CN114456478B - Antistatic master batch for plastics and plastic film containing same - Google Patents
Antistatic master batch for plastics and plastic film containing same Download PDFInfo
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- CN114456478B CN114456478B CN202210158713.5A CN202210158713A CN114456478B CN 114456478 B CN114456478 B CN 114456478B CN 202210158713 A CN202210158713 A CN 202210158713A CN 114456478 B CN114456478 B CN 114456478B
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- modified graphene
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- antistatic master
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 58
- 239000002985 plastic film Substances 0.000 title claims abstract description 19
- 229920006255 plastic film Polymers 0.000 title claims abstract description 19
- 229920003023 plastic Polymers 0.000 title claims abstract description 16
- 239000004033 plastic Substances 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 14
- 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 49
- 239000000047 product Substances 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 229920005610 lignin Polymers 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 28
- 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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 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
- 238000000034 method Methods 0.000 claims description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- 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
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000344 soap Substances 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002360 preparation method 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 11
- 239000003063 flame retardant Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000012760 heat stabilizer Substances 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 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
- 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
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 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
- 238000001035 drying Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 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 claims description 3
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-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
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 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
- 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 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
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229940023569 palmate Drugs 0.000 claims 1
- 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
- 230000002045 lasting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 239000000155 melt Substances 0.000 description 13
- 239000002216 antistatic agent Substances 0.000 description 11
- 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
- 238000012545 processing Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- GEXXRGPMFWDDHM-UHFFFAOYSA-N 1-butylperoxy-3-(2-butylperoxypropan-2-yl)benzene Chemical compound C(CCC)OOC(C)(C)C1=CC(=CC=C1)OOCCCC GEXXRGPMFWDDHM-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
- 239000002585 base Substances 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- 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
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical group CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 description 1
- 206010015866 Extravasation Diseases 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
- 230000009286 beneficial effect Effects 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
- 230000036251 extravasation 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 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
- 239000013049 sediment Substances 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
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-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 modified graphene loaded poly-N-methylpyrrole gel and polyethylene glycol in a mass ratio of 1 (1-4). The plastic film material prepared from the antistatic master batch not only has good dimensional stability, excellent heat resistance and chemical corrosion resistance, but also meets the environmental protection requirement, has high-efficiency, lasting and stable antistatic effect, and has good surface glossiness and good application prospect in the development of the high polymer material technical 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 have been widely used in various aspects of people's production and life, and have become important processing materials for electric products due to their light weight, easy processing, high electrical insulation, and good characteristics that can be designed according to the use. However, since the insulation of the plastic itself is too high, in practical application, a large amount of charges are often generated due to friction and accumulated 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 potential safety hazard. For example, polypropylene resin, which is an engineering plastic with good comprehensive properties, has excellent heat stability, cold resistance, fluidity and chemical medium stability, and good processability and dimensional stability, but has very limited application in the field of electronic and electric appliances due to poor antistatic property.
In view of the above problems, the prior art has often improved the antistatic properties of materials by employing antistatic agents during the plastic production process. At present, more common antistatic agents comprise a surfactant type antistatic agent and a polymer type antistatic agent, wherein the surfactant type antistatic agent achieves the antistatic purpose by absorbing environmental moisture and reducing surface resistivity, and has larger dependence on environmental humidity. The polymer type antistatic agent is a permanent antistatic agent, but it generally has problems such as poor compatibility with a base material, easy occurrence of extravasation during processing and molding, poor stability of antistatic effect, and influence on the appearance of a product.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides 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 polymer antistatic agent is easy to leak 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.
Another object of the present invention is to provide a plastic film comprising the above antistatic master batch.
Still another object of the present invention is to provide a method for preparing the plastic film.
The aim of the invention can be achieved by the following technical scheme:
according to one aspect of the invention, an antistatic master batch for plastics is provided, which comprises a resin carrier and a conductive active component compounded with the resin carrier, wherein the resin carrier is ethylene-vinyl acetate copolymer, and the conductive active component comprises modified graphene loaded poly-N-methylpyrrole gel and polyethylene glycol in a mass ratio of (1-4).
