CN108559076A - A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it - Google Patents

A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it Download PDF

Info

Publication number
CN108559076A
CN108559076A CN201810307404.3A CN201810307404A CN108559076A CN 108559076 A CN108559076 A CN 108559076A CN 201810307404 A CN201810307404 A CN 201810307404A CN 108559076 A CN108559076 A CN 108559076A
Authority
CN
China
Prior art keywords
acid
semi
aromatic polyamide
diamines
aromatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810307404.3A
Other languages
Chinese (zh)
Inventor
张传辉
曹民
王道波
姜苏俊
黄险波
常欢
阎昆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
Original Assignee
Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kingfa Science and Technology Co Ltd, Zhuhai Vanteque Speciality Engineering Plastics Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Priority to CN201810307404.3A priority Critical patent/CN108559076A/en
Publication of CN108559076A publication Critical patent/CN108559076A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of Semi-aromatic polyamide resins, including：a）Based on all two acid contents, other diacid of the terephthalic acid (TPA) of 70mol% 100mol% and 0 30mol%；b）Based on whole diamine contents, 1,6 hexamethylene diamines of the straight-chain aliphatic diamines and 0 90mol% containing 11 24 carbon atoms of 10mol% 100mol%；c）Amount based on whole diamines and diacid, the amino acid or lactams of 0 30mol%；d）Based on terephthalic acid units content, 0 10mol% contains the monocarboxylic acid of 2 24 carbon atoms；Also, the Semi-aromatic polyamide resin is derived from a there are three types of at least containing）、b）Or c）Repetitive unit.The present inventor has now surprisingly been found that, by using the straight-chain aliphatic diamines and diacid of 11 24 carbon atoms based on specific composition, obtained Semi-aromatic polyamide resin has excellent color；Simultaneously but also there is excellent color by the polyamide moulding composition that the Semi-aromatic polyamide resin forms.

