer core is made up of divinyl, isoprene or alkyl acrylate, and there is the graft shell that is made up of polystyrene or can be nonpolar or polar olefin homopolymer or multipolymer, such as ethylene-propylene rubber(EPR), ethylene/propylene/diene rubber, or Ethylene-octene rubber, or ethylene-vinyl acetate rubber, by grafting or with acid anhydride, (methyl) vinylformic acid or its ester copolymerization and the nonpolar or polar olefin homopolymer that obtains or multipolymer; Described impact modifying agent can also be carboxylic acid functionalized multipolymer, such as poly-(ethene-altogether-(methyl) vinylformic acid) or poly-(ethene-1-alkene-altogether-(methyl) vinylformic acid), wherein 1-alkene unsaturated (methyl) acrylate of being alkene or having more than 4 atoms, comprises acid groups and is neutralized those multipolymers to a certain extent by metal ion.
The impact modifying agent of styrene-based monomer (vinylbenzene and styrene derivatives) and other vi-ny l aromatic monomers, it is the segmented copolymer be made up of alkenyl aromatic compounds and conjugated diene, with the hydrogenated block copolymer be made up of alkenyl aromatic compounds and conjugated diene, and the combination of these type impact modifying agents.Described segmented copolymer comprises at least one derived from the block a of alkenyl aromatic compounds and at least one block b derived from conjugated diene.When hydrogenated block copolymer, the ratio of the unsaturated carbon-to-carbon double bond of aliphatics is reduced by hydrogenation.Suitable segmented copolymer is two, three, four and the segmented copolymer with linear chain structure.But, also can use branching and star structure according to the present invention.Obtain branched block copolymer in a known way, such as, by the graft reaction of polymkeric substance " collateral chain " to main polymer chain.
Can use together with vinylbenzene or with other alkenyl aromatic compounds used with cinnamic form of mixtures be aromatic ring and/or in C=C double bond by C1-20 alkyl or the vi-ny l aromatic monomers that replaced by halogen atom.
The example of alkenyl aromatic monomer is vinylbenzene, p-methylstyrene, alpha-methyl styrene, ethyl styrene, t-butyl styrene, Vinyl toluene, 1,2-diphenylethlene, 1，1-diphenylethylene, vinyl-dimethyl benzene, Vinyl toluene, vinyl naphthalene, Vinylstyrene, bromostyrene and chlorostyrene and combination thereof.Optimization styrene, p-methylstyrene, alpha-methyl styrene and vinyl naphthalene.
The mixture of preferred use vinylbenzene, alpha-methyl styrene, p-methylstyrene, ethyl styrene, t-butyl styrene, Vinyl toluene, 1,2-diphenylethlene, 1，1-diphenylethylene or these materials.Particularly preferably be use vinylbenzene.But, also can usage chain thiazolinyl naphthalene.
The example of operable diolefinic monomer is 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, isoprene, chloroprene and m-pentadiene.Preferred 1,3-butadiene and isoprene, especially 1,3-butadiene (hereinafter representing with abbreviated form divinyl).
The alkenyl aromatic monomer used preferably includes vinylbenzene, and the diolefinic monomer used preferably includes divinyl, this means optimization styrene-butadiene block copolymer.Described segmented copolymer is prepared in a manner which is in itself known by anionoid polymerization usually.
Except styrene monomer and diolefinic monomer, the monomer that can also simultaneously use other other.Based on the total amount of used monomer, the ratio of comonomer is preferably 0-50wt%, is particularly preferably 0-30wt%, is particularly preferably 0-15wt%.The example of suitable comonomer is acrylate respectively, especially vinylformic acid C1 ~ C12 alkyl ester, such as n-butyl acrylate or 2-EHA, and methacrylic ester, especially methacrylic acid C1 ~ C12 alkyl ester, such as methyl methacrylate (MMA).Other possible comonomer is (methyl) vinyl cyanide, (methyl) glycidyl acrylate, vinyl methyl ether, the diallyl of dibasic alcohol and divinyl ether, Vinylstyrene and vinyl-acetic ester.
