CN106046365A - Semi-aromatic copolyamide resin and polyamide molding composition made of semi-aromatic copolyamide resin - Google Patents
Semi-aromatic copolyamide resin and polyamide molding composition made of semi-aromatic copolyamide resin Download PDFInfo
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- CN106046365A CN106046365A CN201610559103.0A CN201610559103A CN106046365A CN 106046365 A CN106046365 A CN 106046365A CN 201610559103 A CN201610559103 A CN 201610559103A CN 106046365 A CN106046365 A CN 106046365A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
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Abstract
The invention discloses a semi-aromatic copolyamide resin which comprises repetitive units derived from the following components: (A) diamine, which comprises 30 mol% to 100 mol% of 1,11-undecylene and 0 to 70 mol% of other diamine containing 4 to 36 carbon atoms based on the amount of all diamine; (B) diacid, which comprises 30 mol% to 100 mol% of terephthalic acid and 0 to 70 mol% of other diacid containing 6 to 36 carbon atoms based on the amount of all diacid; (C) lactam or amino acid, which comprises 1.5 mol% to 51 mol% of lactam and/or amino acid containing 7 to 12 carbon atoms based on the amount of all monomers. According to the semi-aromatic copolyamide resin, diamine containing 11 carbon atoms is adopted as a copolymer component, and the proportion of diamine to diacid to lactam or amino acid is controlled to meet specific requirements, so as to obtain the semi-aromatic copolyamide resin with remarkably improved color performance, low water absorption rate and good dimensional stability. A polyamide molding composition made of the semi-aromatic copolyamide resin also has the remarkably improved color performance, low water absorption rate and good dimensional stability.
Description
Technical field
The present invention relates to engineering plastics technical field, particularly to a kind of semi-aromatic copolyamide resin and consisting of
Polyamide moulding composition.
Background technology
Polyamide is because having good combination property, including mechanical property, thermostability, mar proof, chemically-resistant medicine
Moral character and self lubricity, and coefficient of friction is low, has certain anti-flammability etc., it is generally applied with glass fibre and other filler
Filling enhancing modified, improves performance and expands the aspects such as range of application.Semiaromatic polyamide composition was due to its thermostability in recent years
Can and mechanical property more excellent and by focus development.
But, the usual water absorption rate of PA6T semiaromatic polyamide composition is higher, and color is poor.Water absorption rate is higher is easily caused backflow
In welding procedure, product bubbles, and color is poor, can cause producing light color product.
For the problems referred to above of PA6T semiaromatic polyamide composition, the most general solution is to use Long carbon chain diamidogen to take
For hexamethylene diamine, reduce amido link concentration, thus reduce water absorption rate.As: CN101298517 uses decamethylene diamine and hexamethylene diamine copolymerization
Method obtains PA10T/6T, and this material has relatively low water absorption rate.CN1477153 uses 1,9-nonamethylene diamine and 2-methyl isophthalic acid, 8-
Octamethylenediamine substitutes hexamethylene diamine, can reduce water absorption rate equally, solves the product bubble problem in SMT technique.
Long-standing for the be correlated with research of semiaromatic polyamide composition of Long carbon chain diamine in the industry, but be mostly based on nonyl two
Amine, decamethylene diamine and 12 diamidogen, the disclosure for semiaromatic polyamide compositions based on 11 diamidogen is the most rare.As:
US3515703 proposes a kind of method synthesizing PA11T/6 copolymer, wherein, and caprolactam unit containing in copolyamide
Amount is 3-40wt%.PA11T/6 copolymer has good thermostability, Young's modulus and spinnability.(Wang, the W. such as Wang;
Wang, X.; Li, R.; Liu, B.; Wang, E.; Zhang, Y., "Environment-friendly
synthesis of long chain semiaromatic polyamides with high heat resistance."
Journal of Applied Polymer Science, 2009,114 (4): 2036-2042.) use environment-friendly method
Having synthesized 4 kinds of Long carbon chain semiaromatic polyamide composition PA10T, PA11T, PA12T and PA13T, these polyamide have good resistance to
Hot and low water absorption.
CN104710612 proposes a kind of ceramic whisker and strengthens the preparation method of high temperature resistant nylon composite material, its explanation
Embodiment 11 in book proposes, and carries out the highest after 11T salt, silicon nitride single crystal whisker, deionized water and other small powder being mixed
Pressure melt polymerization, obtains silicon nitride high temperature resistant, that good stability of the dimension, water absorption rate are low and strengthens PA11T semi-aromatic polyamides
Amine.
CN103122063 proposes the preparation method of a kind of Semi-aromatic polyamide resin from bio-based monomer, will
After aminoundecanoic acid, para-amino benzoic acid, distilled water and catalyst are mixed into salt, carry out melt polymerization, obtain this patent
In the polyamide of referred to as " PA11T ".It practice, this polyamide is distinct from traditional PA11T, but two kinds amino acid whose
Copolymer.
In general, a kind of half virtue having and improving color characteristics, low water absorption, good dimensional stability is needed in this field badly
Fragrant race's copolyamide resin and polyamide moulding composition thereof.
The present inventor is found by great many of experiments, uses and has the diamidogen of 11 carbon atoms as copolymerization component, and controls
Diamidogen processed, diacid and lactams or amino acid whose ratio, be allowed to meet particular requirement, it is possible to obtains having the face being obviously improved
Color performance, low water absorption, the semi-aromatic copolyamide resin of good dimensional stability, by this semi-aromatic copolyamide resin
The polyamide moulding composition of composition also has color characteristics, low water absorption and the good dimensional stability being obviously improved.
Summary of the invention
In order to overcome shortcoming that prior art exists with not enough, the primary and foremost purpose of the present invention is to provide one to have substantially
The color characteristics of improvement, low water absorption, the semi-aromatic copolyamide resin of good dimensional stability.
It is a further object of the present invention to provide the polyamide moulding composition comprising above-mentioned semi-aromatic copolyamide resin.
The present invention is achieved by the following technical solutions:
A kind of semi-aromatic copolyamide resin, by mole meter, the repetitive including derived from following component:
(A) diamidogen, including
Amounts based on whole diamidogen, the 1 of 30mol%-100mol%, 11-11 diamidogen and 0-70mol% to have 4-36 carbon former
Other diamidogen of son；
(B) diacid, including
Amounts based on whole diacid, the p-phthalic acid of 30mol%-100mol% and 0-70mol% have 6-36 carbon atom
Other diacid；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% and/or aminoacid.
Preferably, described semi-aromatic copolyamide resin, by mole meter, including derived from following component
Repetitive:
(A) diamidogen, including
Amounts based on whole diamidogen, the 1 of 30mol%-95mol%, 11-11 diamidogen and 5mol%-70mol% have 4-36 carbon
Other diamidogen of atom；1,11-11 diamidogen of preferably 40mol%-80mol% and 20mol%-60mol% have 4-36 carbon
Other diamidogen of atom；
(B) amounts based on whole diacid, the p-phthalic acid of 100mol%；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% or aminoacid.