Description

A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide being made from it Moulding compound
Technical field
The present invention relates to polymeric material field, more particularly to a kind of Semi-aromatic polyamide resin and preparation method thereof and The polyamide moulding composition being made from it.
Background technology
Polyamide is because having good comprehensive performance, including mechanical property, heat resistance, wear resistance, chemical resistance And self lubricity, and friction coefficient is low, there is certain anti-flammability, and it is easy to process etc., it is generally applied with glass fibre and its Its filler filling enhancing modified improves performance and expands application range.Semiaromatic polyamide composition was due to its heat resistance in recent years Can and mechanical property it is more excellent and by focus development.
Semiaromatic polyamide composition generally use melt polymerization or Solid State Tackifing Technique synthesis：Melt polymerization process flow letter It is single, but reaction temperature is more than fusing point, due to semiaromatic polyamide composition fusing point is higher, close to decomposition temperature, it is easy to there is heat drop The problems such as solution, and then molecular weight distribution is caused to be widened, resin property declines；Solid State Tackifing Technique is in the condition less than melting point resin Under the problem of being reacted, avoiding melt polymerization process resin decomposition, but due to polymer molecular chain under the conditions of solid-phase tack producing It cannot move freely, also result in the distribution of molecular resin amount and widen, influence processing performance.
Therefore, the molecular weight distribution problem of Semi-aromatic polyamide resin becomes the problem of urgent need to resolve.
The present inventor has now surprisingly been found that, by using the straight chain fatty of the 11-24 carbon atom based on specific composition Race's diamines and diacid, obtained Semi-aromatic polyamide resin have excellent color；Simultaneously but also by the semiaromatic adoption The polyamide moulding composition of amide resin composition has excellent color.
Invention content
In order to overcome the disadvantages and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of with excellent face The Semi-aromatic polyamide resin of color.
The present invention also provides a kind of based on the polyamide molding group being made of Semi-aromatic polyamide resin of the present invention Close object.
The present invention is achieved by the following technical solutions：
A kind of Semi-aromatic polyamide resin by mole percent, including is derived from repetitive unit below：
a）Based on all two acid contents, the terephthalic acid (TPA) of 70mol%-100mol% and other diacid of 0-30mol%；
b）Based on whole diamine contents, the straight-chain aliphatic diamines and 0- containing 11-24 carbon atom of 10mol%-100mol% The 1,6- hexamethylene diamines of 90mol%；
c）Amount based on whole diamines and diacid, the amino acid or lactams of 0-30mol%；
d）Based on terephthalic acid units content, 0-10mol% contains the monocarboxylic acid of 2-24 carbon atom；
Also, the Semi-aromatic polyamide resin is derived from a there are three types of at least containing）、b）Or c）Repetitive unit.
Wherein, the molecular weight distributing index of the Semi-aromatic polyamide resin is 1.5-4.0, preferably 2.0-3.0；It is described Molecular weight distributing index passes through gel permeation chromatography（GPC）Test obtains.
Wherein, the Semi-aromatic polyamide resin, by mole percent, component d）In, the monocarboxylic acid unit contains The ratio that amount accounts for terephthalic acid units content is 2 mol%-8mol%, preferably 3mol%-6mol%.
Wherein, component a）In, other two acid contents are 0.
Wherein, component b）In, the straight-chain aliphatic diamines containing 11-24 carbon atom is selected from 1,11- hendecanes two Amine, 1,12- dodecamethylene diamine, 1,13- tridecane diamine, one or more of 1,14- tetradecane diamines；Component a）In, institute It states other diacid and is selected from other aromatic dicarboxylic acids, aliphatic dicarboxylic acid or cycloaliphatic dicarboxylic acid with 6-36 carbon atom One or more of；Other aromatic dicarboxylic acids with 6-36 carbon atom be selected from naphthalene dicarboxylic acids NDA and/or Phthalic acid IPS；The aliphatic dicarboxylic acid with 6-36 carbon atom is selected from adipic acid, suberic acid, azelaic acid, the last of the ten Heavenly stems two Acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane two One or more of acid, dimer acids；The cycloaliphatic dicarboxylic acid with 6-36 carbon atom is selected from cis- and/or anti- One or more of formula hexamethylene-Isosorbide-5-Nitrae-dicarboxylic acids, cis- and/or trans cyclohexane -1,3- dicarboxylic acids CHDA；Component c） In, the amino acid or lactams are selected from caprolactam CPL, α, omega-amino caproic acid, α, omega-amino n-nonanoic acid, α, omega-amino ten One acid AUA, lauric lactam LL, α, one or more of omega-amino lauric acid/dodecanoic acid ADA；Component d）In, it is described to contain 2-24 The monocarboxylic acid of carbon atom is selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2 ethyl hexanoic acid, cyclohexylenedinitrilotetraacetic acid, benzene One or more of formic acid.
Wherein, component b）In, based on the mole percent of whole diamines, the content of 1, the 6- hexamethylene diamines is 20mol%- 80mol%, preferably 40mol%-60mol%.
Wherein, component b）In, based on the mole percent of whole diamines, the straight chain fat containing 11-24 carbon atom The content of 1,12- dodecamethylene diamines is 100mol% in fat race diamines.
Wherein, the semiaromatic polyamide composition tree of a concentration of 10mg/ml is measured in 25 DEG C ± 0.01 DEG C of 98% concentrated sulfuric acid The relative viscosity of fat is 1.7-2.8, preferably 1.85-2.45, more preferable 2.0-2.3.
Wherein, the fusing point of the Semi-aromatic polyamide resin be 260 DEG C -340 DEG C, preferably 280 DEG C -330 DEG C, more preferably 295℃-305℃。
Wherein, only there are one fusing points for the Semi-aromatic polyamide resin.
In addition, the invention also discloses the preparation method of above-mentioned Semi-aromatic polyamide resin, the preparation method is poly- Phosphorus-containing antioxidant is used during closing；The phosphorus-containing antioxidant is selected from double（2,4-dicumylphenyls）Pentaerythrite diphosphorous acid It is one or more of in ester Doverphos S-9228, BRUGGOLEN H10；It is preferably double（2,4-dicumylphenyls）Ji Wusi Alcohol diphosphites Doverphos S-9228.
A kind of polyamide moulding composition including above-mentioned Semi-aromatic polyamide resin, by weight percentage, including Following composition：
（a）The Semi-aromatic polyamide resin of 30wt%-99wt%；
（b）The reinforcing filler of 0-70wt%；
（c）The fire retardant of 0-50wt% and/or other polymer；
Wherein, component（a）+（b）+（c）=100wt%.
The component（b）Content be preferably 10wt%-50wt%, more preferably 15wt%-40wt%；
Reinforcing filler content is too low, causes daiamid composition mechanical property poor；Too high levels, polyamide compositions Tetramune table There is floating fine or gas line etc. in face, influences product appearance.
The shape of the reinforcing filler is threadiness, average length 0.01mm-20mm, preferably 0.1mm-6mm；Its Draw ratio is 5:1~2000:1, preferably 30:1~600:1, when threadiness reinforcing filler content within the above range when, polyamides The high temperature rigid that amine composition will show high heat distortion temperature and increase.
The reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers；
The inorganic reinforcing filler includes but are not limited to glass fibre, potassium titanate fibre, the glass fibre of clad, ceramics Fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, stone The one or more of cream fiber or boron fibre, preferably glass fibre；
The mouldability of daiamid composition not only can be improved using glass fibre, but also mechanical property can be improved and for example stretch by force Degree, bending strength and bending modulus, and heat distortion temperature when improving heat resistance for example thermoplastic resin composition molding.
The organic reinforcing fillers include but are not limited to aramid fibre and/or carbon fiber.
The shape of the reinforcing filler is Non-fibrous, such as powdered, graininess, plate, needle-shaped, fabric or felted, Its average grain diameter is 0.001 μm -100 μm, preferably 0.01 μm -50 μm.
When the average grain diameter of reinforcing filler is less than 0.001 μm of melt processable that will lead to polyamide difference；Work as enhancing The average grain diameter of filler is more than 100 μm, will lead to undesirable injection-molded article appearance.
The average grain diameter of above-mentioned reinforcing filler is measured by absorption method, may include but be not limited only to potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophillite, bentonite, Montmorillonite, lithium montmorillonite, synthetic mica, asbestos, alumino-silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, oxygen Change iron, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, pottery The one or more of porcelain bead, boron nitride, silicon carbide or silica.
These reinforcing fillers can be hollow；In addition, molten for bentonite, montmorillonite, lithium montmorillonite, synthetic mica etc. Swollen property phyllosilicate can use and interlayer ion is carried out to the organic montmorillonite after cationic exchange using organic ammonium salt.
In order to make daiamid composition obtain more excellent mechanical performance, can be used coupling agent to inorganic reinforcing filler into Row functional processing.
Wherein coupling agent includes but are not limited to isocyanates based compound, organosilan based compound, organic titanate Based compound, organo-borane based compound, epoxide；Preferably organosilan based compound；
Wherein, the organosilan based compound includes but are not limited to the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group, contains The alkoxysilane compound containing trialkylsilyl group in molecular structure of sulfydryl, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxy silane containing isocyanate group Compound, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, contains carbon-to-carbon insatiable hunger at the alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido With the alkoxysilane compound containing trialkylsilyl group in molecular structure of base, the one or more of the alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group includes but are not limited to γ-glycidoxypropyl group trimethoxy One kind of base silane, γ-glycidoxypropyl group triethoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane Or it is several；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl include but are not limited to γ mercaptopropyitrimethoxy silane and/or γ-Mercaptopropyltriethoxysilane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups includes but are not limited to γ-ureidopropyltriethoxysilane, γ-urea The one or more of base propyl trimethoxy silicane, the ends γ-(2- urea groups ethyl) aminocarbonyl propyl trimethoxy silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group includes but are not limited to γ-three ethoxy of isocyanate group propyl Base silane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-are different Cyanic acid ester group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group The one or more of ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido includes but are not limited to γ-(ends 2- amido ethyl) and holds aminocarbonyl propyl Methyl dimethoxysilane, the ends γ-(ends 2- amido ethyl) aminocarbonyl propyl trimethoxy silane, γ-end aminocarbonyl propyl trimethoxy The one or more of base silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl include but are not limited to γ-hydroxypropyl trimethoxy silane and/or γ-hydroxypropyl triethoxysilane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group includes but are not limited to γ-methacryloxy third Base trimethoxy silane, vinyltrimethoxysilane, N- β-(the N- vinyl benzyl cardinal extremity amidos ethyl) ends-γ-aminocarbonyl propyl The one or more of trimethoxy silane hydrochloride；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group includes but are not limited to 3- trimethoxy-silylpropyl ambers Acid anhydrides；
