CN101759974A - Low-odor antistatic and high tenacity polycarbonate composite - Google Patents
Low-odor antistatic and high tenacity polycarbonate composite Download PDFInfo
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- CN101759974A CN101759974A CN200810203118A CN200810203118A CN101759974A CN 101759974 A CN101759974 A CN 101759974A CN 200810203118 A CN200810203118 A CN 200810203118A CN 200810203118 A CN200810203118 A CN 200810203118A CN 101759974 A CN101759974 A CN 101759974A
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Abstract
The invention discloses a low-odor antistatic and high tenacity polycarbonate composite, comprising 30-75 parts of polycarbonate by weight parts, and the polymerized ingredients are as follows by weight parts: 10-65 parts of acrylonitrile-butadiene-styrene grafting copolymer ABS, 5-15 parts of macromolecule antistatic agents and 2-10 parts of styrene-N-benzyl maleimide-maleic anhydride copolymer; the olycarbonate composite prepared by the technical proposal is manufactured into automobile plastic interior decorating products, has the advantages of low odor and high shock resistance and being hard to stick and adsorb the dust, and is used for manufacturing various automobile interior decorating products, such as automobile instrument panel, door panel and the like.
Description
Technical field
The present invention relates to a kind of polycarbonate compositions, be specially a kind of polycarbonate compositions with low smell, antistatic, high tenacity.
Background technology
Polycarbonate (PC) plastics have the thermotolerance height, and transparency is good, the gloss height, and advantages such as good toughness, but it is mobile poor, difficult forming; Goods are to the breach sensitivity, and not anti-solvent is easy to generate stress cracking.
Have and manyly knownly improve these shortcomings by the method for preparing the PC polyblend, wherein the PC/ABS polyblend is modal method, for example U.S. Pat 3130177, US 4624986 etc. have obtained high impact toughness and have improved mobile low-cost PC/ABS polyblend composition by the blending technology with ABS and PC.
In modern industry production and daily life, plastics gather static and the sticking dust of inhaling easily, static hazard even may cause heavy losses and disaster when serious.In general, prevent that polymer surfaces from producing the electrostatic method and mainly containing air ionization method, metallic contact electric discharge, conducting material introductory technique, surface formation moisture absorption embrane method and use static inhibitor etc.
Use maximum antistatic modes at present and be to use static inhibitor.Static inhibitor is a kind of accumulation of electrostatic charge that can prevent to produce, or the chemical additive based on tensio-active agent of the static charge that can dissipate effectively.Because the chemicals-resistant corrosive nature of polycarbonate is poor, and processing temperature can be up to 300 ℃, and therefore, for polycarbonate and composition alloy plastic goods thereof, the mode of using static inhibitor generally is to adopt the method for surface-coated.
Simultaneously, the important goal that automotive trim is pursued is to reduce the volatility of material, improves the Air quality of automotive interior, and low smell material is one of common target of pursuing of automaker and automotive material manufacturers.Conflictingly therewith be, because normally used static inhibitor generally all is the organic molecule material, under the automobile indoor air quality requirements, small molecules organic volatile in the plastics is easy to move to the surface of plastics, and evaporate in the room air, cause bad sense of smell to the occupant.
Summary of the invention
The object of the invention provides a kind of high tenacity, has a polycarbonate compositions of excellent antistatic energy and low volatility, low smell simultaneously.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of low smell, antistatic, high tenacity polycarbonate composite comprise acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), polymer static inhibitor, the compatilizer vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride of polycarbonate, mass polymerization.Described polycarbonate is 30～75 weight parts, the acrylonitrile-butadiene-phenylethene grafted copolymer ABS of mass polymerization is 10～65 weight parts, the polymer static inhibitor is 5～15 weight parts, and vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride is 2～10 weight parts.
Described polycarbonate is the bisphenol A-type aromatic copolycarbonate.
Polycarbonate resin component of the present invention is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.
In preferred embodiments, the weight-average molecular weight of polycarbonate resin of the present invention is 20000-40000g/mol, and polycarbonate resin of the present invention is known and can obtains by a plurality of commercial source.