Illustratively, the ethylene-vinyl acetate copolymer has a VA (vinyl acetate) content of 32wt% and a melt index of 43g/10min (190 ℃,2.16 kg).
As a preferred embodiment of the invention, the preparation method of the modified graphene loaded poly-N-methylpyrrole gel comprises the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 30-60min, adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, regulating the pH of the solution to 5-6, then adding potassium persulfate, heating to 85-95 ℃ for constant-temperature reaction 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 1-2 hours, slowly dropwise adding ferric sulfate solution in a stirring state, reacting in an ice water bath for 2-4 hours after dropwise adding, 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, wherein 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 steps of:
step i: preparing graphene oxide by adopting a Hummers method;
step ii: weighing about 500mg of graphene oxide, performing ultrasonic dispersion in about 500ml of DMF (N-N dimethylformamide) for 5 hours to prepare a graphene oxide suspension, adding about 40g of an organic amine modifier and about 8g of dicyclohexylcarbodiimide, performing ultrasonic treatment for 20 minutes, then reacting at 140 ℃ for 24 hours, adding about 60ml of absolute ethyl alcohol, and standing; removing supernatant, filtering with polytetrafluoroethylene membrane to obtain lower precipitate, and washing with absolute ethanol 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 be neutral (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 invention, 0.1-1.2g of modified graphene is added to every 100ml of deionized water in the step 1.
As a preferred embodiment of the 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, 0.02-0.2g of potassium persulfate is added per 100ml of deionized water in step 1.
As a preferred embodiment of the invention, the mass ratio of the N-methylpyrrole, 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).
As a preferred embodiment of the present invention, the mass concentration of the ferric sulfate solution in the step 2 is 10-15wt%, and the dropping time of the ferric sulfate solution is 1-3h.
As a preferred embodiment of the present invention, the antistatic master batch further comprises 0.1 to 0.5% of peroxide and 10 to 40% of conductive active component, the balance being resin carrier, in terms of 100% by mass.
Illustratively, the peroxide is selected from one or more of 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 1, 3-bis-butylperoxyisopropyl benzene, dibenzoyl peroxide, t-amyl acetate peroxide, t-butyl peroxybenzoate, or dicumyl peroxide.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned antistatic master batch for plastics, comprising the steps of:
step (1): the materials are prepared 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 (2): and (3) adding the components in the step (1) into a double-screw extruder, carrying out melt blending at 110-130 ℃, and carrying out 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 master batch.
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 absorber, 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 ℃ C., 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 present invention, the flame retardant comprises tris (2-ethylhexyl) phosphate, antimony trioxide and zinc borate in a mass ratio of 1 (1-2): 3. .
As 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 at least one selected from the group consisting of calcium stearate soap, calcium oleate soap, calcium palmitoleate soap and calcium linoleate soap.
According to another aspect of the invention, a preparation method of the plastic film is provided, namely, 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%, then the components are added into a high-speed mixer according to the weight ratio for mixing treatment to obtain a uniform mixture, and the mixture is added into a double-screw extruder for melt blending, and extrusion granulation is carried out to obtain the plastic film.
As a preferred embodiment of the present invention, the temperature of the high-speed mixer is 150-160 ℃ and the mixing treatment time is 10-20min.
As a preferred embodiment of the present invention, the process parameters of the twin-screw extruder are as follows:
the temperature of the first area is 170-190 ℃, the temperature of the second area is 215-230 ℃, the temperatures of the third area, the fourth area and the fifth area are 235-250 ℃, the temperature of the sixth area is 215-230 ℃, the temperature of the die head is 250-260 ℃, and the rotating speed of the screw is 200-600r/min.
