CN104497539A - Highlight high-impact abrasion-resistant PC/ABS alloy and preparation method thereof - Google Patents
Highlight high-impact abrasion-resistant PC/ABS alloy and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
Provided are a highlight high-impact abrasion-resistant PC/ABS alloy and a preparation method thereof. The highlight high-impact abrasion-resistant PC/ABS alloy is formed by causing PC, ABS, PBT/PEG-g-MSA and silicone powder to be evenly mixed and then undergo melt blending with surface modification HGB. The PC/ABS alloy contains surface modification HGB and silicone powder, the 60-degree gloss (GU) reaches over 80, the cantilever beam notch impact strength reaches over 600J/m; the highlight high-impact abrasion-resistant PC/ABS alloy has the advantages of high gloss, high normal temperature impact and low temperature impact toughness and abrasion resistance, paint spraying secondary processing processes are reduced, and the highlight high-impact abrasion-resistant PC/ABS alloy is low in cost and has wide market value.
Description
Technical field
What the present invention relates to is a kind of modification technology of polymeric material field, be specifically related to a kind of high light HI high impact wear-resisting modification PC/ABS alloy material and preparation method thereof, this alloy material contains surface modification HGB (Hollow Glass Ball hollow glass ball) and silicone powder, 60 ° of gloss (GU) reach more than 80, Izod notched impact strength reaches more than 600J/m.
Background technology
Polycarbonate (PC) is the engineering plastics of excellent performance, there is good comprehensive platform performance, physical strength be high, tough good, dimensional stabilizing, heat-resisting better, electrical insulating property is good; Bing Xi Qing ?Ding bis-Xi ?styrol copolymer (ABS), have that excellent shock-resistance, good low-temperature performance and chemical proofing, good stability of the dimension, surface luster property are good, good fluidity, be easy to processing.PC/ABS alloy product had both retained toughness, thermotolerance, the dimensional stability of PC resin, having again the excellent low-temperature impact resistance of ABS, processing fluidity and surface luster property, is therefore manufacture the ideal materials such as inner and outer decorative parts of automobile, appliance shell and telecommunications equipment shell.
But when being applied to the field such as household electrical appliances (as casing of liquid crystal television set, casing of sound equipment etc.), Communication Equipment (as smart mobile phone shell, wireless network card shell etc.), often need to carry out secondary processing (as electroplated, spraying paint) with this to meet the requirement of the aspects such as people are attractive in appearance to product, wear-resisting, but secondary processing can bring the problem such as raising, environmental pollution of production cost, therefore develop high gloss and exempt from having a extensive future of the PC/ABS alloy of spraying abrasion-proof.Be applied to the product requirements such as smart mobile phone shell simultaneously and there is high impact toughness, reduce the breakage that mobile phone accidental fall causes, and high abrasion can avoid the surface abrasion that causes when clearing up mobile phone.
Be add high photopolymer resin, filler, improving gloss agent etc. for PC/ABS gloss modification usual method, high hardness resin, wear resistant filler, high molecular abrasion-proof agent etc. are added in wear-resisting modification usually, and toughness is improved and usually added toughner.In prior art, Chinese patent literature CN103232701 discloses a kind of scrape resistant height light PC/ABS composition and method of making the same; Its composition is made up of each component of following weight part: PC resin 55 ~ 90 parts, ABS resin 5 ~ 25 parts, PMMA resin 5 ~ 20 parts, compatilizer 0.5 ~ 2 part, 0.1 ~ 1 part, oxidation inhibitor, lubricant 0.1 ~ 1 part; But the alloy that this technology prepares is not shock-resistant.
Open (bulletin) the day 2008.09.17 of Chinese patent literature CN101268144, disclose and a kind of there is the scratch resistant of improvement and the polymkeric substance of light stability and coating composition, it comprises: a) polymeric matrix or binder for film formation, b) olefin polymer that carboxylic acid reagent is functionalized or multipolymer, and c) uncle or secondary fatty acid amide; Prerequisite is the polyolefine that polymeric matrix not only comprises polyolefine or modified rubber.But this technology needs secondary spray process, bring the problems such as the raising of production cost, environmental pollution.
