CN107083030A - A kind of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials and preparation method thereof - Google Patents
A kind of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials and preparation method thereof Download PDFInfo
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- 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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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a kind of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials, by weight, including：The parts by weight of PBT resin 30~50；The parts by weight of ASA resin 15~30；The parts by weight of glass fibre 20~30；The parts by weight of compatible toughening agents 2~6；The parts by weight of that resist warping agent 6~10；The parts by weight of antioxidant 0.1~0.5；The parts by weight of lubricant 0.1~0.5；The parts by weight of flow ability modifying agent 0.1~0.8.The invention also discloses a kind of preparation method of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials.The material solves fiberglass reinforced and causes the serious deficiency of warpage, while ensure that alloy material excellent mechanical property and weatherability.
Description
Technical field
The invention belongs to modified polymer material technical field, more particularly to a kind of low warpage high intensity fiberglass reinforced
PBT/ASA alloy materials and preparation method thereof.
Background technology
Polybutylene terephthalate (PBT) (PBT) have high temperature resistant, moisture-proof, wear-resisting, resistant to chemical etching, hot property it is excellent,
The advantages of good mechanical performance, good forming ability, its product be widely used in electronic apparatus, plant equipment, automobile, communication,
The fields such as illumination.
But PBT molding shrinkages are big, and notch impact strength is low, and volume resistance, dielectric loss are big.PBT uses fiberglass reinforced,
Tensile strength, bending strength, heat distortion temperature can be improved, can the long-term work at 140 DEG C.But the anisotropy of glass is special
Property so that fiber glass reinforced PBT is asked when preparing large-scale thin wall parts or complex geometry product in the presence of more serious warpage
Topic.ASA is acrylonitrile-acrylate-styrene terpolymer, with good weatherability, if PBT and ASA are made altogether
Mixing gold, the advantage of the existing PBT resin of obtained alloy, toughness, weatherability and the dimensional stability with ASA resin.
PBT and ASA resin crystal property have differences, and generally require the suitable compatible toughening agents of addition, improve matrix tree
Compatibility between fat, it is ensured that the performance of alloy material.
The content of the invention
It is an object of the invention to overcome shortcoming and deficiency present in above-mentioned prior art, there is provided a kind of low warpage is high-strength
Fiber glass reinforced PBT/ASA alloy materials are spent, the material solves fiberglass reinforced and causes the serious deficiency of warpage, while ensure that conjunction
Golden material excellent mechanical property and weatherability.
Another object of the present invention is to provide a kind of preparation side of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials
Method.
The purpose of the present invention is achieved through the following technical solutions：A kind of low warpage high-strength glass fiber enhanced PBT/ASA alloys
Material, by weight, including:
The PBT resin is the polymerization that butanediol and terephthalic acid (TPA) or its class ester derivative are obtained by polycondensation reaction
Thing, its intrinsic viscosity is 0.8-1.3ml/g.
The ASA resin for by matrix of SAN by emulsion method or mass polymerization obtain with containing acrylate-based
Group rubber elastomer be core, using SAN as shell, i.e., the acrylonitrile-styrene with core-shell structure-
In acrylate terpolymer, the terpolymer weight content of the rubber elastomer containing acrylate group be 10~
80%.
The glass fibre is what is be surface-treated by the silane coupler containing epoxide group or amido functional group
Glass fibre.
The compatible toughening agents are maleic anhydride grafted ethene and octene copolymer, acrylate acrylonitrile styrene block
One or more in copolymer, polyester elastomer, polyolefin elastomer, ethylene-methyl acrylate copolymer.
That resist warping agent is the one or more in mica, wollastonite, hollow glass micropearl.
The antioxidant is any one in Hinered phenols, phosphorous acid esters and thioether antioxidants or two or more
Composition.
The lubricant is group more than one or both of Tissuemat E, silicone master batch or pentaerythritol stearate
Compound.
