CN101104732B - Nylon/acrylonitrile-butadiene-styrene resin mixing material - Google Patents
Nylon/acrylonitrile-butadiene-styrene resin mixing material Download PDFInfo
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- CN101104732B CN101104732B CN 200610028938 CN200610028938A CN101104732B CN 101104732 B CN101104732 B CN 101104732B CN 200610028938 CN200610028938 CN 200610028938 CN 200610028938 A CN200610028938 A CN 200610028938A CN 101104732 B CN101104732 B CN 101104732B
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Abstract
The invention discloses a nylon/acrylonitrile-butadiene-styrene resin blending material, which comprises the component of nylon, ABS resin, antioxidant and graft compatibilizer. The invention is characterized in that the graft compatibilizer is styrene-N- phenyl maleimide-maleic anhydride copolymer. The components are counted by weight: nylon 50 to 80 portions, the ABS resin 10 to 35 portions, the styrene-N- phenyl maleimide-maleic anhydride copolymer 4 to 15 portions and the antioxidant 0.1 portion. The nylon/acrylonitrile-butadiene-styrene resin blending material of the invention has the advantages of low density, good fluidity, fine hear resistance, chemical resistance and mechanical property, which can be used for making inner decorative parts, and used as the material for making an air exhaust grill and a defroster grill of a vehicle, vehicle door components and a motorcycle baffle.
Description
Technical field
The present invention relates to a kind of intermingling material, relate in particular to a kind of intermingling material of forming by nylon (PA), acrylonitrile-butadiene-styrene ternary copolymerized resin (ABS), grafting expanding material.
Background technology
Nylon, it is polyamide 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, and therefore, this has limited its further application space again.In order to improve these shortcomings of nylon, people have done the improvement of a lot of aspects.In the middle of these work, a kind of method commonly used is to adopt the mode of nylon and various rubber mix, can fully merge between nylon and the rubber in order to allow simultaneously, adds corresponding expanding material in the middle of the material prescription system again, thereby improves its notched Izod impact strength.As U.S. Pat P4,174,358 have just introduced and have adopted a kind of carboxylic acid or the anhydride grafting modified olefines rubber method as nylon resin and olefines rubber blend expanding material, and Zhi Bei nylon blending material notch shock toughness is high by this method.Yet these methods have but greatly reduced the resistance toheat of material simultaneously, and the moulding flowing property of material also is subjected to very big influence.
At present, the trend of another kind of development is that nylon and other various thermoplastic resins are formed intermingling material.These intermingling materials combine the common advantage of nylon and other blending resins usually, their original some shortcomings have been overcome simultaneously again, therefore, the intermingling material that adopts this method to obtain not only can overcome some defect problems of above-mentioned nylon, and, the excellent specific property of nylon self can not be subjected to very big influence yet, will obtain bigger application space.It is good that acrylonitrile-butadiene-styrene copolymer (ABS) resin itself has a dimensional stability, the characteristics that the notch shock performance is high, and, the common mechanical property of ABS resin is also very desirable, 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.
U.S. Pat P4,499,690 have introduced a kind of method that adopts the multipolymer of acrylamide and ABS resin as PA/ABS intermingling material expanding material, and Zhi Bei intermingling material normal temperature notch shock performance, thermotolerance and dimensional stability all is guaranteed by this method.Yet, the low temperature impact properties of this material very poor (0 ℃, the notched Izod impact strength of 3.2mm batten has only 50J/m).
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 experiment finds, anhydride content increases a per-cent or reduces notch shock degradation that a per-cent all will make material about half in the middle of this expanding material, thereby makes that the performance that adopts the prepared material of this method is extremely unstable.And the color and luster of prepared material is also undesirable, and the color of common prepared material is an xanchromatic.U.S. Pat 5,248,726 have introduced a kind of method that adopts the acidated butyronitrile rubber of carboxylic as PA/ABS intermingling material expanding material.This method exists the problem that makes that material thermal resistance can seriously descend equally.
Summary of the invention
The purpose of this invention is to provide a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material with higher notch shock performance, good heat resistance energy, chemical resistance and dimensional stability.
For achieving the above object, a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material of the present invention, by nylon, ABS resin, oxidation inhibitor, the grafting expanding material is formed, be characterised in that described grafting expanding material is vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride; Each component is counted by weight:
Nylon 50-80 part,
ABS resin 10-35 part,
Vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride 4-15 part,
0.1 part in oxidation inhibitor.
