CN104004338B - Hydrolysis antistatic PC/ASA Alloy And Preparation Method - Google Patents
Hydrolysis antistatic PC/ASA Alloy And Preparation Method Download PDFInfo
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- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004417 polycarbonate Substances 0.000 claims abstract description 46
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 42
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- -1 alkene nitrile Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 101100170343 Arabidopsis thaliana At5g08505 gene Proteins 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000005815 base catalysis Methods 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000003017 thermal stabilizer Substances 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 9
- 150000001336 alkenes Chemical class 0.000 claims 3
- 108010000126 Gabolysat PC60 Proteins 0.000 claims 1
- 239000001120 potassium sulphate Substances 0.000 claims 1
- 230000003068 static effect Effects 0.000 abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 28
- 229920001155 polypropylene Polymers 0.000 description 28
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 19
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Hydrolysis antistatic PC/ASA Alloy And Preparation Method of polymeric material field, by by PPR MWCNT mixture and ASA g MAH graft copolymer and obtain bisphenol A type epoxy resin (EP E51) with dihydroxyphenyl propane and epoxy chloropropane by polycondensation and obtain with polycarbonate (PC) blending extrusion.The PC/ASA alloy material that the present invention obtains not only has excellent static resistance, and there is excellent hydrolytic resistance, adapt to moist rainwater weather, there is excellent impelling strength and lower processing viscosity simultaneously, be easy to processing, be suitable for scale operation and popularization, can be used for the inner and outer decorative parts of automobile such as rear view mirror shell of automobile, door panel and outdoor activity sports equipment goods.
Description
Technical field
What the present invention relates to is a kind of method of technical field of polymer materials, specifically a kind of hydrolysis anti-static polycarbonate (PC)/Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers (ASA) Alloy And Preparation Method.
Background technology
The rubbery kernel layer polypropylene acid esters rubber of ASA graft copolymer is saturated structures, not containing residual double bonds, dissociate under the high energy gamma source light of below 300nm wavelength, this high energy gamma source light is there is not in tellurian solar ray, namely the molecular structure of ASA resin is not easily by high energy gamma source photolysis, then PC/ASA has high weathering resistance.PC/ASA alloy can comprehensive PC and ASA premium properties separately, improves the thermotolerance of ASA, shock resistance and tensile strength, reduces PC melt viscosity, improve processing characteristics, reduce goods internal stress, significantly improve the outdoor weatherability of PC.
Affect plastic degradation Wu Li ?chemical factor more, have heat, mechanical force, ultrasonic wave, light, oxygen, water, pharmaceutical chemicals, microorganism etc.Under moist, warm environment, water molecules destroys the macromole long-chain forming polymkeric substance, causes the polymkeric substance phenomenon even losing any performance of degrading at leisure to be called hydrolysis.Hydrocarbon polymer is more stable to moisture, but polycarbonate (PC) and Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers (ASA) containing a large amount of ester group height polar groups, when temperature is higher and relative humidity is larger, the polar group of water and polymer molecular chain reacts and causes degraded.The PC/ASA alloy that hydrolysis occurs then can losing property antistatic property, even causes colour-change, mechanical property degradation.Meanwhile, static resistance is also required for exterior trimming parts such as automobiles, avoid adsorbing a large amount of dust and affecting gadget effect.
Through finding the retrieval of prior art, open (bulletin) the day 2014.04.23 of Chinese patent literature CN103740081A, disclose a kind of low smell, high-impact PC/ASA intermingling material and preparation method thereof, comprise the raw material of following weight percent meter: polycarbonate (PC): 20 ?80%, Bing Xi Qing ?phenylethene grafted copolymer: 10 ?55%, Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers ASA:5 ?35%, compatilizer: 2 ?15%, deodovization agent: 0.2 ?2%.Raw material through mixing is placed in screw diameter 35mm, length-to-diameter ratio L/D=36 is in twin screw extruder main barrel, main barrel exports point nine sections of control temperature from charging opening to head, be followed successively by 200 DEG C, 230 DEG C, 255 DEG C, 255 DEG C, 255 DEG C, 255 DEG C, 255 DEG C, 255 DEG C, 240 DEG C, twin screw rotating speed is 300 revs/min, extrudes material strip pelletizing after tank cooling and obtains product.The automotive upholstery goods that the PC/ASA intermingling material obtained by this technical scheme is made, have low smell, high-impact, the advantages such as good weatherability, can be widely used in automotive upholstery, as sun visor, fascia etc.But the defect of this technology and deficiency are: these materials can not be exposed to hot and humid environment and be applied as exterior trimming parts, do not have static resistance can resist the erosion of exterior trim ambient dust simultaneously.
