CN114456478A - Antistatic master batch for plastics and plastic film containing antistatic master batch - Google Patents
Antistatic master batch for plastics and plastic film containing antistatic master batch Download PDFInfo
- Publication number
- CN114456478A CN114456478A CN202210158713.5A CN202210158713A CN114456478A CN 114456478 A CN114456478 A CN 114456478A CN 202210158713 A CN202210158713 A CN 202210158713A CN 114456478 A CN114456478 A CN 114456478A
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- Prior art keywords
- master batch
- modified graphene
- antistatic master
- antioxidant
- gel
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Links
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 63
- 229920003023 plastic Polymers 0.000 title claims abstract description 18
- 239000004033 plastic Substances 0.000 title claims abstract description 18
- 239000002985 plastic film Substances 0.000 title claims abstract description 18
- 229920006255 plastic film Polymers 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 117
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 13
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 229920005610 lignin Polymers 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 31
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 23
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 150000002978 peroxides Chemical class 0.000 claims description 20
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000344 soap Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003063 flame retardant Substances 0.000 claims description 10
- 239000012760 heat stabilizer Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 8
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- ROZZMLUWBPPEMU-GRVYQHKQSA-L Calcium linoleate Chemical compound [Ca+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O ROZZMLUWBPPEMU-GRVYQHKQSA-L 0.000 claims description 4
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical group CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 8
- 239000011541 reaction mixture Substances 0.000 claims 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 46
- 239000000243 solution Substances 0.000 description 28
- 239000000155 melt Substances 0.000 description 13
- 239000002216 antistatic agent Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Abstract
The invention relates to an antistatic master batch for plastics and a plastic film containing the antistatic master batch, wherein the antistatic master batch comprises a resin carrier and a conductive active component compounded with the resin carrier, the resin carrier is an ethylene-vinyl acetate copolymer, and the conductive active component comprises poly (N-methyl pyrrole) gel and polyethylene glycol which are loaded with modified graphene and have a mass ratio of 1 (1-4). The plastic film material prepared from the antistatic master batch has good dimensional stability, excellent heat resistance and chemical corrosion resistance, meets the environmental protection requirement, has an efficient, lasting and stable antistatic effect, has good surface glossiness and has a good application prospect in the development of the polymer material technology industry.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antistatic master batch for plastics and a plastic film containing the antistatic master batch.
Background
Nowadays, plastic products are widely used in various aspects of production and life, and have become important processing materials for electrical products due to their excellent characteristics such as light weight, easy processing, high electrical insulation, and capability of being designed according to the application. However, since the insulation property of the plastic itself is too high, in practical application, a large amount of charges are often generated due to friction and accumulated and gathered on the surface of the plastic, and the charges are difficult to completely eliminate, which not only limits the application of the plastic in the field of electrical products, but also has a great safety hazard. For example, polypropylene resin, as an engineering plastic with good comprehensive performance, has excellent thermal stability, cold resistance, good fluidity and chemical medium stability, and good processability and dimensional stability, but its application in the field of electronic and electrical appliances is greatly limited due to its poor antistatic property.
In order to solve the above problems, the prior art often adopts antistatic agent in the plastic production process to improve the antistatic property of the material. At present, the common antistatic agents comprise a surfactant type antistatic agent and a polymer type antistatic agent, wherein the surfactant type antistatic agent achieves the purpose of antistatic by absorbing environmental moisture and reducing surface resistivity, and has larger dependence on environmental humidity. The polymer antistatic agent is a permanent antistatic agent, but the polymer antistatic agent has the problems of poor compatibility with a base material, easy appearance of external seepage during processing and molding, poor stability of antistatic effect, influence on the appearance of a product and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the antistatic master batch which has good compatibility with a base material, stable antistatic effect and small dependence on environmental humidity and can effectively overcome the technical defects that the conventional high-molecular antistatic agent is easy to cause outward permeation and influence the appearance of a product in the process of processing and forming.
The invention also aims to provide a preparation method of the antistatic master batch.
The invention also aims to provide a plastic film containing the antistatic master batch.
The invention also aims to provide a preparation method of the plastic film.
The purpose of the invention can be realized by the following technical scheme:
according to one aspect of the invention, the antistatic master batch for plastics comprises a resin carrier and a conductive active component compounded with the resin carrier, wherein the resin carrier is an ethylene-vinyl acetate copolymer, and the conductive active component comprises poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol in a mass ratio of 1 (1-4).
Illustratively, the ethylene-vinyl acetate copolymer has a VA (vinyl acetate) content of 32 wt% and a melt index of 43g/10min (190 ℃, 2.16 kg).