Except conjugated diene, if properly, hydrogenated block copolymer also comprises lower hydrocarbon part, such as ethene, propylene, 1-butylene, Dicyclopentadiene (DCPD) or non-conjugated diene hydrocarbon.The ratio of unreduced aliphatics unsaturated link(age) in hydrogenated block copolymer coming from block b is less than 50%, is preferably less than 25%, is especially less than 10%.Aromatic fractions derived from block a reverts to the degree of at the most 25%.By the hydrogenation of styrene-butadiene copolymer and the hydrogenation of styrene-butadiene-styrene, obtain hydrogenated block copolymer, i.e. vinylbenzene-(Ethylene/Butylene) diblock copolymer and vinylbenzene-(Ethylene/Butylene)-styrene triblock copolymer.
Segmented copolymer preferably comprises the block a of block a, the especially 50wt%-85wt% of 20wt%-90wt%.Diolefine can be incorporated in block b with 1,2-orientation or Isosorbide-5-Nitrae-orientation.
The molar mass of segmented copolymer is 5000g/mol-500000g/mol, preferred 20000g/mol-300000g/mol, particularly 40000g/mol-200000g/mol.
Suitable hydrogenated block copolymer is the product that can buy from the market, such as (Kraton polymkeric substance) G1650, G1651 and G1652, and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141 and H1272.
The example of non-hydrogenated segmented copolymer is polystyrene-polybutadiene, polystyrene-poly (ethylene-propylene), polystyrene-poly isoprene, poly-(alpha-methyl styrene)-polyhutadiene, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly (ethylene-propylene)-polystyrene, polystyrene-poly isoprene-polystyrene and poly-(alpha-methyl styrene) polyhutadiene-poly-(alpha-methyl styrene) and combination thereof.
The suitable non-hydrogenated segmented copolymer that can buy from the market has trade mark to be the multiple product of (Phillips), (Shell), (Dexco) and (Kuraray).
The polyamide moulding composition comprising above-mentioned polyamide resin of the present invention, described binder component can also comprise other polymkeric substance, and other polymkeric substance described is selected from fatty polyamide, polyolefin homopolymer or ethene-alpha-olefin copolymer, ethylene-acrylate copolymer.
Described fatty polyamide includes but are not limited to the aliphatic diacid and aliphatie diamine that are derived from 4 ~ 20 carbon atoms, or the lactan of 4 ~ 20 carbon atoms, or one or more in the polymkeric substance of the aliphatic diacid of 4 ~ 20 carbon atoms, aliphatie diamine and lactan.Include but are not limited to, polyhexamethylene adipamide (PA66), polycaprolactam (PA6), polyhexamethylene sebacamide (PA610), nylon 1010 (PA1010), hexanodioic acid-hexanediamine-caprolactam copolymer (PA66/6), poly-11 lactan (PA11), nylon 12 (PA12), and two or more mixture.
The preferred EP elastomerics of described ethene-alpha-olefin copolymer and/or EPDM elastomerics (being ethylene-propylene rubber and ethylene/propylene/diene rubber respectively).Such as, elastomerics can comprise based on the elastomerics containing 20wt%-96wt%, the preferably ethene-C3 ~ C12-alpha-olefin copolymer of 25wt%-85wt% ethene, wherein particularly preferably be C3 ~ C12-alpha-olefin herein and comprise the alkene being selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and/or 1-laurylene, particularly preferably other polymkeric substance comprise ethylene-propylene rubber, LLDPE, VLDPE one or more.
