CN103073853B - Environmental-protection fire retardation enhancement PBT/PET/PA6 alloy and manufacturing method thereof - Google Patents

Environmental-protection fire retardation enhancement PBT/PET/PA6 alloy and manufacturing method thereof Download PDF

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Publication number
CN103073853B
CN103073853B CN201210300263.5A CN201210300263A CN103073853B CN 103073853 B CN103073853 B CN 103073853B CN 201210300263 A CN201210300263 A CN 201210300263A CN 103073853 B CN103073853 B CN 103073853B
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pet
district
pbt
alloy
retardant
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CN103073853A (en
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阳瑞
皮正亮
徐建辉
刘广闻
葛嘉宝
郭建强
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GUANGDONG WAYLAM ENGINEERING PLASTICS Co Ltd
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GUANGDONG WAYLAM ENGINEERING PLASTICS Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

Abstract

The present invention discloses an environmental-protection fire retardation enhancement PBT/PET/PA6 alloy and a manufacturing method thereof. The environmental-protection fire retardation enhancement PBT/PET/PA6 alloy comprises PBT, PET, PA6, a toughening compatibilizer, a compound fire retardation agent, a synergistic fire retardation agent, glass fibers, an antioxidant and a lubrication dispersing agent. The environmental-protection fire retardation enhancement PBT/PET/PA6 alloy has advantages of high glow wire temperature, low warping, excellent comprehensive performance, high performance-price ratio and the like, wherein a fire retardation performance of the environmental-protection fire retardation enhancement PBT/PET/PA6 alloy stably achieves the UL94-V0 fire retardation grade.