As a preferred embodiment of the present invention, the preparation method of the modified graphene-loaded poly-N-methylpyrrole gel is as follows:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 30-60min, then adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH value of the solution to 5-6, then adding potassium persulfate, heating to 85-95 ℃, reacting at constant temperature for 1-3h, and naturally cooling to room temperature to obtain modified graphene/lignin gel;
step 2: adding N-methylpyrrole and p-toluenesulfonic acid into deionized water, stirring and mixing uniformly, adding the modified graphene/lignin gel prepared in the step 1, stirring at a constant temperature of 70-90 ℃ for 1-2h, then slowly dropwise adding a ferric sulfate solution under a stirring state, after dropwise adding, placing in an ice water bath for reaction for 2-4h, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene-loaded poly N-methylpyrrole gel.
In a preferred embodiment of the present invention, the modified graphene is obtained by modifying the surface of graphene with an organic amine modifier, and the organic amine modifier is at least one selected from triethylenetetramine, triethylenediamine, and hexamethylenetetramine.
Illustratively, the modified graphene used in the present invention is prepared by the following steps:
step i: preparing graphene oxide by using a Hummers method;
step ii: weighing about 500mg of graphene oxide, ultrasonically dispersing the graphene oxide in about 500ml of DMF (namely N-N dimethylformamide) for 5h to prepare graphene oxide suspension, adding about 40g of organic amine modifier and about 8g of dicyclohexylcarbodiimide, ultrasonically treating for 20min, reacting at 140 ℃ for 24h, adding about 60ml of absolute ethyl alcohol, and standing; removing the supernatant, filtering with a polytetrafluoroethylene membrane to obtain a lower precipitate, and washing with absolute ethyl alcohol and deionized water for multiple times to obtain modified graphene oxide;
step iii: dispersing the washed and undried modified graphene oxide in about 60ml of absolute ethyl alcohol, performing ultrasonic dispersion for 2 hours to form uniform and stable modified graphene oxide dispersion liquid, adding about 1.36g of hydrazine hydrate, and reducing for 36 hours at 72 ℃; and washing the obtained product with absolute ethyl alcohol and deionized water to neutrality (the pH is 6.5-7.5), and drying the product at 95 ℃ for 48 hours to obtain the modified graphene.
As a preferred embodiment of the present invention, 0.1 to 1.2g of the modified graphene is added to 100ml of deionized water in the step 1.
In a preferred embodiment of the present invention, the mass ratio of the lignin powder to the modified graphene in the step 1 is (1-4): 1.
As a preferred embodiment of the present invention, 0.02 to 0.2g of potassium persulfate is added to 100ml of deionized water in said step 1.
According to a preferred embodiment of the invention, the mass ratio of the N-methyl pyrrole, the p-toluenesulfonic acid, the deionized water, the modified graphene/lignin gel and the ferric sulfate solution in the step 2 is (3-5):1, (20-40):100, (15-20).
In a preferred embodiment of the present invention, the mass concentration of the ferric sulfate solution in the step 2 is 10-15wt%, and the dripping time of the ferric sulfate solution is 1-3 h.
As a preferred embodiment of the invention, the antistatic master batch further comprises 0.1-0.5% of peroxide and 10-40% of conductive active component by mass fraction of 100%, and the balance is resin carrier.
Illustratively, the peroxide is selected from one or more of 1, 1-bis (tert-butyl peroxy) -3,3, 5-trimethylcyclohexane, 1, 3-dibutyl peroxyisopropylbenzene, dibenzoyl peroxide, tert-amyl peroxyacetate, tert-butyl peroxybenzoate and dicumyl peroxide.
According to another aspect of the present invention, there is provided a method for preparing the antistatic master batch for plastics, comprising the following steps:
the method comprises the following steps: preparing materials according to the following mass percentages:
10-40% of conductive active component, 0.1-0.5% of peroxide and the balance of resin carrier;
step two: adding the components in the step I into a double-screw extruder, melting and blending at the temperature of 110-130 ℃, and performing extrusion granulation to obtain the antistatic master batch.
According to another aspect of the present invention, there is provided a plastic film comprising the above antistatic mother particle.
As a preferred embodiment of the present invention, the plastic film comprises the following raw materials in parts by weight: 100 parts of PC resin, 5-15 parts of antistatic master batch, 0.2-0.6 part of ultraviolet absorbent, 1-3 parts of flame retardant, 1-2 parts of antioxidant and 1-2 parts of heat stabilizer.
As a preferred embodiment of the present invention, the PC resin has a melt index of 10 to 35g/10min (300 ℃, 1.2 kg).
