CN107459807A - A kind of PPO/LCP/PET ternary-alloy materials and preparation method thereof - Google Patents

A kind of PPO/LCP/PET ternary-alloy materials and preparation method thereof Download PDF

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CN107459807A
CN107459807A CN201710744086.2A CN201710744086A CN107459807A CN 107459807 A CN107459807 A CN 107459807A CN 201710744086 A CN201710744086 A CN 201710744086A CN 107459807 A CN107459807 A CN 107459807A
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parts
ternary
ppo
pet
lcp
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王强
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Guangdong New Material Polytron Technologies Inc
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Guangdong New Material Polytron Technologies Inc
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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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to technical field of polymer materials, and in particular to a kind of PPO/LCP/PET ternary-alloy materials and preparation method thereof.The ternary-alloy material includes the raw material of following parts by weight：10 40 parts of liquid crystal polymers, 10 40 parts of polyphenylene oxide, 10 40 parts of polyethylene terephthalates, 5 40 parts of glass fibres, 3 15 parts of compatilizers, 3 15 parts of fire retardants, 0.1 0.5 parts of antioxidant, 0.2 2 parts of lubricants and 12 parts of modifying agent.The ternary-alloy material of the present invention has the mechanical properties such as excellent toughness, impact strength, tensile strength, bending strength, and fire protecting performance is good, heat-resist, and water absorption rate is low, good stability of the dimension, crystalline rate is high, and processability is good, processing characteristics is good, and cost is low, and use value is high；The preparation method of the present invention is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, is adapted to large-scale industrial production.

Description

A kind of PPO/LCP/PET ternary-alloy materials and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of PPO/LCP/PET ternary-alloy materials and its Preparation method.
Background technology
Polyphenylene oxide（PPO）Strand due to containing substantial amounts of benzene ring structure, therefore there is good physical property, it is water-fast Good, the good stability of the dimension of property, and due to not having highly polar group in polyphenyl ether structure, therefore have good electrical property, by frequency, The influence very little of temperature and humidity, but the glass transition temperature of polyphenylene oxide it is higher, up to 210 DEG C, heat distortion temperature is up to 190 DEG C, melt fluidity is poor, and processing and forming is difficult, therefore current market sales of PPO products, and most of is all the production after being modified Product.
PPO/PA alloys are also a kind of PPO modified products of the comparative maturity of exploitation, and it is excellent that PPO/PA alloys had both maintained PPO Good physical and mechanical property, electrical property and heat resistance, it may have good stress cracking resistance, resistance to dissolubility and shaping specific to PA Processing characteristics.But PPO/PA belongs to Immiscible Polymer Blends, it is necessary to add compatilizer, could improve the compatibility of co-mixing system, so as to Its mechanical property is improved, although the modified pure PA of PPO/PA alloy ratios water absorption rate is low, the overall suction of PPO/PA alloys Water-based still higher, size and physical property are influenceed bigger by absorbing water, thus are difficult to for being molded large-scale precision product.
And polyethylene terephthalate（PET）For hypocrystalline blend, its crystallization rate is relatively low, in injection moulding process In, occur sticking to mould, the difficult demoulding because PET is not crystallized completely, rise during the demoulding（There is not plane in product surface）, top it is white（Product There is albefaction shape）Deng the bad phenomenon of injection so that formed product is poor, heat resistance is low, processing characteristics is low made from last Etc. bad problem.
The content of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide a kind of PPO/LCP/ PET ternary-alloy materials, the PPO/LCP/PET ternary-alloy materials have excellent toughness, impact strength, tensile strength, The mechanical properties such as bending strength, temperature tolerance is good, and water absorption rate is low, good stability of the dimension, and crystalline rate is high, and processability is good, processing Performance is good, and cost is low, and use value is high.
Another object of the present invention is to provide a kind of preparation method of PPO/LCP/PET ternary-alloy materials, the preparation Method is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, is adapted to large-scale industrial production.
The purpose of the present invention is achieved through the following technical solutions：A kind of PPO/LCP/PET ternary-alloy materials, the ternary are closed Golden material includes the raw material of following parts by weight：
Liquid crystal polymer 10-40 parts
Polyphenylene oxide 10-40 parts
Polyethylene terephthalate 10-40 parts
Glass fibre 5-40 parts
Compatilizer 3-15 parts
Fire retardant 5-15 parts
Antioxidant 0.1-0.5 parts
Lubricant 0.2-2 parts
Modifying agent 1-2 parts.
The PPO/LCP/PET ternary-alloy materials of the present invention cooperate by using above-mentioned raw materials, between each raw material to be made With, concerted reaction, it can make obtained PPO/LCP/PET ternary-alloy materials that there is excellent impact resistance, tensile strength, bending The mechanical properties such as intensity, fire protecting performance is good, heat-resist, and crystalline rate is high, and processability is good, and processing characteristics is good, and cost is low, makes With value, while there is relatively low water absorption rate, PPO/LCP/PET ternary-alloy materials is still had in wet environment excellent Size and physical property, good stability of the dimension, original size and physical property will not be changed because of wet environment, available for doing Postulate the fields such as standby, automobile decoration, electronic apparatus, in the wet environment for being equally applicable to have material higher force requirement, and Using both LCP and PPO, PBT crystalline rate is improved in the presence of both LCP and PPO, makes PET crystallizations more abundant, complete Entirely, solve PET material crystallization it is incomplete caused by sticking to mould, difficult be stripped, rise, pushing up the problems such as white.
Wherein, by using liquid crystal polymer, the water absorption rate of alloy material system can be effectively reduced, and liquid crystal polymer has There are the performances such as preferable toughness, weatherability, impact strength, anti-flammability, hydrolytic resistance, effectively improve the mechanical property of alloy material Energy；The glass fibre of use has preferable dielectricity and heat resistance, and hygroscopicity is small, improves PPO/LCP/PET ternary alloy three-partalloys The mechanical properties such as the impact resistance of material, tensile strength, bending strength；By using compatilizer, reduce between each raw material Interfacial tension, the interface cohesive force between each raw material is improved, improve the compatible work of PPO/LCP/PET ternary-alloy materials With；By using fire retardant, make PPO/LCP/PET ternary-alloy materials that there is excellent fire protecting performance；By using antioxidant, The thermal-oxidative degradation degree of PPO/LCP/PET ternary-alloy materials can be effectively reduced, preferable mechanical property can be kept for a long time；It is logical Cross and use lubricant, internal lubrication and external lubrication are played a part of to PPO/LCP/PET ternary-alloy materials, improve PPO/ The processability and processing characteristics of LCP/PET ternary-alloy materials；By using modifying agent, the hard of PPO/LCP/PET is improved The mechanical property such as degree, shock resistance hardness, tensile strength, toughness.Preferably, the polyethylene terephthalate used is PET Section, and viscosity is 0.6-1.0dL/g, the glass fibre used is alkali-free roving long glass fibres or alkali-free roving Short glass fiber.