Preferably, described semi-aromatic copolyamide resin, by mole meter, including derived from following component
Repetitive:
(A) amounts based on whole diamidogen, the 1 of 100mol%, 11-11 diamidogen；
(B) diacid, including
Amounts based on whole diacid, the p-phthalic acid of 30mol%-95mol% and 5mol%-70mol% to have 6-36 carbon former
Other diacid of son；The p-phthalic acid of preferably 60mol%-90mol% and 10mol%-40mol% have 6-36 carbon atom
Other diacid；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% or aminoacid.
Preferably, described semi-aromatic copolyamide resin, by mole meter, including derived from following component
Repetitive:
(A) amounts based on whole diamidogen, the 1 of 100mol%, 11-11 diamidogen；
(B) amounts based on whole diacid, the p-phthalic acid of 100mol%；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% or aminoacid.
Preferably, described semi-aromatic copolyamide resin, component (C) lactams or aminoacid, based on whole monomers
Amount, including the lactams with 7-12 carbon atom or the aminoacid of 5mol%-30mol%.
Wherein, have described in other diamidogen of 4-36 carbon atom selected from straight or branched aliphatic diamine, cycloaliphatic diamine,
One or more in aryl aliphatic diamine；Described straight or branched aliphatic diamine selected from Putriscine, 1,5-pentanediamine, 2-first
Base-1,5-pentanediamine (MPMD), 1,8-octamethylenediamine (OMDA), 1,9-nonamethylene diamine (NMDA), 2-methyl isophthalic acid, 8-octamethylenediamine
(MODA), 2,2,4-trimethylhexamethylenediamines (TMHMD), 2,4,4-trimethylhexamethylenediamines (TMHMD), 5-first
Base-1,9-nonamethylene diamine, 1,11-hendecane diamidogen, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecamethylene diamine, 1,13-
Tridecane diamine, 1,14-tetradecane diamidogen, 1,16-hexadecane diamidogen, 1, one or more in 18-octadecamethylene diamine；Institute
State cycloaliphatic diamine selected from cyclohexanediamine, 1,3-double (amino methyl) hexamethylene (BAC), isophorone diamine, norcamphane diformazan
Amine, 4,4 '-diamino-dicyclohexyl methane (PACM), 2,2-(4,4 '-diaminocyclohexyl) propane (PACP), 3,3 '-two
Methyl-4, one or more in 4 '-diamino-dicyclohexyl methane (MACM)；Described aryl aliphatic diamine is selected from isophthalic diformazan
Amine (MXDA).
Wherein, have described in other diacid of 6-36 carbon atom selected from naphthalene dicarboxylic acids (NDA), isophthalic acid (IPS), oneself
Diacid, suberic acid, Azelaic Acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, 15
Docosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid, dimer acids, cis and/or trans cyclohexane-Isosorbide-5-Nitrae-dicarboxylic acids, cis and/
Or trans cyclohexane-1, one or more in 3-dicarboxylic acids (CHDA).
Wherein, lactams or the aminoacid described in 7-12 carbon atom are selected from α, omega-amino n-nonanoic acid, α, ω-amino
One or more in undecanoic acid (AUA), lauric lactam (LL), omega-amino lauric acid/dodecanoic acid (ADA).
The invention also discloses a kind of polyamide moulding composition comprising above-mentioned semi-aromatic copolyamide resin, by weight
Amount percentages, including following component:
A, semi-aromatic copolyamide resin 30wt%-100wt%；
B, reinforcer 0-70wt%；
C, additive and/or other polymer 0-50wt%；
Wherein, the percetage by weight sum of tri-kinds of components of a, b, c is 100wt%.
Gross weight based on polyamide moulding composition, the content of described component b is preferably 10wt%-50wt%, more preferably
For 15wt%-40wt%；
Reinforcer content is too low, causes polyamide moulding composition mechanical property poor；Reinforcer too high levels, polyamide
Moulding compound product surface is floating fine serious, affects product appearance.
Described reinforcer be shaped as threadiness, its average length is 0.01mm-20mm, preferably 0.1mm-6mm；Its
Draw ratio is 5:1-2000:1, preferably 30:1-600:1, when fibrous reinforcer content within the above range time, polyamides
Amine moulding compound will show high heat distortion temperature and the high temperature rigid increased.
Described reinforcer is inorganic reinforcing filler or organic reinforcing fillers；
Described inorganic reinforcing filler is selected from glass fibre, potassium titanate fibre, metalclad glass fibre, ceramic fibre, silicon ash
Mineral wool, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum fiber or
One or more of boron fibre, preferably glass fibre；
Use glass fibre not only can improve the mouldability of polyamide moulding composition, and mechanical property can be improved and such as draw
Stretch intensity, bending strength and bending modulus, and thermal deformation when improving thermostability such as thermoplastic resin composition molds
Temperature.
Described organic reinforcing fillers is selected from aramid fibre and/or carbon fiber.
Described reinforcer be shaped as Non-fibrous, such as powder, graininess, tabular, needle-like, fabric or felted,
Its mean diameter is 0.001 μm-100 μm, preferably 0.01 μm-50 μm.
When the mean diameter of reinforcer will cause the melt processable of polyamide difference less than 0.001 μm；Work as enhancing
The mean diameter of filler is more than 100 μm, will cause bad injection-molded article appearance.
The mean diameter of above-mentioned reinforcer is measured by absorption method, its be selected from potassium titanate crystal whisker, ZnOw,
Aluminium borate whisker, wollastonite, zeolite, sericite, Kaolin, Muscovitum, Talcum, clay, pyrophillite, bentonite, montmorillonite, lithium cover
De-soil, synthetic mica, asbestos, aluminosilicate, aluminium oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, ferrum oxide, calcium carbonate,
Magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride,
One or more of carborundum or silicon dioxide.
These reinforcers can be hollow；Additionally, it is molten for bentonite, montmorillonite, lithium montmorillonite, synthetic mica etc.
Swollen property phyllosilicate, it is possible to use the organic montmorillonite after using organic ammonium salt that interlayer ion carries out cation exchange.