Alternatively or additionally (such as in the mixture), other polymkeric substance described can also comprise the terpolymer based on ethene-C3 ~ C12-alpha-olefin and non-conjugated diene hydrocarbon, herein preferably its contain 25wt%-85wt% ethene and at the most maximum be the non-conjugated diene hydrocarbon of 10wt%, particularly preferably C3 ~ C12-alpha-olefin comprises and is selected from propylene herein, 1-butylene, 1-amylene, 1-hexene, 1-octene, the alkene of 1-decene and/or 1-laurylene, and/or wherein non-conjugated diene hydrocarbon is preferably selected from two rings [2.2.1] heptadiene, 1, 4-hexadiene, dicyclopentadiene and/or especially 5-ethylidene norbornene.
Ethylene-acrylate copolymer also can be used as the composition of other polymkeric substance described.
Other of other polymkeric substance described may form be ethylene-butene copolymer and the mixture (blend) comprising these systems respectively.
Preferably, other polymkeric substance described comprises the composition with anhydride group, these by trunk polymer and unsaturated dicarboxylic anhydride, with unsaturated dicarboxylic acid or with the thermal response of the mono alkyl ester of unsaturated dicarboxylic acid or free radical reaction, to be enough to introduce with the concentration of polymeric amide good combination, and herein preferably use be selected from following reagent:
Toxilic acid, maleic anhydride, butyl maleate, fumaric acid, equisetic acid and/or itaconic anhydride.The unsaturated acid anhydride of preferred 0.1wt%-4.0wt% is grafted in the shock resistance component as the composition of C, or unsaturated dicarboxylic anhydride or its precursor are applied by grafting together with other unsaturated monomer.Usually preferably graft(ing) degree is 0.1%-1.0%, is particularly preferably 0.3%-0.7%.Another of other polymkeric substance may composition be the mixture be made up of ethylene-propylene copolymer and ethylene-butene copolymer, and maleic anhydride graft degree (MA graft(ing) degree) is 0.3%-0.7% herein.
May system can also use as a mixture for the above-mentioned of this other polymkeric substance.
In addition, described binder component can comprise the component with functional group, described functional group is such as hydroxy-acid group, ester group, epoxide group, oxazoline group, carbodiimide group, isocyanate groups, silanol and carboxylate group, or described binder component can comprise the combination of two or more in above-mentioned functional group.The monomer with described functional group can be combined by copolymerization or be grafted on elastomeric polyolefin.
In addition; impact modifying agent based on olefin polymer can also by carrying out modification with unsaturated silane compound grafting, and described unsaturated silane compound is such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetylsilane, methacryloxypropyl trimethoxy silane or propenyl Trimethoxy silane.
Elastomeric polyolefin is have straight chain, side chain or nucleocapsid structure random, alternately or segmented copolymer, and containing the functional group can reacted with the end group of polymeric amide, provides enough tolerability thus between polymeric amide and impact modifying agent.
Therefore, impact modifying agent of the present invention comprises homopolymer or the multipolymer of alkene (such as ethene, propylene, 1-butylene), or the multipolymer of alkene and copolymerisable monomer (such as vinyl-acetic ester, (methyl) acrylate and methyl hexadiene).
The example of crystalline olefin polymkeric substance is low density, Midst density and high density polyethylene(HDPE), polypropylene, polyhutadiene, poly-4-methylpentene, Ethylene-Propylene Block Copolymer, or ethylene-propylene random copolymer, ethene-methyl hexadiene multipolymer, propylene-methyl hexadiene multipolymer, ene-propylene-butene multipolymer, Ethylene-propylene-hexene Copolymer, ethylene-propylene-methyl hexadiene multipolymer, poly-(ethane-acetic acid ethyenyl ester) (EVA), poly-(ethylene-ethylacrylate) (EEA), ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, ethylene/propylene/diene terpolymer, and the combination of above-mentioned polymkeric substance.
The commercially available impact modifying agent example that may be used for described binder component has:
TAFMER MC201:g-MA (-0.6%) 67%EP multipolymer (20mol% propylene)+33%EB multipolymer (15mol%1-butylene)) blend: Mitsui Chemicals, Japan.
TAFMER MH5010:g-MA (-0.6%) ethylene-butene copolymer; Mitsui.