Preferably, the structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number in 1-18, R2The aryl for being 6-20 for carbon number, R3For halogen atom, R4For hydrogen Atom.
The present invention can have PPO/LCP/PET ternary-alloy materials preferable by using the polyphenylene oxide of mentioned kind Water resistance, dimensional stability, and water absorption rate is low, remains to keep preferable mechanical property and dimensional stability in wet environment.
Preferably, the liquid crystal polymer be molecular weight in 5000-80000, characteristic density in 1.35-1.45g/cm3's TLCP.The present invention strictly controls the molecular weight of liquid crystal polymer by using TLCP And density, the water absorption rate of alloy material system can be effectively reduced, the toughness of raising alloy material system, weatherability, shock resistance are strong The performances such as degree, anti-flammability, hydrolytic resistance.
Preferably, the polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether, gather（2- methyl -6- ethyl-Isosorbide-5-Nitraes - Phenylene）Ether and poly-（2,6- diethyl-Isosorbide-5-Nitrae-phenylene）At least one of ether.
The present invention can have PPO/LCP/PET ternary-alloy materials preferable by using the polyphenylene oxide of mentioned kind Water resistance, dimensional stability, and water absorption rate is low, remains to keep preferable mechanical property and dimensional stability in wet environment. Preferably, the polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether and poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene） Ether is using weight ratio as 2.5-3.5:The mixture of 1 composition；Another preferable, the polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-Asia Phenyl）Ether.
Preferably, the compatilizer is that the polystyrene blend containing epoxide group or the polystyrene containing anhydride group are total to Mixed thing；The polystyrene blend containing anhydride group is styrene-grafted maleic anhydride and styrene-acrylonitrile-maleic acid At least one of anhydride copolymer；The polystyrene blend containing epoxide group is hydrogenated styrene-butadiene-styrene Copolymer grafted GMA, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate, ethene- Acrylic acid-butyl ester graft glycidyl methacrylate and the acrylonitrile copolymer grafted methacrylic acid of styrene one shrink sweet At least one of grease.
The present invention can effectively reduce the interface between PPO, LCP, PET three by using the compatilizer of mentioned kind Power, the interface cohesive force between PPO, LCP, PET three is improved, and then improve the phase of PPO/LCP/PET ternary-alloy materials Appearance acts on.Preferably, the compatilizer is that styrene-grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer connect Branch GMA, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and ethylene-acrylic acid- At least one of butyl ester graft glycidyl methacrylate；It is more highly preferred to, the compatilizer is styrene-grafted horse Come acid anhydrides, hydrogenated styrene-butadiene-styrene copolymer grafted GMA, ethylene-acrylic acid-first Ester graft glycidyl methacrylate and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate are with weight ratio For 1.2-1.8:2.5-3.5:1:1.6-2.2 the mixture of composition.
Preferably, the fire retardant is sodium antimonate, bromide fire retardant or organophosphorus ester based flame retardant；The bromine system is fire-retardant Agent is brominated Polystyrene, brominated epoxy resin, TDE, 2,4,6- tribromo-benzenes, double (the 2,4,6- tribromo-benzenes of 1,2- Epoxide) ethane, 1,2- double (pentabromo- phenoxy group) ethane, 2,4,6- tribromos phenyl allyl ether, tetrabromophthalic anhydride, 1,2- At least one of double (pi-allyl) ethers (four bromo-ethers) of double (tetrabromo phthalimide) ethane and tetrabromobisphenol A；It is described to have Machine phosphate ester flame retardants are triphenyl phosphate, tetraphenyl resorcinol group bisphosphate, bisphenol-A tetraphenylphosphonium acid esters, alcohol alkane Base aryl phosphate ester, aromatic diphosphate, Polyphenyl phosphate, tricresyl phosphate（α-chloroethyl）Ester and tricresyl phosphate（Bis- chloro- 2- of 1,3- Propyl group）At least one of ester.
The bromide fire retardant that the present invention uses can improve the fire protecting performance of PPO/LCP/PET ternary-alloy materials, and bromine system The dosage of fire retardant is fewer, and flame retarding efficiency is higher, smaller to the performance impact of PPO/LCP/PET ternary-alloy materials, and uses Phosphate ester flame retardants can be dissolved each other with PPO, LCP, PET three, improve the fire-retardant effect of PPO/LCP/PET ternary-alloy materials Fruit.Preferably, the fire retardant is sodium antimonate, 1,2- double (tetrabromo phthalimide) ethane, tetraphenyl resorcinol groups Bisphosphate and brominated epoxy resin are using weight ratio as 2.5-3.5:0.8-1.2：1.6-2.4:The mixture of 1 composition.
Preferably, the antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate, four [methyl-β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester] pentaerythritol ester, the double diphosphites two of pentaerythrite（2, 4- di-tert-butyl-phenyls）Ester, N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5- tri- (3,5- Di-tert-butyl-hydroxy phenyl) isocyanates, three (2,4- di-tert-butyl-phenyl) phosphite esters, 1,3,5- tri-（3,5- tertiary fourths Base -4- hydroxybenzyls）Trimethylbenzene, β-（3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl, 2,6- di-t-butyls pair Cresols and four（2,4- di-tert-butyl-phenyl -4,4 '-xenyl）At least one of biphosphonate.
Antioxidant of the invention by using mentioned kind, it can effectively reduce the heat of PPO/LCP/PET ternary-alloy materials Oxygen palliating degradation degree, the hydrolysis and degraded for effectively avoiding PET from occurring at high temperature by the presence of minor amount of water, and improve PPO, LCP Inoxidizability, make PPO/LCP/PET ternary-alloy materials that there is preferable inoxidizability, extend service life.Preferably, The antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanates, four [methyl-β-（3,5- bis- tertiary fourths Base -4- hydroxy phenyls）Propionic ester] pentaerythritol ester, β-（3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl and season The double diphosphites two of penta tetrol（2,4- di-tert-butyl-phenyls）Ester is using weight ratio as 1.6-2.4:2.5-3.5：1:1.0-1.5 group Into mixture.