The organosilan based compound is preferably γ-methacryloxypropyl trimethoxy silane, the γ-(ends 2- amidos Ethyl) hold aminocarbonyl propyl methyl dimethoxysilane, the ends γ-(ends 2- amido ethyl) aminocarbonyl propyl trimethoxy silane, γ-end Aminocarbonyl propyl trimethoxy silane or 3- trimethoxy-silylpropyl succinic anhydrides.
Conventionally inorganic reinforcing filler can be surface-treated using above-mentioned organosilan based compound, Then itself and polyamide are subjected to melting mixing again, to prepare the daiamid composition.
Organosilicon methane series chemical combination can also be added directly while inorganic reinforcing filler and polyamide melting mixing Object carries out in-situ blending.
Wherein, the dosage of the coupling agent is the 0.05wt%-10wt% relative to inorganic reinforcing filler weight, preferably 0.1wt%-5wt%。
When the dosage of coupling agent is less than 0.05wt%, the effect of apparent improved mechanical properties is not achieved；Work as coupling agent Dosage be more than 10wt% when, inorganic reinforcing filler is easy to happen cohesion, and disperses undesirable risk in polyamide, Mechanical performance is eventually led to decline.
The additive include but are not limited to fire retardant, impact modifying agent, other polymer, processing aid one kind or It is several.
Commercially available additive, as stabilizer (such as ultra-violet stabilizer, heat stabilizer (inorganic and organic)), softening agent, Free radical scavenger, nucleating agent, polymerization adjuvant, dyestuff, fire retardant, filler, functional materials, lubricant, antistatic agent are (such as Flue dust), reinforce medicament (such as glass fibre, carbon fiber, mica, glass marble) and/or pigment or their compositions or mixing Object is mixed in polyamide blend moulding material as required.
By containing stabilizer, can not damage heat resistance, mobility, toughness, low water absorbable and rigidity etc. it is excellent In the case of the property of polyamide, obtain even if as daiamid composition heat resistance, mobility, toughness, low water absorbable and just Property is also excellent and resistance to thermochromism and the excellent daiamid composition of weatherability.
The stabilizer used in present embodiment is to include but are not limited to be stablized by phenol stabilizer, phosphorous acid esters At least one in the group that agent, hindered amines stabilizer, triazine type stabilizer, sulphur-containing stabilizer and inorganic phosphorated stabilizer form Kind.
These stabilizers can use one kind, can also be used in combination.
It as phenol stabilizer, is not particularly limited, can enumerate for example：Hindered phenol compound.
As hindered phenol compound, can enumerate for example：Bis- [3- (3, the 5- di-t-butyls-of N, N '-hexane -1,6- diyl 4- hydroxy phenylpropionyls amine)], pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], N ,-six methylenes of N ' Bis- [3- (3- tertiary butyl -5- methyl -4- the hydroxy benzenes of base bis- (3,5- di-t-butyl -4- hydroxyhydrocinnamamides), triethylene glycol Base) propionic ester], 3,9- bis- { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propargyl alcoholate] -1,1- dimethyl ethyls } - 2,4,8,10- tetra- oxaspiro [5.5] hendecanes, 3,5- di-tert-butyl-4-hydroxyl benzyls diethyl phosphonate, 1,3,5- trimethyls- 2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene and 1,3,5- tri- (4- tertiary butyl -3- hydroxyl -2,6- dimethylbenzyls Base) isocyanuric acid etc..
These phenol stabilizers can use one kind, can also be used in combination.
It as phosphite-type stabilisers, is not particularly limited, can enumerate for example：Three monooctyl ester of phosphorous acid, phosphorous acid three Lauryl, tridecyl phosphite, octyl diphenyl phosphite, triisodecyl phosphite ester, one benzene diisodecyl ester of phosphorous acid, phosphorous acid one Benzene two (tridecyl) ester, isooctyl diphenyl phosphite, diphenyl isophthalate, phosphorous acid hexichol (tridecyl) ester, Asia Triphenyl phosphate, phosphorous acid three (nonyl phenyl) ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, phosphorous acid three (2,4- bis- Tertiary butyl -5- aminomethyl phenyls) ester, phosphorous acid three (butoxyethyl group) ester, 4,4 '-fourths fork-bis- (3- methyl-6-tert butyl phenyl Four (tridecyls)) diphosphites, four (C12~C15 mixed alkyls) -4,4 '-isopropylidene diphenyl diphosphites, 4, 4 '-isopropylidenes bis- (2- tert-butyl-phenyls), two (nonyl phenyl) phosphite ester, phosphorous acid three (xenyl) ester, four (tridecanes Base) -1,1,3- tri- (2- methyl -5- tert-butyl-hydroxy phenyls) butane diphosphites, four (tridecyl) -4,4 '-fourths fork Bis- (3- methyl-6-tert butyl phenyl) diphosphites, four (C1~C15 mixed alkyls) -4,4 '-isopropylidene diphenyl, two phosphorous Acid esters, three (mono-, two- mixing nonyl phenyl) phosphite esters, 4,4 '-isopropylidenes bis- (2- tert-butyl-phenyls) two (nonyl benzenes Base) phosphite ester, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, three (3,5- di-tert-butyl-hydroxy phenyls) Phosphite ester, the poly- phosphite ester of 4,4 '-isopropylidene diphenyl of hydrogenation, bis- (octyl phenyls) bis- (bis- (3- first of 4,4 '-butanes Base -6- tert-butyl-phenyls)) 1,6- hexanols diphosphites, six (tridecyl) -1,1,3- tri- (2- methyl -4- hydroxyls -5- Tert-butyl-phenyl) butane triphosphite ester, three (4,4 '-isopropylidenes are bis- (2- tert-butyl-phenyls)) phosphite esters, three (1,3- is stearic Acyl-oxygen isopropyl) phosphite ester, 2,2- di-2-ethylhexylphosphine oxides (4,6- di-tert-butyl-phenyl) octyl phosphite ester, 2,2- di-2-ethylhexylphosphine oxides (3- methyl -4,6- di-tert-butyl-phenyl) -2- ethylhexyls phosphite ester, four (2,4- di-t-butyl -5- aminomethyl phenyls) -4, 4 '-biphenylene diphosphites and four (2,4- di-tert-butyl-phenyl) -4,4 '-biphenylene diphosphites etc..
These phosphite-type stabilisers can use one kind, can also be used in combination.
As phosphite-type stabilisers, pentaerythrite type bi-ester of phosphite can also be enumerated.
As pentaerythrite type bi-ester of phosphite, can enumerate for example：2,6- di-t-butyl -4- aminomethyl phenyl benzene Base pentaerythritol diphosphites, 2,6- di-t-butyl -4- methylphenylmethyls pentaerythritol diphosphites, 2,6- Di-t-butyl -4- aminomethyl phenyl 2- ethylhexyls pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyls Isodecyl pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyl lauryl pentaerythrite diphosphorous acids Ester, 2,6- di-t-butyl -4- aminomethyl phenyl isotridecyls pentaerythritol diphosphites, 2,6- di-t-butyl -4- first Base phenyl stearyl pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyl cyclohexyl pentaerythrites Diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyl benzyls pentaerythritol diphosphites, 2,6- di-t-butyls -4- Aminomethyl phenyl ethyl cellosolve pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyl butyl cards must Alcohol pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyl octyl phenyls pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyl nonyl phenyl pentaerythritol diphosphites, bis- (2,6- di-t-butyl -4- methyl Phenyl) pentaerythritol diphosphites, bis- (2,6- di-t-butyl -4- ethylphenyls) pentaerythritol diphosphites, 2,6- bis- Tertiary butyl -4- aminomethyl phenyls 2,6- di-tert-butyl-phenyls pentaerythritol diphosphites, 2,6- di-t-butyl -4- methylbenzenes Base 2,4- di-tert-butyl-phenyls pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyls 2,4- bis- is tertiary pungent Base phenyl pentaerythritol diphosphites, 2,6- di-t-butyl -4- aminomethyl phenyl 2- cyclohexyl phenyls pentaerythrite two Phosphite ester, 2,6-, bis- tertiary pentyl -4- methyl phenyl phenyls pentaerythritol diphosphites, bis- (2,6- bis- tertiary pentyl -4- Aminomethyl phenyl) pentaerythritol diphosphites and bis- (2,6- bis- t-octyl -4- aminomethyl phenyls) pentaerythritol diphosphites Deng.
These pentaerythrite type phosphite-type stabilisers can use one kind, can also be used in combination.
As pentaerythrite type bi-ester of phosphite, preferably bis- (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythrites Diphosphites, bis- (2,6- di-t-butyl -4- ethylphenyls) pentaerythritol diphosphites, bis- (2,6- bis- tertiary pentyl -4- first Base phenyl) pentaerythritol diphosphites and bis- (2,6- bis- t-octyl -4- aminomethyl phenyls) pentaerythritol diphosphites etc., More preferable bis- (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphites.
It as hindered amines stabilizer, is not particularly limited, can enumerate for example：4- acetoxyl groups -2,2,6,6- tetramethyls Phenylpiperidines, 4- stearoyl-oxies -2,2,6,6- tetramethyl piperidines, 4- acryloxies -2,2,6,6- tetramethyl piperidines, 4- (benzene Base acetoxyl group) -2,2,6,6- tetramethyl piperidines, 4- benzoyloxys -2,2,6,6- tetramethyl piperidines, 4- methoxyl groups -2,2, 6,6- tetramethyl piperidines, 4- tristearin oxygroups -2,2,6,6- tetramethyl piperidines, 4- cyclohexyloxies -2,2,6,6- tetramethyl piperidines, 4- Benzyloxy -2,2,6,6- tetramethyl piperidines, 4- phenoxy groups -2,2,6,6- tetramethyl piperidines, 4- (ethylcarbamoyl oxygroup) -2, 2,6,6- tetramethyl piperidines, 4- (cyclohexyl carboxyamide oxygroup) -2,2,6,6- tetramethyl piperidines, 4- (phenylcarbamoyl oxygen Base) -2,2,6,6- tetramethyl piperidines, bis- (2,2,6,6- tetramethyl -4- piperidyls) carbonic esters, bis- (2,2,6,6- tetramethyl -4- Piperidyl) oxalate, bis- (2,2,6,6- tetramethyl -4- piperidyls) malonates, bis- (2,2,6,6- tetramethyl -4- piperidyls) Sebacate, bis- (2,2,6,6- tetramethyl -4- piperidyls) adipate esters, bis- (2,2,6,6- tetramethyl -4- piperidyls) are to benzene Bis- (2,2,6,6- tetramethyl -4- piperidines the oxygroup)-ethane of dicarboxylic acid esters, 1,2-, α, bis- (2,2,6, the 6- tetramethyl -4- piperidines of α ' - Oxygroup) paraxylene, bis- (2,2,6,6- tetramethyl -4- piperidyls)-Toluene-2,4-diisocyanates, 4- diurethanes, bis- (2,2,6,6- tetra- Methyl -4- piperidyls)-hexa-methylene -1,6- diurethane, three (2,2,6,6- tetramethyl -4- piperidyls)-benzene -1,3, 5- front threes acid esters, three (2,2,6,6- tetramethyl -4- piperidyls)-benzene -1,3,4- front threes acid esters, 1- [2- { 3- (3,5- bis- tertiary fourths Base -4- hydroxy phenyls) propionyloxy } butyl] -4- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionyloxy] -2,2,6,6- Tetramethyl piperidine and 1,2,3,4- butane tetracarboxylic acid, 1,2,2,6,6- pentamethyl -4- piperidine alcohols and β, β, β ', β '-tetramethyls - The condensation product etc. of 3,9- [2,4,8,10- tetra- oxaspiro (5.5) hendecane] diethanols.
These hindered amines stabilizers can use one kind, can also be used in combination.
It as triazine type stabilizer, is not particularly limited, can enumerate for example：Hydroxyphenyltriazinuv class etc..