Summary of the invention
The present invention is directed to prior art above shortcomings, the wear-resisting PC/ABS Alloy And Preparation Method of a kind of high light HI high impact is proposed, containing surface modification HGB and silicone powder composition, there is high gloss, high normal temperature impacts and low-temperature impact toughness, antiwear characteristic, reduce secondary processing operation of spraying paint, cost is low, has more extensive marketable value.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of preparation method of PC/ABS alloy, by by PC, ABS, PBT/PEG ?g ?MSA (poly-to this two first acid ?glycol ether segmented copolymer grafted methacrylic acid first ester ?third alkene nitrile ?styrol copolymers) and silicone powder after Homogeneous phase mixing with surface modification HGB together melt blending obtain, wherein: MMA (methyl methacrylate), St (vinylbenzene), AN (vinyl cyanide) and PBT/PEG block copolymerization graft copolymers are obtained by solution grafting by PBT/PEG ?g ?MSA.
Described melt blending preferably adds oxidation inhibitor, anti ultraviolet agent, lubricant and thermo-stabilizer further.
Described melt blending adopts twin screw extruder, is added by surface modification HGB side feeding manner, side feed screw rotating speed be 200 ?250r/min, screw speed be 250 ?350r/min, the residence time be 1 ?2 minutes.
The temperature of described melt blending is: district's temperature is 200 DEG C, and two district's temperature are 230 DEG C, and three district's temperature are 240 DEG C, four district's temperature are 250 DEG C, and five district's temperature are 255 DEG C, and six district's temperature are 255 DEG C, seven district's temperature are 255 DEG C, and eight district's temperature are 255 DEG C, and nine district's temperature are 255 DEG C.
Described PBT/PEG ?g ?MSA prepare in the following manner: in four-hole boiling flask agitator, thermometer, reflux condensing tube being housed and passing into nitrogen device, first add dichloroethane solvent, the PBT/PEG segmented copolymer of 50 mass parts be dissolved in dichloroethane solvent; Heated and stirred is back to PBT/PEG and all dissolves, then at 70 DEG C, add MMA and the 0.1 part chlorsulfonic acid of 10 parts, after constant temperature 70 DEG C reaction 8h, add St, AN of 10 parts and the BPO (benzoyl peroxide) of 0.1 part again, again after constant temperature 70 DEG C reaction 8h, reaction system being cooled to 50 DEG C pours in culture dish, in 0.1MPa, 80 DEG C of vacuum drying ovens, be dried to constant weight; Reaction product is film like, film is cut into fragment and wraps in filter paper, use methylbenzene extraction 20h in apparatus,Soxhlet's, make PBT/PEG ?g ?MSA.
Described surface modification specifically refers to rare earth ion surface modification, and described lanthanon acetate is preferably acetic acid thulium, acetic acid dysprosium or acetic acid terbium.
Described surface modification HGB prepares in the following manner: the HGB of 10 mass parts is added deionized water for stirring and filter, then add in dehydrated alcohol and stir and leave standstill 18h, stand-by after filtering drying; Then configure the lanthanon acetate deionized water solution also standing 18h of 1% mass concentration, then the HGB after cleaning is added rear ultrasonic wave dispersion 1h and standing 36h, filtration final vacuum is dried to constant weight and makes rare earth ion surface modification HGB.