Preferably, the lubricant is pentaerythritol stearate, silicone powder, hydrogenation ethylenebisstearamide, poly- second At least one of alkene wax and N, N '-ethylenebisstearamide.
The present invention plays internal lubrication by using the lubricant of mentioned kind to LCP/PBT/PET ternary-alloy materials With the effect of external lubrication, the processability and processing characteristics of LCP/PBT/PET ternary-alloy materials are improved.Preferably, institute Lubricant is stated to be silicone powder and hydrogenate ethylenebisstearamide using weight ratio as 1.4-2.2：The mixture of 1 composition.
Preferably, the modifying agent is the talcum powder with layer structure, and the draw ratio of the talcum powder is 10-25.This Invention by using talcum powder as modifying agent, and strictly control talcum powder structure and draw ratio, PPO/ can be effectively improved The mechanical properties such as the hardness of LCP/PET ternary-alloy materials, shock resistance hardness, tensile strength, bending strength.
Preferably, the ternary-alloy material also includes 0.5-2 part coupling agents, and the coupling agent is silane coupler or titanium Acid esters coupling agent；The silane coupler is γ aminopropyltriethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy Base silane, 3- TSL 8330s, γ-methacryloxypropyl trimethoxy silane, N- (β-ammonia second Base)-γ-aminopropyltrimethoxysilane, vinyltrimethoxy silane, vinyl three（'beta '-methoxy ethyoxyl）Silane and benzene At least one of ethyl triethoxy silicane alkane；The titanate coupling agent is 4- aminobenzenesulfonyls two（Dodecyl benzene sulfonyl Base）Isopropyl titanate, aniline propyl-triethoxysilicane, the oleic acid acyloxy of isopropyl two（Dioctyl phosphoric acid acyloxy）Titanate esters At least one of with tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters.
The present invention can effectively improve matrix resin by using the coupling agent of mentioned kind（PPO、PET）With LCP, glass The adhesion of fiber, improve hardness, shock resistance hardness, tensile strength, the bending strength of PPO/LCP/PET ternary-alloy materials Deng mechanical strength.Preferably, the coupling agent is N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidol Ether oxygen propyl trimethoxy silicane, 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Isopropyl titanate and vinyl three （'beta '-methoxy ethyoxyl）Silane is using weight ratio as 1.2-1.8：2.4-3.2:1.6-2.4:The mixture of 1 composition.If in addition, glass Glass fiber is treated using surface conditioning agent, then it is contemplated that inapplicable coupling agent.
Another object of the present invention is achieved through the following technical solutions：A kind of above-mentioned PPO/LCP/PET ternary alloy three-partalloy materials The preparation method of material, comprises the following steps：According to parts by weight by liquid crystal polymer, polyphenylene oxide, polyethylene terephthalate, Compatilizer, fire retardant, antioxidant, lubricant and modifying agent are mixed, and obtain compound；Compound input extrusion is set It is standby, while glass fibre is fed from extrusion equipment side, it is kneaded, extruded, is granulated, PPO/LCP/PET ternarys is made and close Golden material.
The preparation method of the present invention is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, is adapted to Large-scale industrial production, obtained ternary-alloy material have higher mechanical property, are filled available for office equipment, automobile The fields such as decorations, electronic apparatus, in the wet environment for being equally applicable to have material higher force requirement.
Preferably, the mixing rotating speed of the mixing is 400-800r/min, incorporation time 3-5min；The extrusion One area's temperature of equipment is 260-270 DEG C, and two area's temperature are 265-275 DEG C, and three area's temperature are 275-285 DEG C, and four area's temperature are 275-285 DEG C, five area's temperature are 275-285 DEG C, and six area's temperature are 270-280 DEG C.
Preferably, each raw material residence time in extrusion equipment is 1-1.5min.
Preferably, the extrusion equipment is double screw extruder, glass fibre from the glass fiber opening of double screw extruder add to In raw material.
Temperature of the invention that mix rotating speed, incorporation time and extruding pelletization by strictly controlling raw material, it can make to be made PPO/LCP/PET ternary-alloy materials there is the mechanical properties such as preferable heat resistance, impact resistance, tensile strength, hardness, and Water absorption rate is low, and processability is good, excellent processing performance, solve PET material crystallization it is incomplete caused by sticking to mould, it is difficult be stripped, rise, Push up the problems such as white.
The beneficial effects of the present invention are：The ternary-alloy material of the present invention has excellent toughness, impact strength, drawing The mechanical properties such as intensity, bending strength are stretched, fire protecting performance is good, heat-resist, and water absorption rate is low, good stability of the dimension, crystalline rate Height, processability is good, and processing characteristics is good, and cost is low, and use value is high, available for office equipment, automobile decoration, electronic apparatus etc. Field, in the wet environment for being equally applicable to have material higher force requirement, and it is incomplete and cause to solve PET material crystallization Sticking to mould, difficult be stripped, rise, pushing up the problems such as white.
The ternary-alloy material of the present invention can effectively reduce the water suction of alloy material system by using liquid crystal polymer Rate, and liquid crystal polymer has the performances such as preferable toughness, weatherability, impact strength, anti-flammability, hydrolytic resistance, effectively carries The mechanical property of high alloy material；The glass fibre of use has preferable dielectricity and heat resistance, and hygroscopicity is small, improves The mechanical properties such as the impact resistances of PPO/LCP/PET ternary-alloy materials, tensile strength, bending strength；By using compatilizer, The interfacial tension between each raw material is reduced, improves the interface cohesive force between each raw material, improves PPO/LCP/PET ternarys The compatible role of alloy material；By using fire retardant, make PPO/LCP/PET ternary-alloy materials that there is excellent fire line Energy；By using antioxidant, the thermal-oxidative degradation degree of PPO/LCP/PET ternary-alloy materials can be effectively reduced, can be protected for a long time Hold preferable mechanical property；By using lubricant, internal lubrication and outside profit are played to PPO/LCP/PET ternary-alloy materials Sliding effect, improve the processability and processing characteristics of PPO/LCP/PET ternary-alloy materials；By using modifying agent, carry The mechanical properties such as high PPO/LCP/PET hardness, shock resistance hardness, tensile strength, toughness.