In order to make polyamide moulding composition obtain the most excellent mechanical performance, can use coupling agent that 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；It is preferably organosilan based compound；
Wherein, described organosilan based compound is selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy radicals, the alcoxyl containing sulfydryl
Base silane compound, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing NCO, contain
The end alkoxysilane compound containing trialkylsilyl group in molecular structure of amido, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkoxyl containing carbon-to-carbon unsaturated group
Silane compound, 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 radicals selected from γ-glycidoxypropyltrime,hoxysilane, γ-
One or more of glycidoxypropyl group triethoxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane；
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-mercaptopropyi
Triethoxysilane；
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups is selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl front three
One or more of TMOS, γ-(2-urea groups ethyl) end aminocarbonyl propyl trimethoxy silane；
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing NCO selected from γ-NCO propyl-triethoxysilicane, γ-
NCO propyl trimethoxy silicane, γ-NCO hydroxypropyl methyl dimethoxysilane, γ-NCO third
Ylmethyl diethoxy silane, γ-NCO ethyl dimethoxysilane, γ-NCO ethyl two
One or more of Ethoxysilane, γ-NCO propyltrichlorosilan；
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido holds aminocarbonyl propyl methyl dimethoxy oxygen selected from γ-(2-end amido ethyl)
Base silane, γ-(2-end amido ethyl) end aminocarbonyl propyl trimethoxy silane, the one of γ-end aminocarbonyl propyl trimethoxy silane
Plant or several；
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from γ-hydroxypropyl trimethoxy silane and/or γ-hydroxypropyl
Triethoxysilane；
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group is selected from γ-methacryloxypropyl trimethoxy
Silane, vinyltrimethoxy silane, N-β-(N-vinyl benzyl cardinal extremity amido ethyl)-γ-end aminocarbonyl propyl trimethoxy silicon
One or more of heptane hydrochloride salt；
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3-trimethoxy-silylpropyl succinic anhydrides；
Described organosilan based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2-end amido
Ethyl) hold aminocarbonyl propyl methyl dimethoxysilane, γ-(2-end amido ethyl) end aminocarbonyl propyl trimethoxy silane, γ-end
Aminocarbonyl propyl trimethoxy silane or 3-trimethoxy-silylpropyl succinic anhydrides.
Can conventionally use above-mentioned organosilan based compound that inorganic reinforcing filler is carried out surface process,
The most again itself and polyamide are carried out melting mixing, to prepare described polyamide moulding composition.
Organosilan system chemical combination can also be added directly while inorganic reinforcing filler with polyamide melting mixing
Thing 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 reaches the effect of obvious improved mechanical properties；Work as coupling agent
Consumption more than 10wt% time, inorganic reinforcing filler is susceptible to cohesion, and disperses bad risk in polyamide,
Ultimately result in mechanical performance to decline.
Described additive selected from fire retardant, impact modifying agent, other polymer, processing aid one or more；Described
Other polymer is preferably fatty polyamide, polyolefin homopolymer, ethene-alpha-olefin copolymer, ethylene-acrylate copolymers
One or more of thing；Described processing aid selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, releasing agent, lubricant, pigment,
Dyestuff, plasticizer, antistatic additive one or more.
Described fire retardant is the compositions of fire retardant or fire retardant and fire-retardant assistance agent, total based on polyamide moulding composition
Weight, its content is preferably 0-40wt%；Flame retardant agent content is too low causes flame retardant effect to be deteriorated, and flame retardant agent content is too high causes material
Material mechanical properties decrease.
Described fire retardant is halogenated flame retardant or halogen-free flame retardants；
Described halogenated flame retardant selected from brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-
Copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, the poly-carbonic acid of bromination
One or more of ester, perbromo-three cyclopentadecane or brominated aromatic cross linked polymer, the most preferred brominated Polystyrene；
Described halogen-free flame retardants is selected from one or more of fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus；Excellent
Elect phosphonium flame retardant as.
Described 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 ester, butylbenzene system phosphate ester or phosphinates
One or more；It is preferably phosphinates；
The compound that phosphinate salt compound represents with such as following formula I and/or II is as representative.
In Formulas I and Formula II, R1And R2Can be identical, it is also possible to different, represent straight-chain or the C1-C6-of branch-like respectively
Alkyl, aryl or phenyl.R3Represent straight-chain or the C1-C10-alkylidene of branch-like, C6-C10-arlydene, C6-C10-alkyl
Arlydene, C6-C10-aryl alkylene.M represents calcium atom, magnesium atom, aluminum atom and/or zinc atom.M is 2 or 3, n be 1 or
3, x is 1 or 2.
The more specifically example of phosphinate salt compound includes dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethyl time
Phosphonic acids aluminum, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminum, ethyl
Methyl-phosphinic acid zinc, diethyl phosphinic acid calcium, diethyl phosphinic acid magnesium, aluminum diethylphosphinate, diethyl phosphinic acid zinc, methyl
N-pro-pyl phosphinic acid calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminum, methyl-n-propylphosphinic acid zinc, first are burnt
Two (methyl-phosphinic acid) calcium, methane two (methyl-phosphinic acid) magnesium, methane two (methyl-phosphinic acid) aluminum, 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) aluminum, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, aminomethyl phenyl time phosphine
Acid aluminum, methylphenylphosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminum, diphenyl time phosphine
Acid zinc etc., preferably dimethylphosphinic acid calcium, dimethylphosphinic acid aluminum, dimethylphosphinic acid zinc, ethylimethyphosphinic acid I beggar, second
Ylmethyl phosphinic acid aluminum, ethylimethyphosphinic acid zinc, diethyl phosphinic acid calcium, aluminum diethylphosphinate, diethyl phosphinic acid zinc,
More preferably aluminum diethylphosphinate.
Phosphinate salt compound as fire retardant can easily obtain from market.The phosphinic acid salinization that can obtain from market
The example of compound include EXOLIT OP1230 that Clariant Corporation (Clariant) manufactures, OP1311, OP1312, OP930,
OP935 etc..
The polyamide moulding composition comprising above-mentioned semi-aromatic copolyamide resin of the present invention, based on polyamide molding
The gross weight of compositions, described additive component may also contain up to the one or more of impact modifying agents of 45wt%, preferably
For 5wt%-30wt%.
Wherein, described impact modifying agent can be natural rubber, polybutadiene, polyisoprene, polyisobutylene, butadiene
And/or isoprene and styrene or with styrene derivative and with the copolymer of other comonomer, hydrogenated copolymer and/
By grafting or with acid anhydride, (methyl) acrylic acid or its ester copolymerization and prepared copolymer；Described impact modifying agent can also is that
Having the graft rubber of cross-linked elastomer core, described cross-linked elastomer core is by butadiene, isoprene or alkyl acrylate structure
Become, and there is the graft shell being made up of polystyrene or can be nonpolar or polar olefin homopolymer or copolymer, example
Such as EP rubbers, ethylene/propylene/diene rubber, or Ethylene-octene rubber, or ethylene-vinyl acetate rubber, or pass through
Grafting or with acid anhydride, (methyl) acrylic acid or its ester copolymerization and the nonpolar or polar olefin homopolymer that obtains or copolymer；Described
Impact modifying agent can also is that carboxylic acid functionalized copolymer, the most poly-(ethylene-co-(methyl) acrylic acid) or poly-(ethylene-1-
Alkene-co-(methyl) acrylic acid), wherein 1-alkene is olefine or has unsaturation (methyl) propylene more than 4 atoms
Acid esters, is neutralized those copolymers to a certain extent including acid groups by metal ion.
