CN116082671A - Method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder - Google Patents
Method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder Download PDFInfo
- Publication number
- CN116082671A CN116082671A CN202310064786.2A CN202310064786A CN116082671A CN 116082671 A CN116082671 A CN 116082671A CN 202310064786 A CN202310064786 A CN 202310064786A CN 116082671 A CN116082671 A CN 116082671A
- Authority
- CN
- China
- Prior art keywords
- rubber powder
- parts
- waste rubber
- eva
- master batch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 146
- 239000005060 rubber Substances 0.000 title claims abstract description 146
- 239000000843 powder Substances 0.000 title claims abstract description 94
- 239000002699 waste material Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 title abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000003607 modifier Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 56
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 56
- -1 polypropylene Polymers 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 19
- 238000004132 cross linking Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 14
- 239000001993 wax Substances 0.000 claims description 14
- 238000010008 shearing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000009775 high-speed stirring Methods 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000004831 Hot glue Substances 0.000 claims description 8
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000010837 adhesive waste Substances 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000003892 spreading Methods 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- QEMOCCHONHPVPW-UHFFFAOYSA-N 1-(2-tert-butylperoxypropan-2-yl)-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C QEMOCCHONHPVPW-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000003014 reinforcing effect Effects 0.000 abstract description 7
- 239000000428 dust Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000004636 vulcanized rubber Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000013040 rubber vulcanization Methods 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- C08J2307/00—Characterised by the use of natural rubber
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K3/34—Silicon-containing compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder, which comprises the following materials in parts by weight: 50 to 70 parts of EVA waste rubber powder, 0.1 to 2 parts of peptizer, 0.1 to 5 parts of compatilizer, 20 to 40 parts of inorganic filler, 0.1 to 3 parts of dispersant, 0.1 to 2 parts of cross-linking agent and 0.1 to 3 parts of modifier. The novel rubber environment-friendly reinforcing pre-dispersion filler prepared by adopting the pre-dispersion filler ensures that the organic modifier and the dispersing agent are uniformly coated on the surface of the superfine inorganic filler through the synergistic effect of the superfine inorganic filler, the organic modifier and the dispersing agent and through strong blending and heat treatment, thereby improving the active groups on the surface of the superfine inorganic filler, further improving the chemical adsorption effect with a rubber molecular chain, improving the mechanical property of vulcanized rubber and improving the reinforcing effect of the inorganic filler in rubber products. The process is simple to operate, and dust pollution in the production process is reduced by closed operation.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder.
Background
Ethylene-vinyl acetate copolymer, EVA for short. Generally, the content of Vinyl Acetate (VA) is 5% -40%, and compared with Polyethylene (PE), EVA has the advantages that vinyl acetate monomer is introduced into a molecular chain, so that high crystallinity is reduced, toughness, impact resistance, filler compatibility and heat sealing performance are improved, and the EVA is widely applied to the fields of foaming shoe materials, functional greenhouse films, packaging molds, hot melt adhesives, wires, cables, toys and the like. Due to the reasons of technology, mould structure and the like, waste materials such as stub bars, defective products and the like exist in the production process, and due to the reasons of the components of EVA plastics, the raw material processing technology and the like, manufacturing enterprises serving as terminal products cannot recycle the waste materials; because the proportion of the vinyl acetate contained in EVA plastics with different brands and purposes is quite different, the vinyl acetate content cannot be distinguished after centralized recovery, and the filler and other additives contained in waste materials of different products are different, so that the purposes cannot be determined after centralized recovery and regeneration of EVA waste materials with quite different component structures, and the regeneration value cannot be obtained. Conventional practice is generally used for landfill or incineration and power generation of other garbage power plants. However, these waste materials have considerable utility if they can be recycled in terms of market price of raw materials, and are a great waste of resources once they are burned.
In addition, with the rapid development of the modern automobile industry, people consume more and more rubber products, particularly tires, and the reinforcing materials produced every year in China are gradually increased, wherein the maximum consumption of the reinforcing materials is N series of carbon black, 89.5% of the world consumption of the carbon black is applied to the rubber industry, and the tire consumption rate is 67.5%. However, as the price of N-series carbon black is continuously increased, the cost of rubber products is also continuously increased, and the rubber products bring more and more burden to enterprises, and simultaneously, the N-series carbon black is also a non-renewable resource and continuously consumes resources such as petroleum, natural gas and the like.
