CN101265360B - High heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material - Google Patents
High heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material Download PDFInfo
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Abstract
The invention discloses a high heat-resistant nylon/acrylonitrile-butadiene-styrene resin mixed material, which consists of nylon in an amount of 50 to 75 parts by weight, ABS resin in an amount of 10 to 25 parts by weight, styrene-N-phenyl maleimide copolymer in an amount of 5 to 15 parts by weight, and an inorganic filler in an amount of 5 to 15 parts by weight. The heat-resistant nylon/acrylonitrile-butadiene-styrene resin mixed material has excellent heat resistance, chemical resistance and mechanical property, and has the characteristics of low coefficient of linear thermal expansion, and excellent liquidity, so as to be sprayed on line, and be used for manufacturing such components as automobile fenders, rearview mirrors, tank cups and so on.
Description
Technical field
The present invention relates to a kind of intermingling material, relate in particular to and a kind ofly be the intermingling material of chief component by nylon (PA) and acrylonitrile-butadiene-styrene ternary copolymerized resin (ABS).
Background technology
Nylon, it is polymeric amide (PA) resin, not only every mechanical property is excellent, but also have excellent chemical reagent-resistant performance, good self-lubricating property and snappiness, therefore be widely used in every field, such as various trolley parts, electric power tool shell, electronic commerce device component, sports goods etc.Yet meanwhile, nylon also exists the shortcomings such as notch shock poor performance, dimensional stability be not good.
It is good that acrylonitrile-butadiene-styrene copolymer (ABS) resin itself has a dimensional stability, the characteristics that the notch shock performance is high, therefore, if nylon and ABS resin are made intermingling material, then may obtain a kind of so high notch shock performance, good dimensional stability, other properties are good material all.Yet ABS resin and nylon are substantially inconsistent in theory, will obtain above-mentioned desirable material for this reason, must adopt the technology of increase-volume.
European patent EP 0,202,214 have introduced a kind of styrene-acrylonitrile copolymer of modified by maleic acid anhydride graft that adopts as the method for PA/ABS intermingling material expanding material.Yet the PA/ABS intermingling material that obtains according to this method exists the problem that resistance toheat and rigidity (Young's modulus) descend.
At present, the blend of nylon and ABS resin is widely used in the preparation such as the outside component of the bodies of a motor car such as splash pan.Generally speaking, the body exterior part that is made of plastics all must spray paint.Be installed to the temporal difference of body exterior according to the plastic paste that sprays, can be divided into " off-line (off-line) " and " online (on-line) " two kinds of method for paint spraying.
In the lower situation of plastic hot stability, the method that can adopt what is called " off-line " to spray paint, namely spray paint plastic paste at low temperatures in the place beyond painting line first, then just is installed to vehicle body and gets on.The shortcoming of this method is to cause not mating of color.
And so-called " online " spray paint, directly to be installed to plastic paste first on the body exterior, then be incorporated in the lump in the painting line, so just require plastic paste must be able to resist the whole process of nearly 200 ℃ of high temperature in impregnated cathode coating (CDC) process, this thermostability for plastics has proposed very high requirement." online " method for paint spraying is the preferred of automotive industry, because it has simplified algorithm to greatest extent, in addition, also can obtain color-match best between plastics and the metal sheet.
So, the requirement of the body exterior plastic paste that sprays paint for " online ", except having good japanning and surface quality, good chemical resistance, good mechanical property and low thermal expansivity, also must have splendid resistance toheat, can tolerate the high temperature of the baking oven that sprays paint and do not deform.In addition, the plastic composition for the production of the body exterior part must show good flowability in molten state.
Summary of the invention
The purpose of this invention is to provide a kind of have splendid resistance toheat, good chemical resistance, good mechanical property and the high heat resistance nylon/acrylonitrile-butadiene-styrene resin of dimensional stability.