The preparation method of the present invention is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, is adapted to Large-scale industrial production.
Embodiment
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of PPO/LCP/PET ternary-alloy materials, the ternary-alloy material include the raw material of following parts by weight：
10 parts of liquid crystal polymer
20 parts of polyphenylene oxide
40 parts of polyethylene terephthalate
5 parts of glass fibre
3 parts of compatilizer
15 parts of fire retardant
0.1 part of antioxidant
0.2 part of lubricant
1 part of modifying agent.
The structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number 1, R2The aryl for being 20 for carbon number, R3For halogen atom, R4For hydrogen atom.
The liquid crystal polymer is for molecular weight in 5000, characteristic density in 1.45g/cm3TLCP.
The polyphenylene oxide is poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether.
The compatilizer is styrene-grafted maleic anhydride.
The fire retardant is 2,4,6- tribromos phenyl allyl ether, tetrabromophthalic anhydride, the double (tetrabromo-phthalics two of 1,2- Carboximide) at least one of ethane and double (pi-allyl) ethers (four bromo-ethers) of tetrabromobisphenol A.
The antioxidant is 1,3,5- tri-（3,5- tertiary butyl-4-hydroxy benzyls）Trimethylbenzene and β-（3,5- di-t-butyls- At least one of 4- hydroxy phenyls) propionic acid octadecyl.
The lubricant is pentaerythritol stearate.
The ternary-alloy material also includes 0.5 part of coupling agent, and the coupling agent is N- (β-aminoethyl)-γ-aminopropyl At least one of trimethoxy silane and tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters.
A kind of preparation method of above-mentioned PPO/LCP/PET ternary-alloy materials, comprises the following steps：Will according to parts by weight Liquid crystal polymer, polyphenylene oxide, polyethylene terephthalate, compatilizer, fire retardant, antioxidant, lubricant and modifying agent enter Row mixes, and obtains compound；Compound is put into extrusion equipment, while glass fibre is fed from extrusion equipment side, It is kneaded, extruded, is granulated, PPO/LCP/PET ternary-alloy materials is made.
The mixing rotating speed of the mixing is 400/min, incorporation time 5min；
One area's temperature of the extrusion equipment is 260 DEG C, and two area's temperature are 265 DEG C, and three area's temperature are 275 DEG C, and four area's temperature are 285 DEG C, five area's temperature are 275 DEG C, and six area's temperature are 270 DEG C.
Each raw material residence time in extrusion equipment is 1min.
Embodiment 2
A kind of PPO/LCP/PET ternary-alloy materials, the ternary-alloy material include the raw material of following parts by weight：
10 parts of liquid crystal polymer
10 parts of polyphenylene oxide
30 parts of polyethylene terephthalate
13 parts of glass fibre
6 parts of compatilizer
12 parts of fire retardant
0.2 part of antioxidant
0.6 part of lubricant
1.2 parts of modifying agent.
The structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number 5, R2The aryl for being 17 for carbon number, R3For halogen atom, R4For hydrogen atom.
The liquid crystal polymer is for molecular weight in 25000, characteristic density in 1.42g/cm3TLCP.
The polyphenylene oxide is poly-（2,6- diethyl-Isosorbide-5-Nitrae-phenylene）Ether.
The compatilizer is ethylene-acrylic acid-methyl esters graft glycidyl methacrylate.
The fire retardant is triphenyl phosphate, tetraphenyl resorcinol group bisphosphate, bisphenol-A tetraphenylphosphonium acid esters and phosphorus Acid three（α-chloroethyl）At least one of ester.
The antioxidant is 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanates and three (2,4- bis- tertiary fourths At least one of base phenyl) phosphite ester.
The lubricant is silicone powder.
The ternary-alloy material also includes 0.85 part of coupling agent, and the coupling agent is 3- TSL 8330s At least one of with γ-methacryloxypropyl trimethoxy silane.
A kind of preparation method of above-mentioned PPO/LCP/PET ternary-alloy materials, comprises the following steps：Will according to parts by weight Liquid crystal polymer, polyphenylene oxide, polyethylene terephthalate, compatilizer, fire retardant, antioxidant, lubricant and modifying agent enter Row mixes, and obtains compound；Compound is put into extrusion equipment, while glass fibre is fed from extrusion equipment side, It is kneaded, extruded, is granulated, PPO/LCP/PET ternary-alloy materials is made.
The mixing rotating speed of the mixing is 500r/min, incorporation time 4.5min；
One area's temperature of the extrusion equipment is 262 DEG C, and two area's temperature are 268 DEG C, and three area's temperature are 278 DEG C, and four area's temperature are 283 DEG C, five area's temperature are 278 DEG C, and six area's temperature are 272 DEG C.
Each raw material residence time in extrusion equipment is 1.1min.
Embodiment 3
A kind of PPO/LCP/PET ternary-alloy materials, the ternary-alloy material include the raw material of following parts by weight：
30 parts of liquid crystal polymer
30 parts of polyphenylene oxide
10 parts of polyethylene terephthalate
22 parts of glass fibre
9 parts of compatilizer
9 parts of fire retardant
0.3 part of antioxidant
1 part of lubricant
1.5 parts of modifying agent.
The structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number 9, R2The aryl for being 13 for carbon number, R3For halogen atom, R4For hydrogen atom.
The liquid crystal polymer is for molecular weight in 45000, characteristic density in 1.40g/cm3TLCP.
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether.
The compatilizer be hydrogenated styrene-butadiene-styrene copolymer grafted GMA or The acrylonitrile copolymer graft glycidyl methacrylate of styrene one.
The fire retardant is at least one in sodium antimonate, brominated Polystyrene, brominated epoxy resin and TDE Kind.
The antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate and four [methyl- β-（3,5- di-tert-butyl-hydroxy phenyls）At least one of propionic ester] pentaerythritol ester }.
The lubricant is hydrogenation ethylenebisstearamide.
The ternary-alloy material also includes 1.25 parts of coupling agents, and the coupling agent is gamma-amino propyl-triethoxysilicane Alkane, γ-glycidyl ether oxygen propyl trimethoxy silicane and 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Metatitanic acid is different At least one of propyl ester.