As a preferred embodiment of the present invention, the ultraviolet absorber is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
As a preferred embodiment of the invention, the flame retardant comprises tris (2-ethylhexyl) phosphate, antimony trioxide and zinc borate in a mass ratio of 1 (1-2): 3. .
In a preferred embodiment of the present invention, the antioxidant is at least one selected from the group consisting of antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 1024, antioxidant B215 and antioxidant B225.
As a preferred embodiment of the present invention, the heat stabilizer is selected from at least one of calcium stearate soap, calcium oleate soap, calcium palmitoleate soap, or calcium linoleate soap.
According to another aspect of the present invention, a method for preparing the above plastic film is provided, which comprises drying the PC resin at a temperature of 120-130 ℃ to a water content of less than or equal to 0.05%, adding the components in a high-speed mixer according to the weight ratio to perform mixing treatment to obtain a uniform mixture, adding the mixture into a twin-screw extruder to perform melt blending, and performing extrusion granulation to obtain the plastic film.
As a preferred embodiment of the invention, the temperature of the high-speed mixer is 150-160 ℃, and the mixing treatment time is 10-20 min.
As a preferred embodiment of the invention, the process parameters of the twin-screw extruder are as follows:
the temperature of the first zone is 190 ℃ in 170-.
Compared with the prior art, the invention at least comprises the following beneficial effects:
1) the antistatic master batch provided by the invention adopts the ethylene-vinyl acetate copolymer with the VA (vinyl acetate) content of 32 wt% and the melt index of 43g/10min (190 ℃, 2.16kg) as the carrier resin, and the conductive active component is loaded on the ethylene-vinyl acetate copolymer through chemical bonding, so that the selected ethylene-vinyl acetate copolymer has good compatibility with a resin base material (such as PC resin), which is beneficial to uniformly dispersing the conductive active component in the resin base material, and can effectively solve the technical problems that the appearance of a product is influenced and the like because the conventional antistatic agent is easy to precipitate and seep in the material processing and forming process;
2) the conductive active components selected in the antistatic master batch comprise, by mass, 1: (1-4) the poly-N-methylpyrrole gel loaded with the modified graphene and the polyethylene glycol, wherein the molecular chain of the poly-N-methylpyrrole has a conjugated structure, and the poly-N-methylpyrrole is a polymer with good conductive capability, in order to further enhance the conductive performance of the poly-N-methylpyrrole, the modified graphene is reacted with the lignin firstly, the modified graphene is bonded in the three-dimensional network structure by utilizing all three-dimensional network structures of the lignin, then the lignin is used as an intermediate carrier, active groups such as hydroxyl, quinone groups and the like contained in the lignin can be effectively combined into the molecular chain of the poly-N-methylpyrrole to form the poly-N-methylpyrrole gel loaded with the modified graphene, and the polyethylene glycol is favorable for uniformly dispersing the poly-N-methylpyrrole gel loaded with the modified graphene in the ethylene-vinyl acetate copolymer, the obtained antistatic master batch can form abundant and stable conductive paths in a resin base material, can play a permanent antistatic effect, and is favorable for enhancing the strength of a resin matrix due to the introduction of the modified graphene;
3) the plastic film prepared from the antistatic master batch disclosed by the invention has good dimensional stability, excellent heat resistance and chemical corrosion resistance by utilizing the interaction among the components, meets the environmental protection requirement, has a high-efficiency, durable and stable antistatic effect, has good surface glossiness and has a good application prospect in the development of the polymer material technology industry.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
As used herein, the term "about" when used to modify a numerical value means within 5% of the error margin measured for that value.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism. The present invention will be described in detail with reference to specific examples.
