CN116574334A - Regenerated polyolefin plastic composition and preparation method thereof - Google Patents
Regenerated polyolefin plastic composition and preparation method thereof Download PDFInfo
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- CN116574334A CN116574334A CN202310709849.5A CN202310709849A CN116574334A CN 116574334 A CN116574334 A CN 116574334A CN 202310709849 A CN202310709849 A CN 202310709849A CN 116574334 A CN116574334 A CN 116574334A
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- polyolefin
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- 229920003023 plastic Polymers 0.000 title claims abstract description 101
- 239000004033 plastic Substances 0.000 title claims abstract description 101
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 68
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000003607 modifier Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 7
- -1 polyethylene Polymers 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 29
- 239000004743 Polypropylene Substances 0.000 claims description 25
- 229920001155 polypropylene Polymers 0.000 claims description 24
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 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 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000002087 whitening effect Effects 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000012963 UV stabilizer Substances 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000010304 firing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 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 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- 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
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a regenerated polyolefin plastic composition and a preparation method thereof, belonging to the field of regenerated polyolefin plastics. The composition comprises: 10-90 parts of polyolefin recycled plastic, 0.5-3 parts of nano carbon material, 1-15 parts of coupling agent and 2-20 parts of modifier and/or reinforcing agent; the nano carbon material is prepared by sintering polyolefin reclaimed plastic and a catalyst. According to the invention, the nano carbon material with very low addition amount can play a remarkable role in enhancing is used as the modifier, so that the mechanical, weather-proof and electromagnetic properties of the regenerated polyolefin plastic are improved. In addition, the invention realizes that the nano carbon material used as the auxiliary agent and the recycled polyolefin plastic used for regeneration are homologous, ensures that part of impurities contained in the nano carbon material obtained by firing can be added back into the recycled polyolefin plastic together to a certain extent, plays a role of synergistic enhancement, does not introduce exogenous unknown substances, and obtains more benefits in two aspects of environmental protection and regeneration enhancement.
Description
Technical Field
The invention belongs to the field of regenerated polyolefin plastics, and particularly relates to a regenerated polyolefin plastic composition and a preparation method thereof.
Background
Plastic materials are widely used in various industries worldwide, and hundreds of millions of tons of plastic produced annually at present accumulate in landfill sites or remain in the natural environment after the end of service. With the increasing production and consumption of plastic products, the increasingly worsened environmental and social problems are further aggravated, and the disposal problem of waste plastics is also more serious, for example, waste plastics enter a marine ecosystem to be changed into micro plastics after natural circulation, and then permeate into human bodies through marine products to influence health. In addition, in recent years, due to the fact that the price fluctuation of raw materials of plastics is abnormal caused by the price fluctuation of petroleum, the recycling of waste plastic products is widely focused and highly valued in all countries of the world due to the superposition of various factors.
Currently, polyolefin typified by polyethylene and polypropylene is the highest percentage of all waste plastics. In order to solve the problem of a large amount of plastic garbage, the scientific research and industry always seek a path for changing waste into valuable, such as degradation and recycling of monomers and raw materials, degradation and use, etc., however, the methods have problems of more or less energy consumption, low added value, etc. With the emphasis of carbon emission and environmental protection in countries around the world, the re-modification of recycled plastics to increase the value thereof has been increasingly paid high attention by national planning and industry. The most common method at present is to select proper auxiliary agents for addition modification according to the raw material conditions so as to enhance the mechanical properties of the materials or adapt the materials to some special types of uses.