Styrene-based monomer (styrene and styrene derivative) and the impact modifying agent of other vi-ny l aromatic monomers,
It is the block copolymer being made up of alkenyl aromatic compounds and conjugated diene, and by alkenyl aromatic compounds and conjugation two
The hydrogenated block copolymer that alkene is constituted, and the combination of these type impact modifying agents.Described block copolymer comprises at least one
Kind derived from the block a of alkenyl aromatic compounds with at least one is derived from the block b of conjugated diene.At hydrogenated diblock altogether
In the case of polymers, the ratio of aliphatic unsaturation carbon-to-carbon double bond is reduced by hydrogenation.Suitably block copolymer is to have
The two of linear chain structure, three, four 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 by the graft reaction of polymer " collateral chain " to main polymer chain.
Can be used together with styrene or with other alkenyl aromatic chemical combination used with cinnamic form of mixtures
Thing be aromatic ring and/or in C=C double bond by C1～20 alkyl or the vi-ny l aromatic monomers replaced by halogen atom.
The example of alkenyl aromatic monomer is styrene, p-methylstyrene, α-methyl styrene, ethyl styrene, uncle
Butylstyrene, vinyltoluene, 1,2-diphenylethlene, 1，1-diphenylethylene, vinyl-dimethyl benzene, vinyltoluene,
Vinyl naphthalene, divinylbenzene, bromostyrene and chlorostyrene, and combinations thereof.Optimization styrene, p-methylstyrene,
α-methyl styrene and vinyl naphthalene.
Styrene, α-methyl styrene, p-methylstyrene, ethyl styrene, t-butyl styrene, ethylene are preferably used
Base toluene, 1, the mixture of 2-diphenylethlene, 1，1-diphenylethylene or these materials.Particularly preferably use benzene second
Alkene.But it is also possible to use alkenyl naphthalene.
The example of the diolefinic monomer that can use is 1,3-butadiene, 2-methyl isophthalic acid, 3-butadiene, 2,3-dimethyl-
1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, isoprene, chlorobutadiene and pentadiene.Preferably 1,3-butadiene and
Isoprene, especially 1,3-butadiene (hereinafter represent with abbreviated form butadiene).
The alkenyl aromatic monomer used preferably includes styrene, and the diolefinic monomer used preferably includes fourth two
Alkene, it means that optimization styrene-butadiene block copolymer.Described block copolymer generally passes through anionic polymerisation with it
Known to body prepared by mode.
In addition to styrene monomer and diolefinic monomer, it is also possible to use other other monomer simultaneously.Based on being made
By the total amount of monomer, the ratio of comonomer is preferably 0-50wt%, particularly preferably 0-30wt%, particularly preferably 0-15wt%.
Suitably the example of comonomer is acrylate, especially acrylic acid C1～C12 Arrcostab, such as n-butyl acrylate respectively
Or 2-EHA, and methacrylate, especially methacrylic acid C1～C12 Arrcostab, such as metering system
Acid methyl ester (MMA).Other possible comonomer is (methyl) acrylonitrile, (methyl) glycidyl acrylate, vinyl first
Base ether, the diallyl of dihydroxylic alcohols and divinyl ether, divinylbenzene and vinyl acetate.
In addition to conjugated diene, if appropriate, hydrogenated block copolymer also comprises lower hydrocarbon part, such as second
Alkene, propylene, 1-butylene, bicyclopentadiene or non-conjugated diene hydrocarbon.Come from the unreduced aliphatic unsaturated bond of block b at hydrogen
Change the ratio in block copolymer and be less than 50%, preferably smaller than 25%, especially less than 10%.Derived from block a aromatic fractions also
Former at most 25% degree.By the hydrogenation of SB and styrene-butadiene-styrene
Hydrogenation, obtains hydrogenated block copolymer, i.e. styrene-(Ethylene/Butylene) diblock copolymer and styrene-(Ethylene/Butylene)-
Styrene triblock copolymer.
Block copolymer preferably comprises the block a of the block a, especially 50wt%-85wt% of 20wt%-90wt%.Alkadienes
Can be with 1,2-orientation or Isosorbide-5-Nitrae-orientation are incorporated in block b.
The molal weight of block copolymer is 5000g/mol-500000g/mol, preferably 20000g/mol-300000g/
Mol, particularly 40000g/mol-200000g/mol.
Suitably hydrogenated block copolymer is the product that can buy 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, poly-(α-methyl styrene)-polybutadiene, polystyrene-polybutadiene-polystyrene (SBS), poly-
Styrene-poly-(ethylene-propylene)-polystyrene, polystyrene-polyisoprene-polystyrene and poly-(α-methyl styrene)
Polybutadiene-poly-(α-methyl styrene), and combinations thereof.
The suitable non-hydrogenated block copolymer that can buy from the market have trade mark be (Phillips), (Shell),
And the multiple product of (Kuraray) (Dexco).
The polyamide moulding composition comprising above-mentioned semi-aromatic copolyamide resin of the present invention, described additive component
Can also comprise other polymer, other polymer described is selected from fatty polyamide, polyolefin homopolymer or ethene-alpha-olefin
Copolymer, vinyl-acrylate copolymer.
Described fatty polyamide includes but are not limited to be derived from the aliphatic diacid of 4-20 carbon atom and aliphatic two
Amine, or the lactams of 4-20 carbon atom, or the aliphatic diacid of 4-20 carbon atom, aliphatic diamine and lactams
One or more in polymer.Include but are not limited to, polyhexamethylene adipamide (PA66), polycaprolactam (PA6), the poly-last of the ten Heavenly stems
Two acyl hexamethylene diamines (PA610), nylon 1010 (PA1010), adipic acid-hexamethylene diamine-caprolactam copolymer (PA66/
6), poly-11 lactams (PA11), nylon 12 (PA12), and the mixture of two or more.
Described ethene-alpha-olefin copolymer preferred EP elastomer and/or EPDM elastomer (are ethylene-propylene rubber respectively
With ethylene/propylene/diene rubber).Such as, elastomer can include based on containing 20wt%-96wt%, preferred 25wt%-
The elastomer of the ethylene-C3-C12-alpha olefin copolymer of 85wt% ethylene, is particularly preferably C3-C12-alpha-olefin the most herein
Including selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and/or the alkene of 1-laurylene, particularly preferably its
Its polymer include ethylene-propylene rubber, LLDPE, VLDPE one or more.