A kind of preparation method of above-mentioned PPO/LCP/PET ternary-alloy materials, comprises the following steps：Will according to parts by weight Liquid crystal polymer, polyphenylene oxide, polyethylene terephthalate, compatilizer, fire retardant, antioxidant, lubricant and modifying agent enter Row mixes, and obtains compound；Compound is put into extrusion equipment, while glass fibre is fed from extrusion equipment side, It is kneaded, extruded, is granulated, PPO/LCP/PET ternary-alloy materials is made.
The mixing rotating speed of the mixing is 600r/min, incorporation time 4min；
One area's temperature of the extrusion equipment is 265 DEG C, and two area's temperature are 270 DEG C, and three area's temperature are 280 DEG C, and four area's temperature are 280 DEG C, five area's temperature are 280 DEG C, and six area's temperature are 275 DEG C.
Each raw material residence time in extrusion equipment is 1.2min.
Embodiment 4
A kind of PPO/LCP/PET ternary-alloy materials, the ternary-alloy material include the raw material of following parts by weight：
40 parts of liquid crystal polymer
10 parts of polyphenylene oxide
20 parts of polyethylene terephthalate
31 parts of glass fibre
12 parts of compatilizer
6 parts of fire retardant
0.4 part of antioxidant
1.5 parts of lubricant
1.8 parts of modifying agent.
The structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number 13, R2The aryl for being 9 for carbon number, R3For halogen atom, R4For hydrogen atom.
The liquid crystal polymer is for molecular weight in 65000, characteristic density in 1.38g/cm3TLCP.
The polyphenylene oxide is poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether.
The compatilizer is ethylene-acrylic acid-butyl ester graft glycidyl methacrylate.
The fire retardant is alcohol alkyl aryl phosphate ester, aromatic diphosphate, Polyphenyl phosphate and tricresyl phosphate（1,3- bis- Chloro- 2- propyl group）At least one of ester.
The antioxidant is the double diphosphites two of pentaerythrite（2,4- di-tert-butyl-phenyls）Ester and N, N '-hexa-methylene It is double（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）At least one of.
The lubricant is Tissuemat E
The ternary-alloy material also includes 1.6 parts of coupling agents, and the coupling agent is vinyltrimethoxy silane, vinyl three （'beta '-methoxy ethyoxyl）At least one of silane and phenyl triethoxysilane.
A kind of preparation method of above-mentioned PPO/LCP/PET ternary-alloy materials, comprises the following steps：Will according to parts by weight Liquid crystal polymer, polyphenylene oxide, polyethylene terephthalate, compatilizer, fire retardant, antioxidant, lubricant and modifying agent enter Row mixes, and obtains compound；Compound is put into extrusion equipment, while glass fibre is fed from extrusion equipment side, It is kneaded, extruded, is granulated, PPO/LCP/PET ternary-alloy materials is made.
The mixing rotating speed of the mixing is 700r/min, incorporation time 3.5min；
One area's temperature of the extrusion equipment is 268 DEG C, and two area's temperature are 273 DEG C, and three area's temperature are 283 DEG C, and four area's temperature are 278 DEG C, five area's temperature are 283 DEG C, and six area's temperature are 278 DEG C.
Each raw material residence time in extrusion equipment is 1.3min.
Embodiment 5
A kind of PPO/LCP/PET ternary-alloy materials, the ternary-alloy material include the raw material of following parts by weight：
10 parts of liquid crystal polymer
40 parts of polyphenylene oxide
20 parts of polyethylene terephthalate
40 parts of glass fibre
15 parts of compatilizer
5 parts of fire retardant
0.5 part of antioxidant
2 parts of lubricant
2 parts of modifying agent.
The structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number 18, R2The aryl for being 6 for carbon number, R3For halogen atom, R4For hydrogen atom.
The liquid crystal polymer is for molecular weight in 80000, characteristic density in 1.35g/cm3TLCP.
The polyphenylene oxide is poly-（2,6- diethyl-Isosorbide-5-Nitrae-phenylene）Ether.
The compatilizer is styrene-acrylonitrile-copolymer-maleic anhydride.
The fire retardant is 2,4,6- tribromo-benzenes, double (2,4,6- tribromophenoxies) ethane of 1,2- and the double (phenyl-pentabromides of 1,2- At least one of epoxide) ethane.
The antioxidant is BHT and four（2,4- di-tert-butyl-phenyl -4,4 '-xenyl）Double phosphorus At least one of acid esters.
The lubricant is N, N '-ethylenebisstearamide.
The ternary-alloy material also includes 2 parts of coupling agents, and the coupling agent is aniline propyl-triethoxysilicane and different The oleic acid acyloxy of propyl group two（Dioctyl phosphoric acid acyloxy）At least one of titanate esters.
A kind of preparation method of above-mentioned PPO/LCP/PET ternary-alloy materials, comprises the following steps：Will according to parts by weight Liquid crystal polymer, polyphenylene oxide, polyethylene terephthalate, compatilizer, fire retardant, antioxidant, lubricant and modifying agent enter Row mixes, and obtains compound；Compound is put into extrusion equipment, while glass fibre is fed from extrusion equipment side, It is kneaded, extruded, is granulated, PPO/LCP/PET ternary-alloy materials is made.
The mixing rotating speed of the mixing is 800r/min, incorporation time 3min；
One area's temperature of the extrusion equipment is 270 DEG C, and two area's temperature are 275 DEG C, and three area's temperature are 285 DEG C, and four area's temperature are 275 DEG C, five area's temperature are 285 DEG C, and six area's temperature are 280 DEG C.
Each raw material residence time in extrusion equipment is 1.5min.
Embodiment 6
The difference of the present embodiment and above-described embodiment 1 is：
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether and poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether with Weight ratio is 2.5:The mixture of 1 composition.
The compatilizer is styrene-grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted methyl Glycidyl acrylate, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and ethylene-acrylic acid-butyl ester connect Branch GMA is using weight ratio as 1.2:3.5:1:The mixture of 1.6 compositions.
The fire retardant is sodium antimonate, 1,2- double (tetrabromo phthalimide) ethane, tetraphenyl resorcinol groups two Phosphate and brominated epoxy resin are using weight ratio as 2.5:1.2：1.6:The mixture of 1 composition.
The antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanates, four [methyl-β-（3,5- Di-tert-butyl-hydroxy phenyl）Propionic ester] pentaerythritol ester, β-（3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl alcolol Ester and the double diphosphites two of pentaerythrite（2,4- di-tert-butyl-phenyls）Ester is using weight ratio as 1.6:3.5：1:1.0 compositions mix Compound.