For achieving the above object, a kind of high heat resistance nylon/acrylonitrile-butadiene-styrene resin of the present invention is comprised of nylon, ABS resin, high heat-resisting expanding material vinylbenzene-N-phenylmaleimide multipolymer, mineral filler and oxidation inhibitor; Each component is counted by weight:
50～75 parts of nylon,
10～25 parts of ABS resin,
5～15 parts of vinylbenzene-N-phenylmaleimide multipolymer,
5～15 parts of mineral fillers;
And 0.3 part of antioxygen thermo-stabilizer.
Described ABS resin by weight percentage meter butadiene content is 40～70%.
Described nylon is number-average molecular weight 10000～28000, and fusing point is at 255～265 ℃, the nylon 66 of relative viscosity index between 2.0～4.0.
Described vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride by weight percentage meter styrene monomer content is 40-50%, and the N-phenylmaleimide monomer content is 45～55%, and maleic anhydride monomer content is 0～5%.
Described mineral filler is one of meta particle diameter talcum powder, wollastonite and white carbon black of being not more than 15 μ m or their mixture.
Adopt the nylon/acrylonitrile-butadiene-styrene resin mixing material of the preparation of technique scheme, have splendid thermotolerance, chemical resistant properties and mechanical property, and the characteristics such as coefficient of linear thermal expansion is lower, good fluidity are arranged, " online " spraying can be carried out, the making material of the component such as automobile fender, rear vision mirror and fuel tank cap can be used for.
Embodiment
The present invention is raw materials used:
Nylon 66 1 (PA66-1): relative viscosity 2.4, number-average molecular weight 14,000, fusing point is 260 ℃, the inferior company of Supreme Being sieve product;
Nylon 66 2 (PA6-2): relative viscosity 2.6, number-average molecular weight 18,000, fusing point is 262 ℃, German BASF AG product;
Nylon 66 3 (PA66-3): relative viscosity 3.4, number-average molecular weight 26,000, fusing point is 263 ℃, German BASF AG product.
ABS-1: the divinyl percentage composition is about 40%, and Korea S LG chemical company produces;
ABS-2: the divinyl percentage composition is about 60%, and the Lanzhou Petrochemical head factory is produced;
ABS-3: the divinyl percentage composition is about 70%, and U.S. GE company produces, Blendex338;
Vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride 1 (SMI-1): the NEC chemistry, MS-NC, percentage meter styrene monomer content is 48% by weight, the N-phenylmaleimide monomer content is 52%.
Vinylbenzene-N-phenylmaleimide multipolymer 2 (SMI-2): the NEC chemistry, MS-NA, percentage meter styrene monomer content is 46% by weight, the N-phenylmaleimide monomer content is 52%, contains in addition about 2% maleic anhydride.
Talcum powder 1, meta particle diameter are about 2 μ m;
Talcum powder 2, meta particle diameter are about 10 μ m;
Talcum powder 3, meta particle diameter are about 18 μ m;
Wollastonite, meta particle diameter are about 5 μ m;
White carbon black, meta particle diameter are about 2 μ m.
Oxidation inhibitor 1098:Ciba company, Irganox1098.
The product performance testing method:
Tensile property: press the ISO527 method, draw speed 50 mm/min.
Bending property: press the ISO178 method, trial speed 2 mm/min.
Charpy notched Izod impact strength: press the ISO179 method.
Heat-drawn wire: press the ISO75 method, 120 ℃/minute of temperature rise rates are tested under the 0.45MPa.
Embodiment 1-4 and comparative example 1
Nylon 66 2, ABS-2, SMI resin, talcum powder-1 and the oxidation inhibitor 1098 through super-dry, mix by the proportion of composing in the table 1 in parts by weight, wherein
Embodiment 1
PA66-2:50 ABS-2:25 SMI-1:10 talcum powder-115
Embodiment 2
PA66-2:55 ABS-2:20 SMI-1:15 talcum powder-110
Embodiment 3
PA66-2:60 ABS-2:20 SMI-1:10 talcum powder-110
Embodiment 4
PA66-2:75 ABS-2:15 SMI-2:5 talcum powder-15
Comparative example 1
PA66-2:65 ABS-2:25 SMI-1:10
And in each embodiment and comparative example 1, all added 0.3 part oxidation inhibitor 1098.