The ABS that the acrylonitrile-butadiene-phenylethene grafted copolymer of described mass polymerization (ABS) is produced for the continuous bulk polymerization method.
In preferred embodiments, mass polymerization ABS melting index of the present invention is 4～25g/10min, and mass polymerization ABS resin of the present invention is known and can obtains by a plurality of commercial source.
Described polymer static inhibitor is one or several the combination in polyether ester amides, polyetheramides and the polyether ester.
Described composition also can comprise tinting material, filler, thermo-stabilizer and lubricant etc.
The automobile plastic interior trim goods that the polycarbonate compositions that is prepared by technical solution of the present invention is made have low smell, high-impact, are not easy the sticking advantage such as dust of inhaling, and can be used for making various automotive upholsteries, as fascia, door-plate etc.
Embodiment
The present invention will be further described below in conjunction with specific embodiment, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.
Embodiments of the invention adopt following material:
Polycarbonate-1, U.S. Dow chemical company, weight-average molecular weight is about 27,000, trade mark Calibre201-10;
Polycarbonate-2, U.S. Dow chemical company, weight-average molecular weight is about 32,000, trade mark Calibre301-5
Body ABS-1, U.S. Dow chemical company, melting index is 4.8g/10min, trade mark Magnum 3904;
Body ABS-2, U.S. Dow chemical company, melting index is 21g/10min, trade mark Magnum 342EZ;
Vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride (SMI): NEC chemistry, MS-NA;
Static inhibitor-1, Pelestat NC6321, Japanese Sanyo company, the agent of polyether ester amides type polymer anti static;
Static inhibitor-2, Pebax MV-1074, Arkema company, the agent of polyetheramides type polymer anti static;
Static inhibitor-3, ATMER 129, Ciba company, small molecules type static inhibitor;
Oxidation inhibitor, Dover chemical company, Dovernox D-731, the mixture of hindered phenol antioxygen and phosphite ester kind antioxidant.
The product performance testing method:
Tensile strength: 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, 120 ℃/minute of temperature rise rates are tested under 5 kilograms of load.
Surface resistivity: press ASTM D257 method, adopt 80 millimeters of diameters, thick 3.2 millimeters sample.
Smell: press PV 1303 C3 methods, 80 ℃ of temperature, (the smell evaluating system comprises 6 grades: 1=odorlessness, 2=scent of but non interference smell, obvious smell is arranged 3=but non interference smell, 4=have interference smell, 5=to have strong interference smell 6=to make us and can't stand in 2 hours; Smell is passed judgment on the situation that can occur between two kinds of judge grades.)
Embodiment 1-3 and comparative example 1:
After mixing by proportion of composing in the table 1, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, ABS, static inhibitor, oxidation inhibitor etc.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and 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, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result sees Table 1.
Table 1:
| Form | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| ??PC-1 | ??50 | ??30 | ??50 | ??75 |
| Body ABS-1 | ??50 | ??63 | ??25 | ??10 |
| Static inhibitor-1 | ??5 | ??15 | ??10 | |
| Static inhibitor-3, the small molecules type | ??2 | |||
| ??SMI | ??2 | ??10 | ??5 | |
| Oxidation inhibitor D-731 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| Test result | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Tensile strength (MPa) | ??50.2 | ??46.7 | ??49.6 | ??58.3 |
| Modulus in flexure (MPa) | ??2360 | ??2160 | ??2080 | ??2270 |
| Notched Izod impact strength (J/m) | ??420 | ??376 | ??517 | ??561 |
| Vicat softening temperature (℃) | ??115 | ??108 | ??118 | ??130 |
| Surface resistivity (Ω) | ??＞10 12 | ??10 12 | ??10 10 | ??10 11 |
| Smell | ??5 | ??3.5 | ??3.5 | ??3.5 |
By table 1 as seen, the PC/ABS composition material surface resistivity by the present invention's preparation can reach 10
10-10
12(it is generally acknowledged that the surface resistivity of plastics is 10 between the Ω
12Has certain antistatic property when Ω is following); Volatility is little simultaneously, does not almost have the interference smell, can meet the general requirement of≤4 grades of automotive interior material smell scorings.
Embodiment 4-8:
After mixing by proportion of composing in the table 2, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, ABS, static inhibitor, oxidation inhibitor etc.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and 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, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result sees Table 2.