The mode adopted for recycling the polyolefin waste plastics is usually to supplement flame retardant, antioxidant, ultraviolet resistant agent, brightening agent, glass fiber and inorganic particles with reinforcing effect, lubricant and the like, and polyolefin elastomer (POE) obtained by copolymerizing ethylene and 1-octene/1-hexene is also used as filler to toughen PP and PE. However, the reinforcing and additive often needs a larger addition amount, and the density of part of the filler is much higher than that of the polyolefin plastic, so that the density of the regenerated product is increased, and the aim of light weight of the materials in the current industry is not met; in addition, the addition of excessive inorganic filler can increase the internal friction resistance of polyolefin resin processing and affect the processability; meanwhile, the fluidity of the polyolefin material can be influenced, and higher requirements on equipment and energy consumption can be met. The addition of an elastomer such as POE, while improving the impact resistance and processability of the product, tends to reduce its rigidity and strength. In addition, for the most part of post-consumer recycled plastics and industrial recycled plastics, polyethylene and polypropylene mixtures added with various auxiliary agents are often ambiguous in composition and filler, and the auxiliary agents which are required to be added in high amounts to play a significant role are often limited so as not to react with the components in the original recycled materials, so that the recycling effect of the recycled plastics is affected.
With the sequential discovery and preparation of nano carbon materials with excellent performances such as fullerene, graphene, carbon nanotube and the like, the nano carbon materials gradually become a very important industrial material and auxiliary agent. Nanocarbon materials have been a hotspot for international industrial material development and application, but the use of nanocarbon materials in large industrial products has been limited in the early days due to the high cost of preparation and processing processes. Along with the mature application of the preparation method of the nano material such as chemical vapor deposition and the subsequent evolution of the purification technology in the field of the nano carbon material, the cost of the nano carbon material has been greatly reduced to a valence range which can be born by industrial products, and besides graphite and carbon black which are widely applied for a long time, graphene and carbon nano tubes are also used as conductive aids of electrode materials of lithium ion batteries. The carbon material is used as a reinforcing agent in the rubber industry for a long time, and has wide application in the field of composite materials by utilizing the unique one-dimensional and two-dimensional characteristics of the nano carbon material under the nano scale. The nano carbon material/polymer composite material has the structural advantage of large contact area, and the sufficient combination of the nano carbon material and the polymer composite material greatly improves various properties of the material, including mechanical property, heat conduction property and electrical property, and the nano carbon material is different from common filler, so that the performance of the polymer material can be greatly enhanced by only needing very low addition amount, and meanwhile, the nano carbon material can also endow the matrix material with certain heat conduction and electric conduction capability by utilizing the electrical and thermal properties of the nano carbon material/polymer composite material. This is because carbon nanofibers and carbon nanotubes have a large aspect ratio, and a three-dimensional network structure can be formed in a polymer with a small amount of addition. The characteristics make the nano carbon material become a modifying auxiliary agent of polymer materials which are widely focused in the industry and scientific research.
Disclosure of Invention
The invention provides a regenerated polyolefin plastic composition and a preparation method thereof, and the composition can improve the mechanical, weather-proof and electromagnetic properties of the regenerated polyolefin plastic by using a nano carbon material with very low addition amount as a modifier.
The invention firstly provides a regenerated polyolefin plastic composition which comprises the following components in parts by mass:
10-90 parts of polyolefin recycled plastic, 0.5-3 parts of nano carbon material, 1-15 parts of coupling agent and 2-20 parts of modifier and/or reinforcing agent;
the polyolefin reclaimed plastic comprises at least more than 60% of polyethylene and polypropylene blend/copolymer by mass percent;
the nano carbon material is prepared by sintering polyolefin plastic and a catalyst.
Preferably, the polyethylene and polypropylene blend/copolymer has a polyethylene to polypropylene molar ratio of (0.5-9.8): 0.2-9.5.
Preferably, the melt flow rate of the polyolefin recycled plastic is 1-15g/10min (230 ℃ C./2.16 kg, ISO 1133).
Preferably, the polyolefin recycled plastic further comprises polystyrene, polyamide 6, polycarbonate, calcium carbonate, silica, talc, aluminum hydroxide, magnesium hydroxide, silicone rubber or an auxiliary agent.