After pressing the mixing of above-described embodiment and comparative example, add twin screw extruder (screw diameter 35mm with the Double-screw feeder continuous uniform, length-to-diameter ratio L/D=36) in the main barrel, it is 220 ℃, 240 ℃, 260 ℃, 265 ℃, 260 ℃ that main barrel divides ten sections control temperature (exporting from charging opening to head), the twin screw rotating speed is 300 rev/mins, extrudes material strip and obtains product through pelletizing after the tank cooling.The said products is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 260 ℃ of injection temperatures.The batten of injection formed is put into immediately the glass moisture eliminator and carry out performance test after room temperature is placed at least 24 hours.Test result sees Table 1.
Composition and the performance of table 1PA/ABS blend
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| PA66-2 | 50 | 55 | 60 | 75 | 65 |
| ABS-2 | 25 | 20 | 20 | 15 | 25 |
| SMI-1 | 10 | 15 | 10 | 10 | |
| SMI-2 | 5 | ||||
| Talcum powder-1 | 15 | 10 | 10 | 5 |
| Oxidation inhibitor 1098 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Performance | |||||
| Tensile strength, MPa | 53.5 | 59.4 | 60.1 | 65.3 | 56.7 |
| Flexural strength, MPa | 88.3 | 80.2 | 82.6 | 90.5 | 78.3 |
| Modulus in flexure, MPa | 4600 | 3020 | 2880 | 2500 | 2040 |
| The Charpy notched Izod impact strength, kJ/m2 | 8.1 | 9.6 | 10.1 | 16.2 | 17 |
| Heat-drawn wire, ℃ | 151 | 164 | 178 | 201 | 114 |
Can find out from the test result of upper table comparative example and embodiment, the composition of PA66 and ABS (comparative example 1) is in the situation of not adding mineral filler, heat-drawn wire is not high, and add 5～15 parts mineral filler (embodiment 1-4) in the composition of PA66 and ABS after, heat-drawn wire namely is greatly improved.
Embodiment 5-7 and comparative example 2
Employing is just used respectively the ABS resin of the nylon 66 of different molecular weight, different rubber contents and different mineral fillers with complete processing and the testing method of embodiment 1-4, wherein:
Embodiment 5
PA66-1:60 ABS-1:20 SMI-1:10 talcum powder-210
Embodiment 6
PA66-1:60 ABS-3:20 SMI-1:10 wollastonite 10
Embodiment 7
PA66-3:60 ABS-1:20 SMI-1:10 white carbon black 10
Comparative example 2
PA66-1:60 ABS-1:20 SMI-1:10 talcum powder-310
In above each embodiment and comparative example 2, all added 0.3 part oxidation inhibitor 1098
Proportion of composing by above-mentioned comparative example and embodiment has prepared the PA/ABS resin combination, and performance test is as shown in table 2.