Open (bulletin) the day 2014.04.09 of Chinese patent literature CN103709712A, disclose a kind of heat-resisting hydrolysis PC/ASA alloy material, belong to technical field of polymer materials, comprise the following component according to weight parts: polycarbonate 80 ~ 100 parts, Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers 20 ~ 50 parts, 6 ~ 10 parts, carbon fiber, Ben Yi Xi ?maleic anhydride graft copolymer 4 ~ 9 parts, polycarbodiimide 1 ~ 3 part, photostabilizer 6221 ~ 4 parts, 0.5 ~ 3 part, oxidation inhibitor, lubricant 1.2 ~ 3.5 parts.This technology adopt Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers, i.e. ASA resin, with PC plastic blend, and with the addition of carbon fiber and Ben Yi Xi ?maleic anhydride graft copolymer strengthen, make blended after PC/ASA alloy material heat resisting temperature high, weather resistance is excellent, shock resistance is good, meanwhile, there is good anti-hydrolytic performance and processing characteristics.But the defect of this technology and deficiency are: this kind of material does not have static resistance as during exterior trimming parts, can not resist the erosion of exterior trim ambient dust, cannot prolonged application in exterior trim environment, be unfavorable for this kind of material large-scale promotion and application.
Summary of the invention
The present invention is directed to prior art above shortcomings, propose a kind of polycarbonate/Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers Alloy And Preparation Method, by add self-control epoxy resin EP ?E51, epoxy addition reaction can catch the carboxyl that polymkeric substance hydrolysis produces effectively, generate and stablize harmless product, stop polymkeric substance to be hydrolyzed further, thus make PC/ASA alloy material have superelevation hydrolytic resistance and excellent static resistance; Simultaneously because alloy contains Co-polypropylene (PPR), PPR has flexibility and makes alloy material have excellent impact property and good processing characteristics; ASA ?g ?MAH make alloy have good consistency.
The present invention is achieved by the following technical solutions: the present invention by respectively by atactic copolymerized polypropene (PPR) and multi-walled carbon nano-tubes (MWCNT) melt blending, by Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers (ASA) and maleic anhydride (MAH) melt blending, extrude separately pelletizing obtain PPR ?MWCNT mixture and ASA ?g ?MAH graft copolymer; Obtain bisphenol A type epoxy resin (EP ?E51) with dihydroxyphenyl propane and epoxy chloropropane by polycondensation in addition, then by polycarbonate (PC), ASA ?g ?MAH, PPR ?MWCNT, EP ?E51 blending extrusion obtain polycarbonate/Bing Xi Jing ?Ben Yi Xi ?acrylate copolymer alloy.
Described blending extrusion refers to: by PC, ASA ?g ?MAH, PPR ?MWCNT, EP ?E51 and auxiliary agent melt blending to squeeze temperature be 200 ~ 250 DEG C, screw speed is 200 ~ 300r/min.
Described PC, ASA ?g ?MAH, PPR ?MWCNT, EP ?the weight ratio of E51 and auxiliary agent be: PC40 ?80 parts, ASA ?g ?MAH20 ?60 parts, PPR ?MWCNT5 ?20 parts, EP ?E511 ?10 parts, auxiliary agent 0.5 ?5 parts.
Described auxiliary agent comprises: oxidation inhibitor, thermo-stabilizer, lubricant, anti ultraviolet agent; Its weight ratio is: oxidation inhibitor 0.1 ?1 part, thermo-stabilizer 0.1 ?1 part, lubricant 0.1 ?1 part, anti ultraviolet agent 0.2 ?2 parts.
By dihydroxyphenyl propane and epoxy chloropropane, polycondensation under base catalysis condition forms described bisphenol A type epoxy resin, wherein: dihydroxyphenyl propane and epoxy chloropropane mol ratio are (n+1): (n+2), in embodiment, n value is 80 ~ 100, and oxirane value is 0.48 ~ 0.54mol/100g; The equation of this polycondensation is:
Described ASA ?g ?MAH obtained by ASA and MAH melt blending reactive extrursion, adopt dicumyl peroxide (DCP) as catalyzer, melt blending extrusion temperature is 180 ~ 200 DEG C, and screw speed is 150 ~ 250r/min; Percentage of grafting is 5 ~ 15%.