The preparation method of the modified graphene adopted in the following examples is as follows:
step i: preparing graphene oxide by using a Hummers method, specifically, mixing 2g of graphite, 1g of NaNO3 and 46ml of concentrated sulfuric acid with the mass concentration of 98% in an ice-water bath, stirring for 30 minutes to fully mix the graphite, weighing 6g of KMnO4, adding the mixture into the mixed solution in portions, continuously stirring for 2 hours, and transferring the mixture into a warm water bath at 35 ℃ to continuously stir for 30 minutes; slowly adding 92ml of distilled water, controlling the temperature of the reaction solution to about 98 ℃ for 15 minutes, adding a proper amount of 30% H2O2 to remove excessive oxidant, adding 140ml of distilled water for dilution, filtering while hot, and washing with 0.01mol/L HCl, absolute ethyl alcohol and deionized water in sequence until no SO exists in the filtrate4 2-Until the graphite exists, preparing graphite oxide; then ultrasonically dispersing graphite oxide in water to prepare a dispersion liquid of graphene oxide; drying the dispersion liquid of the graphene oxide in a vacuum drying oven at 60 ℃ for 48 hours to obtain a graphene oxide sample, and storing for later use;
step ii: weighing about 500mg of graphene oxide, ultrasonically dispersing the graphene oxide in about 500ml of DMF (namely N-N dimethylformamide) for 5h to prepare graphene oxide suspension, adding about 40g of organic amine modifier and about 8g of dicyclohexylcarbodiimide, ultrasonically treating for 20min, reacting at 140 ℃ for 24h, adding about 60ml of absolute ethyl alcohol, and standing overnight; removing the supernatant, filtering the lower precipitate with a polytetrafluoroethylene membrane, and washing with absolute ethyl alcohol and deionized water for multiple times to obtain modified graphene oxide;
step iii: dispersing the washed and undried modified graphene oxide in about 60ml of absolute ethyl alcohol, performing ultrasonic dispersion for 2 hours to form uniform and stable modified graphene oxide dispersion liquid, adding about 1.36g of hydrazine hydrate, and reducing for 36 hours at 72 ℃; and washing the obtained product with absolute ethyl alcohol and deionized water to neutrality, and drying the product at 95 ℃ for 48 hours to obtain the modified graphene.
In step ii above, the organic amine modifier can be selected from different kinds to obtainModified graphene oxide of the same kind, for example, with triethylenetetramine, correspondingly, modified graphene obtainable
Modified graphene obtainable with triethylenediamine, correspondingly
Modified graphene obtainable with hexamethylenetetramine, correspondingly
。
Example 1:
the antistatic master batch I provided by the embodiment comprises the following raw materials in percentage by mass: 10% of conductive active component, 0.1% of peroxide and the balance of resin carrier; wherein the resin carrier is ethylene-vinyl acetate copolymer, the VA content is 32 wt%, the melt index is 43g/10min (190 ℃, 2.16kg), and the peroxide is dibenzoyl peroxide.
The conductive active components adopted in this embodiment include poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol at a mass ratio of 1:1 (note that the modified graphene adopted is modified graphene
) The modified graphene loaded poly-N-methylpyrrole gel is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 30min, then adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH value of the solution to 5.5, then adding potassium persulfate, heating to 85 ℃, reacting at constant temperature for 3h, and naturally cooling to room temperature to obtain modified graphene/lignin gel;
step 2: adding N-methylpyrrole and p-toluenesulfonic acid into deionized water, stirring and mixing uniformly, adding the modified graphene/lignin gel prepared in the step 1, stirring at a constant temperature of 70 ℃ for 2 hours, then slowly dropwise adding a ferric sulfate solution under a stirring state, placing in an ice water bath for reaction for 4 hours after dropwise adding is finished, and repeatedly washing with absolute ethyl alcohol to obtain the poly-N-methylpyrrole gel loaded with the modified graphene.
In the above process of preparing the modified graphene-loaded poly N-methylpyrrole gel:
aiming at the step 1, 0.1g of modified graphene is added into every 100ml of deionized water, the mass ratio of lignin powder to the modified graphene is 4:1, and the addition amount of potassium persulfate is 0.02g of potassium persulfate added into every 100ml of deionized water;
according to the step 2, the mass ratio of the N-methylpyrrole, the p-toluenesulfonic acid, the deionized water, the modified graphene/lignin gel to the ferric sulfate solution is 3:1:20:100:15, the mass concentration of the ferric sulfate solution is 10 wt%, and the dropping time is 1 h.
The preparation of the antistatic masterbatch of this embodiment includes the following steps:
the method comprises the following steps: preparing materials according to the following mass percentage:
10% of conductive active component, 0.1% of peroxide and the balance of resin carrier;
step two: adding the components into a double-screw extruder, melting and blending at 110 ℃, and performing extrusion granulation to obtain the antistatic master batch I.
Example 2:
the antistatic master batch II provided by the embodiment comprises the following raw materials in percentage by mass: 24 percent of conductive active component, 0.2 percent of peroxide and the balance of resin carrier; wherein the resin carrier is ethylene-vinyl acetate copolymer, the VA content of the resin carrier is 32 wt%, the melt index of the resin carrier is 43g/10min (190 ℃, 2.16kg), and the peroxide is tert-amyl peroxyacetate.