Preferably, the nano carbon material comprises carbon nano tube, graphene or nano graphite.
Preferably, the coupling agent is maleic anhydride functionalized polyethylene or polypropylene or ethylene propylene copolymer.
Preferably, the modifier is a copolymerized elastomer of ethylene and 1-octene.
Preferably, the reinforcing agent is an antioxidant, an ultraviolet stabilizer, a flame retardant, a whitening agent or a lubricant.
The invention also provides a preparation method of the regenerated polyolefin plastic composition, which comprises the following steps:
step one: preparation and treatment of nanocarbon materials
1) Dissolving a soluble salt of a transition metal and a ligand compound for complexation in water to obtain a solution;
placing the solution in a container and heating to obtain gel;
heating the gel muffle furnace or the pit furnace, and decomposing and oxidizing the gel to obtain a catalyst;
mixing the catalyst with polyolefin plastic, and sintering at high temperature under inert atmosphere to obtain a nano carbon material;
2) The nano carbon material treatment process comprises the following steps: extracting the crude product of the nano carbon material in acid liquor by a Soxhlet extraction method, and then extracting by deionized water until the PH value of the nano carbon material is close to neutral; and (3) centrifugally separating the extracted nano carbon material, and drying for later use.
Step two: treatment of polyolefin recycled plastics
Waste plastic recycled products from consumer products and/or industrial products are subjected to pretreatment procedures such as classification, cleaning, crushing, smelting, impurity removal and the like to obtain treated polyolefin recycled plastics;
step three: mixing material
Uniformly mixing the treated nano carbon material obtained in the first step and a coupling agent in an internal mixer, heating to obtain a blend, adding the treated polyolefin reclaimed plastic obtained in the second step into the internal mixer, and after the plastic is softened, adding the blend, a modifier and/or a reinforcing agent, and banburying to obtain a melt;
step four: extrusion granulation
And (3) feeding the banburying melt into a double-screw extruder, extruding, melting and blending again, extruding, granulating, air cooling, and discharging to obtain the regenerated polyolefin plastic composition.
Preferably, the sintering temperature in the first step is 600-1200 ℃ and the sintering time is 12-15min.
The beneficial effects of the invention are that
The invention provides a regenerated polyolefin plastic composition, which comprises the following components in parts by mass:
10-90 parts of polyolefin recycled plastic, 0.5-3 parts of nano carbon material, 1-15 parts of coupling agent and 2-20 parts of modifier and/or reinforcing agent; the polyolefin reclaimed plastic comprises at least more than 60% of polyethylene and polypropylene blend/copolymer by mass percent; the nano carbon material is prepared by sintering polyolefin reclaimed plastic and a catalyst. Compared with the prior art, the invention uses the nano carbon material with very low addition amount to play a role in remarkable enhancement as the modifier, thereby improving the mechanical, weather-proof and electromagnetic properties of the regenerated polyolefin plastic. In addition, the invention realizes that the nano carbon material used as the auxiliary agent and the recycled polyolefin plastic used for regeneration are homologous, ensures that part of impurities contained in the nano carbon material obtained by firing can be added back into the recycled polyolefin plastic together to a certain extent, plays a role of synergistic enhancement, does not introduce exogenous unknown substances, and obtains more benefits in two aspects of environmental protection and regeneration enhancement.
The recycled polyolefin plastic compositions of the present invention are widely useful in the manufacture of structural components, containers, automotive articles, pipes, films, roofing applications, packaging, lids and closures, as well as in the core layer of multi-layer polyolefin sheets or films, especially in fields involving electrostatic protection and electromagnetic wave management.