The weight ratio of described ASA and MAH is (70 ~ 80): (20 ~ 30).
Described PPR ?MWCNT extrude obtained by PPR and MWCNT melt blending, melt blending extrusion temperature is 200 ~ 220 DEG C, and screw speed is 200 ~ 250r/min.
The weight ratio of described PPR and MWCNT is (70 ~ 95): (5 ~ 30).
Described first melt blending extrude pelletizing obtain PPR ?MWCNT particle, then by PPR ?MWCNT particle and PC, ASA ?g ?the melt blending such as MAH prepare PC/ASA alloy material, this preparation method solves MWCNT scattering problem in PC/ASA alloy material, makes it be uniformly dispersed.
Described maleic anhydride (MAH) is colourless acicular crystal, and by infrared spectrum characterization, acid anhydrides charateristic avsorption band is at 1778.68cm
?1place.
Described atactic copolymerized polypropene (PPR) adopts Kpic RP2400.
Section epoch nanometer M1205 during described multi-walled carbon nano-tubes (MWCNT) adopts, mean length be 10 ?30 μm, mean diameter 20 ?30nm.
Described oxidation inhibitor is one or more in Hinered phenols antioxidant and phosphite ester kind antioxidant, is preferably Hinered phenols antioxidant 1010, i.e. four [first base ?β ?(3,5 ?bis-tertiary Ding Ji ?4 ?hydroxy phenyl) propionic ester] tetramethylolmethane.
Described lubricant be fatty acid ester or oxidized polyethlene wax one or more, preferably use pentaerythritol stearate (PETS).
Described anti ultraviolet agent be benzotriazole category, triazines, benzophenone, hindered amines one or more, preferred benzotriazole category light absorber.
Described thermo-stabilizer be organic tin thermo-stabilizer, metal soap thermal stabilizers one or more, preferred toxilic acid pink salt organo-tin het stabilizer.
The Izod notched impact strength of described PC/ASA alloy material is greater than 650J/m under 23 DEG C of environment, and surface resistivity reaches 10
9ohm, through 90 DEG C, 96RH% fixed temperature and humidity 24h hydrolysis reaction rear surface resistance reaches 10
9ohm, there is not hydrolysis phenomena in material.
The present invention relates to above-mentioned polycarbonate/Bing Xi Jing ?Ben Yi Xi ?the application of acrylate alloy, use it for and prepare the inner and outer decorative parts of automobile such as automobile rearview mirror, door panel, can be used for other outdoor activity sports equipment goods simultaneously.
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.
Embodiment 1
The present embodiment comprises the following steps:
1) polycarbonate that following examples the use bisphenol A polycarbonate PClexan141R that is GE company, molecular weight be 25000 ?28000g/mol.Bing Xi Jing ?Ben Yi Xi ?acrylate graft copolymers be the strange beautiful PW957 in Taiwan, by weight percentage acrylic elastomer content be 40 ?80%.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 ZE that the present invention uses German Berstorff company to produce ?25 twin screw extruders.
The present embodiment comprises the following steps:
1) grafting ASA ?g ?the preparation of MAH:
First 80 parts of ASA, 20 parts of MAH, 1.5 parts of dicumyl peroxides (DCP), 0.1 part of Hinered phenols antioxidant 1010 are joined in twin screw extruder after 5 minutes with high-speed mixer Homogeneous phase mixing and carry out melt blending, one district's temperature is 180 DEG C, two district's temperature are 185 DEG C, three district's temperature are 190 DEG C, four district's temperature are 190 DEG C, five district's temperature are 195 DEG C, six district's temperature are 195 DEG C, seven district's temperature are 200 DEG C, eight district's temperature are 200 DEG C, nine district's temperature are 195 DEG C, and screw speed is 200 revs/min, the residence time be 1 ?3 minutes.Cool after extruding, dry, pelletizing, obtain ASA ?g ?MAH graft copolymer;
2) PPR ?the preparation of MWCNT mixture:
90 parts of PPR, 10 parts of MWCNT, 0.1 part of Hinered phenols antioxidant 1010 are joined in twin screw extruder after 5 minutes with high-speed mixer Homogeneous phase mixing and carries out melt blending, one district's temperature is 200 DEG C, two district's temperature are 200 DEG C, three district's temperature are 205 DEG C, four district's temperature are 205 DEG C, five district's temperature are 210 DEG C, six district's temperature are 210 DEG C, seven district's temperature are 215 DEG C, and eight district's temperature are 220 DEG C, and nine district's temperature are 215 DEG C, screw speed is 200 revs/min, the residence time be 1 ?3 minutes, through cooling, dry, pelletizing, obtain PPR ?MWCNT mixture.