The rheology modifier is the polyamidoamine dendrimer rheology of amino end group, terminal hydroxy group or end carboxyl
Modifying agent.
The implementation method of above-mentioned low warpage high-strength glass fiber enhanced PBT/ASA alloy materials, comprises the following steps：
(1), by the PBT resin being separately dried in advance, ASA resin, compatible toughening agents, that resist warping agent, antioxidant, lubrication
Agent and rheology modifier, by weight, the parts by weight of PBT resin 30~50；The parts by weight of ASA resin 15~30；Glass fibre 20
~30 parts by weight；The parts by weight of compatible toughening agents 2~6；The parts by weight of that resist warping agent 6~10；The parts by weight of antioxidant 0.1~0.5；Lubrication
The parts by weight of agent 0.1~0.5；It is well mixed rear stand-by that the ratio of the parts by weight of flow ability modifying agent 0.1~0.8 is added to high mixer；
(2), the mixture that the first step is obtained is fed into double screw extruder by main feeding hopper, at 205-245 DEG C
Within the temperature range of extruding pelletization, by glass fibre from glass fiber opening add, last tie rod, pelletizing.
The present invention has the following advantages and effect relative to prior art：
Product of the present invention selects the glass fibre of the coupling agent modified processing of silane surface, and glass is good with resin compatible, power
Excellent performance is learned, stability is good.Product of the present invention is from maleic anhydride grafted ethene and octene copolymer, acrylate acrylonitrile
One or more in styrene block copolymer, polyester elastomer, polyolefin elastomer, ethylene-methyl acrylate copolymer
It is used as compatible toughening agents, it is ensured that the mechanical property of alloy material.Product of the present invention selects spherical, sheet or whisker class filler, carries
High dimension stability and resistance to warping energy.Product of the present invention selects rheology modifier, improves alloy material ensemble stream
Dynamic property, improves the moulding processability of material.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
Weigh the parts by weight of PBT resin 45, the parts by weight of ASA resin 20, the weight of acrylate acrylonitrile styrene block copolymer 2
Measure part, the parts by weight of ethylene-methyl acrylate copolymer 2, antioxidant (Hinered phenols, phosphite ester based composition, by weight 1：
2 mixing) 0.2 parts by weight, the parts by weight of lubricant (Tissuemat E) 0.3 are added to high-speed mixer and mixing uniformly in certain sequence, logical
Cross main feeding hopper to be added in double screw extruder, while the surface modified glass fiber of 30 parts by weight is added by glass fiber opening
Enter, melt, knead, extrude, granulate through double screw extruder, obtain low warpage high-strength glass fiber enhanced PBT/ASA alloy materials,
Each section of temperature be respectively：One 210 DEG C of area's temperature, two 240 DEG C of area's temperature, three 240 DEG C of area's temperature, four 240 DEG C of area's temperature, five area's temperature
235 DEG C of degree, six 230 DEG C of area's temperature, seven 230 DEG C of area's temperature, eight 225 DEG C of area's temperature, 245 DEG C of head temperature；Engine speed
400rpm。
Embodiment 2
Weigh the parts by weight of PBT resin 40, the parts by weight of ASA resin 25, the weight of acrylate acrylonitrile styrene block copolymer 2
Measure part, the parts by weight of ethylene-methyl acrylate copolymer 2, antioxidant (Hinered phenols, thioether based composition, by weight 1：2 mix
Close) 0.2 parts by weight, the parts by weight of lubricant (Tissuemat E) 0.3, it is uniform to be added to high-speed mixer and mixing in certain sequence, passes through
Main feeding hopper is added in double screw extruder, while the surface modified glass fiber of 30 parts by weight is added by glass fiber opening,
Melt, knead, extrude, granulate through double screw extruder, obtain low warpage high-strength glass fiber enhanced PBT/ASA alloy materials, respectively
Duan Wendu is respectively：One 210 DEG C of area's temperature, two 240 DEG C of area's temperature, three 240 DEG C of area's temperature, four 240 DEG C of area's temperature, five area's temperature
235 DEG C, six 230 DEG C of area's temperature, seven 230 DEG C of area's temperature, eight 225 DEG C of area's temperature, 245 DEG C of head temperature；Engine speed 400rpm.