The conductive active component adopted in this embodiment includes poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol at a mass ratio of 1:1 (note that the modified graphene adopted is modified graphene
) poly-N-methyl pyrrole gel loaded with modified grapheneThe preparation method comprises the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 40min, then adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH of the solution to 5, then adding potassium persulfate, heating to 90 ℃, reacting at constant temperature for 2h, and naturally cooling to room temperature to obtain modified graphene/lignin gel;
step 2: adding N-methylpyrrole and p-toluenesulfonic acid into deionized water, stirring and mixing uniformly, adding the modified graphene/lignin gel prepared in the step 1, stirring at a constant temperature of 80 ℃ for 2 hours, then slowly dropwise adding a ferric sulfate solution under a stirring state, placing in an ice water bath for reaction for 3 hours after dropwise adding is finished, and repeatedly washing with absolute ethyl alcohol to obtain the poly-N-methylpyrrole gel loaded with the modified graphene.
In the above process of preparing the modified graphene-loaded poly N-methylpyrrole gel:
aiming at the step 1, 0.4g of modified graphene is added into every 100ml of deionized water, the mass ratio of lignin powder to the modified graphene is 2:1, and the addition amount of potassium persulfate is 0.08g of potassium persulfate added into every 100ml of deionized water;
according to the step 2, the mass ratio of the N-methylpyrrole, the p-toluenesulfonic acid, the deionized water, the modified graphene/lignin gel to the ferric sulfate solution is 3:1:25:100:18, the mass concentration of the ferric sulfate solution is 12 wt%, and the dropping time is 1.5 h.
The preparation of the antistatic masterbatch of this embodiment includes the following steps:
the method comprises the following steps: preparing materials according to the following mass percentages:
24 percent of conductive active component, 0.2 percent of peroxide and the balance of resin carrier;
step two: adding the components into a double-screw extruder, melting and blending at 118 ℃, and performing extrusion granulation to obtain the antistatic master batch II.
Example 3:
the antistatic master batch III provided by the embodiment comprises the following raw materials in percentage by weight: 30% of conductive active component, 0.4% of peroxide and the balance of resin carrier; wherein the resin carrier is ethylene-vinyl acetate copolymer, the VA content of the resin carrier is 32 wt%, the melt index of the resin carrier is 43g/10min (190 ℃, 2.16kg), and the peroxide is 1, 3-dibutyl peroxyisopropylbenzene.
The conductive active component adopted in this embodiment includes poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol at a mass ratio of 1:2.5 (note that the modified graphene adopted is modified graphene
) The modified graphene loaded poly-N-methylpyrrole gel is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 45min, then adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH of the solution to 5, then adding potassium persulfate, heating to 95 ℃, reacting at constant temperature for 1h, and naturally cooling to room temperature to obtain modified graphene/lignin gel;
step 2: adding N-methylpyrrole and p-toluenesulfonic acid into deionized water, stirring and mixing uniformly, adding the modified graphene/lignin gel prepared in the step 1, stirring at a constant temperature of 90 ℃ for 1h, then slowly dropwise adding a ferric sulfate solution under a stirring state, placing in an ice water bath for reaction for 2h after dropwise adding is finished, and repeatedly washing with absolute ethyl alcohol to obtain the poly-N-methylpyrrole gel loaded with the modified graphene.
In the above process of preparing the modified graphene-loaded poly N-methylpyrrole gel:
aiming at the step 1, adding 1.0g of modified graphene into every 100ml of deionized water, wherein the mass ratio of lignin powder to the modified graphene is 2:1, and the adding amount of potassium persulfate is 0.1g of potassium persulfate into every 100ml of deionized water;
according to the step 2, the mass ratio of the N-methylpyrrole, the p-toluenesulfonic acid, the deionized water, the modified graphene/lignin gel to the ferric sulfate solution is 4:1:30:100:20, the mass concentration of the ferric sulfate solution is 15wt%, and the dropping time is 2 hours.
The preparation of the antistatic masterbatch of this embodiment includes the following steps:
the method comprises the following steps: preparing materials according to the following mass percentages:
30% of conductive active component, 0.4% of peroxide and the balance of resin carrier;
step two: adding the components into a double-screw extruder, melting and blending at 123 ℃, and performing extrusion granulation to obtain the antistatic master batch III.
Example 4:
the antistatic master batch IV provided by the embodiment comprises the following raw materials in percentage by mass: 32% of conductive active component, 0.2% of peroxide and the balance of resin carrier; wherein the resin carrier is ethylene-vinyl acetate copolymer, the VA content is 32 wt%, the melt index is 43g/10min (190 ℃, 2.16kg), and the peroxide is 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane.