Compared with the prior art, the invention at least comprises the following beneficial effects:
1) According to the antistatic master batch provided by the invention, the ethylene-vinyl acetate copolymer with the VA (vinyl acetate) content of 32wt% and the melt index of 43g/10min (190 ℃ C., 2.16 kg) is adopted 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 substrate (such as PC resin), the conductive active component can be uniformly dispersed in the resin substrate, and the technical problems that the existing antistatic agent is easy to separate out and extravasate in the material processing and forming process, so that the appearance of a product is influenced and the like can be effectively solved;
2) The conductive active components selected in the antistatic master batch comprise the following components in percentage by mass: the modified graphene-loaded poly-N-methylpyrrole gel and polyethylene glycol in the invention (1-4) are characterized in that the poly-N-methylpyrrole gel has a conjugated structure in a molecular chain, and is a polymer with good conductivity, in order to further enhance the conductivity of the poly-N-methylpyrrole, the modified graphene is firstly reacted with lignin, all three-dimensional network structures of the lignin are utilized, so that the modified graphene is bonded in the three-dimensional network structure, lignin is taken as an intermediate carrier, active groups such as hydroxyl groups and quinone groups contained in the lignin can be effectively combined into the molecular chain of the poly-N-methylpyrrole, so that the poly-N-methylpyrrole gel loaded with the modified graphene is formed, the polyethylene glycol is favorable for uniformly dispersing the poly-N-methylpyrrole gel loaded with the modified graphene in an ethylene-vinyl acetate copolymer, and the obtained antistatic master batch can form a rich and stable conductive path in a resin substrate, thus the introduction of the modified graphene can play a permanent antistatic effect, and the strength of the resin substrate is also favorable for enhancing;
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 an efficient, durable and stable antistatic effect, has good surface glossiness, and has a good application prospect in the development of the high polymer material technical industry.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed embodiment and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention.
As used herein, the term "about" when used to modify a numerical value means a margin of error measured within + -5% of the numerical value.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the 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 adopting a Hummers method, specifically, mixing 2g of graphite, 1g of NaNO3 and 46ml of 98% concentrated sulfuric acid in an ice-water bath, stirring for 30 minutes, fully mixing, weighing 6g of KMnO4, adding the mixture into the mixture for continuous stirring for 2 hours, and then transferring into a warm water bath at 35 ℃ for continuous stirring for 30 minutes; then 92ml of distilled water is slowly added, and the reaction solution is controlled at about 98 DEG CFor 15 minutes, adding a proper amount of 30% H2O2 to remove excessive oxidant, adding distilled water to dilute the mixture by 140ml, filtering the mixture while the mixture is hot, and washing the mixture with 0.01mol/L HCl, absolute ethyl alcohol and deionized water in sequence until the filtrate is free of SO 4 2- Until it exists, preparing graphite oxide; then, ultrasonically dispersing graphite oxide in water to prepare a dispersion liquid of the graphene oxide; drying the graphene oxide dispersion liquid in a vacuum drying oven at 60 ℃ for 48 hours to obtain a graphene oxide sample, and preserving for later use;
step ii: weighing about 500mg of graphene oxide, performing ultrasonic dispersion in about 500ml of DMF (N-N dimethylformamide) for 5 hours to prepare a graphene oxide suspension, adding about 40g of an organic amine modifier and about 8g of dicyclohexylcarbodiimide, performing ultrasonic treatment for 20 minutes, then reacting at 140 ℃ for 24 hours, adding about 60ml of absolute ethyl alcohol, and standing overnight; removing supernatant, filtering lower-layer sediment by using a polytetrafluoroethylene film, and washing for a plurality of times by using absolute ethyl alcohol and deionized water 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 be neutral, and drying the product at 95 ℃ for 48 hours to obtain the modified graphene.
In the above step ii, different kinds of organic amine modifiers can be selected to obtain different modified graphene oxides, for example, triethylenetetramine is adopted, and correspondingly, the obtained modified graphene can be obtainedModified graphene +.>Modified graphene +.>。
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 32wt%, the melt index is 43g/10min (190 ℃,2.16 kg), and the peroxide is dibenzoyl peroxide.