TAFMER MH7010:g-MA (-0.7%) ethylene-butene copolymer; Mitsui.
TAFMER MH7020:g-MA (-0.7%) EP multipolymer; Mitsui.
EXXELOR VA1801:g-MA (-0.7%) EP multipolymer; Exxon Mobile Chemicals, US.
EXXELOR VA1803:g-MA (0.5-0.9%) EP multipolymer, amorphous, Exxon.
EXXELOR VA1810:g-MA (-0.5%) EP multipolymer, Exxon.
EXXELOR MDEX 941l：g-MA(0.7%)EPDM，Exxon。
FUSABOND MN493D:g-MA (-0.5%) ethylene-octene copolymer, DuPont, US.
FUSABOND A EB560D:(g-MA) ethylene/n-butyl acrylate multipolymer, DuPont ELVALOY, DuPont.
Also be preferably ionic polymer, wherein the carboxyl of polymer-bound is by metal ion all mutually bondings or be bonded to a certain degree.
The divinyl that particularly preferably maleic anhydride graft is functionalized and cinnamic multipolymer, by the nonpolar or polar olefin homopolymer that obtains with maleic anhydride graft and multipolymer and carboxylic acid functionalized multipolymer, such as poly-(ethene-(methyl) vinylformic acid altogether) or poly-(ethene--1-alkene altogether-altogether-(methyl) vinylformic acid), wherein said acid groups is neutralized by metal ion to a certain extent.
In addition, in the scope not destroying effect of the present invention, various processing aid can be added at any time in polyamide resin of the present invention, such as antioxidant and/or heat-resisting stabilizing agent (hindered phenol system, quinhydrones system, phosphorous acid ester system and their replacement body, copper halide, iodine compound etc.), weather resisting agent (Resorcinol system, salicylate system, benzotriazole system, benzophenone series, hindered amine system etc.), releasing agent and lubricant (fatty alcohol, aliphatic amide, aliphatics bisamide, two ureas and polyethylene wax etc.), pigment (Cadmium Sulfide, phthalocyanine, carbon black etc.), dyestuff (nigrosine, nigrosine etc.), softening agent (P-hydroxybenzoic acid monooctyl ester, N-butylbenzenesulfonamide etc.), static inhibitor (alkyl sulphate type negatively charged ion system static inhibitor, quaternary ammonium salt cationic system static inhibitor, the nonionic system static inhibitor such as polyoxyethylene sorbitan monostearate, trimethyl-glycine system both sexes static inhibitor etc.).
In order to obtain products formed of the present invention, can polyamide resin of the present invention or Amilan polyamide resin composition be come shaping by random molding methods such as injection molding, extrusion moulding, blow molding, vacuum forming, melt-spinning, film are shaping.These products formeds can be molded into desired shape, and can in middle uses such as the synthetic resins of trolley part, mechanical part etc.As concrete purposes, it is useful in following purposes: automobile engine cooling water based part, the particularly radiator water box part such as top and bottom of radiator tank, cooling fluid reserve tank, water pipe, water pump shell, water pump impeller, the parts used under the pump parts etc. such as valve contact with water coolant in car engine machine room, with Switch, subminiature slide switch, DIP switch, the shell of switch, lamp socket, strapping tape, junctor, the shell of junctor, the shell of junctor, IC socket class, roll, bobbin cover, rly., relay1 box, capacitor casing, the internal part of motor, small size motor shell, gear cam, dancing pulley, pad, isolator, fastening piece, button, wire clamp, cycle wheel, caster, safety helmet, terminal board, the shell of power tool, the insulated part of trigger, spoiler, tank, radiator tank, chamber tank (Chamber tank), receiver, fuse unit, shell of air purifier, air-conditioning fan, the shell of terminal, wheel cover, suction tracheae, bearing retainer, cylinder head cover, intake manifold, water pipe impeller (waterpipe impeller), clutch lever, speaker diaphragm, thermally resistant container, microwave oven component, electric cooker parts, the electrical/electronic associated components that printer color tape guider etc. are representative, automobile/vehicle associated components, household electrical appliances/office electrical component, computer associated components, facsimile recorder/duplicating machine associated components, machinery associated components, other various uses.