Embodiment 3
Weigh the parts by weight of PBT resin 40, the parts by weight of ASA resin 25, the weight of acrylate acrylonitrile styrene block copolymer 4
Measure part, antioxidant (Hinered phenols, phosphite ester based composition, by weight 1：2 mixing) 0.2 parts by weight, the weight of lubricant 0.3
Part, it is uniform to be added to high-speed mixer and mixing in certain sequence, is added to by main feeding hopper in double screw extruder, while by 30
The surface modified glass fiber of parts by weight is added by glass fiber opening, is melted, kneads, extrudes, is granulated through double screw extruder, obtains
Low warpage high-strength glass fiber enhanced PBT/ASA alloy materials, each section of temperature be respectively：One 210 DEG C of area's temperature, two area's temperature 240
DEG C, three 240 DEG C of area's temperature, four 240 DEG C of area's temperature, five 235 DEG C of area's temperature, six 230 DEG C of area's temperature, seven 230 DEG C of area's temperature, 8th area
225 DEG C of temperature, 245 DEG C of head temperature；Engine speed 400rpm.
Embodiment 4
Weigh the parts by weight of PBT resin 40, the parts by weight of ASA resin 25, the parts by weight of ethylene-methyl acrylate copolymer 4, antioxygen
Agent (Hinered phenols, phosphite ester based composition, by weight 1：2 mixing) 0.2 parts by weight, the weight of lubricant (Tissuemat E) 0.3
Part is measured, high-speed mixer and mixing is added in certain sequence uniformly, is added to by main feeding hopper in double screw extruder, simultaneously will
The surface modified glass fiber of 30 parts by weight is added by glass fiber opening, is melted, kneads, extrudes, is granulated through double screw extruder, obtains
To low warpage high-strength glass fiber enhanced PBT/ASA alloy materials, each section of temperature is respectively：One 210 DEG C of area's temperature, two area's temperature
240 DEG C, three 240 DEG C of area's temperature, four 240 DEG C of area's temperature, five 235 DEG C of area's temperature, six 230 DEG C of area's temperature, seven 230 DEG C of area's temperature,
Eight 225 DEG C of area's temperature, 245 DEG C of head temperature；Engine speed 400rpm.
Embodiment 5
Weigh the parts by weight of PBT resin 40, the parts by weight of ASA resin 25, the weight of acrylate acrylonitrile styrene block copolymer 2
Measure part, the parts by weight of ethylene-methyl acrylate copolymer 2, mica powder (1250 mesh) 6 parts by weight, antioxidant (Hinered phenols, phosphorous
Acid esters based composition, by weight 1：2 mixing) 0.2 parts by weight, the parts by weight of lubricant (Tissuemat E) 0.3, in certain sequence plus
Enter to high-speed mixer and mixing uniformly, be added to by main feeding hopper in double screw extruder, while the surface of 24 parts by weight is changed
Property glass fibre is added by glass fiber opening, is melted, kneads, extrudes, is granulated through double screw extruder, obtains low warpage high-strength glass
Fiber enhanced PBT/ASA alloy materials, each section of temperature be respectively：One 210 DEG C of area's temperature, two 240 DEG C of area's temperature, three area's temperature 240
DEG C, four 240 DEG C of area's temperature, five 235 DEG C of area's temperature, six 230 DEG C of area's temperature, seven 230 DEG C of area's temperature, eight 225 DEG C of area's temperature, head