Detailed Description
The invention discloses a regenerated polyolefin plastic composition, which comprises the following components in parts by mass:
10-90 parts of polyolefin recycled plastic, 0.5-3 parts of nano carbon material, 1-15 parts of coupling agent and 2-20 parts of modifier and/or reinforcing agent;
the polyolefin recycled plastic comprises at least more than 60% of polyethylene and polypropylene blend/copolymer by mass, and the total mass of the polyethylene and polypropylene blend/copolymer is at least more than 60%, preferably more than 70%, more preferably more than 80%; in the blend/copolymer of polyethylene and polypropylene, the molar ratio of polyethylene to polypropylene is preferably (0.5-9.8): 0.2-9.5, more preferably (3.3-9.7): 3-9.67.
The polyolefin recycled plastic further preferably comprises 0 to 5% by mass of polystyrene, 0 to 1% by mass of polyamide 6, 0 to 1% by mass of polycarbonate, 0 to 10% by mass of calcium carbonate, 0 to 10% by mass of silica, 0 to 5% by mass of talc, 0 to 20% by mass of aluminum hydroxide, 0 to 20% by mass of magnesium hydroxide, 0 to 5% by mass of silicone rubber or 0 to 5% by mass of an auxiliary agent, the kind of which is not particularly limited, and is preferably an anti-ultraviolet stabilizer or an antioxidant stabilizer.
According to the present invention, the melt flow rate (MFR@230 ℃/2.16kg, ISO 1133-1:2022) of the polyolefin reclaimed plastic is preferably 1g/10min-15g/10min, more preferably 5g/10 min-15g/10min, most preferably 7g/10 min-15g/10min, and the higher the melt flow rate is, the better from the viewpoint of the reprocessing after recycling.
The nano carbon material preferably comprises a carbon nano tube, graphene or nano graphite, and is prepared by sintering polyolefin plastic and a catalyst; the polyolefin plastic is a composition/copolymer of polyethylene and polypropylene, the composition/copolymer of polyethylene and polypropylene is a composition/copolymer (G) of polyethylene and polypropylene in the polyolefin reclaimed plastic, namely, the raw materials for preparing the nano carbon material by co-high temperature reaction with a catalyst can be the same as the polymer used for modification and reinforcement. According to the invention, the nano carbon material serving as the auxiliary agent is homologous to the recycled polyolefin plastic for regeneration, so that part of impurities contained in the nano carbon material obtained by firing can be added back into the recycled polyolefin plastic together to a certain extent, the synergistic enhancement effect is achieved, and no exogenous unknown substance is introduced.
According to the invention, the coupling agent is a functionalized product of polyethylene or polypropylene, preferably a polyethylene or polypropylene or ethylene-propylene copolymer functionalized with maleic anhydride, and the coupling agent can be obtained commercially or by methods conventional in the art, the type of said commercially available coupling agent being not particularly limited, preferably EXXONMOBIL ExxelorPO 1020, easy to mould TM Plas-Easy TM A1028, duPontP613, etc.
According to the invention, the modifier is preferably an impact modifier, more preferably a copolymerized elastomer of ethylene and 1-octene (POE), preferably vistamax of exxonmobil, ENGAGE of Dow, three-well Tafmer or Lucene of LG chemistry.
According to the present invention, the type of the reinforcing agent is not particularly limited, and preferably an antioxidant, an ultraviolet stabilizer, a flame retardant, a whitening agent or a lubricant, and the type of the antioxidant, the ultraviolet stabilizer, the flame retardant, the whitening agent or the lubricant is not particularly limited, and may be a classical type or a combination well known in the art.