Table 2:
| Form | Comparative example 2 | Comparative example 3 | Embodiment 4 | Embodiment 5 |
| ??PC-2 | ??60 | ??60 | ??60 | ??60 |
| Body ABS-2 | ??30 | ??15 | ??28 | ??22 |
| Static inhibitor-2 | ??10 | ??10 | ??10 | ??10 |
| ??SMI | ??15 | ??2 | ??8 | |
| Oxidation inhibitor D-731 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| Test result | Comparative example 2 | Comparative example 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength (MPa) | ??52.4 | ??53.6 | ??52.8 | ??53.1 |
| Modulus in flexure (MPa) | ??2130 | ??2370 | ??2240 | ??2250 |
| Notched Izod impact strength (J/m) | ??348 | ??303 | ??560 | ??610 |
| Vicat softening temperature (℃) | ??120 | ??130 | ??122 | ??125 |
| Surface resistivity (Ω) | ??10 11 | ??10 11 | ??10 11 | ??10 11 |
| Smell | ??3.5 | ??3.5 | ??3.5 | ??3.5 |
Can find out from the test result of last table comparative example and embodiment, the composition (comparative example 2) that PC, ABS and the agent of polyetheramides type polymer anti static are independent, and the vinylbenzene-N-phenylmaleimide-weight percent of copolymer-maleic anhydride SMI in composition surpass 10% o'clock composition (comparative example 3), its Izod notched Izod impact strength not high (general automotive trim PC/ABS material requirements reaches 〉=400J/m).And add weight percent in the composition of PC, ABS and the agent of polyetheramides type polymer anti static is the S-MI-MAH resin (embodiment 1-5) of 2-10%, and the Izod notched Izod impact strength promptly is improved largely.The applicant thinks that the SMI resin has the effect of compatilizer in the composition of PC, ABS and the agent of polyetheramides type polymer anti static, is because SMI contains the result of the maleic acid anhydride group with reactive behavior.Thereby the maleic acid anhydride group can improve the interface binding power of polyetheramides polymer anti static agent and PC/ABS matrix with the end amido generation chemical reaction of polyetheramides polymkeric substance, it is more even that the agent of polyetheramides polymer anti static is disperseed in composition substrate, so the Izod notched Izod impact strength can increase substantially.
PC composition of the present invention has good antistatic property and low volatility, hangs down smell. Automobile plastic interior trim goods by polycarbonate compositions of the present invention is made have low smell, high-impact, are not easy to glue advantages such as inhaling dust, can be used for making various automotive upholsteries, such as fascia, door-plate etc.
Claims (8)
1. a low smell, antistatic, high tenacity polycarbonate composite, prescription by weight is: polycarbonate is 30～75 weight parts, mass polymerization ABS is 10～65 weight parts, and the polymer static inhibitor is 5～15 weight parts, and compatilizer is 2～10 weight parts.
2. a kind of low smell according to claim 1, antistatic, high tenacity polycarbonate composite is characterized in that: polycarbonate is the bisphenol A-type aromatic copolycarbonate.
3. a kind of low smell according to claim 1, antistatic, high tenacity polycarbonate composite is characterized in that: the weight-average molecular weight of described polycarbonate resin is 20000-40000g/mol.
4. a kind of low smell according to claim 1, antistatic, high tenacity polycarbonate composite is characterized in that: the ABS that described mass polymerization ABS produces for the continuous bulk polymerization method.
5. a kind of low smell according to claim 4, antistatic, high tenacity polycarbonate composite is characterized in that: described mass polymerization ABS melting index is 4～25g/10min.
6. a kind of low smell according to claim 1, antistatic, high tenacity polycarbonate composite is characterized in that: described polymer static inhibitor is one or several the combination in polyether ester amides, polyetheramides and the polyether ester.
7. a kind of low smell according to claim 1, antistatic, high tenacity polycarbonate composite is characterized in that: described compatilizer is vinylbenzene-N-phenylmaleimide-copolymer-maleic anhydride.
8. a kind of low smell according to claim 1, antistatic, high tenacity polycarbonate composite, it is characterized in that: described composition also can comprise tinting material, filler, thermo-stabilizer and lubricant etc.