245 DEG C of temperature；Engine speed 400rpm.
Embodiment 6
Weigh the parts by weight of PBT resin 40, the parts by weight of ASA resin 25, the weight of acrylate acrylonitrile styrene block copolymer 2
Measure part, the parts by weight of ethylene-methyl acrylate copolymer 2, the parts by weight of hollow glass micropearl 6, antioxidant (Hinered phenols, phosphorous acid
Ester composition, by weight 1：2 mixing) 0.2 parts by weight, the parts by weight of lubricant (Tissuemat E) 0.3 add in certain sequence
It is uniform to high-speed mixer and mixing, it is added to by main feeding hopper in double screw extruder, while the surface of 24 parts by weight is modified
Glass fibre is added by glass fiber opening, is melted, kneads, extrudes, is granulated through double screw extruder, obtains low warpage high intensity glass
Strengthen PBT/ASA alloy materials, each section of temperature is respectively：One 210 DEG C of area's temperature, two 240 DEG C of area's temperature, three 240 DEG C of area's temperature,
Four 240 DEG C of area's temperature, five 235 DEG C of area's temperature, six 230 DEG C of area's temperature, seven 230 DEG C of area's temperature, eight 225 DEG C of area's temperature, head temperature
245 DEG C of degree；Engine speed 400rpm.
Embodiment 7
Weigh the parts by weight of PBT resin 40, the parts by weight of ASA resin 25, the weight of acrylate acrylonitrile styrene block copolymer 2
Measure part, the parts by weight of ethylene-methyl acrylate copolymer 2, the parts by weight of hollow glass micropearl 6, the weight of antioxidant (Hinered phenols) 0.2
Part, the parts by weight of lubricant (Tissuemat E) 0.3, rheology modifier (the polyamidoamine dendrimer rheology of amino end group
Modifying agent) 0.2 parts by weight, high-speed mixer and mixing is added in certain sequence uniformly, and being added to twin-screw by main feeding hopper squeezes
Go out in machine, while the surface modified glass fiber of 24 parts by weight is added by glass fiber opening, melt, mix through double screw extruder
Refining, extrusion, granulation, obtain low warpage high-strength glass fiber enhanced PBT/ASA alloy materials, each section of temperature is respectively：One area's temperature
210 DEG C, two 240 DEG C of area's temperature, three 240 DEG C of area's temperature, four 240 DEG C of area's temperature, five 235 DEG C of area's temperature, six 230 DEG C of area's temperature,
Seven 230 DEG C of area's temperature, eight 225 DEG C of area's temperature, 245 DEG C of head temperature；Engine speed 400rpm.
Product of the present invention is according to following standard testing performance：
Tensile strength, bending strength and impact strength are carried out according to ISO 527-2, ISO 178 and the standards of ISO 179 respectively
Test；Melt index is according to ISO1133 standard testings；Molding shrinkage is according to GB/T 17037.4-2003 standard testings, with hanging down
Nogata is to shrinkage factor and flows to the warpage degree that direction shrinkage factor difference characterizes material.1-7 performance test knots of the embodiment of the present invention
Fruit is as shown in table 1：The embodiment 1-7 the performance test results of table 1
The compounding use that can be seen that compatible toughening agents from above-described embodiment properties of product result can protect alloy material
Hold preferable comprehensive mechanical property；Mica powder and hollow glass micropearl can improve the warpage issues of material to a certain extent,
But the mechanical property of material can be reduced；Rheology modifier can then significantly improve the mobility of alloy.Therefore, embodiment 7 is comprehensive
Close performance optimal, not only ensure that alloy material has excellent mechanical property, and improve warpage issues, improve shaping and add
Work performance.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials, it is characterised in that by weight, including:
2. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 1, it is characterised in that：It is described
PBT resin is the polymer that butanediol and terephthalic acid (TPA) or its class ester derivative are obtained by polycondensation reaction, and its characteristic is glued
Number is 0.8-1.3ml/g.
3. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 2, it is characterised in that：It is described
ASA resin for by matrix of SAN by emulsion method or mass polymerization obtain with the caoutchouc elasticity containing acrylate group
Body is core, using SAN as shell, i.e., the acrylonitrile-styrene-acrylic ester ternary with core-shell structure
The weight content of the rubber elastomer containing acrylate group is 10~80% in copolymer, the terpolymer.
4. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 3, it is characterised in that：It is described
Glass fibre is the glass fibre being surface-treated by the silane coupler containing epoxide group or amido functional group.
5. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 3, it is characterised in that：It is described
Compatible toughening agents are maleic anhydride grafted ethene and octene copolymer, acrylate acrylonitrile styrene block copolymer, polyester
One or more in elastomer, polyolefin elastomer, ethylene-methyl acrylate copolymer.
6. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 5, it is characterised in that：It is described
That resist warping agent is the one or more in mica, wollastonite, hollow glass micropearl.
7. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 6, it is characterised in that：It is described
Antioxidant is any one in Hinered phenols, phosphorous acid esters and thioether antioxidants or two or more compositions.
8. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 7, it is characterised in that：It is described
Lubricant is composition more than one or both of Tissuemat E, silicone master batch or pentaerythritol stearate.
9. low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to claim 8, it is characterised in that：It is described
Rheology modifier is the polyamidoamine dendrimer rheology modifier of amino end group, terminal hydroxy group or end carboxyl.
10. the realization of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials according to any one of claim 1~9
Method, it is characterised in that comprise the following steps：
(1), by the PBT resin being separately dried in advance, ASA resin, compatible toughening agents, that resist warping agent, antioxidant, lubricant and
Rheology modifier, by weight, the parts by weight of PBT resin 30~50；The parts by weight of ASA resin 15~30；Glass fibre 20~30
Parts by weight；The parts by weight of compatible toughening agents 2~6；The parts by weight of that resist warping agent 6~10；The parts by weight of antioxidant 0.1~0.5；Lubricant
0.1~0.5 parts by weight；It is well mixed rear stand-by that the ratio of the parts by weight of flow ability modifying agent 0.1~0.8 is added to high mixer；
(2), the mixture that the first step is obtained is fed into double screw extruder by main feeding hopper, in 205-245 DEG C of temperature
Extruding pelletization in the range of degree, glass fibre is added from glass fiber opening, last tie rod, pelletizing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047659A (en) * | 2017-11-21 | 2018-05-18 | 横店集团得邦工程塑料有限公司 | A kind of PBT/PC/ASA composite materials and preparation method thereof |
| CN109401221A (en) * | 2018-09-30 | 2019-03-01 | 金旸（厦门）新材料科技有限公司 | Weather-proof low warp glass fiber enhancing PBT/AS/ASA material of one kind and preparation method thereof |
| CN109575551A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Modified resin and its preparation method and application for heat conduction and heat radiation |
| CN109836783A (en) * | 2018-12-29 | 2019-06-04 | 太仓市华鼎塑料有限公司 | A kind of antistatic fiber glass reinforced PBT/ASA composite material and preparation method thereof |
| CN110804282A (en) * | 2019-11-14 | 2020-02-18 | 福建华塑新材料有限公司 | Modified flat glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
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| CN115594954A (en) * | 2022-10-11 | 2023-01-13 | 河南天海电器有限公司（Cn） | PBT/ASA alloy material and preparation method and application thereof |
| CN115926399A (en) * | 2023-01-03 | 2023-04-07 | 亚瀚材料科技(上海)有限公司 | Low-warpage ultrasonic welding material and preparation process thereof |
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| CN113337089A (en) * | 2021-07-22 | 2021-09-03 | 合肥圆融新材料有限公司 | Glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
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| CN115594954A (en) * | 2022-10-11 | 2023-01-13 | 河南天海电器有限公司（Cn） | PBT/ASA alloy material and preparation method and application thereof |
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