Alternatively or additionally (the most in the mixture), other polymer described can also comprise based on ethylene-
C3-C12-alpha-olefin and the terpolymer of non-conjugated diene hydrocarbon, the most preferably it contains 25wt%-85wt% ethylene and extremely
Many maximums are the non-conjugated diene hydrocarbon of 10wt%, and particularly preferably C3-C12-alpha-olefin includes selected from propylene, 1-butylene, 1-herein
Amylene, 1-hexene, 1-octene, 1-decene and/or the alkene of 1-laurylene, and/or wherein non-conjugated diene hydrocarbon is preferably chosen from
Bicyclo-[2.2.1] heptadiene, Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene and/or especially 5-ethylidene norbornene.
Vinyl-acrylate copolymer is also used as the composition of other polymer described.
Other of other polymer described may form be ethylene-butene copolymer and the mixing comprising these systems respectively
Thing (blend).
Preferably, other polymer described comprises the composition with anhydride group, and these are by trunk polymer and unsaturation
Dicarboxylic anhydride and unsaturated dicarboxylic or with the thermal response of the mono alkyl ester of unsaturated dicarboxylic or radical reaction, be enough to
The concentration of polyamide good combination introduces, and herein preferably with selected from following reagent:
Maleic acid, maleic anhydride, butyl maleate, fumaric acid, equisetic acid and/or itaconic anhydride.Preferably 0.1wt%-4.0wt%
Unsaturated acid anhydride be grafted in the shock resistance component of the composition as C, or unsaturated dicarboxylic anhydride or its precursor by with its
Its unsaturated monomer is grafted together and applies.Generally preferably grafting degree is 0.1%-1.0%, particularly preferably 0.3%-0.7%.Other
Another of polymer may composition be the mixture being made up of ethylene-propylene copolymer and ethylene-butene copolymer, herein Malaysia
Acid anhydride-grafted degree (MA grafting degree) is 0.3%-0.7%.
Above-mentioned for this other polymer may system can also use as a mixture.
Additionally, described additive component can comprise the component with functional group, described functional group for example, hydroxy-acid group,
Ester group, epoxide group, oxazoline group, carbodiimide group, isocyanate groups, silanol and carboxylate group,
Or described additive component can comprise the combination of two or more in above-mentioned functional group.There is the list of described functional group
Body can be by copolymerization or be grafted on elastomeric polyolefin combine.
Additionally, impact modifying agent based on olefin polymer can also be by changing with unsaturated silane compound grafting
Property, described unsaturated silane compound for example, vinyltrimethoxy silane, VTES, vinyl three second
Acyl silanes, methacryloxypropyl trimethoxy silane or acrylic trimethoxy silane.
Elastomeric polyolefin is have straight chain, side chain or nucleocapsid structure random, alternately or block copolymer, and containing can
The functional group reacted with the end group with polyamide, thus provides enough tolerability between polyamide and impact modifying agent.
Therefore, the impact modifying agent of the present invention includes homopolymer or the copolymerization of alkene (such as ethylene, propylene, 1-butylene)
Thing, or alkene and the copolymer of copolymerisable monomer (such as vinyl acetate, (methyl) acrylate and methyl hexadiene).
The example of crystalline olefin polymer be low-density, Midst density and high density polyethylene (HDPE), polypropylene, polybutadiene,
Poly-4-methylpentene, Ethylene-Propylene Block Copolymer or ethylene-propylene random copolymer, ethylene-methyl hexadiene copolymerization
Thing, propylene-methyl hexadiene copolymer, ene-propylene-butene copolymer, Ethylene-propylene-hexene Copolymer, ethylene-propylene-
Methyl hexadiene copolymer, 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 above-mentioned poly-
The combination of compound.
The commercially available impact modifying agent example that may be used for described additive component has:
TAFMER MC201:g-MA (-0.6%) 67%EP copolymer (20mol% propylene)+33%EB copolymer (15mol%1-fourth
Alkene)) 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 copolymer；Mitsui.
EXXELOR VA1801:g-MA (-0.7%) EP copolymer；Exxon Mobile Chemicals, US.
EXXELOR VA1803:g-MA (0.5-0.9%) EP copolymer, amorphous, Exxon.
EXXELOR VA1810:g-MA (-0.5%) EP copolymer, 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。
Being also preferably ionomer, wherein the carboxyl of polymer-bound is all mutually bonded by metal ion or is bonded
To a certain extent.
The butadiene that particularly preferably maleic anhydride is graft-functionalized and cinnamic copolymer, by being grafted with maleic anhydride
Nonpolar or the polar olefin homopolymer prepared and copolymer and carboxylic acid functionalized copolymer, the most poly-((first of ethylene-altogether
Base) acrylic acid) or poly-(ethylene-co-1-alkene-co-(methyl) acrylic acid), wherein said acid groups the most to a certain extent by
Metal ion neutralizes.
Additionally, do not destroying in the range of effect of the present invention, can be at any time in the polyamide of the present invention
Add various processing aid, such as antioxidant and/or heat-resisting stabilizing agent (hindered phenol system, hydroquinone system, phosphite ester system and it
Replacement body, copper halide, iodine compound etc.), weather resisting agent (resorcinol system, salicylate system, benzotriazole system, hexichol first
Ketone system, hindered amine system etc.), releasing agent and lubricant (aliphatic alcohol, aliphatic amide, aliphatic bisamide, two ureas and polyethylene
Wax etc.), pigment (cadmium sulfide, phthalocyanine, white carbon black etc.), dyestuff (nigrosine, nigrosine etc.), (P-hydroxybenzoic acid is pungent for plasticizer
Ester, N-butylbenzenesulfonamide etc.), (alkyl sulphate type anion system antistatic additive, quaternary ammonium salt cationic system resist antistatic additive
Nonionic system antistatic additive, the glycine betaine system both sexes antistatic additive such as electrostatic agent, polyoxyethylene sorbitan monostearate
Deng).
In order to obtain the products formed of the present invention, the polyamide of the present invention or Amilan polyamide resin composition can be passed through
The random molding methods such as injection moulding, extrusion molding, blow molding, vacuum forming, melt spinning, film molding carry out molding.Permissible
These products formeds are molded into required form, it is possible to use in the synthetic resin etc. of automobile component, mechanical part etc..Make
For concrete purposes, it it is useful in following purposes: the top of automobile engine cooling water based part, particularly radiator tank
The pump parts such as the radiator water box part such as portion and bottom, coolant reserve tank, water pipe, water pump shell, water pump vane, valve etc. are at vapour
In car engine room with cooling water contact down use parts, with Switch, microminiature slide switch, DIP switch, switch outside
Shell, lamp socket, strapping tape, adapter, the shell of adapter, the shell of adapter, IC socket class, roll, bobbin cover, relay,
Electrical relaybox, capacitor casing, the internal part of motor, small size motor shell, gear cam, dancing pulley, pad, insulator,
Securing member, buckle, the insulation division of the shell of wire clamp, cycle wheel, caster, safety helmet, terminal board, electric tool, starter
Point, 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 trachea, bearing retainer, cylinder head cover, inlet manifold, water pipe impeller (waterpipe
Impeller), clutch lever, speaker diaphragm, heatproof container, microwave oven component, electric cooker parts, printer color tape
The electrical/electronic associated components that guider etc. are representative, automobile/vehicle associated components, household electrical appliances/office electric component, computer
Associated components, facsimile machine/photocopier associated components, machinery associated components, other various uses.