The preparation method of the regenerated polyolefin plastic composition comprises the following steps:
step one: preparation and treatment of nanocarbon materials
1) Dissolving a soluble salt of a transition metal and a ligand compound for complexation in water to obtain a solution; the ligand compound for complexing is preferably citric acid, and the soluble salt of transition metal comprises inorganic salt and organic alkoxide, preferably nickel nitrate, cobalt nitrate, ferric nitrate, nickel sulfate, nickel hydroxide, cobalt sulfate, nickel chloride and cobalt chloride; the molar ratio of the soluble salt of the transition metal and the ligand compound used for complexation is preferably 1: (0.3-3), the pH of the solution is adjusted by ammonia, hydroxide of the same metal, etc., preferably between 2-7, preferably by ammonia;
heating the solution in a container to obtain gel, wherein the heating temperature is preferably 60-90 ℃, more preferably 75-85 ℃, and the reaction time is preferably 13-24 hours;
heating the gel in a muffle furnace or a pit furnace to 300 ℃, and decomposing and oxidizing the gel to obtain a catalyst;
mixing the catalyst with polyolefin plastic, and sintering at high temperature under inert atmosphere, preferably helium, argon and nitrogen, wherein the sintering temperature is preferably 600-1200 ℃, more preferably 800 ℃, the sintering time is preferably 12-15min, and the mass ratio of the polyolefin plastic to the catalyst is preferably 95:5-4:1;
2) The nano carbon material treatment process comprises the following steps: extracting the crude product of the nano carbon material in acid liquor by a Soxhlet extraction method, wherein the acid liquor is preferably one or more of nitric acid, sulfuric acid and hydrochloric acid, the concentration of the nitric acid is preferably 30-40%, the concentration of the sulfuric acid is preferably 98%, the concentration of the hydrochloric acid is preferably 30%, the extraction temperature is preferably 40-80 ℃ and the extraction time is preferably 1-12 hours, and then extracting the crude product by deionized water until the PH value of the nano carbon material is close to neutral; and (3) centrifugally separating the extracted nano carbon material, and drying for later use.
Step two: treatment of polyolefin recycled plastics
Waste plastic recycled products from consumer products and/or industrial products are subjected to pretreatment procedures such as classification, cleaning, crushing, smelting, impurity removal and the like to obtain treated polyolefin recycled plastics;
step three: mixing material
Uniformly mixing the treated nano carbon material obtained in the first step and a coupling agent in an internal mixer, heating to 170-220 ℃ to obtain a blend, then adding the treated polyolefin reclaimed plastic obtained in the second step into the internal mixer, heating to 170-180 ℃, adding the blend, a modifier and/or a reinforcing agent after the plastic is softened, and heating to 200-210 ℃ to carry out internal mixing for 5-15 minutes to obtain a melt;
according to the present invention, if the nanocarbon material is controlled in flying dust during processing, it can be added to the recovered polyolefin material softened after banburying together with a coupling agent, a modifier and/or a reinforcing agent without pre-mixing.
Step four: extrusion granulation
And (3) feeding the banburying melt into a double-screw extruder for extruding, melting and blending again, wherein the section temperature is preferably 170-220 ℃, the screw speed is 50-60r/min, extruding, granulating and air cooling, and discharging to obtain the regenerated polyolefin plastic composition.
The present invention will be described in further detail with reference to specific examples.
Examples 1 to 5
The feeds were carried out in examples 1 to 5 according to the feed ratios in Table 1
Table 1.
The method of making the recycled polyolefin plastic compositions of examples 1-5, comprising:
step one: preparation and treatment of nanocarbon materials
1) Preparation of nanocarbon materials
Nickel chloride and citric acid are mixed according to a mole ratio of 3:1 dispersing in water to obtain a solution; the pH of the solution is adjusted by ammonia to between 2 and 7.
Placing the solution in a beaker, heating the bottom, heating to 80+/-5 ℃ to raise the temperature to evaporate water until the liquid level is free from naked eyes and colloidal floccules exist in the solution to obtain gel.
Transferring the gel obtained above into a crucible, heating to 300 ℃ by a muffle furnace or a pit furnace, and decomposing and oxidizing the gel until a large amount of fine powder catalyst is generated.