Composition and the performance of table 2PA/ABS composition
| Form | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 2 |
| PA66-1 | 60 | 60 | 60 | |
| PA66-3 | 60 | |||
| ABS-1 | 20 | 20 | ||
| ABS-3 | 20 | 20 | ||
| SMI-1 | 10 | 10 | 10 | 10 |
| Talcum powder-2 | 10 | |||
| Wollastonite | 10 | |||
| White carbon black | 10 | |||
| Talcum powder-3 | 10 | |||
| Oxidation inhibitor 1098 | 0.3 | 0.3 | 0.3 | 0.3 |
| Performance | ||||
| Tensile strength, MPa | 58.6 | 68.6 | 56.5 | 52.1 |
| Flexural strength, MPa | 83.5 | 102 | 77.5 | 81.6 |
| Modulus in flexure, MPa | 2800 | 3100 | 2760 | 2900 |
| The Charpy notched Izod impact strength, kJ/m2 | 10.8 | 10.5 | 15.2 | 5.1 |
| Heat-drawn wire, ℃ | 176 | 181 | 171 | 146 |
Can find out from the test result of above-described embodiment, use the nylon 66 (PA6-1 of different molecular weight, 2,3) and divinyl rubber content at the ABS resin (ABS-1 of 40-70%, 2,3), and particle diameter be not more than the mineral fillers such as talcum powder, wollastonite and white carbon black of 15 μ m, adopt method of the present invention all to prepare and have splendid resistance toheat, have simultaneously the PA/ABS intermingling material than high impact; But when using particle diameter greater than the mineral filler (talcum powder-3) of 15 μ m, resulting PA/ABS composition has lower heat-drawn wire and Charpy notched Izod impact strength (comparative example 2).
Adopt the high heat resistance nylon/acrylonitrile-butadiene-styrene resin of technique scheme preparation, have splendid thermotolerance, chemical resistant properties and mechanical property, and the characteristics such as coefficient of linear thermal expansion is lower, good fluidity are arranged, " online " spraying can be carried out, the making material of the component such as automobile fender, rear vision mirror and fuel tank cap can be used for.
Claims (1)
1. high heat resistance nylon/acrylonitrile-butadiene-styrene resin, by nylon, ABS resin, oxidation inhibitor, grafting expanding material and mineral filler form; Each component is counted by weight:
50～75 parts of nylon,
10～25 parts of ABS resin,
5～15 parts of grafting expanding materials,
5～15 parts of mineral fillers,
And 0.3 part in oxidation inhibitor;
Wherein, described nylon is number-average molecular weight 10000～28000, fusing point is 255～265, the nylon 66 of relative viscosity index between 2.0～4.0, ABS resin is 40～70% ABS resin for the content of percentage meter divinyl by weight, the grafting expanding material is vinylbenzene-N-phenylmaleimide multipolymer or vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride, mineral filler be the meta particle diameter be not more than 15 μ m talcum powder, wollastonite and white carbon black in one or more mixture.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051042B (en) * | 2009-10-30 | 2013-04-17 | 上海普利特复合材料股份有限公司 | Low-gloss and scratch-resistant nylon/acrylonitrile-butadiene-styrene resin blending material |
| CN103160110A (en) * | 2011-12-14 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flame retardant PA / ABS blend and preparation method thereof |
| CN103044847A (en) * | 2012-12-30 | 2013-04-17 | 苏州旭光聚合物有限公司 | ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof |
| CN103884513B (en) * | 2014-02-27 | 2015-03-25 | 宁波工程学院 | Automotive rearview mirror fatigue strength reliability testing device |
| CN104119637A (en) * | 2014-07-18 | 2014-10-29 | 滁州诺恩金塑制品有限公司 | Nylon ABS (Acrylonitrile Butadiene Styrene) composite plastic material |
| CN104744873A (en) * | 2014-12-30 | 2015-07-01 | 南京金杉汽车工程塑料有限责任公司 | Low/high-heat-resistant ABS resin and preparation method thereof |
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Patent Citations (7)
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| US5965666A (en) * | 1919-10-19 | 1999-10-12 | Cheil Industries, Inc. | Thermoplastic resin composition with high impact strength at low temperatures |
| EP0276512A1 (en) * | 1986-12-20 | 1988-08-03 | Dsm N.V. | Thermoplastic polymer mixtures |
| EP0277381A1 (en) * | 1986-12-20 | 1988-08-10 | Dsm N.V. | Thermoplastic polymer mixtures |
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| CN1681883A (en) * | 2002-09-17 | 2005-10-12 | Umgabs株式会社 | Thermoplastic resin composition and moldings thereof |
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