CN104725844A - Micro-foaming PA/ASA (polyamide/acrylonitrile styrene acrylate) material and preparation method thereof - Google Patents
Micro-foaming PA/ASA (polyamide/acrylonitrile styrene acrylate) material and preparation method thereof Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- 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
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a micro-foaming PA/ASA (polyamide/acrylonitrile styrene acrylate) material and a preparation method thereof. The micro-foaming PA/ASA material is prepared from PA resin, ASA resin, a toughening agent, a lubricating agent, a compatilizer, an antioxidant and a foaming agent in parts by weight by virtue of two-step method fusion and extrusion as well as injection molding. The toughness of the material is improved, and the material has excellent mechanical properties of both PA and ASA, and is stable in size, good in fluidity and excellent in weathering resistance; and meanwhile, the problems of poor fluidity and shrinkage marks during injection molding of a PA/ASA product are solved, so that the micro-foaming PA/ASA material can be widely applied to the fields of automobiles, electronic appliances, electric tools and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of special feel fretting map PA/ASA material and preparation method thereof.
Background technology
Polyamide (PA) is commonly called as nylon (Nylon), as the plastics that five large-engineering plastics are the most frequently used, is widely used in machinery, instrument, power tool, automobile and other industries.There is the plurality of advantages such as wear-resisting, oil resistant, self-lubricating, good mechanical performance, but the shortcomings such as its water-intake rate is large, poor dimensional stability, ageing-resistant deficiency also limit its application.
ASA resin is by styrene-acrylonitrile-acrylate copolymer and SAN melt blending gained, compared with ABS, introduce not double bond containing acrylate and instead of divinyl, the weathering resistance of ASA is made to obtain the improvement of essence, the severe environment such as outdoor high light, humidity, oxidation can be chronically exposed to and keep physical property to stablize, being therefore widely used in the fields such as electronic apparatus, automobile, exterior decorative materials, material of construction.
PA/ASA has the thermotolerance of the good toughness of ASA, weathering resistance, dimensional stability and PA concurrently, and as a kind of material having special feel, in automotive trim, Application comparison is ripe.But PA is a kind of strong polarity crystalline material, melt viscosity is large, ASA is a kind of low-pole amorphous material, both solubility parameters differences are larger, therefore there is the problem that two-phase interface is compatible, easily cause mechanical property to be deteriorated, and batch mixing inequality very easily cause course of processing material local incompatible and make shaping product mechanical degradation.
Summary of the invention
The object of this invention is to provide a kind of special feel fretting map PA/ASA material and preparation method thereof, this material solves existing PA/ASA material in preparation process, occurs processing stability problem, the product of preparation have good stability of the dimension, shock strength high, have excellent weather resistance, the advantage such as easy-formation processing.
The present invention adopts following technical scheme to achieve these goals:
A kind of fretting map PA/ASA matrix material, is made up of by weight following component:
PA resin 40-70 part
ASA resin 20-70 part
Toughner 5-20 part
Oxidation inhibitor 0.4-1.0 part
Lubricant 0.2-1 part
Compatilizer 5-10 part
Whipping agent 0.1-10 part.
Further, described PA resin is one or both mixing in PA6 and PA66, its relative viscosity 2.0-4.0.
Further, described ASA resin is styrene-acrylonitrile-acrylate terpolymer, and wherein the mass percentage of rubber is 30-70%.
Further, described toughner is one or both in POM grafted maleic anhydride and EPDM grafted maleic anhydride
Further, described lubricant is selected from pentaerythritol stearate, N, N-and has supportted at least one in bis-stearamides, montanin wax, monoglyceride acid number, amide waxe, butyl stearate, ethylene bis stearamide.
Further, described compatilizer is ABS grafted maleic anhydride (ABS-g-MAH) or ASA grafted maleic anhydride (ASA-gMAH).
Further, oxidation inhibitor used is a kind of in suffocated amine antioxidant, phosphorous acid lipid or complex class oxidation inhibitor.The present invention particularly preferably suffocated amine antioxidant is N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098), phosphorous acid lipid is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (irgasfos 168).
