CN102337025A - High notched impact PA/ASA alloy material and its preparation method - Google Patents

High notched impact PA/ASA alloy material and its preparation method Download PDF

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Publication number
CN102337025A
CN102337025A CN2010102300619A CN201010230061A CN102337025A CN 102337025 A CN102337025 A CN 102337025A CN 2010102300619 A CN2010102300619 A CN 2010102300619A CN 201010230061 A CN201010230061 A CN 201010230061A CN 102337025 A CN102337025 A CN 102337025A
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China
Prior art keywords
asa
notch shock
abs
alloy according
high notch
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Pending
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CN2010102300619A
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Chinese (zh)
Inventor
代汝军
王海波
马俊杰
马庆维
韩杰
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Heilongjiang Xinda Enterprise Group Co Ltd
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HARBIN XINDA POLYMER MATERIAL ENGIENERING CENTER CO Ltd
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Priority to CN2010102300619A priority Critical patent/CN102337025A/en
Publication of CN102337025A publication Critical patent/CN102337025A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a high notched impact PA/ASA alloy material and its preparation method. The high notched impact PA/ASA alloy material comprises the following components of: by weight, 30-90 parts of PA, 20-80 parts of ASA, 3-15 parts of a compatilizer, 3-20 parts of a flexibilizer, 0.2-0.5 part of a lubricant, 0.2-1 part of an anti-oxidant. The raw materials are weighed according to the above proportion and are mixed and extruded by a double screw extruder to prepare the PA/ASA alloy. Similar to PA/ABS, the prepared PA/ASA has good impact strength, good thermal stability and more excellent dimensional stability than PA. As ASA is used to replace ABS, PA/ASA has better weatherability and chemical resistance than PA/ABS. Due to self-lubricating property of PA, PA/ASA has better wear resistance than PC/ASA. The PA crystal material and the ASA amorphous material are mixed to possess good noise abatement and damping performance. The preparation method provided by the invention is used to greatly raise the notched impact strength of alloy without influencing processing performance and other mechanical properties, and is suitable for products which have high requirements on toughness. The product provided by the invention is an excellent substitutive material in the fields of automobile, electronics and electricity and the like.