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| CN101967274A (en) * | 2010-10-11 | 2011-02-09 | 余林华 | Permanent antistatic polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) composite material and preparation method thereof |
| CN101982499A (en) * | 2010-11-02 | 2011-03-02 | 苏州旭光聚合物有限公司 | Low-odor dispersed PC/ABS composite material and preparation method thereof |
| CN104559108A (en) * | 2014-12-22 | 2015-04-29 | 上海普利特复合材料股份有限公司 | Spray-free PC/ABS composite material with high gloss and high impact resistance and preparation method of spray-free PC/ABS composite material |
| CN106046661A (en) * | 2016-07-25 | 2016-10-26 | 苏州创新达成塑胶模具有限公司 | Antistatic injection molding material for preparing electronic parts |
| CN106317826A (en) * | 2016-08-23 | 2017-01-11 | 锦州希尔达汽车零部件有限公司 | PC/ABS alloy material for automotive trim and preparation method thereof |
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| WO2017186663A1 (en) | 2016-04-27 | 2017-11-02 | Covestro Deutschland Ag | Anti-static thermoplastic molding materials |
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| CN101982499A (en) * | 2010-11-02 | 2011-03-02 | 苏州旭光聚合物有限公司 | Low-odor dispersed PC/ABS composite material and preparation method thereof |
| CN104559108A (en) * | 2014-12-22 | 2015-04-29 | 上海普利特复合材料股份有限公司 | Spray-free PC/ABS composite material with high gloss and high impact resistance and preparation method of spray-free PC/ABS composite material |
| US11352494B2 (en) | 2016-04-27 | 2022-06-07 | Covestro Deutschland Ag | Anti-static thermoplastic molding materials |
| US10655011B2 (en) | 2016-04-27 | 2020-05-19 | Covestro Deutschland Ag | Antistatic and light-stable thermoplastic polycarbonate moulding compounds |
| CN109071930A (en) * | 2016-04-27 | 2018-12-21 | 科思创德国股份有限公司 | Anti-static thermoplastic moulding compound |
| WO2017186663A1 (en) | 2016-04-27 | 2017-11-02 | Covestro Deutschland Ag | Anti-static thermoplastic molding materials |
| WO2017186690A1 (en) | 2016-04-27 | 2017-11-02 | Covestro Deutschland Ag | Antistatic and light-stable thermoplastic polycarbonate moulding compounds |
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| CN106317826A (en) * | 2016-08-23 | 2017-01-11 | 锦州希尔达汽车零部件有限公司 | PC/ABS alloy material for automotive trim 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 |
| CN106751658B (en) * | 2016-12-09 | 2019-05-17 | 上海中镭新材料科技有限公司 | A kind of PC/ABS alloy material, preparation method and the usage |
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| CN109735047B (en) * | 2018-12-06 | 2021-05-25 | 安徽集虹材料科技有限公司 | Low-filling antistatic ABS (acrylonitrile-butadiene-styrene) modified plastic and preparation method thereof |
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| CN112251009A (en) * | 2020-10-20 | 2021-01-22 | 江苏金发科技新材料有限公司 | Low-gloss permanent antistatic polycarbonate/styrene resin alloy and preparation method thereof |
| GB2613819A (en) * | 2021-12-15 | 2023-06-21 | Univ Stellenbosch | Terpolymers for lipid nanodisc formation |
| GB2613819B (en) * | 2021-12-15 | 2024-08-07 | Univ Stellenbosch | Terpolymers for lipid nanodisc formation |
| CN114181509A (en) * | 2021-12-27 | 2022-03-15 | 东莞市创之润新材料有限公司 | Modified antistatic PC plastic |
| CN115710422A (en) * | 2022-11-16 | 2023-02-24 | 江苏沃特新材料科技有限公司 | High-performance PC/ABS blending material, preparation method and application |
| CN115678242A (en) * | 2022-12-13 | 2023-02-03 | 江苏尚艾新材料科技有限公司 | High-performance low-odor antistatic regenerated PC/ABS alloy material for vehicles and preparation method thereof |
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Open date: 20100630 |