The conductive active component adopted in the embodiment comprises poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol (note that the modified graphene is modified graphene) in a mass ratio of 1:1) The poly-N-methylpyrrole gel loaded with the modified graphene is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 30min, adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, regulating the pH of the solution to 5.5, then adding potassium persulfate, heating to 85 ℃ for constant-temperature reaction 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, slowly dropwise adding ferric sulfate solution in a stirring state, after the dropwise adding is finished, placing in an ice water bath for reacting for 4 hours, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene loaded poly-N-methylpyrrole gel.
In the process of preparing the modified graphene-loaded poly-N-methylpyrrole gel, the following steps are adopted:
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 modified graphene is 4:1, and the addition amount of potassium persulfate is 0.02g of potassium persulfate is 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 and the ferric sulfate solution is 3:1:20:100:15, the mass concentration of the ferric sulfate solution is 10wt%, and the dripping time is 1h.
The preparation of the antistatic master batch in this example comprises the following steps:
step (1): the materials are prepared according to the following mass percentages:
10% of conductive active component, 0.1% of peroxide and the balance of resin carrier;
step (2): adding the components into a double-screw extruder, melting and blending at 110 ℃, and extruding and granulating 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% 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 32wt%, the melt index is 43g/10min (190 ℃,2.16 kg), and the peroxide is tert-amyl peroxyacetate.
The conductive active component adopted in the embodiment comprises poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol according to the mass ratio of 1:1 (note that the modified graphene is modified graphene)) The poly-N-methylpyrrole gel loaded with the modified graphene is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 40min, 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 ℃ for constant-temperature reaction 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, slowly dropwise adding ferric sulfate solution in a stirring state, after the dropwise adding is finished, placing in an ice water bath for reacting for 3 hours, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene loaded poly-N-methylpyrrole gel.
In the process of preparing the modified graphene-loaded poly-N-methylpyrrole gel, the following steps are adopted:
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 modified graphene is 2:1, and the addition amount of potassium persulfate is 0.08g of potassium persulfate is 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 and the ferric sulfate solution is 3:1:25:100:18, the mass concentration of the ferric sulfate solution is 12wt%, and the dripping time is 1.5h.
The preparation of the antistatic master batch in this example comprises the following steps:
step (1): the materials are prepared according to the following mass percentages:
24% of conductive active component, 0.2% of peroxide and the balance of resin carrier;
step (2): adding the components into a double-screw extruder, melt blending at 118 ℃, and extruding and granulating to obtain the antistatic master batch II.
Example 3:
the antistatic master batch III provided in the embodiment comprises the following raw materials in percentage: 30% of conductive active component, 0.4% of peroxide and the balance of resin carrier; wherein the resin carrier is an ethylene-vinyl acetate copolymer having a VA content of 32wt% and a melt index of 43g/10min (190 ℃ C., 2.16 kg) and the peroxide is 1, 3-bis-butylperoxyisopropyl benzene.
The conductive active component adopted in the embodiment comprises poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol in a mass ratio of 1:2.5 (note that the modified graphene is modified graphene)) Poly-N-methylpyrrole loaded with modified grapheneThe gel is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 45min, 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 ℃ for constant-temperature reaction 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, slowly dropwise adding ferric sulfate solution in a stirring state, after the dropwise adding is finished, placing in an ice water bath for reacting for 2h, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene loaded poly-N-methylpyrrole gel.
In the process of preparing the modified graphene-loaded poly-N-methylpyrrole gel, the following steps are adopted:
aiming at the step 1, 1.0g of modified graphene is added into every 100ml of deionized water, the mass ratio of lignin powder to modified graphene is 2:1, and the addition amount of potassium persulfate is 0.1g 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 and the ferric sulfate solution is 4:1:30:100:20, the mass concentration of the ferric sulfate solution is 15wt%, and the dripping time is 2h.