Description

A kind of environment-friendly flame-retardant reinforced PBT/PET/PA6 Alloy And Preparation Method
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of environment-friendly flame-retardant reinforced PBT/PET/PA6 Alloy And Preparation Method.
Background technology
Polybutylene terephthalate (PBT) is the thermoplastic polyester that 20 century 70s grow up, there is excellent machinery, electric, high temperature resistant, moisture-proof, resistance to chemical attack, electrical insulation capability is good, good elasticity, crystallization velocity are fast, good fluidity and be easy to the features such as forming process, and can good mechanical property be kept in wide temperature range.Due to the performance of PBT product uniqueness, PBT engineering plastics and various alloy are widely used in electric, home electric, automobile, machinery, instrument, light textile and the every field such as civilian, are a kind of indispensable type materials.Along with the progress of science and technology and the development of industry, higher requirement be it is also proposed to the application of material, require higher intensity, higher precision, flame retardant properties, environmental protection, low cost etc.And PBT exists the shortcomings such as large, the easy warpage of molding shrinkage, notch shock sensitivity, this has just driven the development of modified PBT material and PBT alloy.
Pet resin (PET) has excellent electrical property, mechanical property, resistance toheat and lower production cost, be widely used in the fields such as electronic apparatus, machinery, automobile component, but PET resin exists, and crystallization velocity is slow, moulded products shrinking percentage large, poor dimensional stability and the shortcoming such as matter own is crisp, seriously limit its application as engineering plastics.High performance at present to PET, be the focus of research, the method for improvement concentrates on and adds crystallization nucleating agent or crystallization promoter and glass fibre compound, or adds certain fire retardant, make fiberglass reinforced PET or flame-retardant strengthening polythylene terephthalate (PET), the alloying of PET is also the emphasis of research in addition.
PBT/PET alloy can comprehensive both advantage, and improve the performance of material, many research both at home and abroad is many at present.21 century is electric, the equipment such as household electrical appliances develop to high-performance microization, also more and more higher to the requirement of flame-retardant reinforced PBT/PET alloy material, simultaneously along with the mankind are to the understanding of environmental protection, Green Product is subject to common concern, so it is following development trend that environmental protection high-performance refractory strengthens PBT/PET alloy, some traditional fire-retardant compound systems: as glass fibre+TDE+antimonous oxide, the compound systems such as glass fibre+brominated Polystyrene+antimonous oxide cannot meet the requirement of high glow wire temperature, be not suitable for preparing capacitor case, load break switch, motor case, terminal strip etc.And PBT/PET alloy still exists, and heat-drawn wire is lower, shrinking percentage large, to shortcomings such as notch sensitive, significantly limit the application of PBT/PET alloy, be therefore necessary that alloy proceeds research.
Polyamide 6 (PA6) is a kind of polymkeric substance of crystallization of excellent combination property, there is the features such as good toughness, chemicals-resistant, crystallization velocity be fast, for this reason, by adding the composite of PA6 and flame-retardant system in PBT/PET alloy, successfully preparing a kind of novel environment-friendly flame-retardant reinforced PBT/PET/PA alloy, having there is flame retardant properties and stablize the flame retardant rating reaching UL94-V0, high glow wire temperature, low warpage, excellent combination property, cost performance advantages of higher.
Summary of the invention
The object of the invention is to solve in prior art shortcoming in PBT/PET alloy and a kind of moderate cost proposed and the higher environment-friendly flame-retardant reinforced PBT/PET/PA alloy of environmental protection flame retardant, good stability of the dimension, rigidity, toughness, heat-drawn wire, glow wire temperature.
Another object of the present invention is the preparation method providing above-mentioned alloy.
Object of the present invention can be realized by following technical scheme:
Above-mentioned environment-friendly flame-retardant reinforced PBT/PET/PA alloy, be made up of the component of following weight percent: PBT:12-32%, PET:12-32%, PA6:0-8%, toughness reinforcing compatilizer: 3-8%, compound flame retardant: 10-20%, synergistic flame retardant: 3-5%, glass fibre: 20-30%, oxidation inhibitor: 0.1-1%, lubrication dispersing agent: 0.1-1%;
As a kind of preferred version, above-mentioned PBT is sticky in being, limiting viscosity is 1.000 ± 0.015dl/g; Above-mentioned PET is low sticky, and limiting viscosity is 0.670 ± 0.015 dl/g; Above-mentioned PA6 is sticky in being, relative viscosity is 2.83 ± 0.07; Above-mentioned toughness reinforcing compatilizer is the Bifunctionalized vinyl elastomerics of acrylate and glycidyl ester.Described glass fibre is the alkali free glass fibre of a kind of surface through silane coupling agent process; Described compound flame redundant is mixed by brominated Polystyrene (BPS) 65wt%, melamine polyphosphates (MPP) 22wt%, talcum powder 13wt% tri-kinds of components; Described synergistic flame retardant is mixed by component in sodium antimonate 35wt%, zinc borate 65wt% two; Described oxidation inhibitor is Hinered phenols primary antioxidant 1010 [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, synergistic oxidation inhibitor phosphoric acid ester irgasfos 168 three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester two kinds of oxidation inhibitor compound compositions.; Described a kind of environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy, is characterized in that, described lubrication dispersing agent is the TAF based on ethylene bis-fatty acid amides (EBS) after modification.