Description

A kind of high notch shock PA/ASA alloy material and preparation method thereof
Technical field
The invention discloses a kind of high notch shock PA/ASA alloy material and preparation method thereof.
Background technology
Because the polymkeric substance that PA is a kind of crystallinity, strong polarity, melt strength is very low; And ASA is the polymkeric substance of a kind of amorphism, low-pole; The SP of the two differs bigger; It is incompatible to belong to thermodynamics, and simple blend causes two-phase interface tension force very big, thereby causes mechanical property relatively poor.
The ASA resin is the melt blended material of ASA (Acrylate-Styrene-Acrylonitrile) graft copolymer and styrene-acrylonitrile copolymer (SAN resin).Compare with ABS, replace divinyl rubber, thereby weathering resistance there has been essential improvement, exceeded about 10 times than ABS owing to introduce not double bond containing acrylic elastomer; And other mechanical properties, processing characteristics, electrical insulating property, chemical resistance are similar with ABS.
The rubbery kernel strata acrylic elastomer of ASA graft copolymer is a saturated structures; Do not contain residual double bonds; Hydrogen dissociation energy in this rubber is 90kcal/mol; Under the high energy gamma source light (not existing in the tellurian solar ray) of the following wavelength of 300nm, dissociate, promptly the molecular structure of ASA resin is difficult for by the high energy gamma source photolysis.And remaining α-hydrogen dissociation energy is 39kcal/mol in the rubber layer polyhutadiene of ABS toughner, be prone to by the low energy light of the following wavelength of 700nm or by airborne oxygen, and ozone, photolysis, its rerum natura also sharply descends thereupon, the concurrent look that changes.Therefore the ASA resin has high weathering resistance, shelves outdoorly for a long time, and the cosmetic variation of its resin properties and moulding article significantly reduces than ABS resin, and the ASA resin obviously is superior to ABS resin aspect chemical resistant properties in addition.
It is less relatively that domestic relevant research is carried out, and domestic enterprise does not grasp ASA resin industrialization production technology.Have only a spot of ABS manufacturers to produce ASA simultaneously in the world; Though reason is manufacturing processed and has tangible similarity; But aspect synthetic, significant difference is arranged also; External product all is overseas to produce in China, and the core production technology is only grasped abroad in the minority large chemical complex hand, like BASF AG and Saudi Aribian Basic Industry Company's (former U.S. GE plastics) of Germany.
PA/ASA is the same with PA/ABS, has high shock strength, good thermostability, has than PA excellent size stability; Replaced ABS with ASA, PA/ASA has than PA/ABS better weather resistance and chemical-resistant; Because the self lubricity of PA, the wear resistance of PA/ASA is superior to PC/ASA; PA crystalline material and the blend of ASA amorphous material have good sound deadening shock absorption performance; In addition, PA/ASA also has special surperficial soft sedate matt effect, is specially adapted in the automotive upholstery.
Summary of the invention
Technical problem to be solved by this invention provides high, good, the good fluidity of dimensional stability of a kind of jagged shock strength, PA and ASA Alloy And Preparation Method.
A kind of high notch shock PA/ASA alloy material is characterized in that shock strength is high, good fluidity, comprises following component and content:
PA 30-90 part
ASA 20-80 part
Compatilizer 3-15 part
Toughner 3-20 part
Lubricant 0.2-0.5 part
Oxidation inhibitor 0.2-1 part.
Described PA is one or both mixing among PA6 and the PA66, and relative viscosity is between 2.0-4.0.
Described ASA is a kind of or two kinds of mixing in ASA resin and the ASA grafting powder.
The melt flow rate(MFR) of described ASA is between 2-10g/min.
Described compatilizer is one or more in ABS grafted maleic anhydride (ABS-g-MAH), ASA grafted maleic anhydride (ASA-g-MAH), the polystyrene-maleic anhydride multipolymer (SMA).
The content of the maleic anhydride of said compatilizer is 3-30%
Described toughner is one or both mixtures among grafting POE, the grafting EPDM.
Described lubricant is one or more of ethylene bis stearic acid amide (EBS), silicone oil, Hydrocerol A three (18) ester.
Described oxidation inhibitor is that alkyl list phenolic antioxidant is 1076, alkyl Polyphenols oxidation inhibitor is 1010, the hydrazides class is 1024, phosphite ester kind antioxidant is in 168 and 626 one or more.
A kind of preparation method of high notch shock PA/ASA alloy material may further comprise the steps
(1) takes by weighing raw material by proportioning;
(2) PA, ASA, compatilizer, toughner and an amount of silicone oil were put into high-speed mixer and mixing 1-5 minute;
(3) again lubricant and oxidation inhibitor were added high-speed mixer and mixing 1-5 minute;
(4) discharging
(5) with mixed raw materials extruding pelletization in twin screw, screw speed is 150-900 rev/min, temperature 210-280 ℃.
PA/ASA alloy material of the present invention and preparation method thereof makes the PA/ASA alloy at comprehensive PA with beyond the ASA premium properties separately, has solved the shortcoming that the nylon cloth size is unstable, be prone to suction; Owing to adopted not double bond containing ASA to replace ABS, the weather resistance of alloy material improves greatly, when adding compatilizer, material has been carried out toughness reinforcing processing in addition; Not only solved the thermodynamics inconsistent problem of PA and ASA; And the alloy material of preparation has outstanding notch shock performance, and processing characteristics is good, can replace the PC/ASA alloy product; And have matt effect, can be used for the demanding product of automotive upholstery and toughness of products.
Embodiment
To further explain of the present invention, but the present invention is not limited to each example of following enforcement below in conjunction with specific embodiment:
Main use starting material are following:
PA be U.S. Honeywell and Japanese Asahi Chemical Industry in sticking PA; ASA is the 777K that BASF AG produces, the LI 913 that bright and beautiful lake company produces, the 960A of Chemtura, the ASA powder of Japanese UMG; Compatilizer is that SMA is a last maritime affairs Bi Da High-tech company, the KT-5A that Shenyang section is logical etc.; Toughner is mainly five or three grafting POE, the grafting POE of the liter of day and grafting EPDM.
Embodiment 1-3
The prescription of embodiment 1-3 is seen table 1.
Table 1
Whole components of embodiment 1-3 in the last table are joined discharging behind the stirring 3min in the high-speed mixer in proportion respectively, use the twin screw extruder granulation then, the screw speed of forcing machine is 150-900 commentaries on classics/min, and processing temperature is 210-280 ℃.
Prepare product with above according to embodiment 1-3, prepare test bars according to same injecting condition, concrete injecting condition is: injection temperature: 220-270 ℃, and injection pressure 40-60MPa.
Concrete Performance Detection is following:
Shock strength: detect according to ISO 179.
Tensile strength and elongation at break: detect according to ISO527.
Flexural strength and modulus in flexure: detect according to ISO 178.
Ball-indentation hardness: detect according to ISO 2039.
Melt flow rate(MFR): according to 250 ℃ of Comparative Examples reference standards, 5Kg detects.
The properties of sample that makes of embodiment 1-3 is seen table 2, and Comparative Examples is the commercial PA/ASA product of German Schulman company
Table 2
From table 2, can find out: 1) proportioning of PA and ASA is bigger to the final performance impact of product; 2) different compatilizer impact performance impacts are bigger; 3) different auxiliary agents and ASA influence the processing characteristics 4 of the finished product) adding of toughner can improve the shock strength of product.
Through adjustment PA auxiliary agent and the auxiliary agent different with use with the proportioning of ASA, the notched Izod impact strength of product can be greater than 50KJ/m 2, the notched Izod impact strength of product is far longer than external PA/ASA alloy product and PA and ASA product, and other performances also can surpass external imported product performance, and processing characteristics is good simultaneously, is easy to painted.