The preparation of the antistatic master batch in this example comprises the following steps:
step (1): the materials are prepared according to the following mass percentages:
30% of conductive active component, 0.4% of peroxide and the balance of resin carrier;
step (2): adding the components into a double-screw extruder, melt blending at 123 ℃, and extruding and granulating 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 an ethylene-vinyl acetate copolymer having a VA content of 32wt% and a melt index of 43g/10min (190 ℃ C., 2.16 kg) and the peroxide is 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane.
The conductive active component adopted in the embodiment comprises poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol (note that the modified graphene is modified graphene) in a mass ratio of 1:2) The poly-N-methylpyrrole gel loaded with the modified graphene is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 50min, adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, regulating the pH of the solution to 5.5, then adding potassium persulfate, heating to 92 ℃ for constant-temperature reaction 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 1.5 hours, slowly dropwise adding ferric sulfate solution in a stirring state, reacting in an ice water bath for 3.5 hours after the dropwise addition is finished, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene-loaded poly-N-methylpyrrole gel.
In the process of preparing the modified graphene-loaded poly-N-methylpyrrole gel, the following steps are adopted:
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 modified graphene is 3:1, and the addition amount of potassium persulfate is 0.16g of potassium persulfate is 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 and the ferric sulfate solution is 4:1:32:100:18, the mass concentration of the ferric sulfate solution is 15wt%, and the dripping time is 3h.
The preparation of the antistatic master batch in this example comprises the following steps:
step (1): the materials are prepared according to the following mass percentages:
32% of conductive active component, 0.2% of peroxide and the balance of resin carrier;
step (2): adding the components into a double-screw extruder, melt blending at 126 ℃, extruding and granulating 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 is 32wt%, the melt index is 43g/10min (190 ℃,2.16 kg), and the peroxide is tert-butyl peroxybenzoate.
The conductive active component adopted in the embodiment comprises poly-N-methylpyrrole gel loaded with modified graphene and polyethylene glycol (note that the modified graphene is modified graphene) in a mass ratio of 1:4) The poly-N-methylpyrrole gel loaded with the modified graphene is prepared by the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 60min, adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, adjusting the pH of the solution to 6, then adding potassium persulfate, heating to 87 ℃ for constant-temperature reaction 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, slowly dropwise adding ferric sulfate solution in a stirring state, after the dropwise adding is finished, placing in an ice water bath for reacting for 2h, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene loaded poly-N-methylpyrrole gel.
In the process of preparing the modified graphene-loaded poly-N-methylpyrrole gel, the following steps are adopted:
aiming at the step 1, 1.2g of modified graphene is added into every 100ml of deionized water, the mass ratio of lignin powder to modified graphene is 4:1, and the addition amount of potassium persulfate is 0.2g 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 and the ferric sulfate solution is 5:1:40:100:20, the mass concentration of the ferric sulfate solution is 13wt%, and the dripping time is 3h.
The preparation of the antistatic master batch in this example comprises the following steps:
step (1): the materials are prepared according to the following mass percentages:
40% of conductive active component, 0.5% of peroxide and the balance of resin carrier;
step (2): adding the components into a double-screw extruder, melt blending at 130 ℃, extruding and granulating to obtain the antistatic master batch V.
Example 6
There is provided a plastic film comprising the antistatic master batch provided in the above examples, the components of the film material and their ratios are shown in table 1.
TABLE 1
| Project | PC resin | Antistatic master batch | Ultraviolet absorber | Flame retardant | Antioxidant | 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 PC resin is 10g/10min (300 ℃,1.2 kg), the antistatic master batch is antistatic master batch I, the flame retardant is formed by mixing tri (2-ethylhexyl) phosphate, antimony trioxide and zinc borate with the mass ratio of 1:1:3, the antioxidant is a commercially available antioxidant 168, and the heat stabilizer is calcium stearate soap;
in the product 2, the melt index of PC resin is 16g/10min (300 ℃,1.2 kg), the antistatic master batch is antistatic master batch II, the flame retardant is formed by mixing tri (2-ethylhexyl) phosphate, antimonous oxide 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 PC resin is 21g/10min (300 ℃,1.2 kg), the antistatic master batch is antistatic master batch III, the flame retardant is formed by mixing tri (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 calcium palmitoleate soap;
in the product 4, the melt index of PC resin is 27g/10min (300 ℃,1.2 kg), the antistatic master batch is antistatic master batch IV, the flame retardant is formed by mixing tri (2-ethylhexyl) phosphate, antimonous oxide and zinc borate with 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 ℃,1.2 kg), the antistatic master batch is antistatic master batch V, the flame retardant is formed by mixing tri (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 above products 1 to 5 are all 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 parts by weight for mixing treatment to obtain a mixture, and the mixture is added into a double-screw extruder for melt blending, and extrusion granulation is carried out to obtain the plastic film.