Described ABS resin percentage meter butadiene content by weight is 50-70%.
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 nylon is number-average molecular weight 15000-28000, and fusing point is at 215-225 ℃, and the relative viscosity index is at the nylon 6 of 2.0-4.0.
It is low that a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material of the present invention of employing technique scheme has density, the characteristics of good fluidity, and good thermotolerance, chemical resistant properties and mechanical property are arranged, can be used for automotive upholstery; And can be used for automobile air exhausting grille and defroster grille and door assembly, and the making material of motorcycle plate washer etc.
Embodiment
The present invention is raw materials used:
Nylon 61 (P A6-1): relative viscosity 2.5, number-average molecular weight 15,000, fusing point is 218 ℃, Ube chemical industrial company product;
Nylon 62 (P A6-2): relative viscosity 3.0, number-average molecular weight 24,000, fusing point is 223 ℃, German BASF AG product;
Nylon 63 (PA6-3): relative viscosity 3.6, number-average molecular weight 28,000, fusing point is 225 ℃, German BASF AG product.
ABS-1: the divinyl percentage composition is about 50%, and Lanzhou general petrochemicals factory 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, Blendex338;
ABS-4: the divinyl percentage composition is about 20%, and Qi Mei company in Taiwan produces, Polylac747
Vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride 1 (S-MI-MAH): NEC chemistry, MS-NA, percentage meter styrene monomer content is 46.1% by weight, and the N-phenylmaleimide monomer content is 51.6%, and maleic anhydride monomer content is 2.3%.
Vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride 2 (S-MI): the NEC chemistry, MS-NC, percentage meter styrene monomer content is 48.4% by weight, and the N-phenylmaleimide monomer content is 51.6%, and maleic anhydride monomer content is 0%.
Oxidation inhibitor 1098:Ciba company, Irganox 1098.
The product performance testing method:
Melt mass flow rate MFR: press ASTM D1238 method at 240 ℃, test under 10 kilograms of load.
Tensile property: press ASTM D638 method, draw speed 50 mm/min.
Bending property: press ASTM D790 method, trial speed 2 mm/min.
Izod notched Izod impact strength: press ASTM D256 method, the sample of 3.2 mm thick.
Vicat softening temperature: press ASTM D1525 method, 50 ℃/minute of temperature rise rates are tested under 5 kilograms of load.
Embodiment 1-4 and comparative example 1
Through exsiccant Nylon 62, ABS-2, S-MI-MAH resin (comparative example 1-2 does not add the S-MI-MAH resin) and oxidation inhibitor 1098 in parts by weight by embodiment in the table 11 to implementing 4 and the proportion of composing mixing of comparative example 1, wherein
Embodiment 1
PA6-2:55 ABS-2:30 S-MI-MAH:15 oxidation inhibitor 1098:0.1
Embodiment 2
PA6-2:65 ABS-2:25 S-MI-MAH:10 oxidation inhibitor 1098:0.1
Embodiment 3
PA6-2:75 ABS-2:20 S-MI-MAH:5 oxidation inhibitor 1098:0.1
Embodiment 4
PA6-2:50 ABS-1:35 S-MI-MAH:2 S-MI:13 oxidation inhibitor 1098:0.1
Comparative example 1
PA6-2:70 ABS-2:30 oxidation inhibitor 1098:0.1
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 180 ℃, 200 ℃, 220 ℃, 240 ℃, 240 ℃, 245 ℃, 240 ℃ 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, 240 ℃ 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 1 PA/ABS blend
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| PA6-2 | 55 | 65 | 75 | 50 | 70 |
| ABS-1 | 35 | ||||
| ABS-2 | 30 | 25 | 20 | 30 | |
| Copolymer 1, S-MI-MAH | 15 | 10 | 5 | 2 | |
| Multipolymer 2, S-MI | 13 | ||||
| Oxidation inhibitor 1098 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Performance | |||||
| Tensile strength, MPa | 49.5 | 52.4 | 54.1 | 51.3 | 42.3 |
| Elongation at break, % | 90 | 62 | 40 | 88 | 45 |
| Flexural strength, MPa | 68.5 | 70.2 | 72.6 | 70.5 | 65.3 |
| Modulus in flexure, MPa | 1900 | 2010 | 2080 | 2000 | 1740 |
| The Izod notched Izod impact strength, J/m | 920 | 760 | 470 | 520 | 160 |
| Vicat softening temperature, ℃ | 122 | 130 | 146 | 127 |
Can find out that from the test result of last table comparative example and embodiment the Izod notched Izod impact strength of the composition (comparative example 1) that PA6 and ABS are independent is not high (to be 2 of pure nylon resin approximately
-3 times), and add weight percent in the composition of PA6 and ABS is the S-MI-MAH resin (embodiment 1-4) of 5-15%, the Izod notched Izod impact strength promptly is improved largely, and shock strength has reached the level (it is generally acknowledged that Izod notched Izod impact strength 〉=700J/m is super toughness nylon) of super-toughened nylon.The applicant thinks that the S-MI-MAH resin has a compatilizer in the PA6/ABS composition effect is because S-MI-MAH contains the result of the maleic acid anhydride group with reactive behavior, thereby the maleic acid anhydride group can change the interface binding power of PA6 and ABS with the macromolecular end amido of PA6 generation chemical reaction, it is more even that ABS is disperseed in PA6, so the Izod notched Izod impact strength can increase substantially.Can find out also that from table 1 nylon composite of the present invention also has very high notched Izod impact strength and good processing flowability (high vicat softening temperature).