3) polycarbonate/Bing Xi Jing ?Ben Yi Xi ?the preparation of acrylate copolymer alloy
By PC, ASA ?g ?MAH, EP ?E51, PPR ?MWCNT, Hinered phenols antioxidant, thermo-stabilizer, lubricant and anti ultraviolet agent join in twin screw extruder after 10 minutes according to the weight proportion high-speed mixer Homogeneous phase mixing of embodiment and carry out melt blending, one district's temperature is 200 DEG C, two district's temperature are 210 DEG C, three district's temperature are 220 DEG C, four district's temperature are 230 DEG C, five district's temperature are 240 DEG C, six district's temperature are 240 DEG C, seven district's temperature are 250 DEG C, eight district's temperature are 250 DEG C, nine district's temperature are 245 DEG C, screw speed is 250 revs/min, the residence time is 2 minutes.Cooling after extruding, dry, pelletizing, obtain PC/ASA alloy.
Notched Izod impact strength is tested by ASTMD256, 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.
Surface resistivity test press IEC60093, testing apparatus be U.S. ACL ?800 surface resistivity instrument.
Each weight percent and test physical property result are as following table:
Table 1
In embodiment, add self-control Co-polypropylene and multi-walled carbon nano-tubes mixture PPR ?after MWCNT, make polycarbonate/Bing Xi Jing ?Ben Yi Xi ?acrylate copolymer (PC/ASA) alloy material there is excellent static resistance, and with PPR ?MWCNT content increase static resistance better, surface resistivity arrive 10
9ohm.
In embodiment, add self-control PPR ?after MWCNT mixture, because PC/ASA alloy material contains flexible PPR, make alloy material have higher notch impact toughness, normal temperature notched Izod impact strength with PPR ?MWCNT content increase and increase.
In embodiment, add epoxy resin EP ?after E51, make PC/ASA alloy material have superelevation hydrolytic resistance, alloy material through 90 DEG C, there is not hydrolysis phenomena after 96RH% fixed temperature and humidity 24h, surface resistivity reaches 10 equally
9ohm.
Claims (9)
1. the preparation method of a polycarbonate/the third alkene nitrile ?benzene second alkene ?acrylate graft copolymers alloy, it is characterized in that, by respectively by PPR and MWCNT melt blending, by ASA and MAH melt blending, extrude separately pelletizing obtain PPR ?MWCNT mixture and ASA ?g ?MAH graft copolymer; In addition with dihydroxyphenyl propane and epoxy chloropropane by polycondensation obtain EP ?E51, then by PC, ASA ?g ?MAH, PPR ?MWCNT, EP ?E51 blending extrusion obtain polycarbonate/Bing Xi Jing ?Ben Yi Xi ?acrylate copolymer alloy;
The equation of described polycondensation is:
In described blending extrusion PC, ASA ?g ?MAH, PPR ?MWCNT, EP ?the weight ratio of E51 be: PC40 ?80 parts, ASA ?g ?MAH20 ?60 parts, PPR ?MWCNT5 ?20 parts, EP ?E511 ?10 parts;
By dihydroxyphenyl propane and epoxy chloropropane, polycondensation under base catalysis condition forms described bisphenol A type epoxy resin, wherein: dihydroxyphenyl propane and epoxy chloropropane mol ratio are (n+1): (n+2), n be 80 ?100, oxirane value is 0.48 ~ 0.54mol/100g.
2. method according to claim 1, it is characterized in that, described blending extrusion refers to: by PC, ASA ?g ?MAH, PPR ?MWCNT, EP ?E51 and auxiliary agent melt blending, wherein: PC, ASA ?g ?MAH, PPR ?MWCNT, EP ?the weight ratio of E51 be: PC60 ?80 parts, ASA ?g ?MAH20 ?40 parts, PPR ?MWCNT5 ?20 parts, EP ?E515 ?10 parts, auxiliary agent 0.5 ?5 parts.
3. method according to claim 2, is characterized in that, described auxiliary agent comprises: oxidation inhibitor, thermo-stabilizer, lubricant, anti ultraviolet agent; Its weight ratio is: oxidation inhibitor 0.1 ?1 part, thermo-stabilizer 0.1 ?1 part, lubricant 0.1 ?1 part, anti ultraviolet agent 0.2 ?2 parts.