As hydroxyphenyltriazinuv class, can enumerate for example：2,4,6- tri- (2 '-hydroxyls -4 '-octyloxyphenyl) -1,3, 5- triazines, 2- (2 '-hydroxyls -4 '-Hexyloxy-phenyl) -4,6- diphenyl -1,3,5-triazines, 2- (2 '-hydroxyls -4 '-octyloxy benzene Base) -4,6- bis- (2 ', 4 ' -3,5-dimethylphenyl) -1,3,5-triazines, 2- (2 ', 4 '-dihydroxy phenyl) -4,6- bis- (2 ', 4 '-two Aminomethyl phenyl) -1,3,5-triazines, 2,4- bis- (2 '-hydroxyls -4 '-propoxyphenyl) -6- (2 ', 4 ' -3,5-dimethylphenyl) -1,3, 5- triazines, 2- (2- hydroxyl -4- octyloxyphenyls) -4,6- bis- (4 '-aminomethyl phenyl) -1,3,5-triazines, 2- (2 '-hydroxyls -4 ' - Dodecyloxy phenyl) -4,6- bis- (2 ', 4 ' -3,5-dimethylphenyl) -1,3,5-triazines, 2,4,6- tri- (2 '-hydroxyls -4 '-isopropyl Phenyl) -1,3,5-triazines, 2,4,6- tri- (2 '-hydroxyls -4 '-positive hexyloxy phenyl) -1,3,5-triazines and 2,4,6- tri- (2 '-hydroxyls -4 '-ethoxycarbonylmethoxy phenyl) -1,3,5-triazines etc..
These triazine type stabilizers can use one kind, can also be used in combination.
It as sulphur-containing stabilizer, is not particularly limited, can enumerate for example：(the 3- bay thiohydracrylic acids of pentaerythrite four Ester), 3,3 '-thiodipropionic acid dilauryls, 3,3 '-thiodipropionic acid, two myristin and 3,3 '-thiodipropionic acid distearyl esters etc..
These sulphur-containing stabilizers can use one kind, can also be used in combination.
It as inorganic phosphorated stabilizer, is not particularly limited, can enumerate for example：Phosphoric acid class, phosphorous acids and hypophosphorous acid Class and phosphate metal salt, phosphorous acid metallic salt and hypophosphorous acid metal salt etc..
As phosphoric acid class, phosphorous acids and hypophosphorous acid class, can enumerate for example：Phosphoric acid, phosphorous acid, hypophosphorous acid, burnt phosphorous Acid and diphosphorous acid etc..
As phosphate metal salt, phosphorous acid metallic salt and hypophosphorous acid metal salt, can enumerate for example：Above-mentioned phosphoric acid Etc. compounds and the 1st race's metal of the periodic table of elements salt.
As inorganic phosphorated stabilizer, preferably soluble compound, can enumerate for example：Sodium phosphate, sodium phosphite and secondary Sodium phosphate, more preferable sodium phosphite and sodium hypophosphite, further preferred sodium hypophosphite.
As inorganic phosphorated stabilizer, such as can be its hydrate (preferably hydrate (NaH of sodium hypophosphite2PO2· nH2O))。
These inorganic phosphorated stabilizers can use one kind, can also be used in combination.
The fire retardant is fire retardant or fire retardant and the fire-retardant composition for assisting agent, and content is preferably 10 ~ 40wt%； Flame retardant agent content is too low to cause flame retardant effect to be deteriorated, and flame retardant agent content is excessively high to cause material mechanical performance to decline.
The fire retardant is halogenated flame retardant or halogen-free flame retardants；
The halogenated flame retardant includes but are not limited to hexabromocyclododecane (HBCD), deca-BDE (DBDPO), octabromodiphenyl Ether, tetrabromobisphenol A (TBBA), bis- (tribromophenoxy) ethane, bis- (pentabromo- phenoxy group) ethane (BPBPE), tetrabromobisphenol A epoxy Resin (TBBA epoxies), tetrabromobisphenol A carbonic ester (TBBA-PC), ethylenebis (two formyl of tetrabromo-phthalic) imines (EBTBPI), Five bromo biphenyl of ethylenebis, three (tribromophenoxy) triazines (TTBPTA), bis- (dibromopropyl) tetrabromobisphenol As (DBP-TBBA), Bis- (dibromopropyl) tetrabromo-bisphenol s (DBP-TBBS), brominated polyphenylether (including poly- (two) bromobenzene ether etc.) (BrPPE), bromination are poly- Styrene (including polydibromstyrol, poly- phenylstilbene bromide, crosslinking brominated Polystyrene etc.) (BrPS), bromination crosslinked aromatic Polymer, brominated epoxy resin, bromination phenoxy resin, brominated styrene-copolymer-maleic anhydride, tetrabromo-bisphenol s (TBBS), Three (tribromo neopentyl) phosphates (TTBNPP), poly- trimethylammonium bromide phenyl indan (PBPI) and three (dibromopropyl) isocyanuric acid esters (TDBPIC) etc..
As halogenated flame retardant, the low, Yi Jibiao from the yield of the corrosive gas squeezed out or when the melt-processeds such as molding From the viewpoint of the mechanical properties such as existing anti-flammability, toughness and rigidity, preferably brominated polyphenylether (including poly- (two) bromobenzene ether etc.), bromine Change polystyrene (including polydibromstyrol, poly- phenylstilbene bromide, crosslinking brominated Polystyrene etc.), more preferable brominated polyphenylene second Alkene.
As brominated Polystyrene, it is not particularly limited, it can be for example, by styrene monomer be polymerize manufacture polyphenyl second By the phenyl ring bromination of polystyrene after alkene, or by brominated styrene monomer (bromstyrol, Dowspray 9, phenylstilbene bromide Deng) method of polymerization manufactures.
Bromine content in brominated Polystyrene is preferably 55wt%-75wt%.By the way that bromine content is set as 55wt% or more, Fire-retardant required bromine amount can be met with less brominated Polystyrene use level, it can be in the property do not damaged polyamide and had In the case of, obtain heat resistance, mobility, toughness, low water absorbable and stiff super and the excellent polyamide compositions of anti-flammability Object.In addition, by bromine content is set as 75wt% hereinafter, squeeze out or be molded etc. melt-processeds when be not easy to cause to thermally decompose, It can inhibit gas generation etc., the excellent daiamid composition of resistance to thermochromism can be obtained.
As the daiamid composition of halogen-containing flame retardant, flame retardant can also be contained, it is hereby achieved that anti-flammability More excellent daiamid composition.
It as the flame retardant used in present embodiment, is not particularly limited, can enumerate for example：Antimony oxide, The antimony oxides class such as antimony tetroxide, antimony pentoxide, sodium antimonate；The tin oxide such as tin monoxide, stannic oxide；Iron oxide, γ-oxygen Change the iron oxides such as iron；And zinc oxide, zinc borate, calcium oxide, aluminium oxide (alumina), aluminium oxide (boehmite), silica (silica), titanium dioxide, zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, oxidation The metal oxides such as copper and tungsten oxide；The metal hydroxides such as magnesium hydroxide and aluminium hydroxide；Aluminium, iron, titanium, manganese, zinc, molybdenum, cobalt, The metal powders such as bismuth, chromium, tin, antimony, nickel, copper and tungsten；The metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate and barium carbonate；Boric acid The metal borates such as magnesium, line borate and aluminium borate；And polysiloxanes；Deng.
These flame retardants can use one kind, can also be used in combination.
As the flame retardant being used together with halogen-containing flame retardant, from the viewpoint of flame resistance effect, preferably three oxygen Change the antimony oxides class such as two antimony, antimony tetroxide, antimony pentoxide, sodium antimonate；The tin oxide such as tin monoxide, stannic oxide；Oxidation The iron oxides such as iron, gamma-iron oxide；Zinc oxide and zinc borate etc., more preferable antimony oxide, antimony tetroxide, five oxidations two The antimony oxides such as antimony class or zinc borate, further preferred antimony oxide.
In order to improve flame retardant effect, it is preferable to use 0.01 μm -10 μm of average grain diameter flame retardant.
Average grain diameter can use laser diffraction and scattering particle size distribution device or accurate particle size distribution device into Row measures.
The halogen-free flame retardants includes but are not limited to nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus fire retardant It is one or more of；Preferably phosphonium flame retardant.
The phosphonium flame retardant includes but are not limited to monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkylphosphines Dimethyl phthalate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate, butylbenzene system phosphate or The one or more of phosphinates；Preferably phosphinates；
The compound that phosphinate salt compound is indicated using such as following formula I and/or II is representative.
In formula I and Formula II, R1And R2It may be the same or different, indicate the C1-C6- alkane of straight-chain or branch-like respectively Base, aryl or phenyl；R3Indicate that the C1-C10- alkylidenes, C6-C10- arlydene, C6-C10- alkyl of straight-chain or branch-like are sub- Aryl, C6-C10- aryl alkylenes；M indicates calcium atom, magnesium atom, aluminium atom and/or zinc atom；M is 2 or 3, and n is 1 or 3, x It is 1 or 2.
The more specific example of phosphinate salt compound includes dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethyl Phosphonic acids aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethyl Methyl-phosphinic acid zinc, diethyl phosphinic acids calcium, diethyl phosphinic acids magnesium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, methyl N-propyl phosphinic acids calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc, first are burnt Two (methyl-phosphinic acids）Calcium, methane two（Methyl-phosphinic acid）Magnesium, methane two（Methyl-phosphinic acid）Aluminium, methane two（Methyl time phosphine Acid）Zinc, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Calcium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Magnesium, benzene-Isosorbide-5-Nitrae-(dimethyl time phosphine Acid）Aluminium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid）Zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, aminomethyl phenyl time phosphine Sour aluminium, methylphenylphosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl time phosphine Sour zinc etc., preferably dimethylphosphinic acid calcium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid I beggars, second Ylmethyl phosphinic acids aluminium, ethylimethyphosphinic acid zinc, diethyl phosphinic acids calcium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, More preferable aluminum diethylphosphinate.
As phosphinates, the mechanical properties such as toughness of the molded product being molded from daiamid composition and rigidity and , it is preferable to use the grain size for being crushed to phosphinates is 100 μm of powder below from the viewpoint of appearance of molded articles, more preferably use It is crushed to 50 μm of powder below.
When powdered using 0.5 μm -20 μm（E）When phosphinates, the polyamides of performance high flame retardant can be not only obtained Amine composition, and the intensity of molded product significantly improves, therefore more preferably.
Average grain diameter can use laser diffraction and scattering particle size distribution device or accurate particle size distribution device into Row measures.
As phosphinates, it is not necessary to it is complete pure phosphinates, it can also how many remained unreacted objects or by-product.
Phosphinate salt compound as fire retardant can be obtained easily from market.The phosphinic acids salinization that can be obtained from market The example for closing object includes Clariant Corporation（Clariant）EXOLIT OP1230 of manufacture, OP1311, OP1312, OP930, OP935 etc..
The daiamid composition for including above-mentioned polyamide of the present invention, the gross weight based on polyamide moulding composition Amount, the additive component may also contain up to one or more of impact modifying agents of 45wt%；Preferably 5wt%- 30wt%。