Claims (10)

1. one kind high notch shock PA/ASA alloy material is characterized in that shock strength is high, good fluidity, comprises following component and content:
PA 30-90 part
ASA 20-80 part
Compatilizer 3-15 part
Toughner 3-20 part
Lubricant 0.2-0.5 part
Oxidation inhibitor 0.2-1 part.
2. high notch shock PA/ASA alloy according to claim 1, it is characterized in that: PA is one or both mixing among PA6 and the PA66, and relative viscosity is between 2.0-4.0.
3. high notch shock PA/ASA alloy according to claim 1 is characterized in that: ASA is a kind of or two kinds of mixing in ASA resin and the ASA grafting powder.
4. high notch shock PA/ASA alloy according to claim 1, it is characterized in that: the melt flow rate(MFR) of ASA is between 2-10g/min.
5. high notch shock PA/ASA alloy according to claim 1 is characterized in that: compatilizer is one or more in ABS grafted maleic anhydride (ABS-g-MAH), ASA grafted maleic anhydride (ASA-g-MAH), the polystyrene-maleic anhydride multipolymer (SMA).
6. according to the said compatilizer of claim 5, it is characterized in that: the content of maleic anhydride is 3-30%.
7. high notch shock PA/ASA alloy according to claim 1 is characterized in that: toughner is one or both mixtures among grafting POE, the grafting EPDM.
8. high notch shock PA/ASA alloy according to claim 1 is characterized in that: lubricant is one or more of ethylene bis stearic acid amide (EBS), silicone oil, Hydrocerol A three (18) ester.
9. high notch shock PA/ASA alloy according to claim 1 is characterized in that: oxidation inhibitor is that alkyl list phenolic antioxidant is 1076, alkyl Polyphenols oxidation inhibitor is 1010, the hydrazides class is 1024, phosphite ester kind antioxidant is in 168 and 626 one or more.
10. a preparation method who prepares high notch shock PA/ASA alloy material as claimed in claim 1 is characterized in that: may further comprise the steps
(1) takes by weighing raw material by proportioning;
(2) PA, ASA, compatilizer, toughner and an amount of silicone oil were put into high-speed mixer and mixing 1-5 minute;
(3) again lubricant and oxidation inhibitor were added high-speed mixer and mixing 1-5 minute;
(4) discharging
(5) with mixed raw materials extruding pelletization in twin screw, screw speed is 150-900 rev/min, temperature 210-280 ℃.
CN2010102300619A 2010-07-19 2010-07-19 High notched impact PA/ASA alloy material and its preparation method Pending CN102337025A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104479348A (en) * 2014-12-17 2015-04-01 安徽科聚新材料有限公司 Weather-resistant matte-type high-strength PA6 and ASA alloy material and preparation method thereof
CN104725844A (en) * 2015-03-24 2015-06-24 合肥会通新材料有限公司 Micro-foaming PA/ASA (polyamide/acrylonitrile styrene acrylate) material and preparation method thereof
CN105273400A (en) * 2015-11-18 2016-01-27 上海俊尓新材料有限公司 Weather-resistant PA-ASA alloy material
CN106221103A (en) * 2016-08-05 2016-12-14 苏州创佳塑胶有限公司 High shiny black high glaze exempts from the material and preparation method thereof that sprays paint
CN106751801A (en) * 2016-12-12 2017-05-31 广东威林工程塑料股份有限公司 A kind of weather resistant lightweight shading dumb light PA56/ASA alloy materials and preparation method thereof
CN107513268A (en) * 2017-08-14 2017-12-26 上海长伟锦磁工程塑料有限公司 A kind of high heat-resisting PA/ASA alloy materials
CN107815101A (en) * 2017-11-28 2018-03-20 广东聚航新材料研究院有限公司 A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material and preparation method thereof
CN108034235A (en) * 2018-01-02 2018-05-15 上海中镭新材料科技有限公司 A kind of PA/ASA alloy materials and preparation method thereof
CN109608874A (en) * 2018-12-26 2019-04-12 天津金发新材料有限公司 A kind of antistatic, antibacterial PA6/ASA material, preparation method and applications
CN113136100A (en) * 2021-05-10 2021-07-20 会通新材料股份有限公司 PA6/ASA alloy material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1729252A (en) * 2002-11-29 2006-02-01 罗狄亚工程塑料有限责任公司 Electrically-conductive composition based on a polyamide matrix
CN101407630A (en) * 2008-11-21 2009-04-15 上海锦湖日丽塑料有限公司 PA / ASA alloy material and preparation thereof
CN101486825A (en) * 2008-01-17 2009-07-22 深圳市亚塑科技有限公司 Preparation of weather resistant PC and ASA copolymer alloy