The specific process parameters involved in the preparation process are shown in table 2.
TABLE 2
| Project | Product 1 | Product 2 | Product 3 | Product 4 | Product 5 |
| High speed mixer temperature | 150℃ | 150℃ | 153℃ | 156℃ | 160℃ |
| Mixing treatment time | 20min | 16min | 12min | 10min | 10min |
| One zone temperature | 170℃ | 176℃ | 180℃ | 185℃ | 190℃ |
| Two zone temperature | 215℃ | 219℃ | 224℃ | 226℃ | 230℃ |
| Three zone temperature | 235℃ | 238℃ | 242℃ | 240℃ | 244℃ |
| Four zone temperature | 242℃ | 241℃ | 245℃ | 247℃ | 248℃ |
| Five-zone temperatureDegree of | 246℃ | 245℃ | 248℃ | 250℃ | 250℃ |
| Six zone temperature | 215℃ | 219℃ | 224℃ | 226℃ | 230℃ |
| Die temperature | 250℃ | 252℃ | 254℃ | 258℃ | 260℃ |
| Screw speed | 200r/min | 360r/min | 480r/min | 520r/min | 600r/min |
Control products 1-3 are provided below, with the following specific technical scheme:
control product 1:
the control product differs from product 4 in that it does not contain an antistatic masterbatch IV, the remainder being the same as product 4.
Control product 2:
the control product is different from the product 4 in that the antistatic masterbatch IV is not contained, but common graphene sold in the market is used as an antistatic agent, and the rest is the same as the product 4.
Control product 3:
the control product is different from product 4 in that it does not contain antistatic masterbatch IV, but instead adopts commercially available common poly-N-methylpyrrole as antistatic agent, the remainder being the same as product 4.
The results of the performance tests for the above products 1-5 and control products 1-3 are shown in Table 3.
TABLE 3 Table 3
Note that: in Table 3, the tensile strength test was conducted with reference to ISO1183, the impact strength test was conducted with reference to ISO 180, the flame retardant rating test was conducted with reference to UL-94, and the surface resistance test was conducted with reference to GB/T1410-2006.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (8)
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 modified graphene loaded poly-N-methylpyrrole gel and polyethylene glycol in a mass ratio of 1 (1-4);
the modified graphene is obtained by modifying the surface of graphene by adopting an organic amine modifier, wherein the organic amine modifier is at least one of triethylenetetramine, triethylenediamine or hexamethylenetetramine;
wherein the modified graphene is prepared by the following steps:
step i: preparing graphene oxide by adopting a Hummers method;
step ii: weighing 500mg of graphene oxide, performing ultrasonic dispersion in 500ml of DMF (N-N dimethylformamide) for 5 hours to prepare graphene oxide suspension, then adding 40g organic amine modifier and 8g dicyclohexyl carbodiimide, performing ultrasonic treatment for 20 minutes, then reacting at 140 ℃ for 24h, adding 60ml of absolute ethyl alcohol, and standing; removing supernatant, filtering with polytetrafluoroethylene membrane to obtain lower precipitate, and washing with absolute ethanol and deionized water for multiple times to obtain modified graphene oxide;
step iii: dispersing the washed and undried modified graphene oxide in 60ml of absolute ethyl alcohol, performing ultrasonic dispersion for 2 hours to form uniform and stable modified graphene oxide dispersion liquid, adding 1.36g of hydrazine hydrate, and reducing for 36 hours at 72 ℃; washing the obtained product with absolute ethyl alcohol and deionized water until the pH value is 6.5-7.5, and drying the product at 95 ℃ for 48 hours to obtain modified graphene;
the preparation method of the modified graphene loaded poly-N-methylpyrrole gel comprises the following steps:
step 1: adding modified graphene into deionized water, performing ultrasonic dispersion for 30-60min, adding lignin powder, fully and uniformly stirring, then dropwise adding glacial acetic acid, regulating the pH of the solution to 5-6, then adding potassium persulfate, heating to 85-95 ℃ for constant-temperature reaction 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 1-2 hours, slowly dropwise adding ferric sulfate solution in a stirring state, reacting in an ice water bath for 2-4 hours after dropwise adding, and repeatedly washing with absolute ethyl alcohol to obtain the modified graphene loaded poly-N-methylpyrrole gel.