Further, whipping agent used is Cellmic C 121 or one or both mixtures of azo diformazan diisopropyl ester.
Another object of the present invention is to provide the preparation method of above-mentioned fretting map PA/ASA matrix material, comprises the steps:
(1) after PA resin, toughner, lubricant, oxidation inhibitor being mixed by recipe ratio, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains toughness reinforcing PA material;
(2) after toughness reinforcing PA material, ASA resin and compatilizer together being mixed, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains PA/ASA matrix material;
(3) PA/ASA matrix material is mixed with whipping agent, then injection moulding in injection moulding machine, obtain injection grade fretting map PA/ASA matrix material.
The present invention has following beneficial effect:
(1) the present invention add have compatilizer characteristic concurrently toughner to prepare toughness reinforcing PA material, on the one hand the PA material of toughner and different viscosity can be made fully to merge, the toughening efficiency of alloy material is improved; On the other hand when with ASA resin second melting, its compatilizer characteristic can find full expression, and improves the consistency between PA and ASA; Finally toughness reinforcing PA material and ASA, compatilizer secondary are extruded through forcing machine, degree of making improves further under compatilizer effect again, ensure that the stable of material mechanical performance.So adding of toughner not only serves good toughening effect, more auxiliary compatilizer, makes PA and ASA two-phase consistency better, shows excellent mechanical property.
(2) in PA/ASA matrix material, add whipping agent mixing, then injection moulding, the product that can mold fuller complexity introduced by whipping agent, can be widely used in the fields such as automobile, electronic apparatus, power tool.
(3) the fretting map PA/ASA matrix material prepared of the present invention, the size solving PA is unstable, the shortcoming of easily water suction.
(4) adopt viscosity to be the PA resin of 2.0-4.0 in the present invention, thus well regulate the mobility of alloy material; In addition, the mass percentage of the rubber of ASA resin is 30-70%, and because wherein polyacrylic rubber is saturated structures, not containing double bond, bond energy is higher, not easily decomposes under UV-irradiation, xanthochromia occurs, therefore imparts the weather resistance that alloy material is higher.
Embodiment
In embodiment, PA Choice of Resin relative viscosity is the PA6 of 2.0-4.0 or/or PA66 below;
The mass percentage of ASA Choice of Resin rubber is the styrene-acrylonitrile-acrylate terpolymer of 30-70%.
embodiment 1:
PA resin 55 parts
ASA resin 30 parts
Toughner POE grafted maleic anhydride 10 parts
1,098 0.4 parts, oxidation inhibitor
Lubricant pentaerythritol stearate 0.3 part
Compatilizer ABS-g-MAH 5 parts
Whipping agent Cellmic C 121 0.1 part
Preparation method is as follows:
(1) after PA resin, toughner, lubricant, oxidation inhibitor being mixed by recipe ratio, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains toughness reinforcing PA material;
(2) after toughness reinforcing PA material, ASA resin and compatilizer together being mixed, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains PA/ASA matrix material;
(3) PA/ASA matrix material is mixed with whipping agent, then injection moulding in injection moulding machine, obtain injection grade fretting map PA/ASA matrix material.
embodiment 2:
PA resin 65 parts
ASA resin 20 parts
Toughner POE grafted maleic anhydride 10 parts
1,098 0.4 parts, oxidation inhibitor
Lubricant N, N-have supportted bis-stearamides 0.2 part
Compatilizer ASA-g-MAH 5 parts
Whipping agent azo diformazan diisopropyl ester 0.5 part
Preparation method is with embodiment 1.
embodiment 3:
PA resin 60 parts
ASA resin 20 parts
Toughner POE grafted maleic anhydride 15 parts
1,098 0.4 parts, oxidation inhibitor
Lubricant pentaerythritol stearate 0.3 part
Compatilizer ASA-g-MAH 5 parts
Whipping agent azo diformazan diisopropyl ester 1 part
Preparation method is with embodiment 1.