The present invention compared with prior art, has the advantages that
The present invention use there is the diamidogen of 11 carbon atoms as copolymerization component, and control diamidogen, diacid and lactams or
Amino acid whose ratio, is allowed to meet particular requirement, it is possible to obtain having be obviously improved color characteristics, low water absorption, good chi
The semi-aromatic copolyamide resin of very little stability, the polyamide moulding composition being made up of this semi-aromatic copolyamide resin
Also there is color characteristics, low water absorption and the good dimensional stability being obviously improved.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiment.
The method of testing of the fusing point of semi-aromatic copolyamide resin: with reference to ASTM D3418-2003, Standard
Test Method for Transition Temperatures of Polymers By Differential Scanning
Calorimetry；Concrete method of testing is: use the fusing point of Perkin Elmer Dimond dsc analysis instrument test sample；Nitrogen
Gas atmosphere, flow velocity is 40mL/min；First it is warming up to 340 DEG C with 10 DEG C/min during test, keeps 2min at 340 DEG C, then with 10
DEG C/min is cooled to 50 DEG C, then is warming up to 340 DEG C with 10 DEG C/min, and endotherm peak temperature now is set to fusing pointT m；
The method of testing of semi-aromatic copolyamide resin relative viscosity: with reference to GB12006.1-89, polyamide viscosity number mensuration side
Method；Concrete method of testing is: measure the phase of the polyamide that concentration is 10mg/ml in the concentrated sulphuric acid of the 98% of 25 DEG C ± 0.01 DEG C
To viscosities il r；
The method of testing of water absorption rate: sample is molded into the product of 20mm × 20mm × 2mm, its weight is designated as a0.Then by it
It is placed in 95 DEG C of water after 240h, weighs its weight and be designated as a1.Then water absorption rate=(a1-a0)/a0*100%。
The method of testing of shrinkage factor: sample is molded into the product of 20mm × 10mm × 2mm, is then placed on 95 DEG C of water
After middle 240h, according to the shrinkage factor after its water suction of ISO 294-4 standard testing.
The method of testing of semi-aromatic copolyamide resin (moulding compound) goods color: use colour table mould 50*30*
2mm, takes after 3000g polymer particle is molded, obtains the colour table of one-sided smooth.This colour table is placed in the precious Color-of reason
B value is obtained on Eye7000A Computer color testing instrument.This value can reflect semi-aromatic copolyamide resin (moulding compound) goods
Color, this value is the highest, illustrates that goods color is the poorest.
Semi-aromatic copolyamide Resin A-Q and the synthesis of A '-F '
In the ratio in table 1 in the autoclave pressure being furnished with magnetic coupling stirring, condensing tube, gas phase mouth, charge door, pressure explosion-proof mouth
Add reaction raw materials.Add benzoic acid, sodium hypophosphite and deionized water；The amount of benzoic acid species is all monomer molar amounts
2%-4%, sodium hypophosphite weight is the 1 ‰-5 ‰ of deionizing water other charged material weight outer, and deionized water weight is the weight that always feeds intake
The 25%-30% of amount；Evacuation is filled with high pure nitrogen as protection gas, is warmed up to 210 DEG C-230 under agitation 1-3 hour
DEG C, reactant mixture is stirred 0.5 hour-1.5 hours at 210 DEG C-230 DEG C, the most under agitation makes the temperature liter of reactant
High to 220 DEG C-240 DEG C；Reaction proceeds 1 hour-3 under the constant temperature of 220 DEG C-240 DEG C and the constant voltage of 2.0MPa-2.4MPa
Hour, keep pressure constant by removing formed water；Having reacted rear discharging, prepolymer is vacuum at 70 DEG C-90 DEG C
Being dried 22 hours-26 hours, obtain prepolymer product, described prepolymer product is less than fusing point 30 DEG C-60 DEG C, 40Pa-60Pa vacuum
Under the conditions of solid-phase tack producing, obtain semi-aromatic copolyamide resin.The relative viscosity of gained semi-aromatic copolyamide resin, molten
The performance indications such as point, water absorption rate, shrinkage factor and b value are shown in Table 1.
Table 1
| Resin A | Resin B | Resin C | Resin D | Resin E | Resin F | Resin G | Resin H | Resin I | Resin J | |
| 1,11-11 diamidogen/mol | 100 | 100 | 100 | 100 | 30 | 60 | 95 | 100 | 100 | 100 |
| 1,6-hexamethylene diamine/mol | 70 | 40 | 5 | |||||||
| 1,10-decanedioic acid/mol | 70 | 40 | 5 | |||||||
| 1,6-adipic acid/mol | ||||||||||
| P-phthalic acid/mol | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 30 | 60 | 95 |
| 11-aminoundecanoic acid/mol | 3.5 | 40 | 80 | 200 | 40 | 40 | 40 | 40 | 40 | 40 |
| Lauric lactam/mol | ||||||||||
| Caprolactam/mol | ||||||||||
| Fusing point/oC | 291 | 246 | 211 | 189 | 288 | 267 | 250 | 188 | 201 | 240 |
| Relative viscosity | 2.27 | 2.25 | 2.23 | 2.25 | 2.29 | 2.26 | 2.26 | 2.30 | 2.28 | 2.27 |
| Water absorption rate/% | 2.1 | 2.2 | 2.4 | 2.4 | 2.7 | 2.5 | 2.3 | 2.6 | 2.5 | 2.2 |
| Shrinkage factor/% | 0.2/1.0 | 0.3/0.9 | 0.3/0.8 | 0.2/0.9 | 0.3/0.9 | 0.4/0.9 | 0.2/0.9 | 0.3/1.0 | 0.3/0.8 | 0.2/0.9 |
| B value | -0.7 | -2.0 | -2.2 | -0.8 | -1.6 | -2.1 | -1.6 | -1.6 | -2.0 | -1.4 |
Continued 1
| Resin K | Resin L | Resin M | Resin N | Resin O | Resin P | Resin Q | Resin A ' | Resin B ' | Resin C ' | Resin D ' | Resin E ' | Resin F ' | |
| 1,11-11 diamidogen/mol | 40 | 80 | 100 | 100 | 100 | 100 | 100 | 100 | 10 | 100 | 100 | 100 | |
| 1,6-hexamethylene diamine/mol | 60 | 20 | 90 | ||||||||||
| 1,10-decamethylene diamine/mol | 100 | ||||||||||||
| 1,10-decanedioic acid/mol | 20 | 10 | 90 | ||||||||||
| P-phthalic acid/mol | 100 | 100 | 80 | 90 | 100 | 100 | 100 | 100 | 100 | 10 | 100 | 100 | 100 |
| 11-aminoundecanoic acid/mol | 40 | 40 | 40 | 40 | 400 | 40 | 40 | 40 | |||||
| Lauric lactam/mol | 3.5 | 40 | 200 | ||||||||||
| Caprolactam/mol | 40 | ||||||||||||