Embodiment
The testing method of gained polyamide resin relative viscosity: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: in the vitriol oil of 25 DEG C ± 0.01 DEG C 98%, measure the relative viscosity η r that concentration is the polymeric amide of 10mg/ml;
The testing method of the fusing point of polyamide resin: with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; Concrete testing method is: the fusing point adopting Perkin Elmer Diamond dsc analysis instrument test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First be warming up to 340 DEG C with 10 DEG C/min during test, keep 2min at 340 DEG C, be then cooled to 50 DEG C with 10 DEG C/min, then be warming up to 340 DEG C with 10 DEG C/min, endotherm peak temperature is now set to fusing point
t m.
The pH of polyamide resin measures: get 0.5000g polyamide resin, add phenol 50mL, be chilled to room temperature after reflux, use non-water electrode to test its pH value.
Polyamide resin (moulding compound) melting process rate of weight loss
τtest:
The melting rate of weight loss of test polyamide resin (moulding compound)
τ, produce gas station to simulate in injection moulding process.Concrete testing method is as follows---
Polyamide resin (moulding compound) is placed in 130
oafter keeping 4h in the baking oven of C, take 50.0000g polymkeric substance, put into a 250ml there-necked flask, then insert mechanical stirring oar.Weigh the gross weight of there-necked flask, polymkeric substance and mechanical stirring oar, be designated as
m 0.Connect N
2pipe, condensing works.Wherein, mechanical stirring oar adopts IKA EUROSTAR 20 type product, and arranging stirring velocity is 1500rpm.Be warming up to more than polyamide resin (moulding compound) fusing point 30
othe above-mentioned there-necked flask putting into polyamide resin (moulding compound) also, after constant temperature, is immersed oil bath and keeps 30min by C.Then there-necked flask is taken out, wipe clean outer wall oil, cooling.Weigh the gross weight of there-necked flask, polymkeric substance and mechanical stirring oar, be designated as
m 1.Then polyamide resin (moulding compound) melting rate of weight loss
τ=(
m 0-
m 1)/50.0000 × 100%.
The testing method of gained polyamide resin (moulding compound) goods color: use colour table mould 50*30*2mm, gets after 3000g polymer particle carries out injection moulding, obtains the colour table of one-sided smooth.This colour table is placed on the precious Color-Eye7000A Computer color testing instrument of reason and obtains GanzWhiteness
wvalue.This value can reflect the color of polyamide resin (moulding compound) goods, and this value is higher, illustrates that goods color is better.
The testing method of the apparent carboxyl-content of polyamide moulding composition: with autopotentiometric titrator titration sample carboxyl-content; Get 0.5g polyamide moulding composition particle, add ortho-cresol 50mL, backflow is dissolved, and lets cool and adds rapidly 400 μ L formaldehyde solutions afterwards, with the KOH-ethanolic soln titration carboxyl-content demarcated.This content is the apparent carboxyl-content [m] of polyamide moulding composition.
The polyamide resin used in the present invention is prepared by the following method:
Reaction raw materials is added in the ratio in form in the autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth; Add sodium hypophosphite, phenylformic acid and deionized water again; Sodium hypophosphite weight is the 0.1%-0.5% of deionizing water other charged material weight outer, and the amount of benzoic acid species is the 2%-8% of the total amount of substance of diacid, and deionized water weight is the 20%-40% of total charged material weight.Vacuumize and be filled with high-purity argon gas/carbon dioxide gas mixture as protection gas, start reaction.Reaction mixture is warming up to 220 DEG C-230 DEG C and stirs 3-5 hour, then open valve slowly pressure release draining, keep temperature and pressure constant simultaneously.Draining always to water displacement reaches and drops into 70% of amount of deionized water.Now start to heat up, in 3 hours, be warming up to 250 DEG C-270 DEG C, constant temperature 2 hours.Open valve discharging after having reacted, obtain prepolymer.
