CN101265360A - 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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- CN101265360A CN101265360A CNA2007100381520A CN200710038152A CN101265360A CN 101265360 A CN101265360 A CN 101265360A CN A2007100381520 A CNA2007100381520 A CN A2007100381520A CN 200710038152 A CN200710038152 A CN 200710038152A CN 101265360 A CN101265360 A CN 101265360A
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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, relating in particular to a kind of is the intermingling material of mainly forming by nylon (PA) and acrylonitrile-butadiene-styrene ternary copolymerized resin (ABS).
Background technology
Nylon, it is the polyamide (PA) resin, not only every mechanical property excellence, but also have excellent chemical reagent-resistant performance, good self-lubricating property and snappiness, therefore be widely used in every field, as various trolley parts, power tool shell, ecommerce equipment component, sports goods or the like.Yet meanwhile, nylon also exists 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, the equal excellent material of other every performances.Yet ABS resin and nylon are inconsistent substantially 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 method that adopts the styrene-acrylonitrile copolymer of modified by maleic acid anhydride graft as 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 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 is sprayed, can be divided into " off-line (off-line) " and " online (on-line) " two kinds of method for paint spraying.
Under the lower situation of plastic hot stability, the method that can adopt what is called " off-line " to spray paint, promptly spray paint plastic paste at low temperatures in the place beyond the line that sprays paint earlier, just is installed to vehicle body then and gets on.The shortcoming of this method is to cause not matching of color.
And so-called " online " sprays paint, be directly to be installed to plastic paste on the body exterior earlier, be incorporated in the painting line in the lump then, so just require plastic paste must be able to resist nearly 200 ℃ of pyritous whole processes 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, favorable mechanical performance 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 that is used to produce 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 high heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material with splendid resistance toheat, good chemical resistance, favorable mechanical performance and dimensional stability.
For achieving the above object, a kind of high heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material of the present invention is made up 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 percentage meter butadiene content by weight 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 percentage meter styrene monomer content by weight is 40-50%, and the N-phenylmaleimide monomer content is 45～55%, and maleic anhydride monomer content is 0～5%.
Described mineral filler is not more than one of talcum powder, wollastonite and the white carbon black of 15 μ m or their mixture for the meta particle diameter.
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 characteristics such as coefficient of linear thermal expansion is lower, good fluidity are arranged, " online " spraying can be carried out, the making material of 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 Lanzhou general petrochemicals factory produces;
ABS-3: the divinyl percentage composition is about 70%, and U.S. GE company produces, and Blendex 338;
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 about 2% maleic anhydride in addition.
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, Irganox 1098.
The product performance testing method:
Tensile property: press ISO 527 methods, draw speed 50 mm/min.
Bending property: press ISO 178 methods, trial speed 2 mm/min.
Charpy notched Izod impact strength: press ISO 179 methods.
Heat-drawn wire: press ISO 75 methods, 120 ℃/minute of temperature rise rates, 0.45MPa is test down.
Embodiment 1-4 and comparative example 1
Through exsiccant Nylon 66 2, ABS-2, SMI resin, talcum powder-1 and oxidation inhibitor 1098, 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-1 15
Embodiment 2
PA66-2:55 ABS-2:20 SMI-1:15 talcum powder-1 10
Embodiment 3
PA66-2:60 ABS-2:20 SMI-1:10 talcum powder-1 10
Embodiment 4
PA66-2:75 ABS-2:15 SMI-2:5 talcum powder-1 5
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 the foregoing description and comparative example, evenly add twin screw extruder (screw diameter 35mm continuously with the twin screw feeder, length-to-diameter ratio L/D=36) in the main barrel, it is 220 ℃, 240 ℃, 260 ℃, 265 ℃, 260 ℃ that main barrel divides ten sections controlled temperature (exporting from charging opening to head), the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.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 the glass moisture eliminator immediately and carry out performance test after room temperature is placed at least 24 hours.Test result sees Table 1.
The 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 last table comparative example and embodiment, the composition of PA66 and ABS (comparative example 1) is under 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 promptly is greatly improved.