embodiment 4:
PA resin 60 parts
ASA resin 20 parts
Toughner EPDM grafted maleic anhydride 10 parts
Irgasfos 168 0.4 part
Lubricant monoglyceride acid number 0.3 part
Compatilizer ABS-g-MAH 5 parts
Whipping agent Cellmic C 121 5 parts
Preparation method is with embodiment 1.
embodiment 5:
PA resin 60 parts
ASA resin 20 parts
Toughner POE grafted maleic anhydride 5 parts
Toughner EPDM grafted maleic anhydride 5 parts
Irgasfos 168 0.8 part
Pentaerythritol stearate 0.2 part
Compatilizer ABS-g-MAH 5 parts
Whipping agent azo diformazan diisopropyl ester 5 parts
Preparation method is with embodiment 1.
embodiment 6:
PA resin 55 parts
ASA resin 20 parts
Toughner POE grafted maleic anhydride 10 parts
1,098 1 parts, oxidation inhibitor
Amide waxe 0.5 part
Butyl stearate 0.5 part
Compatilizer ASA-g-MAH 5 parts
Whipping agent azo diformazan diisopropyl ester 5 parts
Cellmic C 121 5 parts
Preparation method is with embodiment 1.
comparative example 1, its composition is with embodiment 2, but employing is that single stage method is made:
PA resin 65 parts
ASA resin 20 parts
Toughner POE grafted maleic anhydride 10 parts
1,098 0.4 parts, oxidation inhibitor
N, N-have supportted bis-stearamides 0.2 part
Compatilizer ASA-g-MAH 5 parts
Preparation method is as follows:
Take each component of above weight percentage, and add in low speed mixer and mix, be added in the hopper of twin screw extruder by the material mixed, through melt blending, extruding pelletization becomes the PA/ASA material of injection grade.
comparative example 2, preparation method with embodiment 2, but adopts ABS resin to carry out modification PA resin:
PA resin 65 parts
ABA resin 20 parts
Toughner POE grafted maleic anhydride 10 parts
1,098 0.4 parts, oxidation inhibitor
N, N-have supportted bis-stearamides 0.2 part
Compatilizer ASA-g-MAH 5 parts
Preparation method is as follows:
(1) after PA resin, toughner, lubricant, oxidation inhibitor being mixed by recipe ratio, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains toughness reinforcing PA material;
(2) after toughness reinforcing PA material, ASA resin and compatilizer together being mixed, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains PA/ASA matrix material.
The correlated performance of alloy material prepared by above-described embodiment 1-4 and comparative example 1-2 detects as shown in following table one:
The main physical index of table one:
| Project | Testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 |
| Melt flow rate (MFR) g/10min | GB/T3682 | 20 | 15 | 10 | 25 | 25 | 30 | 18 | 18 |
| Tensile strength MPa | GB/T1040 | 38 | 35 | 30 | 35 | 32 | 35 | 30 | 33 |
| Flexural strength MPa | GB/T9341 | 41 | 42 | 43 | 48 | 45 | 50 | 35 | 40 |
| Modulus in flexure MPa | GB/T9341 | 1200 | 1300 | 1200 | 1400 | 1400 | 1600 | 1200 | 1300 |
| Notched Izod impact strength KJ/m2 | GB/T1843 | 70 | 75 | 90 | 50 | 48 | 40 | 30 | 70 |
| Product outward appearance | Not easily xanthochromia, product are full | Not easily xanthochromia, product are full | Not easily xanthochromia, product are full | Not easily xanthochromia, product are full | Not easily xanthochromia, product are full | Not easily xanthochromia, product are full | Not easily xanthochromia, easily layering | Easy xanthochromia |
As can be seen from upper table one, embodiment 1 is compared with embodiment 2, and increase the content of PA, material impact intensity can slightly increase; Embodiment 2, compared with embodiment 3, increases the content of toughner, and alloy material toughness improves clearly; Along with the increase of whipping agent add-on, alloy material toughness meeting decrease to some degree, but its flexural strength and modulus in flexure then can rise, and can better mold fuller product.And comparative example 1 and embodiment 2 are Comparatively speaking, because embodiment 2 is the PA/ASA matrix materials prepared by two-step approach, the tough performance of its material is better improved, and stable performance; And comparative example 1 adopts one-step synthesis method PA/ASA material, its basic mechanical property is on the low side, and its shock strength is very unstable.And undertaken by embodiment 2 and comparative example 2 that UV is aging can be found out, adding of ASA resin makes the weathering resistance of alloy material significantly improve to PA resin modified.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1. a fretting map PA/ASA matrix material, is characterized in that: be made up of by weight following component:
PA resin 40-70
ASA resin 20-70 part
Toughner 5-20 part
Oxidation inhibitor 0.4-1.0 part
Lubricant 0.2-1 part
Compatilizer 5-10 part
Whipping agent 0.1-10 part.