A kind of preparation method of environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy:
(1) raw material drying pre-treatment, the temperature of PBT, PET and PA6 drying controls at 110-120 DEG C, more than 4 hours time of drying; The drying conditions of other raw materials be 70 DEG C * 12 hours.
(2) above-mentioned dried feed is joined in high-speed mixer by proportioning fully mix, stirring at normal temperature 3-5 minute;
(3) the raw material extruding pelletization in twin screw extruder will mixed, screw diameter 35-75mm, twin screw extruder has a district of district to ten, the temperature in each district arranges and is respectively: a district 190-210, two district 220-230, three district 240-255, four district 240-255, five district 210-230, six district 200-210, seven district 200-210, eight 210-220 districts, nine district 220-240, ten district 240-255; Screw speed controls at 350-400rPm.
The present invention adopts suitable Recipe, and is equipped with suitable flame-retardant system, and the high-performance refractory preparing environmental protection flame retardant strengthens PBT/PET/PA6 tertiary blending alloy.This fire-retardant enhancing alloy, compared to the fire-retardant enhancing alloy of PBT/PET, has outstanding advantage, and is easy to forming process in rigidity, toughness, resistance toheat, flame retardant resistance and dimensional stability.This environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy adopts composite flame-retardant system and synergistic flame-retardant system, make the flame retardant rating by UL94-V0 that alloy energy is stable, and can be stable by 850 DEG C of glowing filaments (not on fire), many fire-retardant ranks and the higher occasion of performance requriements can be met, be widely used in capacitor case, load break switch, motor case, terminal strip, coil rack, plug and electric cupler, phone distributor box etc.
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
Comparative example 1-6 and embodiment 7-8
The formula for raw stock of comparative example 1-6 and embodiment 7-8 is as following table 1:
The formula for raw stock of table 1, comparative example 1-6 and embodiment 7-8
Material name 1﹟ 2﹟ 3﹟ 4﹟ 5﹟ 6﹟ 7﹟ 8﹟
PBT 31.1 28.1 23.1 22.1 20.1 19.1 18.6 17.6
PET 31.1 28.1 23.1 22.1 20.1 19.1 18.6 17.6
PA6 - - - - 6 8 6 6
Compound flame redundant 14 18 18 20 18 18 18 18
Synergistic flame retardant 3 5 5 5 5 5 5 5
Glass fibre 20 20 30 30 30 30 30 30
Toughner - - - - - - 3 5
Oxidation inhibitor 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Preparation method and the technique of comparative example and embodiment are as follows:
(1) according to the pre-treatment of raw material raw material drying, the temperature of PBT, PET and PA6 drying controls at 110-120 DEG C, more than 4 hours time of drying; The drying conditions of other raw materials be 70 DEG C * 12 hours.
(2) above-mentioned dried feed is joined in high-speed mixer by comparative example and Example formulations list fully mix, stirring at normal temperature 3-5 minute.
(3) the raw material extruding pelletization in twin screw extruder will mixed, screw diameter 35-75mm, twin screw extruder has a district of district to ten, the temperature in each district arranges and is respectively: a district 190-210, two district 220-230, three district 240-255, four district 240-255, five district 210-230, six district 200-210, seven district 200-210, eight 210-220 districts, nine district 220-240, ten district 240-255; Screw speed controls at 350-400rPm.
The sample obtained according to comparative example 1-6 and embodiment 7-8, carries out performance test comparison, and unified employing national standard, the performance table of its each example is as shown in table 2.
Table 2 comparative example 1-6 and embodiment 7-8 performance test
Project 1﹟ 2﹟ 3﹟ 4﹟ 5﹟ 6﹟ 7﹟ 8﹟
Tensile strength/MPa 115 108 124 121 138 140 131 123
Flexural strength/MPa 161 165 185 189 213 217 205 186
Notched Izod impact strength/kjm -2 7.5 6.8 8.2 7.9 9.5 9.8 11.8 13.5
Flame retardant resistance UL94-1.6mm V0 V0 V0 V0 V0 V0 V0 V0
Glow wire temperature/DEG C, not on fire 810 830 850 840 875 875 870 865
Glass fiber content (wt%) 21 20.5 29.5 31.3 30.3 30.5 31.5 30.8
As can be seen from comparative example 1-4, by optimization design, the flame retardant rating by UL94-V0 that compound flame redundant can be stable, and the increase of glass fiber content, can improve material glow wire temperature and mechanical property.
All improve a lot as can be seen from the tensile strength adding alloy material of comparative example 5-6, PA6, flexural strength, toughness, glow wire temperature.
As can be seen from embodiment 7-8, toughner add the toughness can well improving alloy material, and there is good comprehensive mechanical property, stable flame retardant properties, and there is higher glow wire temperature.
In sum, be preferred embodiment of the present invention, all according to the change done by technical solution of the present invention, the function produced fail the scope exceeding technical solution of the present invention time, all belong to protection scope of the present invention.