According to the fusing point of the method test prepolymer of test polyamide resin fusing point, be set to T DEG C.
Vacuum-drying is after 24 hours at 80 DEG C for prepolymer, and use the mixed gas of high-purity argon gas/carbonic acid gas to carry out solid-phase tack producing as protection gas, solid-phase tack producing temperature is (T-50) DEG C.Constantly sample in solid-phase tack producing process, determine finally to be polymerized terminal by sampling and testing viscosity.
Monomer composition in reasonable adjusting said process and the high-purity argon gas/carbon dioxide gas mixture ratio as protection gas, can obtain the resin of different pH value.
The property indices of polyamide resin is as follows:
PA1:6T/66/6C=50/40/10, relative viscosity 2.152, fusing point 312
oc, pH=2.7;
PA2:6T/66=50/50, relative viscosity 2.175, fusing point 315
oc, 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 1,4 cyclohexanedicarboxylic acid.
embodiment 1-
15 and comparative example 1-4: the preparation of polyamide moulding composition
By table 1 formula by polyamide resin, fire retardant, other auxiliary agents high-speed mixer and mixing evenly after, add in twin screw extruder by main spout, reinforcing filler is fed by feeding scale side, side, extrudes, cross water cooling, granulation also obtains described polyamide moulding composition after drying.
In table 1 following table, formula is weight part
As can be seen from Table 1, relative to comparative example, owing to have employed the polyamide resin with certain ph, the melting rate of weight loss of what embodiment prepared the have polyamide moulding composition of specific acid basicity
τlower, mean that its release gas is less, good for product surface during injection moulding.Meanwhile, the GanzWhiteness of embodiment goods
whigher, color is better.
Claims (10)
1. a low potential of hydrogen polyamide moulding composition, comprises following composition:
The pH value in phenol of A, 30wt%-99wt% presents the polyamide resin of 2≤pH≤6;
The reinforcing filler of B, 0-70wt%;
The additive of C, 0-70wt% and/or other polymkeric substance;
Component A, B and C weight percentage sum are 100wt%;
The apparent carboxyl-content [m]≤550 mole/ton that this low potential of hydrogen polyamide moulding composition is obtained surely by automatic potential titrator tests.
2. a polyamide moulding composition as claimed in claim 1, comprises following composition:
The polyamide resin of A, 30wt%-95wt%;
The reinforcing filler of B, 1wt%-67wt%;
The additive of C, 0.1wt%-60wt% and/or other polymkeric substance;
Component A, B and C weight percentage sum are 100wt%;
The apparent carboxyl-content [m]≤550 mole/ton that this low potential of hydrogen polyamide moulding composition is obtained surely by automatic potential titrator tests.
3. low potential of hydrogen polyamide moulding composition according to claim 1 and 2, is characterized in that, the described polyamide resin that pH value presents 2≤pH≤6 in phenol preferably in phenol pH value present: 3≤pH≤5.
4. low potential of hydrogen polyamide moulding composition according to claim 1 and 2, it is characterized in that, the apparent carboxyl-content [m] that described low potential of hydrogen polyamide moulding composition is obtained surely by automatic potential titrator tests meets following scope: 50 moles/ton≤[m]≤450 mole/ton, preferably 100 moles/ton≤[m]≤300 mole/ton.
5. low potential of hydrogen polyamide moulding composition according to claim 1 and 2, it is characterized in that, described in phenol pH value present the polyamide resin of 2≤pH≤6, based on all derived from the molfraction of diacid repeating unit, has the repeating unit of 20mol% at least derived from terephthalic acid and/or 1,4 cyclohexanedicarboxylic acid.