2. fretting map PA/ASA matrix material according to claim 1, is characterized in that: described PA resin is one or both mixing in PA6 and PA66, its relative viscosity 2.0-4.0.
3. fretting map PA/ASA matrix material according to claim 1, it is characterized in that: described ASA resin is styrene-acrylonitrile-acrylate terpolymer, wherein the mass content of rubber is 30-70%.
4. fretting map PA/ASA matrix material according to claim 1, is characterized in that: described toughner is one or both in POE grafted maleic anhydride and EPDM grafted maleic anhydride.
5. fretting map PA/ASA matrix material according to claim 1, is characterized in that: described lubricant is selected from pentaerythritol stearate, N, N-and has supportted at least one in bis-stearamides, butyl stearate.
6. fretting map PA/ASA matrix material according to claim 1, is characterized in that: described compatilizer is ABS grafted maleic anhydride or ASA grafted maleic anhydride.
7. a fretting map PA/ASA matrix material according to claim 1, is characterized in that: oxidation inhibitor used is a kind of in Hinered phenols antioxidant, phosphorous acid lipid or suffocated amine antioxidant.
8. special feel fretting map PA/ASA material according to claim 1, is characterized in that: described whipping agent is at least one in Cellmic C 121 or azo diformazan diisopropyl ester.
9. prepare a method for fretting map PA/ASA matrix material as claimed in claim 1, it is characterized in that: comprise the steps:
(1) after PA resin, toughner, lubricant, oxidation inhibitor being mixed by recipe ratio, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains toughness reinforcing PA material;
(2) after toughness reinforcing PA material, ASA resin and compatilizer together being mixed, join in twin screw extruder, carry out after melting extruding, cool, air-dry, pelletizing obtains PA/ASA matrix material;
(3), after being mixed with whipping agent by PA/ASA matrix material, injection moulding in injection moulding machine, obtains injection grade fretting map PA/ASA matrix material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178920A (en) * | 2017-12-19 | 2018-06-19 | 会通新材料股份有限公司 | A kind of lightweight, high-ductility, low water absorption 6 micro foaming composite material of ultra-high molecular weight polyethylene/nylon and preparation method thereof |
| CN109276010A (en) * | 2018-09-21 | 2019-01-29 | 雅香丽化妆用品（深圳）有限公司 | A method of makeup bristle head and manufacture makeup bristle head |
| CN110003633A (en) * | 2019-04-28 | 2019-07-12 | 苏州博驰新材料有限公司 | A kind of fretting map PC/ASA alloy material and its chemical foaming technology |
| 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 |
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| CN108178920A (en) * | 2017-12-19 | 2018-06-19 | 会通新材料股份有限公司 | A kind of lightweight, high-ductility, low water absorption 6 micro foaming composite material of ultra-high molecular weight polyethylene/nylon and preparation method thereof |
| CN109276010A (en) * | 2018-09-21 | 2019-01-29 | 雅香丽化妆用品（深圳）有限公司 | A method of makeup bristle head and manufacture makeup bristle head |
| CN110003633A (en) * | 2019-04-28 | 2019-07-12 | 苏州博驰新材料有限公司 | A kind of fretting map PC/ASA alloy material and its chemical foaming technology |
| 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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