Claims (5)

1. environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy, is characterized in that being made up of the following component according to mass percentage: PBT 13 ~ 32%, PET 13 ~ 32%, PA6 0 ~ 6%, toughness reinforcing compatilizer 3 ~ 8%, compound flame retardant 10 ~ 20%, synergistic flame retardant 3 ~ 5%, glass fibre 20 ~ 30%, oxidation inhibitor 0.1 ~ 1% and lubrication dispersing agent 0.1 ~ 1%;
Above-mentioned PBT is sticky in being, limiting viscosity is 1.000 ± 0.015dl/g; Above-mentioned PET is low sticky, and limiting viscosity is 0.670 ± 0.015dl/g; Above-mentioned PA6 is sticky in being, relative viscosity is 2.83 ± 0.07; Above-mentioned toughness reinforcing compatilizer is the Bifunctionalized vinyl elastomerics of acrylate and glycidyl ester;
Described compound flame redundant is mixed by brominated Polystyrene (BPS) 65wt%, melamine polyphosphates (MPP) 22wt%, talcum powder 13wt% tri-kinds of components;
Described synergistic flame retardant is mixed by sodium antimonate 35wt%, zinc borate 65wt% two kinds of components.
2. environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy according to claim 1, is characterized in that described glass fibre is the alkali free glass fibre of surface through silane coupling agent process.
3. environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy according to claim 1, it is characterized in that described oxidation inhibitor is Hinered phenols primary antioxidant 1010 [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, synergistic oxidation inhibitor phosphoric acid ester irgasfos 168 three [2.4-di-tert-butyl-phenyl] phosphorous acid ester two kinds of oxidation inhibitor form according to the part by weight compound of 1:2.
4. environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy according to claim 1, is characterized in that described lubrication dispersing agent is modified ethylene bis-fatty acid amides.
5. the preparation method of environment-friendly flame-retardant reinforced PBT/PET/PA6 alloy described in any claim in Claims 1 to 4, is characterized in that comprising the steps:
(1) raw material drying pre-treatment, the temperature of PBT, PET and PA6 drying controls at 110-120 DEG C, more than 4 hours time of drying; The drying conditions of other raw materials is 70 DEG C, 12 hours.
(2) above-mentioned dried feed is joined in high-speed mixer by proportioning fully mix, stirring at normal temperature 3-5 minute;
(3) the raw material extruding pelletization in twin screw extruder will mixed, screw diameter 35-75mm, twin screw extruder has a district of district to ten, the temperature in each district arranges and is respectively: a district 190-210, two district 220-230, three district 240-255, four district 240-255, five district 210-230, six district 200-210, seven district 200-210, eight 210-220 districts, nine district 220-240, ten district 240-255; Screw speed controls at 350-400rpm.
CN201210300263.5A 2012-08-22 2012-08-22 Environmental-protection fire retardation enhancement PBT/PET/PA6 alloy and manufacturing method thereof Active CN103073853B (en)

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CN105400158B (en) * 2015-12-16 2018-02-23 华南理工大学 One kind enhancing flame-retardant PBT/PA6 composites and preparation method thereof
CN107011654B (en) * 2017-05-24 2020-01-14 武汉理工大学 Halogen-free flame-retardant reinforced PA6/PBT alloy and preparation method thereof
CN107955201B (en) * 2017-11-30 2021-02-12 宁波多力浦工贸有限公司 LED bulb lamp shell
CN108948688A (en) * 2018-08-22 2018-12-07 中广核俊尔(上海)新材料有限公司 A kind of fiber glass reinforced PBT/PET material

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US5708065A (en) * 1995-12-22 1998-01-13 E. I. Du Pont De Nemours And Company Fire resistant resin compositions
WO2005073320A1 (en) * 2004-01-30 2005-08-11 Mitsui Chemicals, Inc. Flame-retardant polyamide composition and use thereof
US20090170985A1 (en) * 2007-12-28 2009-07-02 Rina Ai Polyester-polyamide compositions, articles, and method of manufacture thereof
CN101759983B (en) * 2008-12-23 2012-12-05 上海普利特复合材料股份有限公司 Reinforced polyester alloy composite material and preparation method thereof
US20120108701A1 (en) * 2009-06-19 2012-05-03 Mok-Keun Lim Composition of a blend of polyamide and polyester resins
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