The conductive active components adopted in this embodiment include poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol at a mass ratio of 1:2 (note that the modified graphene adopted is modified graphene
) The modified graphene loaded poly-N-methylpyrrole gel is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 50min, then adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH value of the solution to 5.5, then adding potassium persulfate, heating to 92 ℃, reacting at constant temperature for 2.5h, and naturally cooling to room temperature to obtain modified graphene/lignin gel;
step 2: adding N-methylpyrrole and p-toluenesulfonic acid into deionized water, stirring and mixing uniformly, adding the modified graphene/lignin gel prepared in the step 1, stirring at a constant temperature of 85 ℃ for 1.5h, then slowly dropwise adding a ferric sulfate solution under a stirring state, after dropwise adding, placing in an ice water bath for reaction for 3.5h, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene-loaded poly N-methylpyrrole gel.
In the above process of preparing the modified graphene-loaded poly N-methylpyrrole gel:
aiming at the step 1, 0.8g of modified graphene is added into every 100ml of deionized water, the mass ratio of lignin powder to the modified graphene is 3:1, and the addition amount of potassium persulfate is 0.16g of potassium persulfate added into every 100ml of deionized water;
aiming at the step 2, the mass ratio of the N-methylpyrrole, the p-toluenesulfonic acid, the deionized water, the modified graphene/lignin gel to the ferric sulfate solution is 4:1:32:100:18, the mass concentration of the ferric sulfate solution is 15wt%, and the dropping time is 3 hours.
The preparation of the antistatic masterbatch of the embodiment includes the following steps:
the method comprises the following steps: preparing materials according to the following mass percentages:
32% of conductive active component, 0.2% of peroxide and the balance of resin carrier;
step two: adding the components into a double-screw extruder, melting and blending at 126 ℃, and performing extrusion granulation to obtain the antistatic master batch IV.
Example 5:
the antistatic master batch V provided by the embodiment comprises the following raw materials in percentage by mass: 40% of conductive active component, 0.5% of peroxide and the balance of resin carrier; wherein the resin carrier is ethylene-vinyl acetate copolymer, the VA content of the resin carrier is 32 wt%, the melt index of the resin carrier is 43g/10min (190 ℃, 2.16kg), and the peroxide is tert-butyl peroxybenzoate.
The conductive active components adopted in this embodiment include poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol at a mass ratio of 1:4 (note that the modified graphene adopted is modified graphene
) The modified graphene loaded poly-N-methylpyrrole gel is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 60min, then adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH value of the solution to 6, then adding potassium persulfate, heating to 87 ℃, reacting at constant temperature for 1.5h, and naturally cooling to room temperature to obtain modified graphene/lignin gel;
step 2: adding N-methylpyrrole and p-toluenesulfonic acid into deionized water, stirring and mixing uniformly, adding the modified graphene/lignin gel prepared in the step 1, stirring at a constant temperature of 72 ℃ for 1h, then slowly dropwise adding a ferric sulfate solution under a stirring state, placing in an ice water bath for reaction for 2h after dropwise adding is finished, and repeatedly washing with absolute ethyl alcohol to obtain the poly-N-methylpyrrole gel loaded with the modified graphene.
In the above process of preparing the modified graphene-loaded poly N-methylpyrrole gel:
aiming at the step 1, adding 1.2g of modified graphene into every 100ml of deionized water, wherein the mass ratio of lignin powder to the modified graphene is 4:1, and the adding amount of potassium persulfate is 0.2g of potassium persulfate into every 100ml of deionized water;
according to the step 2, the mass ratio of the N-methylpyrrole, the p-toluenesulfonic acid, the deionized water, the modified graphene/lignin gel to the ferric sulfate solution is 5:1:40:100:20, the mass concentration of the ferric sulfate solution is 13 wt%, and the dropping time is 3 hours.
The preparation of the antistatic masterbatch of the embodiment comprises the following steps:
the method comprises the following steps: preparing materials according to the following mass percentages:
40% of conductive active component, 0.5% of peroxide and the balance of resin carrier;
step two: adding the components into a double-screw extruder, melting and blending at 130 ℃, and performing extrusion granulation to obtain the antistatic master batch V.
Example 6
The plastic film comprises the antistatic master batch provided by the embodiment, and the components and the proportion of the film material are shown in table 1.