The catalyst powder and the reclaimed polyolefin plastics which are separated, cleaned, dried and crushed are mechanically mixed and then are placed in a fluidized bed or a moving bed reactor under the inert gas protection atmosphere to be sintered at 800 ℃ until no smoke is generated and the reaction is terminated. And taking out the carbonized product after cooling, grinding and crushing for standby to obtain the nano carbon material, wherein the mass ratio of the polyolefin plastic to the catalyst is 9:1. The whole operation link is to wear dustproof and acid mist preventing labor protection articles.
2) The treatment process comprises the following steps: extracting the crude product of the nano carbon material in acid liquor by a Soxhlet extraction method at the extraction temperature of 60 ℃ for 8 hours, and extracting with deionized water until the PH value of the nano carbon material is close to neutral; and (3) centrifugally separating the extracted nano carbon material, and drying for later use.
Step two: treatment of polyolefin recycled plastics
The ethylene-propylene copolymer reclaimed material (the ethylene content in the copolymer is about 22 percent by mass and the melt flow rate is 8g/min (230 ℃/2.16kg,ASTM D1238) which is used as reclaimed polyolefin plastics to be modified and enhanced) from an automobile anti-collision plate is subjected to classification, cleaning, crushing, smelting, impurity removal and cooling to obtain the treated polyolefin reclaimed plastics;
step three: mixing material
Mixing the treated nano carbon material obtained in the step one with a coupling agent maleic anhydride functionalized polypropylene in an internal mixer, heating to 200-210 ℃ and mechanically mixing to obtain a blend nano carbon material functionalized polypropylene (wherein the mass ratio of the nano carbon material to the functionalized polypropylene in examples 1-3 is 1:4 and the mass ratio of the nano carbon material to the functionalized polypropylene in examples 4-5 is 1:9);
then adding the polyolefin reclaimed plastic treated in the second step into an internal mixer, heating to 180 ℃ at 4-7 ℃/min, softening, adding a lubricant zinc stearate and a toughening agent POE (ethylene 1-octene copolymer), mixing for 1-2 min, adding the blend obtained in the first step and an anti-aging agent (comprising an antioxidant and a UV agent, wherein the antioxidant 1010, an auxiliary antioxidant 168 and a hindered amine light stabilizer 770 are mixed according to the mass ratio of 1:1:1), continuing mixing for 5min, observing the temperature of materials in the internal mixer at any time during the whole mixing period, and controlling the temperature below 230 ℃ to provide an anaerobic mixing environment.
Step four: extrusion granulation
Transferring the mixed material after banburying to a double-screw extruder, carrying out air cooling or circulating water cooling on the material at 180 ℃ at the material outlet, 180 ℃ at the first section of screw, 185 ℃ at the second section of screw and 175 ℃ at the third section of screw, granulating by a granulator, cooling the granules, and drying at 50 ℃ in a blast dryer to constant weight.
And (3) carrying out melt tabletting on the product granules, cutting the product granules into standard test bars, and carrying out mechanical testing and conductivity testing. The properties are shown in Table 2.
TABLE 2 Properties of the specific embodiments
| Tensile yield strength | Yield strain | Strain at break | Melt flow Rate | Conductivity of | |
| Reclaimed materials (control) | 15MPa | 7％ | 29％ | 8g/10min | 10e-9S/m |
| Example 1 | 22MPa | 5.6％ | 18％ | 5g/10min | 10e-4S/m |
| Example 2 | 23MPa | 6％ | 17％ | 5.5g/10min | 10e-6S/m |
| Example 3 | 20MPa | 6.5％ | 19％ | 6g/10min | 10e-5S/m |
| Example 4 | 21MPa | 6.5％ | 21％ | 6g/10min | 10e-5S/m |
| Example 5 | 18MPa | 7％ | 24％ | 7g/10min | 10e-7S/m |
| Standard of | ASTMD638 | ISO527-2/50 | ASTMD638 | ASTMD1238 | GB/T1410-2006 |
Therefore, the regenerated polyolefin plastic prepared by modifying and reinforcing the reclaimed polyolefin plastic by using the nano carbon material fired by the reclaimed polyolefin plastic provided by the invention can obviously improve the performance of the reclaimed material only by a small amount of nano carbon material, avoid influencing the processability of the resin after a large amount of filler is added, greatly reduce the resistivity of the material and have additional benefits in application scenes such as static resistance and the like.