Embodiment 5-9 and comparative example 2
Employing is just used the ABS resin of the nylon 6 and the different rubber contents of different molecular weight respectively with complete processing and the testing method of embodiment 1-3, wherein:
Comparative example 2
PA6-1:65 ABS-4:25 S-MI-MAH:10 oxidation inhibitor 1098:0.1
Embodiment 5
PA6-2:65 ABS-1:25 S-MI-MAH:10 oxidation inhibitor 1098:0.1
Embodiment 6
PA6-1:65 ABS-2:25 S-MI-MAH:10 oxidation inhibitor 1098:0.1
Embodiment 7
PA6-3:65 ABS-2:25 S-MI-MAH:10 oxidation inhibitor 1098:0.1
Embodiment 8
PA6-1:65 ABS-3:25 S-MI-MAH:10 oxidation inhibitor 1098:0.1
Embodiment 9
PA6-2:80 ABS-3:10 S-MI-MAH:10 oxidation inhibitor 1098:0.1
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 2 table 1PA/ABS composition
| Form | Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| PA6-1 | 65 | 65 | ||||
| PA6-2 | 65 | 65 | 80 | |||
| PA6-3 | 65 | |||||
| ABS-1 | 25 | |||||
| ABS-2 | 25 | 25 | ||||
| ABS-3 | 25 | 10 | ||||
| ABS-4 | 25 | |||||
| S-MI-MAH | 10 | 10 | 10 | 10 | 10 | 10 |
| Oxidation inhibitor 1098 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Performance | ||||||
| Melt flow rate (MFR), g/10min | 43 | 32 | 32 | 12 | 24 | 26 |
| Tensile strength, MPa | 54.4 | 54.6 | 52.6 | 52.5 | 49.1 | 58.3 |
| Elongation at break, % | 32 | 48 | 50 | 60 | 40 | 90 |
| Flexural strength, MPa | 73.2 | 73.5 | 71.5 | 70.5 | 71.6 | 75.3 |
| Modulus in flexure, MPa | 2210 | 2100 | 2000 | 1980 | 2000 | 2240 |
| The Izod notched Izod impact strength, J/m | 310 | 520 | 820 | 1040 | 980 | 500 |
| Vicat softening temperature, ℃ | 136 | 130 | 126 | 128 | 116 | 137 |
Can find out from the test result of the foregoing description, use the nylon 6 (PA6-1 of different molecular weight, 2,3) and divinyl rubber content at the ABS resin (ABS-1 of 40-70%, 2,3), the PA/ABS intermingling material that adopts method of the present invention all to prepare to have super high impact strength can find out that also the PA/ABS composition that adopts high molecular weight nylon 6 resins has higher Izod notched Izod impact strength (embodiment 6 and embodiment 7) than the composition that adopts the preparation of lower molecular weight Nylon 6; When using divinyl rubber content less than 40% ABS resin (ABS-4), resulting PA/ABS composition has lower Izod notched Izod impact strength (comparative example 2).