Embodiment 5-7 and comparative example 2
Employing is just used the ABS resin of the nylon 66 of different molecular weight, different rubber contents and different mineral fillers respectively 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-2 10
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-3 10
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.
The 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 the foregoing description, 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 PA/ABS intermingling material simultaneously 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 mixing material of technique scheme preparation, have splendid thermotolerance, chemical resistant properties and mechanical property, and characteristics such as coefficient of linear thermal expansion is lower, good fluidity are arranged, can
Carry out " online " spraying, can be used for the making material of component such as automobile fender, rear vision mirror and fuel tank cap.
Claims (5)
1. high heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material, by nylon, ABS resin, oxidation inhibitor, grafting expanding material and mineral filler are formed; 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.
2. a kind of high heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material according to claim 1 is characterized in that: in the described ABS resin, percentage meter by weight: the content of divinyl is 40～70%.
3. a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material according to claim 1, it is characterized in that: described nylon is number-average molecular weight 10000～28000, fusing point is at 255～265 ℃, the nylon 66 of relative viscosity index between 2.0～4.0.
4. a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material according to claim 1, it is characterized in that: described vinylbenzene-N-phenylmaleimide multipolymer, percentage meter by weight: styrene monomer content is 40～50%, the N-phenylmaleimide monomer content is 45～55%, and maleic anhydride monomer content is 0～5%.
5. a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material according to claim 1 is characterized in that: described mineral filler is not more than one or more the mixture in talcum powder, wollastonite and the white carbon black of 15 μ m for the meta particle diameter.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200710038152 CN101265360B (en) | 2007-03-16 | 2007-03-16 | High heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material |
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|---|---|---|---|
| CN 200710038152 CN101265360B (en) | 2007-03-16 | 2007-03-16 | High heat resistance nylon/acrylonitrile-butadiene-styrene resin mixing material |
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| CN101265360A true CN101265360A (en) | 2008-09-17 |
| CN101265360B CN101265360B (en) | 2013-01-30 |
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Cited By (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 |
| 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 |
| 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 |
| CN103884513A (en) * | 2014-02-27 | 2014-06-25 | 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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| US5965666A (en) * | 1919-10-19 | 1999-10-12 | Cheil Industries, Inc. | Thermoplastic resin composition with high impact strength at low temperatures |
| NL8603245A (en) * | 1986-12-20 | 1988-07-18 | Stamicarbon | THERMOPLASTIC POLYMER MIXTURES. |
| NL8603246A (en) * | 1986-12-20 | 1988-07-18 | Stamicarbon | THERMOPLASTIC POLYMER MIXTURES. |
| US5202379A (en) * | 1988-06-17 | 1993-04-13 | Monsanto Kasei Company | Impact resistant thermoplastic resin composition |
| FR2807761B1 (en) * | 2000-04-12 | 2002-06-21 | Rhodia Engineering Plastics Sa | POLYMERIC THERMOPLASTIC COMMENTS |
| AU2003264472A1 (en) * | 2002-09-17 | 2004-04-08 | Ube Industries, Ltd. | Thermoplastic resin composition and moldings thereof |
| DE10347870A1 (en) * | 2003-10-10 | 2005-05-04 | Basf Ag | Thermoplastic molding compositions comprise a polyamide with a piperidine compound-derived end-group and a copolymer with a functional group reactive with the polyamide end-group |
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2007
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Cited By (7)
| 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 |
| CN103884513A (en) * | 2014-02-27 | 2014-06-25 | 宁波工程学院 | Automotive rearview mirror fatigue strength reliability testing device |
| 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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| CN101265360B (en) | 2013-01-30 |
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Address after: 201703 12th Floor, Lane 1, 2855, Shanghai Qingping Highway, Zhaoxiang Town, Qingpu District, Shanghai Patentee after: Shanghai Pret Compound Material Co., Ltd. Address before: 200081 2nd Floor, 421 Lane, Siping Road, Hongkou District, Shanghai Patentee before: Pulit Composite Material Co., Ltd., Shanghai |