Technique effect
Compared with prior art, the present invention by solution grafting prepare PBT/PEG segmented copolymer, MMA, St and AN graft copolymer PBT/PEG ?g ?MSA; By surface coating modification legal system for rare earth surface-treated HGB; Then by PC, ABS, PBT/PEG ?g ?MSA, surface-treated HGB, silicone powder and other auxiliary agent melt blendings extrude and obtain PC/ABS alloy.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The polycarbonate that following examples the use bisphenol A polycarbonate PC lexan141R that is GE company, molecular weight be 25000 ?28000g/mol.Bing Xi Jing ?Ding bis-Xi ?styrol copolymer use the ABS 747S of the strange U.S. industry in Taiwan, butadiene content be 20 ?40wt%.PBT/PEG segmented copolymer uses the PBT/PEG segmented copolymer of E.I.Du Pont Company, and the trade mark is Hytrel5526, and shore hardness is 55D.Silicone powder use Dow Corning Corporation RM4 ?7051, silicone content is 40wt%.Hollow glass use Sinosteel Maanshan Institute of Mining Research Co., Ltd. T ?60, particle diameter is at 2 ~ 65 μm, and vacuum density is 0.60g/cm
3.Lanthanon acetate uses the acetic acid thulium of Nanjing Xi Nuo Chemical Industry Science Co., Ltd.Oxidation inhibitor uses four [β ?(3,5 ?bis-special fourth base ?4 ?hydroxy phenyl) propionic acid] pentaerythritol ester, and commodity are called Irganox1010, and Ciba fine chemicals produces.The ZSK using German Coperion company to produce in following examples ?26Mc twin screw extruder.
Embodiment
The present embodiment comprises the following steps:
1) PBT/PEG ?g ?MSA preparation: in the there-necked flask that agitator, thermometer, reflux condensing tube are housed, first add phenolic solvent, the PBT/PEG segmented copolymer of 50 mass parts be dissolved in tetracol phenixin: in the solvent of dimethylbenzene=1:1.Heated and stirred, is back to PBT/PEG and all dissolves, at 70 DEG C, then add MMA, St and AN of each 10 parts, add the BPO of 0.1 part again, after constant temperature 70 DEG C reaction 8h, reaction system is cooled to 50 DEG C and pours in culture dish, in 0.1MPa, 50 DEG C of vacuum drying ovens, be dried to constant weight.Reaction product is film like, and film is cut into fragment, wraps in filter paper, uses phenol extraction 20h in apparatus,Soxhlet's, obtain percentage of grafting be PBT/PEG ?g ?MSA.
Prepared by surface modification HGB: first add in deionized water by the HGB of 10 mass parts, stirs, and filters, then adds in dehydrated alcohol, stirs, and leaves standstill 18h, filters, and dries, stand-by.Configure the lanthanon acetate deionized water solution of 1% mass concentration, leave standstill 18h, then added by the HGB after cleaning, ultrasonic wave dispersion 1h, leaves standstill 36h, filters final vacuum and is dried to constant weight, obtained rare earth ion surface modification HGB.Lanthanon acetate selects acetic acid thulium, acetic acid dysprosium, acetic acid terbium or its combination.
HGB: the ratio of the mass concentration of lanthanon acetate is (10g ~ 20g): (0.5% ~ 2%).
PC/ABS reasonable offer: PC, ABS, PBT/PEG ?g ?MSA, surface modification HGB, silicone powder and other auxiliary agent high speeds blended: 250 ?the blended 10min of 300r/min.
Melt blending extrusion temperature 255 DEG C during PC/ABS alloy, screw speed be 250 ?350r/min, the residence time be 1 ?2 minutes.
PC:ABS:PBT/PEG ?g ?MSA: surface modification HGB: silicone powder ratio is (80 ~ 40): (5 ~ 10): (3 ~ 10): (3 ~ 8).
| Extrude each temperature section | One section | Two sections | Three sections | Four sections | Five sections | Six sections | Seven sections | Eight sections | Nine sections |
| Temperature/DEG C | 200 | 230 | 240 | 250 | 255 | 255 | 255 | 255 | 250 |
ASTM D2457 is pressed in surface luster test, and adopt Gardner's glossmeter to test in the thick specimen surface of smooth 3mm, record 60 ° of gloss numbers, gloss unit is GU, and standard black sheet glass gloss level is wherein 100GU.