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1729252A (en) * 2002-11-29 2006-02-01 罗狄亚工程塑料有限责任公司 Electrically-conductive composition based on a polyamide matrix
CN101486825A (en) * 2008-01-17 2009-07-22 深圳市亚塑科技有限公司 Preparation of weather resistant PC and ASA copolymer alloy
CN101407630A (en) * 2008-11-21 2009-04-15 上海锦湖日丽塑料有限公司 PA / ASA alloy material and preparation thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104479348A (en) * 2014-12-17 2015-04-01 安徽科聚新材料有限公司 Weather-resistant matte-type high-strength PA6 and ASA alloy material and preparation method thereof
CN104725844A (en) * 2015-03-24 2015-06-24 合肥会通新材料有限公司 Micro-foaming PA/ASA (polyamide/acrylonitrile styrene acrylate) material and preparation method thereof
CN105273400A (en) * 2015-11-18 2016-01-27 上海俊尓新材料有限公司 Weather-resistant PA-ASA alloy material
CN106221103A (en) * 2016-08-05 2016-12-14 苏州创佳塑胶有限公司 High shiny black high glaze exempts from the material and preparation method thereof that sprays paint
CN106751801A (en) * 2016-12-12 2017-05-31 广东威林工程塑料股份有限公司 A kind of weather resistant lightweight shading dumb light PA56/ASA alloy materials and preparation method thereof
CN107513268A (en) * 2017-08-14 2017-12-26 上海长伟锦磁工程塑料有限公司 A kind of high heat-resisting PA/ASA alloy materials
CN107815101A (en) * 2017-11-28 2018-03-20 广东聚航新材料研究院有限公司 A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material and preparation method thereof
CN108034235A (en) * 2018-01-02 2018-05-15 上海中镭新材料科技有限公司 A kind of PA/ASA alloy materials and preparation method thereof
CN109608874A (en) * 2018-12-26 2019-04-12 天津金发新材料有限公司 A kind of antistatic, antibacterial PA6/ASA material, preparation method and applications
CN113136100A (en) * 2021-05-10 2021-07-20 会通新材料股份有限公司 PA6/ASA alloy material and preparation method thereof
CN113136100B (en) * 2021-05-10 2022-03-22 会通新材料股份有限公司 PA6/ASA alloy material and preparation method thereof

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