High impact of the present invention, that high heat-resisting PA6/ABS resin alloy material has density is low, the characteristics of good fluidity, and good thermotolerance, chemical resistant properties and mechanical property are arranged, can be used for automotive upholstery; And can be used for automobile air exhausting grille and defroster grille and door assembly, and the making material of motorcycle plate washer etc.
Claims (4)
1. nylon/acrylonitrile-butadiene-styrene resin mixing material, by nylon, ABS resin, auxiliary agent, the grafting expanding material is formed, and is characterised in that described grafting expanding material is vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride; Each component is counted by weight:
Nylon 50-80 part,
ABS resin 10-35 part,
Vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride 4-15 part,
0.1 part of auxiliary agent.
2. a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material according to claim 1 is characterized in that: described ABS resin percentage meter butadiene content by weight is 50-70%.
3. a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material according to claim 1, it is characterized in that: described vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride percentage meter styrene monomer content by weight is 40-50%, the N-phenylmaleimide monomer content is 45-55%, and maleic anhydride monomer content is 0-5%.
4. a kind of nylon/acrylonitrile-butadiene-styrene resin mixing material according to claim 1 is characterized in that: described nylon is number-average molecular weight 15000-28000, and fusing point is at 215-225 ℃, and the relative viscosity index is at the nylon 6 of 2.0-4.0.
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| 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 |
| CN101870797B (en) * | 2010-03-29 | 2013-07-03 | 金发科技股份有限公司 | Polyacrylonitrile-butadiene-styrene modified compound and preparation method thereof |
| CN102276981A (en) * | 2010-06-09 | 2011-12-14 | 中国科学院化学研究所 | Alloy material of nylon 66 and ABS resin, and preparation method thereof |
| CN102532874B (en) * | 2010-12-29 | 2014-06-11 | 上海普利特复合材料股份有限公司 | Thermo-oxidative ageing-resistant nylon/acrylonitrile-butadiene-styrene resin mixed material |
| CN102199347A (en) * | 2011-03-31 | 2011-09-28 | 上海金玺实验室有限公司 | Modified PA/ABS composite material with boiling resistance, high intensity and superior toughness and preparation method thereof |
| CN102807752B (en) * | 2011-05-31 | 2015-04-15 | 合肥杰事杰新材料股份有限公司 | PA6 (Polyamide 6)/ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof |
| CN104119635A (en) * | 2013-04-25 | 2014-10-29 | 上海杰事杰新材料(集团)股份有限公司 | ABS / PA6 material for extrusion technology and preparation method thereof |
| CN104292740A (en) * | 2014-09-29 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Fatigue-resistant mud guard material and preparation method thereof |
| CN106433112A (en) * | 2016-10-09 | 2017-02-22 | 上海金发科技发展有限公司 | PA (polyamide)/AS (acrylonitrile-styrene) based resin compound and preparation method thereof |
| CN107298849A (en) * | 2016-12-26 | 2017-10-27 | 上海普利特化工新材料有限公司 | A kind of flame-retardant conductive PA and ABS alloy material and preparation method thereof |
| CN107474467B (en) * | 2017-07-10 | 2020-10-16 | 上海长伟锦磁工程塑料有限公司 | Ultralow-gloss heat-resistant ABS material |
| CN107778855A (en) * | 2017-11-15 | 2018-03-09 | 上海锦湖日丽塑料有限公司 | High heat-resisting PA/ABS resin combinations of a kind of high impact and preparation method thereof |
| CN109593356A (en) * | 2018-11-19 | 2019-04-09 | 江苏金发科技新材料有限公司 | PA66 composite material and preparation method with excellent low temperature toughness, low water absorption and high rigidity |
| CN109456568B (en) * | 2018-11-20 | 2020-10-09 | 安徽江淮汽车集团股份有限公司 | PA composite material and preparation method thereof |
| CN109517373B (en) * | 2018-11-20 | 2020-11-03 | 安徽江淮汽车集团股份有限公司 | PA6/AES composite material and preparation method thereof |
| CN109880352A (en) * | 2019-01-24 | 2019-06-14 | 深圳市富恒新材料股份有限公司 | A kind of heat-resisting PA6/ABS composite material and preparation method of superelevation |
| CN114133733A (en) * | 2021-12-16 | 2022-03-04 | 柏力开米复合塑料(昆山)有限公司 | High-weather-resistance glass fiber reinforced wear-resistant PA-ABS alloy material and preparation method thereof |
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