2. An antistatic master batch for plastics according to claim 1, wherein in step 1,
adding 0.1-1.2g of modified graphene into every 100ml of deionized water; and/or the number of the groups of groups,
the mass ratio of the lignin powder to the modified graphene is (1-4): 1; and/or the number of the groups of groups,
adding 0.02-0.2g of potassium persulfate into every 100ml of deionized water.
3. An antistatic master batch for plastics according to claim 1, wherein in step 2,
the mass ratio of the N-methylpyrrole to the p-toluenesulfonic acid to the deionized water to the modified graphene/lignin gel to the ferric sulfate solution is (3-5) 1 (20-40) 100 (15-20); and/or the number of the groups of groups,
the mass concentration of the ferric sulfate solution is 10-15wt%; and/or the number of the groups of groups,
the dropwise adding time of the ferric sulfate solution is 1-3h.
4. An antistatic master batch for plastics according to claim 1, wherein the antistatic master batch comprises 0.1 to 0.5% of peroxide and 10 to 40% of conductive active component in terms of 100% by mass, and the balance being a resin carrier.
5. A process for the preparation of antistatic master batches for plastics according to any one of claims 1 to 4, comprising the steps of:
step (1): the materials are prepared 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 (2): and (3) adding the components in the step (1) into a double-screw extruder, carrying out melt blending at 110-130 ℃, and carrying out extrusion granulation to obtain the antistatic master batch.
6. A plastic film, the plastic film comprising: the antistatic masterbatch according to any one of claims 1 to 5, 5 to 15 parts, 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.
7. A plastic film according to claim 6, wherein the uv absorber is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole; and/or the number of the groups of groups,
the flame retardant comprises tri (2-ethylhexyl) phosphate, antimonous oxide and zinc borate with the mass ratio of 1 (1-2) to 3; and/or the number of the groups of groups,
the antioxidant is at least one selected from antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 1024, antioxidant B215 and antioxidant B225; and/or the number of the groups of groups,
the heat stabilizer is at least one selected from calcium stearate soap, calcium oleate soap, calcium palmate soap or calcium linoleate soap.
8. A method for preparing a plastic film according to any one of claims 6 to 7, wherein the PC resin is dried at 120 to 130 ℃ to have a water content of less than or equal to 0.05%, the components are added into a high-speed mixer according to a proportion to be mixed to obtain a uniform mixture, and the mixture is added into a twin-screw extruder to be melt-blended and extruded to be granulated to obtain the plastic film;
wherein the temperature of the high-speed mixer is 150-160 ℃, and the mixing treatment time is 10-20min; and/or the number of the groups of groups,
the technological parameters of the double-screw extruder are as follows:
the temperature of the first area is 170-190 ℃, the temperature of the second area is 215-230 ℃, the temperatures of the third area, the fourth area and the fifth area are 235-250 ℃, the temperature of the sixth area is 215-230 ℃, the temperature of the die head is 250-260 ℃, and the rotating speed of the screw is 200-600r/min.
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