The lubricant is silicone powder and hydrogenation ethylenebisstearamide using weight ratio as 1.4：The mixture of 1 composition.
The coupling agent is N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyl ether oxygen propyl three Methoxy silane, 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Isopropyl titanate and vinyl three（'beta '-methoxy second Epoxide）Silane is using weight ratio as 1.2：3.2:1.6：The mixture of 1 composition.
Embodiment 7
The difference of the present embodiment and above-described embodiment 2 is：
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether and poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether with Weight ratio is 2.8:The mixture of 1 composition.
The compatilizer is styrene-grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted methyl Glycidyl acrylate, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and ethylene-acrylic acid-butyl ester connect Branch GMA is using weight ratio as 1.3:3.2:1:The mixture of 1.8 compositions.
The fire retardant is sodium antimonate, 1,2- double (tetrabromo phthalimide) ethane, tetraphenyl resorcinol groups two Phosphate and brominated epoxy resin are using weight ratio as 2.8:1.1：1.8:The mixture of 1 composition.
The antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanates, four [methyl-β-（3,5- Di-tert-butyl-hydroxy phenyl）Propionic ester] pentaerythritol ester, β-（3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl alcolol Ester and the double diphosphites two of pentaerythrite（2,4- di-tert-butyl-phenyls）Ester is using weight ratio as 1.8:3.2：1:1.1 compositions mix Compound.
The lubricant is silicone powder and hydrogenation ethylenebisstearamide using weight ratio as 1.6：The mixture of 1 composition.
The coupling agent is N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyl ether oxygen propyl three Methoxy silane, 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Isopropyl titanate and vinyl three（'beta '-methoxy second Epoxide）Silane is using weight ratio as 1.3：31.8:The mixture of 1 composition.
Embodiment 8
The difference of the present embodiment and above-described embodiment 3 is：
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether and poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether with Weight ratio is 3:The mixture of 1 composition.
The compatilizer is styrene-grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted methyl Glycidyl acrylate, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and ethylene-acrylic acid-butyl ester connect Branch GMA is using weight ratio as 1.5:3:1:1.1.9 the mixture of composition.
The fire retardant is sodium antimonate, 1,2- double (tetrabromo phthalimide) ethane, tetraphenyl resorcinol groups two Phosphate and brominated epoxy resin are using weight ratio as 3:1：2:The mixture of 1 composition.
The antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanates, four [methyl-β-（3,5- Di-tert-butyl-hydroxy phenyl）Propionic ester] pentaerythritol ester, β-（3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl alcolol Ester and the double diphosphites two of pentaerythrite（2,4- di-tert-butyl-phenyls）Ester is using weight ratio as 2:3：1:The mixing of 1.2 compositions Thing.
The lubricant is silicone powder and hydrogenation ethylenebisstearamide using weight ratio as 1.8：The mixture of 1 composition.
The coupling agent is N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyl ether oxygen propyl three Methoxy silane, 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Isopropyl titanate and vinyl three（'beta '-methoxy second Epoxide）Silane is using weight ratio as 1.5：2.8:2:The mixture of 1 composition.
Embodiment 9
The difference of the present embodiment and above-described embodiment 4 is：
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether and poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether with Weight ratio is 3.2:The mixture of 1 composition.
The compatilizer is styrene-grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted methyl Glycidyl acrylate, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and ethylene-acrylic acid-butyl ester connect Branch GMA is using weight ratio as 1.6:2.8:1:The mixture of 2.1 compositions.
The fire retardant is sodium antimonate, 1,2- double (tetrabromo phthalimide) ethane, tetraphenyl resorcinol groups two Phosphate and brominated epoxy resin are using weight ratio as 3.2:0.9：2.2:The mixture of 1 composition.
The antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanates, four [methyl-β-（3,5- Di-tert-butyl-hydroxy phenyl）Propionic ester] pentaerythritol ester, β-（3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl alcolol Ester and the double diphosphites two of pentaerythrite（2,4- di-tert-butyl-phenyls）Ester is using weight ratio as 2.2:2.8：1:1.3 compositions mix Compound.
The lubricant is silicone powder and hydrogenation ethylenebisstearamide using weight ratio as 2：The mixture of 1 composition.
The coupling agent is N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyl ether oxygen propyl three Methoxy silane, 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Isopropyl titanate and vinyl three（'beta '-methoxy second Epoxide）Silane is using weight ratio as 1.6：2.6:2.2:The mixture of 1 composition.
Embodiment 10
The difference of the present embodiment and above-described embodiment 5 is：
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether and poly-（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether with Weight ratio is 3.5:The mixture of 1 composition.
The compatilizer is styrene-grafted maleic anhydride, hydrogenated styrene-butadiene-styrene copolymer grafted methyl Glycidyl acrylate, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and ethylene-acrylic acid-butyl ester connect Branch GMA is using weight ratio as 1.8:2.5:1:The mixture of 2.2 compositions.
The fire retardant is sodium antimonate, 1,2- double (tetrabromo phthalimide) ethane, tetraphenyl resorcinol groups two Phosphate and brominated epoxy resin are using weight ratio as 3.5:0.8：2.4:The mixture of 1 composition.
The antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanates, four [methyl-β-（3,5- Di-tert-butyl-hydroxy phenyl）Propionic ester] pentaerythritol ester, β-（3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl alcolol Ester and the double diphosphites two of pentaerythrite（2,4- di-tert-butyl-phenyls）Ester is using weight ratio as 2.4:2.5：1:1.5 compositions mix Compound.
The lubricant is silicone powder and hydrogenation ethylenebisstearamide using weight ratio as 2.2：The mixture of 1 composition.
The coupling agent is N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyl ether oxygen propyl three Methoxy silane, 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Isopropyl titanate and vinyl three（'beta '-methoxy second Epoxide）Silane is using weight ratio as 1.8：2.4:2.4:The mixture of 1 composition.
Comparative example 1
A kind of PPO/PET materials, the material include the raw material of following parts by weight：
30 parts of polyphenylene oxide
10 parts of polyethylene terephthalate
22 parts of glass fibre
9 parts of compatilizer
9 parts of fire retardant
0.3 part of antioxidant
1 part of lubricant
1.5 parts of modifying agent.
The structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number 9, R2The aryl for being 13 for carbon number, R3For halogen atom, R4For hydrogen atom.