4. method according to claim 1, it is characterized in that, described ASA ?g ?MAH obtained by ASA and MAH melt blending reactive extrursion, adopt dicumyl peroxide as catalyzer, melt blending extrusion temperature is 180 ~ 200 DEG C, and screw speed is 150 ~ 250r/min; Percentage of grafting is 5 ~ 15%.
5. method according to claim 1, is characterized in that, the weight ratio of described ASA and MAH is (70 ~ 80): (20 ~ 30).
6. method according to claim 1, is characterized in that, the weight ratio of described PPR and MWCNT is (70 ~ 95): (5 ~ 30).
7. method according to claim 3, is characterized in that, described oxidation inhibitor is one or more in Hinered phenols antioxidant and phosphite ester kind antioxidant; Described lubricant be fatty acid ester or oxidized polyethlene wax one or more; Described anti ultraviolet agent be benzotriazole category, triazines, benzophenone, hindered amines one or more; Described thermo-stabilizer be organic tin thermo-stabilizer, metal soap thermal stabilizers one or more.
8. polycarbonate/the third alkene nitrile ?benzene second alkene ?acrylate graft copolymers the alloy that method prepares according to above-mentioned arbitrary claim, it is characterized in that, the Izod notched impact strength of this alloy is greater than 650J/m under 23 DEG C of environment, and surface resistivity reaches 10
9ohm, through 90 DEG C, 96RH% fixed temperature and humidity 24h hydrolysis reaction rear surface resistance reaches 10
9ohm, there is not hydrolysis phenomena in material.
9., according to an application for the polycarbonate/the third alkene nitrile ?benzene second alkene ?acrylate graft copolymers alloy described in above-mentioned arbitrary claim, it is characterized in that, use it for and prepare inner and outer decorative parts of automobile or outdoor activity sports equipment goods.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104730A (en) * | 2006-07-14 | 2008-01-16 | 上海普利特复合材料有限公司 | Low-fluorine anti-flaming polycarbonate/cinnamenyl resin composition |
| CN101367991A (en) * | 2008-09-25 | 2009-02-18 | 上海交通大学 | A kind of preparation method of polycarbonate/acrylonitrile-butadiene-styrene copolymer alloy |
| CN102585468A (en) * | 2011-01-06 | 2012-07-18 | 合肥杰事杰新材料股份有限公司 | Highly heat-resisting flame-retardant antistatic PC (polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy material and preparation method thereof |
| CN102757633A (en) * | 2012-07-03 | 2012-10-31 | 金发科技股份有限公司 | PC (poly carbonate) composite material, as well as preparation method and applications thereof and plastic product |
| CN103788611A (en) * | 2012-10-30 | 2014-05-14 | 合肥杰事杰新材料股份有限公司 | High-strength conductive polycarbonate alloy environmental protection composite material and preparation method thereof |
| WO2014076273A1 (en) * | 2012-11-19 | 2014-05-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer composition having improved long-term stability, moulded parts produced therefrom and intended uses thereof |
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|---|---|---|---|---|
| US20080194736A1 (en) * | 2007-02-13 | 2008-08-14 | Minqiu Lu | PVC nanocomposite manufacturing technology and applications |
-
2014
- 2014-06-16 CN CN201410268111.0A patent/CN104004338B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104730A (en) * | 2006-07-14 | 2008-01-16 | 上海普利特复合材料有限公司 | Low-fluorine anti-flaming polycarbonate/cinnamenyl resin composition |
| CN101367991A (en) * | 2008-09-25 | 2009-02-18 | 上海交通大学 | A kind of preparation method of polycarbonate/acrylonitrile-butadiene-styrene copolymer alloy |
| CN102585468A (en) * | 2011-01-06 | 2012-07-18 | 合肥杰事杰新材料股份有限公司 | Highly heat-resisting flame-retardant antistatic PC (polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy material and preparation method thereof |
| CN102757633A (en) * | 2012-07-03 | 2012-10-31 | 金发科技股份有限公司 | PC (poly carbonate) composite material, as well as preparation method and applications thereof and plastic product |
| CN103788611A (en) * | 2012-10-30 | 2014-05-14 | 合肥杰事杰新材料股份有限公司 | High-strength conductive polycarbonate alloy environmental protection composite material and preparation method thereof |
| WO2014076273A1 (en) * | 2012-11-19 | 2014-05-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer composition having improved long-term stability, moulded parts produced therefrom and intended uses thereof |
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