Wherein, the impact modifying agent can be natural rubber, polybutadiene, polyisoprene, polyisobutene, butadiene And/or isoprene and styrene or with styrene derivative and with the copolymer of other comonomers, hydrogenated copolymer and/ By grafting or with acid anhydride,（Methyl）Prepared by acrylic acid or its ester are copolymerized copolymer；The impact modifying agent can also be Graft rubber with cross-linked elastomer core, the cross-linked elastomer core is by butadiene, isoprene or alkyl acrylate structure At, and with the graft shell being made of polystyrene or can be nonpolarity 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）Nonpolarity or polar olefin homopolymer or copolymer obtained from acrylic acid or the copolymerization of its ester；It is described Impact modifying agent can also be carboxylic acid functionalized copolymer, such as poly-（Ethylene -co-（Methyl）Acrylic acid）Or it is poly-（Ethylene -1- Alkene -co-（Methyl）Acrylic acid）, wherein 1- alkene is olefine or with the unsaturation more than 4 atoms（Methyl）Propylene Acid esters, including acid groups neutralize those of to a certain extent copolymer by metal ion.
Styrene-based monomer（Styrene and styrene derivative）With the impact modifying agent of other vi-ny l aromatic monomers, It is the block copolymer being made of alkenyl aromatic compounds and conjugated diene, and by alkenyl aromatic compounds and conjugation two The combination for the hydrogenated block copolymer and these type impact modifying agents that alkene is constituted.The block copolymer includes at least one Block a and at least one block b derived from conjugated diene of the kind derived from alkenyl aromatic compounds.It is total in hydrogenated diblock In the case of polymers, the ratio of aliphatic unsaturation carbon-to-carbon double bond is reduced by hydrogenation.Suitable block copolymer is that have Two, three, the four of linear chain structure and segmented copolymer.But branched and star structure can also be used according to the present invention.With Know that mode obtains branched block copolymer, such as arrives the graft reaction of main polymer chain by polymer " collateral chain ".
The other alkenyl aromatic chemical combination that can be used together with styrene or be used with the form of mixtures with styrene Object is in aromatic ring and/or the vi-ny l aromatic monomers replaced by C1-20 alkyl in C=C double bonds or by halogen atom.
The example of alkenyl aromatic monomer is styrene, p-methylstyrene, α-methylstyrene, ethyl styrene, uncle Butylstyrene, vinyltoluene, 1,2- diphenylethlenes, 1,1- diphenylethlenes, vinyl-dimethyl benzene, vinyltoluene, Vinyl naphthalene, divinylbenzene, bromostyrene and chlorostyrene, and combinations thereof.Optimization styrene, p-methylstyrene, α-methylstyrene and vinyl naphthalene.
It is preferable to use styrene, α-methylstyrene, p-methylstyrene, ethyl styrene, t-butyl styrene, ethylene The mixture of base toluene, 1,2- diphenylethlenes, 1,1- diphenylethlenes or these substances.Particularly preferably use benzene second Alkene.But it is also possible to use alkenyl naphthalene.
The example for the diolefinic monomer that can be used is 1,3-butadiene, 2- methyl-1s, 3- butadiene, 2,3- dimethyl- 1,3-butadiene, 1,3-pentadiene, 1,3- hexadienes, isoprene, chlorobutadiene and pentadiene.It is preferred that 1,3-butadiene and Isoprene, especially 1,3-butadiene (are hereinafter indicated with abbreviated form butadiene).
Used alkenyl aromatic monomer preferably includes styrene, and used diolefinic monomer preferably includes fourth two Alkene, it means that optimization styrene-butadiene block copolymer.The block copolymer is usually by anionic polymerisation with it It is prepared by mode known to body.
Other than styrene monomer and diolefinic monomer, other other monomers can also be used simultaneously.Based on being made The ratio of total amount, comonomer is preferably 0-50wt%, particularly preferably 0-30wt%, particularly preferably 0-15wt%.Properly The example of comonomer be acrylate respectively, especially acrylic acid C1~C12 Arrcostabs, such as n-butyl acrylate or third Olefin(e) acid 2- ethylhexyls and methacrylate, especially methacrylic acid C1~C12 Arrcostabs, such as methyl methacrylate Ester（MMA）.Other possible comonomers are（Methyl）Acrylonitrile,（Methyl）Glycidyl acrylate, vinyl methyl ether, Diallyl and divinyl ether, the divinylbenzene and vinyl acetate of dihydric alcohol.
Other than conjugated diene, if applicable, hydrogenated block copolymer also includes lower hydrocarbon part, such as second Alkene, propylene, 1- butylene, bicyclopentadiene or non-conjugated diene hydrocarbon.Unreduced aliphatic unsaturated bond derived from block b is in hydrogen The ratio changed in block copolymer is less than 50%, preferably smaller than 25%, especially less than 10%.Aromatic fractions derived from block a are also Original arrives at most 25% degree.Pass through the hydrogenation of styrene-butadiene copolymer and styrene-butadiene-styrene Hydrogenation, obtains hydrogenated block copolymer, i.e. styrene-（Ethylene/Butylene）Diblock copolymer and styrene-（Ethylene/Butylene）- Styrene triblock copolymer.
Block copolymer preferably comprises the block a of the block a, especially 50wt%-85wt% of 20wt%-90wt%.Alkadienes It can be orientated with 1,2- or Isosorbide-5-Nitrae-orientation is introduced into block b.
The molal weight of block copolymer is 5000g/mol-500000g/mol, preferably 20000g/mol-300000g/ Mol, especially 40000g/mol-200000g/mol.
Suitable hydrogenated block copolymer is the product that can be bought from the market, such as（Kraton polymer）G1650、 G1651 and G1652, and（Asahi Chemicals）H1041, H1043, H1052, H1062, H1141 and H1272.
The example of non-hydrogenated block copolymer is polystyrene-polybutadiene, polystyrene-poly（Ethylene-propylene）, polyphenyl Ethylene-polyisoprene gathers（α-methylstyrene）Polybutadiene, polystyrene-polybutadiene-polystyrene（SBS）, it is poly- Styrene-is poly-（Ethylene-propylene）Polystyrene, polystyrene-polyisoprene-polystyrene and poly-（α-methylstyrene） Polybutadiene-is poly-（α-methylstyrene）, and combinations thereof.
The suitable non-hydrogenated block copolymer that can be bought from the market has the trade mark to be（Phillips）、（Shell）、 （Dexco）With（Kuraray）Multiple product.
The daiamid composition for including above-mentioned polyamide of the present invention, the additive component can also include other Polymer, other polymer include but are not limited to fatty polyamide, amorphous polyamides, polyolefin homopolymer or second Alkene-alpha olefin copolymer, vinyl-acrylate copolymer.
The fatty polyamide includes but are not limited to aliphatic diacid and aliphatic two from 4~20 carbon atoms Amine either aliphatic diacid, aliphatic diamine and the lactams of the lactams of 4~20 carbon atoms or 4~20 carbon atoms Polymer in it is one or more.It includes but are not limited to, polyhexamethylene adipamide（PA66）, polycaprolactam（PA6）, it is poly- Hexamethylene sebacamide（PA610）, nylon 1010（PA1010）, adipic acid-hexamethylene diamine-caprolactam copolymer （PA66/6）, poly- 11 lactams（PA11）, nylon 12（PA12）And its two or more of mixtures.
The amorphous polyamides include but are not limited to M-phthalic acid/terephthalic acid (TPA)/1,6- hexamethylene diamines/bis-（3- first Base -4- aminocyclohexyls）Condensation polymer, the terephthalic acid (TPA)/2,2,4- trimethyls -1,6- hexamethylene diamines/2,4,4- trimethyls-of methane Condensation polymer, the M-phthalic acid/bis- of 1,6- hexamethylene diamines（3- methyl -4- aminocyclohexyls）The polycondensation of methane/omega-lauric lactam Object, the condensation polymer of M-phthalic acid/terephthalic acid (TPA)/1,6- hexamethylene diamines, M-phthalic acid/2,2,4- trimethyls -1,6- oneself two The condensation polymers of amine/2,4,4- trimethyl -1,6- hexamethylene diamines, M-phthalic acid/terephthalic acid (TPA)/2,2,4- trimethyls -1,6- oneself The polycondensation of the condensation polymer, M-phthalic acid/terephthalic acid (TPA)/other diamine components of diamines/2,4,4- trimethyl -1,6- hexamethylene diamines Object.Can be the raisings such as lustrous surface by adding non-crystalline polyamide.
The preferred EP elastomers of the ethene-alpha-olefin copolymer and/or EPDM elastomers（It is ethylene-propylene rubber respectively With ethylene/propylene/diene rubber）.For example, elastomer may include being based on containing 20wt%-96wt%, preferably 25wt%- The elastomer of the ethylene-C3 of 85wt% ethylene~C12- alpha olefin copolymers, wherein being particularly preferably C3~C12- α-alkene herein Hydrocarbon includes but are not limited to the alkene of propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene and/or 1- laurylenes, special Not preferably other polymer do not include the one or more of ethylene-propylene rubber, LLDPE, VLDPE.
Alternatively or additionally（Such as in the mixture）, other polymer can also include to be based on ethylene- The terpolymer of C3~C12- alpha-olefins and non-conjugated diene hydrocarbon, herein preferably its contain 25wt%-85wt% ethylene and At most maximum be 10wt% non-conjugated diene hydrocarbon, herein particularly preferred C3~C12- alpha-olefins include but are not limited to propylene, The alkene of 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 1- decene and/or 1- laurylenes, and/or wherein non-conjugated diene hydrocarbon are excellent Selection of land includes but are not limited to two rings [2.2.1] heptadiene, Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene and/or especially 5- ethylidene Norbornene.
Vinyl-acrylate copolymer is also used as the ingredient of other polymer.
Other possible forms of other polymer are ethylene-butene copolymer and the mixing comprising these systems respectively Object（Blend）.
Preferably, other polymer include the ingredient with anhydride group, these pass through trunk polymer and unsaturation Dicarboxylic anhydride, with unsaturated dicarboxylic or thermal response or radical reaction with the monoalkyl ester of unsaturated dicarboxylic, be enough with The concentration of polyamide good combination introduces.
As comprising α, the polymer of β unsaturated dicarboxylic acid acid anhydrides can be enumerated for example：Contain α, β unsaturation binary carboxylics Acid anhydrides is as the polymer of copolymer composition or with α, the polymer etc. of β unsaturated dicarboxylic acid anhydride modifications.
As α, β unsaturated dicarboxylic acid acid anhydrides can be enumerated for example：The compound that following general formula (1) indicates.
In general formula (1), R1And R2It is separately hydrogen or alkyl that carbon atom number is 1~3.
As α, β unsaturated dicarboxylic acid acid anhydrides can be enumerated such as maleic anhydride, methyl maleic anhydride, preferably Malaysia Acid anhydrides.
As α is contained, polymer of the β unsaturated dicarboxylic acids acid anhydride as copolymer composition can be enumerated for example：Aromatic series second Alkenyl compound and α, the copolymer etc. of β unsaturated dicarboxylic acid acid anhydrides.
As with α, the polymer of β unsaturated dicarboxylic acid anhydride modifications can be enumerated for example：With α, β unsaturation binary carboxylics Anhydride modified polyphenylene oxide resin or acrylic resin etc..
As include α, the polymer of β unsaturated dicarboxylic acid acid anhydrides, from improve anti-flammability efficiency（With less additive amount To show）From the viewpoint of, optimization aromatic vinyl compound and α, the copolymer of β unsaturated dicarboxylic acid acid anhydrides.
As the aromatic ethenyl compound used in present embodiment, such as following general formula (2) expression can be enumerated Compound.
In general formula (2), R3And R4It is separately hydrogen or the alkyl of carbon atom number 1~3, the integer that k is 1~5.
As aromatic ethenyl compound, can enumerate for example：Styrene, α-methylstyrene, p-methylstyrene Deng optimization styrene.