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether.
The compatilizer be hydrogenated styrene-butadiene-styrene copolymer grafted GMA or The acrylonitrile copolymer graft glycidyl methacrylate of styrene one.
The fire retardant is at least one in sodium antimonate, brominated Polystyrene, brominated epoxy resin and TDE Kind.
The antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate and four [methyl- β-（3,5- di-tert-butyl-hydroxy phenyls）At least one of propionic ester] pentaerythritol ester }.
The lubricant is hydrogenation ethylenebisstearamide.
The ternary-alloy material also includes 1.25 parts of coupling agents, and the coupling agent is gamma-amino propyl-triethoxysilicane Alkane, γ-glycidyl ether oxygen propyl trimethoxy silicane and 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Metatitanic acid is different At least one of propyl ester.
A kind of preparation method of above-mentioned PPO/PET ternary-alloy materials, comprises the following steps：According to parts by weight by polyphenyl Ether, polyethylene terephthalate, compatilizer, fire retardant, antioxidant, lubricant and modifying agent are mixed, and are obtained Compound；Compound is put into extrusion equipment, while glass fibre is fed from extrusion equipment side, is kneaded, extruded, made Grain, PPO/PET ternary-alloy materials are made.
The mixing rotating speed of the mixing is 600r/min, incorporation time 4min；
One area's temperature of the extrusion equipment is 265 DEG C, and two area's temperature are 270 DEG C, and three area's temperature are 280 DEG C, and four area's temperature are 280 DEG C, five area's temperature are 280 DEG C, and six area's temperature are 275 DEG C.
Each raw material residence time in extrusion equipment is 1.2min.
Comparative example 2
A kind of LCP/PPO/PA materials, the material include the raw material of following parts by weight：
30 parts of liquid crystal polymer
30 parts of polyphenylene oxide
10 parts of polyamide
22 parts of glass fibre
9 parts of compatilizer
9 parts of fire retardant
0.3 part of antioxidant
1 part of lubricant
1.5 parts of modifying agent.
The structural formula of the polyphenylene oxide is as follows：
；
Wherein, R1For alkyl of the carbon number 9, R2The aryl for being 13 for carbon number, R3For halogen atom, R4For hydrogen atom.
The liquid crystal polymer is for molecular weight in 45000, characteristic density in 1.40g/cm3TLCP.
The polyphenylene oxide is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether.
The compatilizer be hydrogenated styrene-butadiene-styrene copolymer grafted GMA or The acrylonitrile copolymer graft glycidyl methacrylate of styrene one.
The fire retardant is at least one in sodium antimonate, brominated Polystyrene, brominated epoxy resin and TDE Kind.
The antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate and four [methyl- β-（3,5- di-tert-butyl-hydroxy phenyls）At least one of propionic ester] pentaerythritol ester }.
The lubricant is hydrogenation ethylenebisstearamide.
The ternary-alloy material also includes 1.25 parts of coupling agents, and the coupling agent is gamma-amino propyl-triethoxysilicane Alkane, γ-glycidyl ether oxygen propyl trimethoxy silicane and 4- aminobenzenesulfonyls two（Dodecyl benzenesulfonyl）Metatitanic acid is different At least one of propyl ester.
A kind of preparation method of above-mentioned PPO/LCP/PET ternary-alloy materials, comprises the following steps：Will according to parts by weight Liquid crystal polymer, polyphenylene oxide, polyamide, compatilizer, fire retardant, antioxidant, lubricant and modifying agent are mixed, and are obtained Compound；Compound is put into extrusion equipment, while glass fibre is fed from extrusion equipment side, is kneaded, extruded, made Grain, PPO/LCP/PET ternary-alloy materials are made.
The mixing rotating speed of the mixing is 600r/min, incorporation time 4min；
One area's temperature of the extrusion equipment is 265 DEG C, and two area's temperature are 270 DEG C, and three area's temperature are 280 DEG C, and four area's temperature are 280 DEG C, five area's temperature are 280 DEG C, and six area's temperature are 275 DEG C.
Each raw material residence time in extrusion equipment is 1.2min.
Sample made from above-described embodiment 1-10 and comparative example 1-2 is positioned in air dry oven, dries 3- at 120 DEG C 4h, the above-mentioned sample after baking is then molded into iso standard batten with injection machine, each performance, performance are measured after being cooled to room temperature Test result is as shown in the table.
From upper table data, the present invention solves what PET material occurred in forming process by adding LCP and PPO Sticking to mould, hardly possible are stripped, risen, pushing up the problems such as white, molding cycle is long, efficiency is low, and production is improved while improving mechanical property Efficiency, accelerate production, and solve PET material warpage, it is yielding, linear expansion coefficient is larger the problems such as, obtained PPO/ LCP/PET has the mechanical properties such as excellent toughness, impact strength, tensile strength, bending strength, and fire protecting performance is good, heat-resisting Property it is good, water absorption rate is low, good stability of the dimension, and processability is good, and processing characteristics is good, and cost is low, and use value is high.
Above-described embodiment is the preferable implementation of the present invention, and in addition, the present invention can be realized with other manner, Do not depart from and any on the premise of present inventive concept obviously replace within protection scope of the present invention.

Claims (10)

  1. A kind of 1. PPO/LCP/PET ternary-alloy materials, it is characterised in that：The ternary-alloy material includes the original of following parts by weight Material：
    Liquid crystal polymer 10-40 parts
    Polyphenylene oxide 10-40 parts
    Polyethylene terephthalate 10-40 parts
    Glass fibre 5-40 parts
    Compatilizer 3-15 parts
    Fire retardant 5-15 parts
    Antioxidant 0.1-0.5 parts
    Lubricant 0.2-2 parts
    Modifying agent 1-2 parts.
  2. A kind of 2. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The polyphenylene oxide Structural formula is as follows：
    ；
    Wherein, R1For alkyl of the carbon number in 1-18, R2The aryl for being 6-20 for carbon number, R3For halogen atom, R4For hydrogen Atom.
  3. A kind of 3. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The polymerizable mesogenic Thing is for molecular weight in 5000-80000, characteristic density in 1.35-1.45g/cm3TLCP.
  4. A kind of 4. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The polyphenylene oxide is It is poly-（2,6- dimethyl-Isosorbide-5-Nitrae-phenylene）Ether, gather（2- methyl -6- ethyls-Isosorbide-5-Nitrae-phenylene）Ether and poly-（2,6- diethyl -1, 4- phenylenes）At least one of ether.