Claims (10)
1. A recycled polyolefin plastic composition characterized by comprising, in parts by mass:
10-90 parts of polyolefin recycled plastic, 0.5-3 parts of nano carbon material, 1-15 parts of coupling agent and 2-20 parts of modifier and/or reinforcing agent;
the polyolefin reclaimed plastic comprises at least more than 60% of polyethylene and polypropylene blend/copolymer by mass percent;
the nano carbon material is prepared by sintering polyolefin plastic and a catalyst.
2. The recycled polyolefin plastic composition of claim 1, wherein the polyethylene and polypropylene blend/copolymer has a molar ratio of polyethylene to polypropylene of from 0.5 to 9.8 to 0.2 to 9.5.
3. A recycled polyolefin plastic composition according to claim 1, wherein the melt flow rate of the polyolefin recycled plastic is from 1 to 15g/10min.
4. A recycled polyolefin plastic composition according to claim 1, wherein the polyolefin recycled plastic further comprises polystyrene, polyamide 6, polycarbonate, calcium carbonate, silica, talc, aluminum hydroxide, magnesium hydroxide, silicone rubber or an auxiliary agent.
5. The recycled polyolefin plastic composition of claim 1, wherein the nanocarbon material comprises carbon nanotubes, graphene, or nanographite.
6. A recycled polyolefin plastic composition according to claim 1, wherein the coupling agent is a maleic anhydride functionalized polyethylene or polypropylene or ethylene propylene copolymer.
7. A recycled polyolefin plastic composition according to claim 1, wherein the modifier is a copolymerized elastomer of ethylene and 1-octene.
8. A recycled polyolefin plastic composition according to claim 1, wherein the reinforcing agent is an antioxidant, uv stabilizer, flame retardant, whitening agent or lubricant.
9. A method of preparing a recycled polyolefin plastic composition according to claim 1, comprising:
step one: preparation and treatment of nanocarbon materials
1) Dissolving a soluble salt of a transition metal and a ligand compound for complexation in water to obtain a solution;
placing the solution in a container and heating to obtain gel;
heating the gel muffle furnace or the pit furnace, and decomposing and oxidizing the gel to obtain a catalyst;
mixing the catalyst with polyolefin plastic, and sintering at high temperature under inert atmosphere to obtain a nano carbon material;
2) The nano carbon material treatment process comprises the following steps: extracting the crude product of the nano carbon material in acid liquor by a Soxhlet extraction method, and then extracting by deionized water until the PH value of the nano carbon material is close to neutral; and (3) centrifugally separating the extracted nano carbon material, and drying for later use.
Step two: treatment of polyolefin recycled plastics
Waste plastic recycled products from consumer products and/or industrial products are subjected to pretreatment procedures such as classification, cleaning, crushing, smelting, impurity removal and the like to obtain treated polyolefin recycled plastics;
step three: mixing material
Uniformly mixing the treated nano carbon material obtained in the first step and a coupling agent in an internal mixer, heating to obtain a blend, adding the treated polyolefin reclaimed plastic obtained in the second step into the internal mixer, and after the plastic is softened, adding the blend, a modifier and/or a reinforcing agent, and banburying to obtain a melt;
step four: extrusion granulation
And (3) feeding the banburying melt into a double-screw extruder, extruding, melting and blending again, extruding, granulating, air cooling, and discharging to obtain the regenerated polyolefin plastic composition.
10. The method for producing a recycled polyolefin plastic composition according to claim 9, wherein the sintering temperature in the first step is 600 to 1200 ℃ and the sintering time is 12 to 15 minutes.
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