In present embodiment, contain aromatic ethenyl compound in the polymer comprising α, β unsaturated dicarboxylic acid acid anhydrides In the case of ingredient, it is believed that aromatic ethenyl compound ingredient and halogen-containing flame retardant（Brominated Polystyrene etc.）It is affine, separately Outer α, β unsaturated dicarboxylic acid anhydride component and polyamide are affine or react, and thereby assist in halogen-containing flame retardant and are distributed to polyamides In amido matter, so as to by halogen-containing flame retardant micro disperse.
Aromatic ethenyl compound and α, in the copolymer of β unsaturated dicarboxylic acid acid anhydrides aromatic ethenyl compound at Divide, α, the ratio of β unsaturated dicarboxylic acid anhydride components, considers from viewpoints such as anti-flammability, mobility, resistance to pyrolytics, it is preferably fragrant Fragrant race's vinyl compound ingredient is 50wt%-99wt%, α, and β unsaturated dicarboxylic acid anhydride components are 1wt%-50wt%.More preferably The ratio of α, β unsaturated dicarboxylic acid anhydride component is 5wt%-20wt%, further preferred 8wt%-15wt%.
By the way that the ratio of α, β unsaturated dicarboxylic acid anhydride components are set as 1wt% or more, toughness and rigidity can be obtained Equal mechanical properties and the excellent daiamid composition of anti-flammability.In addition, by by α, the ratio of β unsaturated dicarboxylic acid anhydride components Example is set as 50wt% hereinafter, can prevent by α, the deterioration of daiamid composition caused by β unsaturated dicarboxylic acid acid anhydrides.
Above-mentioned possible system for other polymer can also use as a mixture.
In addition, the additive component can include with functional group component, the functional group be, for example, carboxylic acid group, Ester group, epoxy group, oxazoline group, carbodiimide group, isocyanate groups, silanol and carboxylate group, Or the additive component can include the combination of two or more in above-mentioned functional group.List with the functional group Body can be combined by being copolymerized or being grafted on elastomeric polyolefin.
In addition, the impact modifying agent based on olefin polymer can also be changed by being grafted with unsaturated silane compound Property, the unsaturated silane compound is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, three second of vinyl Acyl silanes, methacryloxypropyl trimethoxy silane or acrylic trimethoxy silane.
Elastomeric polyolefin is have straight chain, branch or nucleocapsid random, alternately or block copolymer, and containing can With the functional group reacted with the end group of polyamide, enough tolerabilities are thus provided between polyamide and impact modifying agent.
Therefore, impact modifying agent of the invention includes alkene（Such as ethylene, propylene, 1- butylene）Homopolymer or copolymerization Object or alkene and copolymerisable monomer（Such as vinyl acetate,（Methyl）Acrylate and methyl hexadiene）Copolymer.
The example of crystalline olefin polymer be low-density, middle density and high density polyethylene (HDPE), polypropylene, polybutadiene, Poly- 4- methylpentenes, Ethylene-Propylene Block Copolymer or ethylene-propylene random copolymer, ethylene-methyl hexadiene copolymerization Object, propylene-methyl hexadiene copolymer, ene-propylene-butene copolymer, Ethylene-propylene-hexene Copolymer, ethylene-propylene- Methyl hexadiene copolymer gathers（Ethane-acetic acid ethyenyl ester）（EVA）, it is poly-（Ethylene-ethylacrylate）（EEA）, ethylene-octene Copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, ethylene/propylene/diene terpolymer and above-mentioned poly- Close the combination of object.
The commercially available impact modifying agent example that can be used for the additive component has：
TAFMER MC201：G-MA (- 0.6%) 67%EP copolymers (20mol% propylene)+33%EB copolymers (15mol%1- fourths 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 copolymers；Mitsui.
EXXELOR VA1801：G-MA (- 0.7%) EP copolymers；Exxon Mobile Chemicals, US.
EXXELOR VA1803：G-MA (0.5-0.9%) EP copolymers, amorphous, Exxon.
EXXELOR VA1810：G-MA (- 0.5%) EP copolymers, Exxon.
EXXELOR MDEX 941l：G-MA (0.7%) EPDM, Exxon.
FUSABOND MN493D：G-MA (- 0.5%) ethylene-octene copolymer, DuPont, US.
FUSABOND A EB560D：(g-MA) ethylene/n-butyl acrylate copolymer, DuPont ELVALOY, DuPont。
Also preferably ionomer, the wherein carboxyl of polymer-bound are all mutually bonded or are bonded by metal ion To a certain extent.
The copolymer of the particularly preferred graft-functionalized butadiene of maleic anhydride and styrene, by being grafted with maleic anhydride Nonpolarity or polar olefin homopolymer and copolymer obtained and carboxylic acid functionalized copolymer, such as poly- (ethylene-is total to (first Base) acrylic acid) or it is poly-（Ethylene -co- 1- alkene -co-s（Methyl）Acrylic acid）, wherein the acid groups to a certain extent by Metal ion neutralizes.
The polyamide moulding composition of present embodiment can use well known forming method, such as compression molding, injection molding Molding, gas assistant injection molding, fusion bonded forming, extrusion molding, blow molding, film forming, hollow molding, multi-layer forming with And melt spinning etc. obtains various molded products.
The present inventor has now surprisingly been found that, by using the straight chain fatty of the 11-24 carbon atom based on specific composition Race's diamines and diacid, obtained Semi-aromatic polyamide resin have excellent color；Simultaneously but also by the semiaromatic adoption The polyamide moulding composition of amide resin composition has excellent color.
Specific implementation mode
The test method of the fusing point of gained Semi-aromatic polyamide resin：With reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry；Specifically test method is：Using the fusing point of Perkin Elmer Diamond dsc analysis instrument test samples； 10 DEG C/min of heating rate.
The test method of gained Semi-aromatic polyamide resin relative viscosity：With reference to GB12006.1-89, polyamide viscosity number Assay method；Specifically test method is：The polyamides of a concentration of 10mg/ml is measured in 25 DEG C ± 0.01 DEG C of 98% concentrated sulfuric acid The relative viscosity η r of amine.
The test method of the molecular weight distributing index of gained Semi-aromatic polyamide resin refers to（Chang Jing, Gu Xueping, Feng Lian Virtue, Hu Guohua .MALDI-TOF MS are to analysis and characterization [J] the spectroscopy of indissoluble Nomex PA6T and spectrum analysis, and 2010, 30(01):159-164.）.Specially：0.5g samples are placed in conical flask, it is closed with the grinding port plug for being connected with rubber tube.Use nitrogen Gas replaces air 3-5 times in conical flask.Later dry dichloromethane 5ml and trifluoroacetic anhydride 2ml are sequentially added with syringe. After reaction for 24 hours, rotary evaporation removes the trifluoroacetic acid and dichloromethane of unreacted trifluoroacetic anhydride and generation at 30 DEG C Solvent, to obtain the polymer samples of trifluoroacetylation.The sample is dissolved in tetrahydrofuran and carries out GPC tests, can be divided Son amount profile exponent.
The characterization of gained Semi-aromatic polyamide resin and polyamide moulding composition（GanzWhiteness）：It first will be partly Aromatic polyamide resin or polyamide moulding composition are projecting pressure 2000kg/cm2, injection temperature is higher than melting point resin by 20 In the case of DEG C, by resin injection molding growth 5cm, wide 3cm, the colour table of thick 2mm, then in X-Rite after solid-phase tack producing GanzWhiteness option is directly selected on ColorEye 7000A colour photometers obtains the GanzWhiteness value WI of resin.WI values are bigger, face Color is whiter；WI values are smaller, and color of resin is poorer.
Embodiment 1-10 and comparative example 1-3：The synthesis of Semi-aromatic polyamide resin：
Equipped with magnetic coupling stirring, condenser pipe, gas phase mouth, charge door, pressure explosion-proof mouth autoclave pressure in the ratio in table Reaction raw materials are added, then the deionized water for accounting for total amount of feeding 30wt% is added thereto, and account for feed intake diamines and diacid weight The different phosphorus-containing antioxidants of 1wt ‰；It vacuumizes and is filled with high-purity argon gas as protection gas, start to react；Reaction mixture is heated up It is stirred -5 hours 3 hours to 220 DEG C -230 DEG C, then opening valve, slowly pressure release drains, while keeping temperature and pressure constant； It drains always to displacement and reaches the 70% of input amount of deionized water；It starts to warm up at this time, 250 DEG C -270 is warming up in 3 hours DEG C, constant temperature 2 hours；Valve discharging is opened after the completion of reaction, obtains prepolymer.
The fusing point that prepolymer is tested according to the method for test polyamide fusing point, is set as T DEG C.
After prepolymer is dried in vacuo 24 hours at 80 DEG C, using the mixed gas of carbon dioxide/vapor as protection Gas carries out solid-phase tack producing.It is warming up to first（T-70）DEG C, constant temperature -5 hours 1 hour；It is continuously heating to（T-50）DEG C, constant temperature 1 is small When -3 hours；Then it is cooled to again（T-60）DEG C, constant temperature -5 hours 1 hour；Finally it is warming up to（T-40）DEG C, constant temperature is until go out Material；It is constantly sampled in last thermostatic process, determines final polymerization terminal to get semiaromatic polyamide composition by sampling and testing viscosity Resin.The performance indicators such as fusing point, the relative viscosity of gained Semi-aromatic polyamide resin are listed in Table 1 below.
Table 1
Embodiment is can be seen that due to using the 11-24 carbon atom based on specific composition from the embodiment and comparative example of table 1 The Semi-aromatic polyamide resin that the structures such as straight-chain aliphatic diamines and diacid, specific comonomer, end-capping reagent obtain has Excellent color.And comparative example due to control Semi-aromatic polyamide resin in monomeric species or comonomer or end-capping reagent etc. no In range, the GanzWhiteness for the Semi-aromatic polyamide resin being prepared is relatively low, and color is bad.
Embodiment 11-20 and comparative example 4-7：The preparation of polyamide moulding composition
It is by the formula of table 2 that above-mentioned Semi-aromatic polyamide resin, fire retardant, other polymer is uniform in high-speed mixer and mixing Afterwards, it is added twin-screw extrude by main spout, reinforcing filler is fed by side feeding scale side；It squeezes out, crosses water cooling, be granulated And the polyamide moulding composition is obtained after drying.The GanzWhiteness performance indicator of gained polyamide moulding composition such as table 2 It is shown.
Table 2
　 Implement Example 11 Implement Example 12 Implement Example 13 Implement Example 14 Implement Example 15 Implement Example 16 Implement Example 17 Implement Example 18 Implement Example 19 Implement Example 20 Comparison Example 4 Comparison Example 5 Comparison Example 6 Comparison Example 7
Polyamide A B C F G A B C F G J M J M
Weight/wt% 50 50 50 50 50 60 60 60 60 60 50 50 60 60
Glass fibre OCV995/wt% 30 30 30 30 30 40 40 40 40 40 30 30 40 40
Phosphinates OP 1230/wt% 15 15 15 15 15 15 15
Wollastonite/wt% 3 3 3 3 3 3 3
PB Polybutene-1/wt% 2 2 2 2 2 2 2
GanzWhiteness 52 64 73 55 56 58 67 78 59 59 41 38 46 41
As can be seen from Table 2, the polyamide moulding composition obtained by the Semi-aromatic polyamide resin by 1 embodiment of table is sweet Thatch whiteness is high, has excellent color.