| Fusing point/oC | 271 | 259 | 242 | 250 | 289 | 243 | 209 | 191 | 293 | 188 | 300 | 255 | 251 |
| Relative viscosity | 2.29 | 2.25 | 2.33 | 2.29 | 2.25 | 2.24 | 2.22 | 2.32 | 2.31 | 2.22 | 2.35 | 2.28 | 2.27 |
| Water absorption rate/% | 2.7 | 2.4 | 2.4 | 2.3 | 2.2 | 2.3 | 2.5 | 2.5 | 3.9 | 2.2 | 2.1 | 3.6 | 2.3 |
| Shrinkage factor/% | 0.4/1.0 | 0.3/0.8 | 0.3/0.8 | 0.3/0.7 | 0.2/0.9 | 0.3/0.8 | 0.2/1.0 | 0.3/0.9 | 0.7/1.3 | 0.2/0.9 | 0.2/0.6 | 0.5/1.1 | 0.2/0.8 |
| B value | -2.2 | -2.0 | -2.1 | -2.2 | -0.8 | -2.1 | -0.6 | 2.4 | 4.0 | 1.3 | 1.1 | 2.7 | 2.2 |
As it can be seen from table 1 the semi-aromatic copolyamide resin that the application prepares have be obviously improved color characteristics,
Low water absorption, good dimensional stability.It addition, Resin A ' due to 11-aminoundecanoic acid too high levels, its color of resin is very poor；
Resin B ' due to 1,11-11 diamine contents is too low, causes its water absorption rate height, shrinkage factor height, simultaneously color very poor；Resin C '
Owing to terephthaldehyde's acid content is too low, color is the most poor；Resin D ' comprises only two kinds of monomer 1,11-11 diamidogen and terephthaldehyde
Acid, for the homopolymer of PA11T, its b value is higher, and color is poor；Resin E ' contains caprolactam monomer, caprolactam copolymer
Water absorption rate is higher, color is poor；Resin F ' is the copolymer of PA10T, and it has obvious inferior position equally in terms of color.
Embodiment 1-8 and comparative example 1-7: the preparation of polyamide moulding composition
By the formula of table 2 by uniform in high-speed mixer and mixing to semi-aromatic copolyamide resin, additive and/or other polymer
After, add in double screw extruder by main spout, reinforcer is fed by feeding scale side, side；Extrusion, crosses water cooling, pelletize
And obtain polyamide moulding composition after drying.Wherein, extrusion temperature is set as more than fusing point 20 DEG C.
In table 2 following table, each component is all weight percentage (%)
From table 2 it can be seen that the polyamide molding group that the semi-aromatic copolyamide resin that the application prepares prepares
Compound has color characteristics, low water absorption and the good dimensional stability being obviously improved.
Claims (13)
1. a semi-aromatic copolyamide resin, it is characterised in that by mole meter, including derived from following component
Repetitive:
(A) diamidogen, including
Amounts based on whole diamidogen, the 1 of 30mol%-100mol%, 11-11 diamidogen and 0-70mol% to have 4-36 carbon former
Other diamidogen of son；
(B) diacid, including
Amounts based on whole diacid, the p-phthalic acid of 30mol%-100mol% and 0-70mol% have 6-36 carbon atom
Other diacid；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% and/or aminoacid.
Semi-aromatic copolyamide resin the most according to claim 1, it is characterised in that by mole meter, including
Repetitive derived from following component:
(A) diamidogen, including
Amounts based on whole diamidogen, the 1 of 30mol%-95mol%, 11-11 diamidogen and 5mol%-70mol% have 4-36 carbon
Other diamidogen of atom；1,11-11 diamidogen of preferably 40mol%-80mol% and 20mol%-60mol% have 4-36 carbon
Other diamidogen of atom；
(B) amounts based on whole diacid, the p-phthalic acid of 100mol%；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% or aminoacid.
3. according to the semi-aromatic copolyamide resin described in claim 1, it is characterised in that by mole meter, including spreading out
It is conigenous the repetitive of following component:
(A) amounts based on whole diamidogen, the 1 of 100mol%, 11-11 diamidogen；
(B) diacid, including
Amounts based on whole diacid, the p-phthalic acid of 30mol%-95mol% and 5mol%-70mol% to have 6-36 carbon former
Other diacid of son；The p-phthalic acid of preferably 60mol%-90mol% and 10mol%-40mol% have 6-36 carbon atom
Other diacid；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% or aminoacid.
Semi-aromatic copolyamide resin the most according to claim 1, it is characterised in that by mole meter, including
Repetitive derived from following component:
(A) amounts based on whole diamidogen, the 1 of 100mol%, 11-11 diamidogen；
(B) amounts based on whole diacid, the p-phthalic acid of 100mol%；
(C) lactams or aminoacid, including
Amounts based on whole monomers, the lactams with 7-12 carbon atom of 1.5mol%-51mol% or aminoacid.
5. according to the semi-aromatic copolyamide resin described in any one of claim 1-4, it is characterised in that described component (C)
Lactams or aminoacid, amounts based on whole monomers, including 5mol%-30mol% the lactams with 7-12 carbon atom or
Aminoacid.
Semi-aromatic copolyamide resin the most according to claim 1 and 2, it is characterised in that described in there is 4-36 carbon
One or more in straight or branched aliphatic diamine, cycloaliphatic diamine, aryl aliphatic diamine of other diamidogen of atom；Described
Straight or branched aliphatic diamine selected from Putriscine, 1,5-pentanediamine, 2-methyl isophthalic acid, 5-pentanediamine (MPMD), 1,8-pungent two
Amine (OMDA), 1,9-nonamethylene diamine (NMDA), 2-methyl isophthalic acid, 8-octamethylenediamine (MODA), 2,2,4-trimethylhexamethylenediamines
(TMHMD), 2,4,4-trimethylhexamethylenediamines (TMHMD), 5-methyl isophthalic acid, 9-nonamethylene diamine, 1,11-hendecane diamidogen, 2-
Butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecamethylene diamine, 1,13-tridecane diamine, 1,14-tetradecane diamidogen, 1,
16-hexadecane diamidogen, 1, one or more in 18-octadecamethylene diamine；Described cycloaliphatic diamine selected from cyclohexanediamine, 1,3-is double
(amino methyl) hexamethylene (BAC), isophorone diamine, norcamphane dimethylamine, 4,4 '-diamino-dicyclohexyl methane
(PACM), 2,2-(4,4 '-diaminocyclohexyl) propane (PACP), 3,3 '-dimethyl-4,4 '-diaminocyclohexyl first
One or more in alkane (MACM)；Described aryl aliphatic diamine is selected from m-xylene diamine (MXDA).