TABLE 1
| Item | PC resin | Antistatic master batch | Ultraviolet absorber | Flame retardant | Antioxidant agent | Heat stabilizer |
| Product 1 | 100 | 5 | 0.2 | 1 | 1 | 1 |
| Product 2 | 100 | 8 | 0.4 | 1 | 1.4 | 1.3 |
| Product 3 | 100 | 10 | 0.4 | 2 | 1.6 | 1.5 |
| Product 4 | 100 | 12 | 0.5 | 2 | 1.5 | 1.8 |
| Product 5 | 100 | 15 | 0.6 | 3 | 2 | 2 |
In the products shown in table 1:
in the product 1, the melt index of the PC resin is 10g/10min (300 ℃, 1.2kg), the antistatic master batch is antistatic master batch I, the flame retardant is prepared by mixing tris (2-ethylhexyl) phosphate, antimony trioxide and zinc borate according to the mass ratio of 1:3, the antioxidant is commercially available antioxidant 168, and the heat stabilizer is calcium stearate soap;
in the product 2, the melt index of the PC resin is 16g/10min (300 ℃, 1.2kg), the antistatic master batch is antistatic master batch II, the flame retardant is prepared by mixing tris (2-ethylhexyl) phosphate, antimony trioxide and zinc borate according to the mass ratio of 1: 1.2: 3, the antioxidant is a commercially available antioxidant 1010, and the heat stabilizer is calcium oleate soap;
in the product 3, the melt index of the PC resin is 21g/10min (300 ℃, 1.2kg), the antistatic master batch is antistatic master batch III, the flame retardant is prepared by mixing tris (2-ethylhexyl) phosphate, antimony trioxide and zinc borate according to the mass ratio of 1: 1.5: 3, the antioxidant is a commercially available antioxidant 1076, and the heat stabilizer is brown calcium oleate soap;
in the product 4, the melt index of the PC resin is 27g/10min (300 ℃, 1.2kg), the antistatic master batch is antistatic master batch IV, the flame retardant is prepared by mixing tris (2-ethylhexyl) phosphate, antimony trioxide and zinc borate according to the mass ratio of 1: 1.8: 3, the antioxidant is a commercially available antioxidant 264, and the heat stabilizer is calcium linoleate soap;
in the product 5, the melt index of the PC resin is 35g/10min (300 ℃, 1.2kg), the antistatic master batch is antistatic master batch V, the flame retardant is prepared by mixing tris (2-ethylhexyl) phosphate, antimony trioxide and zinc borate according to the mass ratio of 1: 2: 3, the antioxidant is a commercially available antioxidant 1024, and the heat stabilizer is calcium linoleate soap.
The ultraviolet absorbers used in the products 1 to 5 are 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
The products 1-5 are all prepared by the following steps:
the PC resin is dried at the temperature of 120-130 ℃ to ensure that the water content is less than or equal to 0.05 percent, then the components are added into a high-speed mixer according to the parts by weight for mixing treatment to obtain a mixture, the mixture is added into a double-screw extruder for melt blending, and the plastic film is prepared through extrusion granulation.
The specific process parameters involved in the above preparation are shown in table 2.
TABLE 2
| Item | Product 1 | Product 2 | Product 3 | Product 4 | Product 5 |
| Temperature of high speed mixer | 150℃ | 150℃ | 153℃ | 156℃ | 160℃ |
| Time of mixing treatment | 20min | 16min | 12min | 10min | 10min |
| Temperature of one zone | 170℃ | 176℃ | 180℃ | 185℃ | 190℃ |
| Temperature of the second zone | 215℃ | 219℃ | 224℃ | 226℃ | 230℃ |
| Three zone temperature | 235℃ | 238℃ | 242℃ | 240℃ | 244℃ |
| Temperature of four zones | 242℃ | 241℃ | 245℃ | 247℃ | 248℃ |
| Temperature of five zones | 246℃ | 245℃ | 248℃ | 250℃ | 250℃ |
| Temperature in six zones | 215℃ | 219℃ | 224℃ | 226℃ | 230℃ |
| Die temperature | 250℃ | 252℃ | 254℃ | 258℃ | 260℃ |
| Screw rotation speed | 200r/min | 360r/min | 480r/min | 520r/min | 600r/min |
The following provides reference products 1-3, the specific technical scheme is as follows:
control product 1:
the comparison product is different from the product 4 in that the product does not contain the antistatic master batch IV, and the rest is the same as the product 4.
Control product 2:
the comparison product is different from the product 4 in that the product does not contain the antistatic master batch IV, but adopts the common graphene sold in the market as the antistatic agent, and the rest is the same as the product 4.
Control product 3:
the comparison product is different from the product 4 in that the product does not contain the antistatic master batch IV, but adopts the common commercial poly N-methyl pyrrole as the antistatic agent, and the rest is the same as the product 4.
The results of the performance tests of the above products 1 to 5 and the comparative products 1 to 3 are shown in Table 3.