PVvalue testing presses ASTM D1894, and sample is the thin slice of 250mm*130mm, and testing apparatus is the friction coefficient tester of TMI company of the U.S..
Notched Izod impact strength is tested by ASTM D256, and specimen size is 64mm*12.7mm*3.2mm, and notch depth is 2.2mm, testing apparatus be Britain Ray ?the shock-testing machine of Ran company.
In embodiment, HGB embodiment proportioning and physical property are as following table:
In embodiment, after adding homemade rare-earth surface modification HGB and silicone powder, the glossiness of PC/ABS alloy is increased, has high-luster, and increase with the increase adding content, 60 ° of gloss are up to 95GU.Embodiment middle-weight rare earths surface modification HGB and silicone powder add simultaneously than add separately wherein a kind of composition time gloss increasing degree large, the two has synergy to the modification of PC/ABS alloy height light.
In embodiment, add homemade PBT/PEG ?g ?after MSA, PC/ABS Impact Toughness of Alloy is increased, has the punching of higher normal temperature and low-temperature impact toughness, and increase with interpolation content and increase, 23 DEG C of Izod notched impact strength are up to 625J/m.
In embodiment, add homemade rare-earth surface modification HGB and silicone powder, PC/ABS Wear Resistance is increased, has comparatively high-wearing feature, and increase with interpolation content and increase, frictional coefficient is minimum reaches 0.12.Embodiment middle-weight rare earths surface modification HGB and silicone powder add simultaneously than add separately wherein a kind of composition time frictional coefficient to reduce amplitude large, the two has certain synergy to the modification of PC/ABS alloy wear-resisting.
Claims (12)
1. the one kind high wear-resisting PC/ABS Alloy And Preparation Method of smooth HI high impact, it is characterized in that, by by PC, ABS, PBT/PEG ?g ?MSA and silicone powder after Homogeneous phase mixing with surface modification HGB together melt blending obtain, wherein: MMA, St, AN and PBT/PEG block copolymerization graft copolymers are obtained by solution grafting by PBT/PEG ?g ?MSA.
2. method according to claim 1, is characterized in that, adds oxidation inhibitor in described melt blending, and this oxidation inhibitor is Hinered phenols antioxidant, phosphite ester kind antioxidant or its combination.
3. method according to claim 1, is characterized in that, adds anti ultraviolet agent in described melt blending, and this anti ultraviolet agent is benzotriazole category, triazines, benzophenone, hindered amines or its combination.
4. method according to claim 1, is characterized in that, adds lubricant in described melt blending, and this lubricant is montanin wax, PE wax, oxidation PE wax, polyol ester, wax ester or its combination.
5. method according to claim 1, is characterized in that, adds thermo-stabilizer in described melt blending, and this thermo-stabilizer is organic tin thermo-stabilizer, metal soap thermal stabilizers or its combination.
6. according to described method arbitrary in claim 1 to 5, it is characterized in that, described melt blending adopts twin screw extruder, surface modification HGB side feeding manner is added, side feed screw rotating speed is 200 ~ 250r/min, main-machine screw rotating speed 250 ?350r/min, the residence time be 1 ?2 minutes.
7. method according to claim 6, it is characterized in that, the temperature of described melt blending is: district's temperature is 200 DEG C, and two district's temperature are 230 DEG C, and three district's temperature are 240 DEG C, four district's temperature are 250 DEG C, five district's temperature are 255 DEG C, and six district's temperature are 255 DEG C, and seven district's temperature are 255 DEG C, eight district's temperature are 255 DEG C, and nine district's temperature are 255 DEG C.