  5. A kind of 5. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The compatilizer is Polystyrene blend containing epoxide group or the polystyrene blend containing anhydride group；The styrene containing anhydride group It is that blend is at least one of styrene-grafted maleic anhydride and styrene-acrylonitrile-copolymer-maleic anhydride；It is described to contain The polystyrene blend of epoxide group is that hydrogenated styrene-butadiene-styrene copolymer grafted Glycidyl methacrylate is sweet Grease, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate, ethylene-acrylic acid-butyl ester grafted methacrylic acid At least one of ethylene oxidic ester and the acrylonitrile copolymer graft glycidyl methacrylate of styrene one.
  6. A kind of 6. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The fire retardant is Sodium antimonate, bromide fire retardant or organophosphorus ester based flame retardant；The bromide fire retardant is brominated Polystyrene, brominated oxygen tree Double (2,4,6- tribromophenoxies) ethane of fat, TDE, 2,4,6- tribromo-benzenes, 1,2-, 1,2- are double (pentabromo- phenoxy group) Double (tetrabromo phthalimide) ethane of ethane, 2,4,6- tribromos phenyl allyl ether, tetrabromophthalic anhydride, 1,2- and At least one of double (pi-allyl) ethers (four bromo-ethers) of tetrabromobisphenol A；The organophosphorus ester based flame retardant be triphenyl phosphate, Tetraphenyl resorcinol group bisphosphate, bisphenol-A tetraphenylphosphonium acid esters, alcohol alkyl aryl phosphate ester, aromatic diphosphate, polyphenyl Base phosphate, tricresyl phosphate（α-chloroethyl）Ester and tricresyl phosphate（The chloro- 2- propyl group of 1,3- bis-）At least one of ester.
  7. A kind of 7. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The antioxidant is Double-the 3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate, four [methyl-β-（3,5- di-t-butyl -4- hydroxyls Base phenyl）Propionic ester] pentaerythritol ester, the double diphosphites two of pentaerythrite（2,4- di-tert-butyl-phenyls）Ester, N, N '-six Di-2-ethylhexylphosphine oxide（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyl) isocyanic acids Ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, 1,3,5- tri-（3,5- tertiary butyl-4-hydroxy benzyls）Trimethylbenzene, β-（3, 5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl, BHT and four（2,4- di-tert-butyl-phenyl -4, 4 '-xenyl）At least one of biphosphonate.
  8. A kind of 8. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The lubricant is Pentaerythritol stearate, silicone powder, hydrogenation ethylenebisstearamide, Tissuemat E and N, N '-ethylenebisstearamide At least one of.
  9. A kind of 9. PPO/LCP/PET ternary-alloy materials according to claim 1, it is characterised in that：The ternary alloy three-partalloy Material also includes 0.5-2 part coupling agents, and the coupling agent is silane coupler or titanate coupling agent；The silane coupler is γ aminopropyltriethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, 3- aminopropyl trimethoxy silicon Alkane, γ-methacryloxypropyl trimethoxy silane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, ethene Base trimethoxy silane, vinyl three（'beta '-methoxy ethyoxyl）At least one of silane and phenyl triethoxysilane；Institute It is 4- aminobenzenesulfonyls two to state titanate coupling agent（Dodecyl benzenesulfonyl）Isopropyl titanate, aniline propyl triethoxy Silane, the oleic acid acyloxy of isopropyl two（Dioctyl phosphoric acid acyloxy）Titanate esters and (the dioctyl phosphito acyl-oxygen of tetra isopropyl two At least one of base) titanate esters.
  10. A kind of 10. preparation method of PPO/LCP/PET ternary-alloy materials as described in claim 1-9, it is characterised in that：Bag Include following steps：According to parts by weight by liquid crystal polymer, polyphenylene oxide, polyethylene terephthalate, compatilizer, fire retardant, Antioxidant, lubricant and modifying agent are mixed, and obtain compound；Compound is put into extrusion equipment, while by glass Fiber is fed from extrusion equipment side, is kneaded, extruded, is granulated, and PPO/LCP/PET ternary-alloy materials are made.
CN201710744086.2A 2017-08-25 2017-08-25 A kind of PPO/LCP/PET ternary-alloy materials and preparation method thereof Pending CN107459807A (en)

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CN109943055A (en) * 2019-01-28 2019-06-28 广东国立科技股份有限公司 Low creep flame-proof glass fibre enhancing PPO/LCP composite alloy material of a kind of high-temperature resistant high rigidity and preparation method thereof
CN110305460A (en) * 2019-07-02 2019-10-08 南京清研高分子新材料有限公司 A kind of PPO/LCP composite material and preparation method
EP3854849A4 (en) * 2018-09-20 2022-06-15 Toray Industries, Inc. Thermoplastic polyester resin composition and molded article

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CN101704993A (en) * 2009-09-30 2010-05-12 东莞市上洲塑胶科技有限公司 PET/LCP flame-retardant plastic and preparation method thereof
CN102719081A (en) * 2012-07-06 2012-10-10 上海日之升新技术发展有限公司 Halogen-free flame-retardant reinforced polyphenyl ether/polyester alloy and preparation method thereof
CN104845163A (en) * 2014-12-13 2015-08-19 青岛佳亿阳工贸有限公司 Modified PET/PTT/PPE composite material

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CN101704993A (en) * 2009-09-30 2010-05-12 东莞市上洲塑胶科技有限公司 PET/LCP flame-retardant plastic and preparation method thereof
CN102719081A (en) * 2012-07-06 2012-10-10 上海日之升新技术发展有限公司 Halogen-free flame-retardant reinforced polyphenyl ether/polyester alloy and preparation method thereof
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Publication number Priority date Publication date Assignee Title
EP3854849A4 (en) * 2018-09-20 2022-06-15 Toray Industries, Inc. Thermoplastic polyester resin composition and molded article
CN109943055A (en) * 2019-01-28 2019-06-28 广东国立科技股份有限公司 Low creep flame-proof glass fibre enhancing PPO/LCP composite alloy material of a kind of high-temperature resistant high rigidity and preparation method thereof
CN110305460A (en) * 2019-07-02 2019-10-08 南京清研高分子新材料有限公司 A kind of PPO/LCP composite material and preparation method
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Application publication date: 20171212