TABLE 3
Note: in Table 3, tensile strength tests were performed with reference to ISO1183, impact strength tests were performed with reference to ISO 180, flame retardancy tests were performed with reference to UL-94, and surface resistance tests were performed with reference to GB/T1410-2006.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The antistatic master batch for the plastic is characterized by comprising a resin carrier and a conductive active component compounded with the resin carrier, wherein the resin carrier is an ethylene-vinyl acetate copolymer, and the conductive active component comprises poly N-methylpyrrole gel loaded with modified graphene and polyethylene glycol in a mass ratio of 1 (1-4).
2. The antistatic master batch for plastics according to claim 1, wherein the preparation method of the modified graphene loaded poly-N-methyl pyrrole gel comprises the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 30-60min, then adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH value of the solution to 5-6, then adding potassium persulfate, heating to 85-95 ℃, reacting at constant temperature for 1-3h, and naturally cooling to room temperature to obtain modified graphene/lignin gel;
step 2: adding N-methylpyrrole and p-toluenesulfonic acid into deionized water, stirring and mixing uniformly, adding the modified graphene/lignin gel prepared in the step 1, stirring at a constant temperature of 70-90 ℃ for 1-2h, then slowly dropwise adding a ferric sulfate solution under a stirring state, after dropwise adding, placing in an ice water bath for reaction for 2-4h, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene-loaded poly N-methylpyrrole gel.
3. The antistatic master batch for plastics as claimed in claim 2, wherein the modified graphene is obtained by modifying the surface of graphene with an organic amine modifier, and the organic amine modifier is at least one selected from triethylenetetramine, triethylenediamine and hexamethylenetetramine.
4. The antistatic master batch for plastics according to claim 2, wherein in the step 1,
adding 0.1-1.2g of modified graphene into 100ml of deionized water; and/or the presence of a catalyst in the reaction mixture,
the mass ratio of the lignin powder to the modified graphene is (1-4) to 1; and/or the presence of a catalyst in the reaction mixture,
0.02-0.2g of potassium persulfate is added to 100ml of deionized water.
5. The antistatic master batch for plastics according to claim 2, wherein in the step 2,
the mass ratio of the N-methylpyrrole, the p-toluenesulfonic acid, the deionized water, the modified graphene/lignin gel and the ferric sulfate solution is (3-5):1, (20-40):100, (15-20); and/or the presence of a catalyst in the reaction mixture,
the mass concentration of the ferric sulfate solution is 10-15 wt%; and/or the presence of a catalyst in the reaction mixture,
the dripping time of the ferric sulfate solution is 1-3 h.
6. The antistatic master batch for plastics according to claim 1, wherein the antistatic master batch comprises 0.1-0.5% of peroxide and 10-40% of conductive active component by 100% of mass fraction, and the balance is resin carrier.
7. The method for preparing the antistatic master batch for plastics according to any one of claims 1 to 6, which is characterized by comprising the following steps:
the method comprises the following steps: preparing materials according to the following mass percentages:
10-40% of conductive active component, 0.1-0.5% of peroxide and the balance of resin carrier;
step two: adding the components in the step I into a double-screw extruder, melting and blending at the temperature of 110-130 ℃, and performing extrusion granulation to obtain the antistatic master batch.
8. A plastic film, comprising: the antistatic master batch according to any one of claims 1 to 6, which comprises 5 to 15 parts of the antistatic master batch, 100 parts of PC resin, 0.2 to 0.6 part of ultraviolet absorber, 1 to 3 parts of flame retardant, 1 to 2 parts of antioxidant and 1 to 2 parts of heat stabilizer.
9. The plastic film according to claim 8, wherein the ultraviolet absorber is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole; and/or the presence of a catalyst in the reaction mixture,
the flame retardant comprises tri (2-ethylhexyl) phosphate, antimony trioxide and zinc borate in a mass ratio of 1 (1-2) to 3; and/or the presence of a catalyst in the reaction mixture,
the antioxidant is at least one selected from antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 1024, antioxidant B215 or antioxidant B225; and/or the presence of a catalyst in the reaction mixture,
the heat stabilizer is at least one of calcium stearate soap, calcium oleate soap, calcium palmitoleate soap or calcium linoleate soap.
10. The preparation method of the plastic film as claimed in any one of claims 8-9, wherein the PC resin is dried at a temperature of 120-130 ℃ to a water content of less than or equal to 0.05%, and then the components are added into a high-speed mixer according to the proportion to be mixed to obtain a uniform mixture, and then the mixture is added into a double-screw extruder to be melted and blended, and then the mixture is extruded and granulated to obtain the plastic film;
wherein the temperature of the high-speed mixer is 150-160 ℃, and the mixing treatment time is 10-20 min; and/or the presence of a catalyst in the reaction mixture,
the technological parameters of the double-screw extruder are as follows:
the temperature of the first zone is 190 ℃ in 170-.
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