7. according to the semi-aromatic copolyamide resin described in claim 1 or 3, it is characterised in that described in there is 6-36 carbon
Other diacid of atom selected from naphthalene dicarboxylic acids (NDA), isophthalic acid (IPS), adipic acid, suberic acid, Azelaic Acid, decanedioic acid, ten
One docosandioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid,
Dimer acids, cis and/or trans cyclohexane-Isosorbide-5-Nitrae-dicarboxylic acids, cis and/or trans cyclohexane-1,3-dicarboxylic acids (CHDA)
In one or more.
8. according to the semi-aromatic copolyamide resin described in any one of claim 1-5, it is characterised in that described in there is 7-12
The lactams of individual carbon atom or aminoacid are selected from α, omega-amino n-nonanoic acid, α, ω-aminoundecanoic acid (AUA), lauric lactam
(LL), one or more in omega-amino lauric acid/dodecanoic acid (ADA).
9. comprise a polyamide moulding composition for semi-aromatic copolyamide resin described in any one of claim 1-8,
By weight percentage, including following component:
A, semi-aromatic copolyamide resin 30wt%-100wt%；
B, reinforcer 0-70wt%；
C, additive and/or other polymer 0-50wt%；
Wherein, the percetage by weight sum of tri-kinds of components of a, b, c is 100wt%.
Polyamide moulding composition the most according to claim 9, it is characterised in that described reinforcer be shaped as fibre
Dimension shape, its average length is 0.01mm-20mm, preferably 0.1mm-6mm；Its draw ratio is 5:1-2000:1, preferably 30:1-
600:1；Gross weight based on polyamide moulding composition, the content of described reinforcer is 10wt%-50wt%, is preferably
15wt%-40wt%；Described reinforcer is inorganic reinforcing filler or organic reinforcing fillers, and described inorganic reinforcing filler is selected from glass
Fiber, potassium titanate fibre, metalclad glass fibre, ceramic fibre, wollastonite fibre, metallic carbide fibres, metal are solid
One or more of chemical fibre dimension, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum fiber or boron fibre, preferably glass
Fiber；Described organic reinforcing fillers is selected from aramid fibre and/or carbon fiber.
11. polyamide moulding compositions according to claim 9, it is characterised in that being shaped as of described reinforcer is non-
Threadiness, its mean diameter is 0.001 μm-100 μm, preferably 0.01 μm-50 μm, selected from potassium titanate crystal whisker, ZnOw,
Aluminium borate whisker, wollastonite, zeolite, sericite, Kaolin, Muscovitum, Talcum, clay, pyrophillite, bentonite, montmorillonite, lithium cover
De-soil, synthetic mica, asbestos, aluminosilicate, aluminium oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, ferrum oxide, calcium carbonate,
Magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride,
One or more of carborundum or silicon dioxide.
12. polyamide moulding compositions according to claim 9, it is characterised in that described additive contains fire retardant；Resistance
Combustion agent is halogenated flame retardant or halogen-free flame retardants, preferably halogen-free flame retardants；Described halogenated flame retardant is selected from brominated Polystyrene, bromine
Change polyphenylene oxide, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination benzene oxygen
Base resin, deca-BDE, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecane or brominated aromatic cross-linked polymeric
One or more of thing, preferably brominated Polystyrene；Described halogen-free flame retardants is selected from nitrogenous flame ratardant, phosphonium flame retardant or contains
One or more in the fire retardant of nitrogen and phosphorus, preferably phosphonium flame retardant；Gross weight based on polyamide moulding composition, institute
The content stating fire retardant is 0-40wt%.
13. polyamide moulding compositions according to claim 12, it is characterised in that described phosphonium flame retardant is selected from single phosphorus
Acid 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 ester, butylbenzene system phosphate ester, phosphinates one or more；Preferably there is following structure
Formulas I and/or the phosphinates of II:
In Formulas I and Formula II, R1And R2Can be identical, it is also possible to different, represent straight-chain or the C1-C6-alkane of branch-like respectively
Base, aryl or phenyl；R3Represent straight-chain or the C1-C10-alkylidene of branch-like, C6-C10-arlydene, C6-C10-alkyl Asia
Aryl, C6-C10-aryl alkylene；M represents calcium atom, magnesium atom, aluminum atom and/or zinc atom；M is 2 or 3, and n is 1 or 3, x
It is 1 or 2.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108559076A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN108559075A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN108586732A (en) * | 2018-04-08 | 2018-09-28 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it |
| WO2020238440A1 (en) * | 2019-05-24 | 2020-12-03 | 金发科技股份有限公司 | Semi-aromatic polyamide, method for synthesis thereof, and polyamide molding composition consisting thereof |
| CN112375376A (en) * | 2020-11-27 | 2021-02-19 | 上海金发科技发展有限公司 | Polyamide composition suitable for liquid-assisted molding and preparation method thereof |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
| CN115490848A (en) * | 2022-09-16 | 2022-12-20 | 珠海万通特种工程塑料有限公司 | Polyamide resin and polymerization method and application thereof |
| CN117203263A (en) * | 2020-10-29 | 2023-12-08 | 株式会社开绿化学 | Polyamide polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
| CN108559076A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN108559075A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN108586732A (en) * | 2018-04-08 | 2018-09-28 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it |
| WO2020238440A1 (en) * | 2019-05-24 | 2020-12-03 | 金发科技股份有限公司 | Semi-aromatic polyamide, method for synthesis thereof, and polyamide molding composition consisting thereof |
| CN117203263A (en) * | 2020-10-29 | 2023-12-08 | 株式会社开绿化学 | Polyamide polymer |
| CN117203263B (en) * | 2020-10-29 | 2024-03-08 | 株式会社开绿化学 | Polyamide polymer |
| CN112375376A (en) * | 2020-11-27 | 2021-02-19 | 上海金发科技发展有限公司 | Polyamide composition suitable for liquid-assisted molding and preparation method thereof |
| CN115490848A (en) * | 2022-09-16 | 2022-12-20 | 珠海万通特种工程塑料有限公司 | Polyamide resin and polymerization method and application thereof |
| CN115490848B (en) * | 2022-09-16 | 2023-12-19 | 珠海万通特种工程塑料有限公司 | Polyamide resin and polymerization method and application thereof |
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