Claims (16)

1. a kind of Semi-aromatic polyamide resin by mole percent, including is derived from repetitive unit below：
a）Based on all two acid contents, the terephthalic acid (TPA) of 70mol%-100mol% and other diacid of 0-30mol%；
b）Based on whole diamine contents, the straight-chain aliphatic diamines and 0- containing 11-24 carbon atom of 10mol%-100mol% The 1,6- hexamethylene diamines of 90mol%；
c）Amount based on whole diamines and diacid, the amino acid or lactams of 0-30mol%；
d）Based on terephthalic acid units content, 0-10mol% contains the monocarboxylic acid of 2-24 carbon atom；
Also, the Semi-aromatic polyamide resin is derived from component a there are three types of at least containing）、b）Or c）Repetitive unit.
2. Semi-aromatic polyamide resin according to claim 1, which is characterized in that the Semi-aromatic polyamide resin Molecular weight distributing index be 1.5-4.0, preferably 2.0-3.0；The molecular weight distributing index passes through gel permeation chromatography （GPC）Test obtains.
3. according to claim 1-2 any one of them Semi-aromatic polyamide resins, which is characterized in that press mole percent Meter, component d）In, the ratio that the monocarboxylic acid unit content accounts for terephthalic acid units content is 2 mol%-8mol%, preferably 3mol%-6mol%。
4. according to claim 1-3 any one of them Semi-aromatic polyamide resins, which is characterized in that component a）In, it is described Other two acid contents are 0.
5. according to claim 1-4 any one of them Semi-aromatic polyamide resins, which is characterized in that component b）In, it is described Straight-chain aliphatic diamines containing 11-24 carbon atom be selected from 1,11- hendecane diamines, 1,12- dodecamethylene diamine, 1,13- ten Three alkane diamines, one or more of 1,14- tetradecane diamines；Component a）In, other diacid, which are selected from, has 6-36 carbon One or more of other aromatic dicarboxylic acids, aliphatic dicarboxylic acid or cycloaliphatic dicarboxylic acid of atom；It is described that there is 6-36 Other aromatic dicarboxylic acids of a carbon atom are selected from naphthalene dicarboxylic acids NDA and/or M-phthalic acid IPS；It is described that there is 6-36 carbon The aliphatic dicarboxylic acid of atom is selected from adipic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, 13 One or more of docosandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid, dimer acids；Institute State the cycloaliphatic dicarboxylic acid with 6-36 carbon atom be selected from cis- and/or trans cyclohexane-Isosorbide-5-Nitrae-dicarboxylic acids, it is cis- and/or One or more of trans cyclohexane -1,3- dicarboxylic acids CHDA；Component c）In, the amino acid or lactams select acyl in oneself Amine CPL, α, omega-amino caproic acid, α, omega-amino n-nonanoic acid, α, omega-amino undecanoic acid AUA, lauric lactam LL, α, omega-amino ten One or more of diacid ADA；Component d）In, the monocarboxylic acid containing 2-24 carbon atom is selected from acetic acid, propionic acid, fourth One or more of acid, valeric acid, caproic acid, lauric acid, stearic acid, 2 ethyl hexanoic acid, cyclohexylenedinitrilotetraacetic acid, benzoic acid.
6. according to claim 1-5 any one of them Semi-aromatic polyamide resins, which is characterized in that component b）In, it is based on The content of the mole percent of whole diamines, 1, the 6- hexamethylene diamines is 20mol%-80mol%, preferably 40mol%-60mol%.
7. according to claim 1-5 any one of them Semi-aromatic polyamide resins, which is characterized in that component b）In, it is based on The mole percent of whole diamines, 1,12- dodecamethylene diamines in the straight-chain aliphatic diamines containing 11-24 carbon atom Content is 100mol%.
8. according to claim 1-5 any one of them Semi-aromatic polyamide resins, which is characterized in that at 25 DEG C ± 0.01 DEG C 98% concentrated sulfuric acid in measure a concentration of 10mg/ml Semi-aromatic polyamide resin relative viscosity be 1.7-2.8, preferably 1.85-2.45, more preferable 2.0-2.3.
9. according to claim 1-8 any one of them Semi-aromatic polyamide resins, which is characterized in that the semiaromatic adoption The fusing point of amide resin is 260 DEG C -340 DEG C, preferably 280 DEG C -330 DEG C, more preferable 295 DEG C -305 DEG C.
10. according to claim 1-9 any one of them Semi-aromatic polyamide resins, which is characterized in that the semi-aromatic Only there are one fusing points for polyamide.
11. a kind of preparation method of such as claim 1-10 any one of them Semi-aromatic polyamide resins, which is characterized in that The preparation method uses phosphorus-containing antioxidant in the course of the polymerization process；The phosphorus-containing antioxidant is selected from double（2,4-dicumylphenyls） It is one or more of in pentaerythritol diphosphites Doverphos S-9228, BRUGGOLEN H10；It is preferably double（2,4-two Cumyl phenyl）Pentaerythritol diphosphites Doverphos S-9228.
12. a kind of polyamide moulding composition including claim 1-10 any one of them Semi-aromatic polyamide resins, It is characterized in that, by weight percentage, including form as follows：
（a）The Semi-aromatic polyamide resin of 30wt%-99wt%；
（b）The reinforcing filler of 0-70wt%；
（c）The fire retardant of 0-50wt% and/or other polymer；
Wherein, component（a）+（b）+（c）=100wt%.
13. polyamide moulding composition according to claim 12, which is characterized in that the shape of the reinforcing filler is fibre Tie up shape, average length 0.01mm-20mm, preferably 0.1mm-6mm；Its draw ratio is 5:1-2000:1, preferably 30:1- 600:1；The content of the reinforcing filler is 10wt%-50wt%, more preferably 15wt%-40wt%；The reinforcing filler is inorganic Reinforcing filler or organic reinforcing fillers, the inorganic reinforcing filler include but are not limited to glass fibre, potassium titanate fibre, metal The glass fibre of covering, ceramic fibre, wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, oxidation The one or more of aluminum fiber, silicon carbide fibre, gypsum fiber or boron fibre, preferably glass fibre；Organic enhancing is filled out Material includes but are not limited to aramid fibre and/or carbon fiber.
14. polyamide moulding composition according to claim 12, which is characterized in that the shape of the reinforcing filler is non- Threadiness, average grain diameter be 0.001 μm -100 μm, preferably 0.01 μm -50 μm, include but are not limited to potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophillite, bentonite, Montmorillonite, lithium montmorillonite, synthetic mica, asbestos, alumino-silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, oxygen Change iron, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, pottery The one or more of porcelain bead, boron nitride, silicon carbide or silica.
15. polyamide moulding composition according to claim 12, which is characterized in that the fire retardant is halogenated flame retardant Or halogen-free flame retardants, preferred halogen-free flame retardants；The halogenated flame retardant includes but are not limited to brominated Polystyrene, brominated polyphenylene Ether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, One kind of deca-BDE, decabromodiphenyl, brominated polycarbonate, three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer Or several, preferably brominated Polystyrene；The halogen-free flame retardants include but are not limited to nitrogenous flame ratardant, phosphonium flame retardant or Nitrogenous and phosphorus one or more of fire retardant, preferably phosphonium flame retardant；Total weight based on polyamide moulding composition, The content of the fire retardant is 10wt%-40wt%.
16. polyamide moulding composition according to claim 15, which is characterized in that the phosphonium flame retardant includes but not It is only limitted to monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenyl phosphate, phosphate trimethylbenzene The one or more of ester, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate, butylbenzene system phosphate, phosphinates；Preferably have The phosphinates of following structural formula I and/or II：
In Formulas I and Formula II, R1And R2It may be the same or different, indicate the C1-C6- alkane of straight-chain or branch-like respectively Base, aryl or phenyl；R3Indicate that the C1-C10- alkylidenes, C6-C10- arlydene, C6-C10- alkyl of straight-chain or branch-like are sub- Aryl, C6-C10- aryl alkylenes；M indicates calcium atom, magnesium atom, aluminium atom and/or zinc atom；M is 2 or 3, and n is 1 or 3, x It is 1 or 2.
CN201810307404.3A 2018-04-08 2018-04-08 A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it Pending CN108559076A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810307404.3A CN108559076A (en) 2018-04-08 2018-04-08 A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810307404.3A CN108559076A (en) 2018-04-08 2018-04-08 A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it