8. method according to claim 1, it is characterized in that, described PBT/PEG ?g ?MSA prepare in the following manner: in four-hole boiling flask agitator, thermometer, reflux condensing tube being housed and passing into nitrogen device, first add dichloroethane solvent, the PBT/PEG segmented copolymer of 50 mass parts be dissolved in dichloroethane solvent; Heated and stirred is back to PBT/PEG and all dissolves, then at 70 DEG C, add MMA and the 0.1 part chlorsulfonic acid of 10 parts, after constant temperature 70 DEG C reaction 8h, add St, AN of 10 parts and the BPO of 0.1 part again, again after constant temperature 70 DEG C reaction 8h, reaction system being cooled to 50 DEG C pours in culture dish, in 0.1MPa, 80 DEG C of vacuum drying ovens, be dried to constant weight; Reaction product is film like, film is cut into fragment and wraps in filter paper, use methylbenzene extraction 20h in apparatus,Soxhlet's, make PBT/PEG ?g ?MSA.
9. method according to claim 1, is characterized in that, described surface modification specifically refers to rare earth ion surface modification, and described lanthanon acetate is acetic acid thulium, acetic acid dysprosium, acetic acid terbium, cerous nitrate, Lanthanum trichloride or its combination.
10. the method according to claim 1 or 9, it is characterized in that, described surface modification HGB prepares in the following manner: the HGB of 10 mass parts is added deionized water for stirring and filter, then add in dehydrated alcohol and stir and leave standstill 18h, stand-by after filtering drying; Then configure the lanthanon acetate deionized water solution also standing 18h of 1% mass concentration, then the HGB after cleaning is added rear ultrasonic wave dispersion 1h and standing 36h, filtration final vacuum is dried to constant weight and makes rare earth ion surface modification HGB.
11. methods according to above-mentioned arbitrary claim, it is characterized in that, PC, ABS, PBT/PEG ?g ?the weight ratio of MSA, silicone powder and surface modification HGB be: (60 ~ 80): (20 ~ 40): (5 ~ 10): (3 ~ 5): (5 ~ 8).
The 12. 1 kinds high wear-resisting PC/ABS alloys of smooth HI high impact, is characterized in that, are prepared by above-mentioned arbitrary method according to claim.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751664A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of wear resistant and impact resistant thermoplastic compounds and preparation method thereof |
| CN106751658A (en) * | 2016-12-09 | 2017-05-31 | 上海中镭新材料科技有限公司 | A kind of PC/ABS alloy materials, Preparation Method And The Use |
| CN108129823A (en) * | 2017-12-25 | 2018-06-08 | 桐城市祥泰塑业有限公司 | A kind of rare earth polyester specular material and preparation method thereof |
| CN109627734A (en) * | 2018-12-26 | 2019-04-16 | 成都其其小数科技有限公司 | For the lightweight of pesticide spraying unmanned plane shell, corrosion-resistant plastic and preparation method |
| CN111004479A (en) * | 2019-11-14 | 2020-04-14 | 苏州市新广益电子有限公司 | PBT/PVDF composite membrane and production process thereof |
| CN112776245A (en) * | 2020-12-31 | 2021-05-11 | 贺盛精密塑胶(苏州)有限公司 | Injection molding process for forming draw bar body of draw bar box |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106751658A (en) * | 2016-12-09 | 2017-05-31 | 上海中镭新材料科技有限公司 | A kind of PC/ABS alloy materials, Preparation Method And The Use |
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| CN108129823A (en) * | 2017-12-25 | 2018-06-08 | 桐城市祥泰塑业有限公司 | A kind of rare earth polyester specular material and preparation method thereof |
| CN109627734A (en) * | 2018-12-26 | 2019-04-16 | 成都其其小数科技有限公司 | For the lightweight of pesticide spraying unmanned plane shell, corrosion-resistant plastic and preparation method |
| CN111004479A (en) * | 2019-11-14 | 2020-04-14 | 苏州市新广益电子有限公司 | PBT/PVDF composite membrane and production process thereof |
| CN112776245A (en) * | 2020-12-31 | 2021-05-11 | 贺盛精密塑胶(苏州)有限公司 | Injection molding process for forming draw bar body of draw bar box |
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