6. low potential of hydrogen polyamide moulding composition according to claim 1 and 2, it is characterized in that, described in phenol pH value present the polyamide resin of 2≤pH≤6, based on all derived from the molfraction of diamines repeating unit, the repeating unit of 20mol% is had at least derived from 1 in described polyamide resin, 6-hexanediamine and/or 1，10-diaminodecane.
7. low potential of hydrogen polyamide moulding composition according to claim 1 and 2, is characterized in that, the shape of described reinforcing filler is threadiness, and its mean length is 0.01mm-20mm, is preferably 0.1mm-6mm; Its length-to-diameter ratio is 5:1-2000:1, is preferably 30:1-600:1; The content of described reinforcing filler is 10wt%-50wt%, is preferably 15wt%-40wt%; Described reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers, described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Described organic reinforcing fillers is selected from Kevlar and/or carbon fiber.
8. low potential of hydrogen polyamide moulding composition according to claim 1 and 2, it is characterized in that, the shape of described reinforcing filler is Non-fibrous, its median size is 0.001 μm-100 μm, be preferably 0.01 μm-50 μm, be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.
9. low potential of hydrogen polyamide moulding composition according to claim 1 and 2, it is characterized in that, described additive contains fire retardant; Fire retardant is halogenated flame retardant or halogen-free flame retardants, preferred halogen-free flame retardants; Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecane or brominated aromatic cross-linked polymer, is preferably brominated Polystyrene; Described halogen-free flame retardants is selected from one or more in the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus, is preferably phosphonium flame retardant; Based on the gross weight of polyamide moulding composition, the content of described fire retardant is 10wt%-40wt%.
10. low potential of hydrogen polyamide moulding composition according to claim 9, it is characterized in that, described phosphonium flame retardant be selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphoric acid ester, butylbenzene system phosphoric acid ester, phosphinates one or more; Preferably there is the phosphinates of following structural formula I and/or II:
In formula I and formula II, R
1and R
2can be identical, also can be different, represent the C1-C6-alkyl of straight-chain or branch-like, aryl or phenyl respectively; R
3represent C1-C10-alkylidene group, C6-C10-arylidene, C6-C10-alkyl arylene, the C6-C10-aryl alkylene of straight-chain or branch-like; M represents calcium atom, magnesium atom, aluminium atom and/or zinc atom; M be 2 or 3, n be 1 or 3, x be 1 or 2.
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| CN103665373A (en) * | 2013-11-12 | 2014-03-26 | 金发科技股份有限公司 | PA10T polyamide resin and polyamide composition composed of same |
| CN104017204A (en) * | 2014-05-20 | 2014-09-03 | 珠海万通化工有限公司 | Polyamide resin and polyamide composition formed by same |
| CN104262952A (en) * | 2014-09-19 | 2015-01-07 | 金发科技股份有限公司 | Low-pH-value polyamide molding composition |
| CN104592509A (en) * | 2014-12-19 | 2015-05-06 | 金发科技股份有限公司 | Low-pH value polyamide molding composition |
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2015
- 2015-03-26 CN CN201510135947.8A patent/CN104804427B/en active Active
Patent Citations (6)
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|---|---|---|---|---|
| JP2007070508A (en) * | 2005-09-08 | 2007-03-22 | Nitto Boseki Co Ltd | Phenol resin-foamed article and method for producing the same |
| 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 |
| CN103665373A (en) * | 2013-11-12 | 2014-03-26 | 金发科技股份有限公司 | PA10T polyamide resin and polyamide composition composed of same |
| CN104017204A (en) * | 2014-05-20 | 2014-09-03 | 珠海万通化工有限公司 | Polyamide resin and polyamide composition formed by same |
| CN104262952A (en) * | 2014-09-19 | 2015-01-07 | 金发科技股份有限公司 | Low-pH-value polyamide molding composition |
| CN104592509A (en) * | 2014-12-19 | 2015-05-06 | 金发科技股份有限公司 | Low-pH value polyamide molding composition |
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