Publications (1)

Publication Number Publication Date
CN108559076A true CN108559076A (en) 2018-09-21

Family

ID=63534169

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810307404.3A Pending CN108559076A (en) 2018-04-08 2018-04-08 A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it

Country Status (1)

Country Link
CN (1) CN108559076A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111748203A (en) * 2020-07-03 2020-10-09 金旸（厦门）新材料科技有限公司 Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof
CN112679728A (en) * 2020-12-29 2021-04-20 南京开创新材料科技有限公司 Semi-aromatic polyamide resin and preparation method thereof
CN112745497A (en) * 2020-12-29 2021-05-04 南京开创新材料科技有限公司 Semi-aromatic polyamide resin and preparation method and application thereof
CN114058009A (en) * 2021-12-13 2022-02-18 山东广垠新材料有限公司 Process for preparing semi-aromatic polyamides with reduced loss of diamine monomer, semi-aromatic polyamides and molding compositions
CN114133560A (en) * 2021-12-13 2022-03-04 山东广垠新材料有限公司 Process for preparing semiaromatic polyamides with improved impact strength, semiaromatic polyamides and moulding compositions
CN115551921A (en) * 2020-05-07 2022-12-30 索尔维特殊聚合物美国有限责任公司 Impact-modified polyamide composition

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539936A (en) * 2012-07-03 2014-01-29 金发科技股份有限公司 Polyamide, synthesis method and application thereof, and polyamide product
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
CN106046365A (en) * 2016-07-15 2016-10-26 珠海万通特种工程塑料有限公司 Semi-aromatic copolyamide resin and polyamide molding composition made of semi-aromatic copolyamide resin
CN106117549A (en) * 2016-07-15 2016-11-16 珠海万通特种工程塑料有限公司 A kind of semi-aromatic copolyamide resin and consisting of polyamide moulding composition
CN106336659A (en) * 2016-08-31 2017-01-18 江门市德众泰工程塑胶科技有限公司 Polyamide composition applicable to high-power LED
CN107903392A (en) * 2017-10-13 2018-04-13 金发科技股份有限公司 A kind of Semi-aromatic polyamide resin and its moulding compound

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539936A (en) * 2012-07-03 2014-01-29 金发科技股份有限公司 Polyamide, synthesis method and application thereof, and polyamide product
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
CN106046365A (en) * 2016-07-15 2016-10-26 珠海万通特种工程塑料有限公司 Semi-aromatic copolyamide resin and polyamide molding composition made of semi-aromatic copolyamide resin
CN106117549A (en) * 2016-07-15 2016-11-16 珠海万通特种工程塑料有限公司 A kind of semi-aromatic copolyamide resin and consisting of polyamide moulding composition
CN106336659A (en) * 2016-08-31 2017-01-18 江门市德众泰工程塑胶科技有限公司 Polyamide composition applicable to high-power LED
CN107903392A (en) * 2017-10-13 2018-04-13 金发科技股份有限公司 A kind of Semi-aromatic polyamide resin and its moulding compound

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115551921A (en) * 2020-05-07 2022-12-30 索尔维特殊聚合物美国有限责任公司 Impact-modified polyamide composition
CN111748203A (en) * 2020-07-03 2020-10-09 金旸（厦门）新材料科技有限公司 Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof
CN112679728A (en) * 2020-12-29 2021-04-20 南京开创新材料科技有限公司 Semi-aromatic polyamide resin and preparation method thereof
CN112745497A (en) * 2020-12-29 2021-05-04 南京开创新材料科技有限公司 Semi-aromatic polyamide resin and preparation method and application thereof
CN114058009A (en) * 2021-12-13 2022-02-18 山东广垠新材料有限公司 Process for preparing semi-aromatic polyamides with reduced loss of diamine monomer, semi-aromatic polyamides and molding compositions
CN114133560A (en) * 2021-12-13 2022-03-04 山东广垠新材料有限公司 Process for preparing semiaromatic polyamides with improved impact strength, semiaromatic polyamides and moulding compositions
CN114058009B (en) * 2021-12-13 2023-11-10 山东广垠新材料有限公司 Process for the preparation of semi-aromatic polyamides with reduced diamine monomer loss, semi-aromatic polyamides and molding compositions
CN114133560B (en) * 2021-12-13 2024-03-08 山东广垠新材料有限公司 Process for the preparation of semiaromatic polyamides with improved impact strength, semiaromatic polyamides and moulding compositions

Similar Documents

Publication Publication Date Title
CN108559076A (en) A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it
CN108586732A (en) A kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it
CN106117549B (en) A kind of semi-aromatic copolyamide resin and the polyamide moulding composition being made from it
CN104211953A (en) Polyamide resin and polyamide composition containing same
CN104672444B (en) A kind of polyamide and consisting of daiamid composition
JP6492199B2 (en) Semi-aromatic copolyamide resin and polyamide molding composition produced therewith
CN107903392B (en) A kind of Semi-aromatic polyamide resin and its moulding compound
CN107057343A (en) A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it
CN110294842A (en) A kind of semiaromatic polyamide composition and its synthetic method and the polyamide moulding composition being made from it
CN106046365A (en) Semi-aromatic copolyamide resin and polyamide molding composition made of semi-aromatic copolyamide resin
CN104804430B (en) A kind of polyamide moulding composition
CN104804429B (en) A kind of polyamide and the daiamid composition being made from it
CN104744688B (en) A kind of polyamide and consisting of polyamide moulding composition
CN104804186B (en) A kind of polyamide and the daiamid composition being made from it
CN104693438B (en) A kind of polyamide and consisting of polyamide moulding composition
CN107057345A (en) A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it
CN107759786A (en) A kind of semiaromatic polyamide composition and preparation method thereof and the polyamide moulding composition being made from it
CN104592509A (en) Low-pH value polyamide molding composition
WO2018049808A1 (en) Semi-aromatic copolyamide resin and polyamide molding composition consisting of semi-aromatic copolyamide resin
CN108586733A (en) A kind of Semi-aromatic polyamide resin and the polyamide moulding composition being made from it
CN107057342A (en) A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it
CN107057344A (en) A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it
CN104804426B (en) A kind of polyamide moulding composition
CN104804414B (en) A kind of polyamide moulding composition
CN108559075A (en) A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20180921