However, if EVA waste rubber powder is directly applied to a rubber matrix, the dispersibility in the rubber matrix is poor due to structural differences, microphase separation phenomenon occurs, and the reinforcing effect is poor. Therefore, development of a rubber reinforcing agent which can realize a strong improvement effect on the comprehensive performance of a rubber material matrix and takes waste EVA waste rubber powder as a raw material has important significance.
In view of this, the present invention has been made.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder, which has a simple and reasonable structure and is convenient to popularize.
A method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder comprises the following materials in parts by weight: 50 to 70 parts of EVA waste rubber powder, 0.1 to 2 parts of peptizer, 0.1 to 5 parts of compatilizer, 20 to 40 parts of inorganic filler, 0.1 to 3 parts of dispersant, 0.1 to 2 parts of cross-linking agent and 0.1 to 3 parts of modifier.
Preferably, the preparation method comprises the following steps:
s1, throwing waste rubber powder into a storage bin cache tank for standby through a ton package disassembly station;
s2, conveying the waste rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, adding a peptizer, mixing for 5-60 min, conveying into a hopper of a double-screw extruder, heating to 200-250 ℃ to soften the waste rubber powder mixture by heating, and spreading and crushing the waste rubber powder under the action of a screw shearing element.
S3, injecting the waste rubber powder plasticized in the S2 into a double-screw extruder again, establishing internal pressure in a machine barrel of the double-screw extruder under the action of a screw shearing element, simultaneously increasing the heating temperature, controlling the temperature to be 280-400 ℃ so that the temperature and the pressure in the double-screw extruder are higher than the critical temperature and the pressure of the waste rubber powder in uncrosslinking, selectively opening crosslinking bonds with weaker bond energy at the moment, and accelerating the uncrosslinking reaction under the action of thermal shearing of the double screws, so that the crosslinking bonds of the thermosetting waste rubber powder are rapidly subjected to uncrosslinking, converted into thermoplastic elastomer materials, and cooled by cooling equipment and crushed to obtain uncrosslinked rubber powder.
S4, conveying the uncrosslinked rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, and setting the temperature to be 100-200 ℃. After the temperature is reached, adding compatilizer, inorganic filler, dispersant, cross-linking agent and modifier in the stirring process, and fully mixing for 10-60 min.
And S5, continuously mixing the mixture by conveying the mixture in the step S4 to mixing equipment.
And S6, extruding and molding the rubber material subjected to mixing and plasticizing in the step S5 through a screw extruder at the molding temperature of 100-200 ℃, connecting a discharge port of the screw extruder with an air cooling machine, cooling and hardening the extruded and molded material through the air cooling machine, and finally granulating, shaping and packaging.
Preferably, the EVA waste rubber powder is at least one of sole waste rubber powder, photovoltaic rubber waste rubber powder, battery adhesive waste rubber powder and coating product waste rubber powder, and the mesh number of the superfine inorganic filler is more than 40 meshes.
Preferably, the peptizer is at least one of polyvinylpyrrolidone, polypropylene wax, unsaturated fatty acid zinc, polyoxyethylene wax, polyvinyl alcohol, and polyethylene wax.
Preferably, the compatilizer is at least one of maleic anhydride grafted polyethylene wax, maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted ethylene-vinyl acetate copolymer, ethylene-vinyl acetate hot melt adhesive, polyglycidyl methacrylate and polyethylene octene copolymer.
Preferably, the inorganic filler is at least one of cracking carbon black, silicon aluminum carbon black, superfine clay, superfine kaolin, nano calcium carbonate, superfine mica powder, superfine sepiolite and superfine montmorillonite.
Preferably, the dispersing agent is at least one of polyethylene glycol, paraffin oil, zinc stearate, sodium stearate, stearic acid and zinc acrylate.
Preferably, the crosslinking agent is at least one of dicumyl peroxide, alpha-bis (tert-butylperoxyisopropyl) cumene, bis (tert-butylperoxyisopropyl) benzene, tert-butylhydroperoxide, triallyl isocyanurate, trimethylolpropane trimethacrylate, and polytriallyl isocyanate.
Preferably, the modifier is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, gamma-glycidoxypropyl trimethoxysilane, triisostearoyl isopropyl titanate, isopropyl dioleoyl (dioctyl acyloxy) titanate, isopropyl tri (dioctyl acyloxy) pyrophosphato) titanate, chelate of bis (dioctyl acyloxy) ethylene pyrophosphato and triethanolamine, bis (dioctyl acyloxy) ethylene pyrophosphato, pyrophosphato monoalkoxy titanate, distearoyl isopropyl aluminate, pyrophosphato aluminate coupling agent and borate coupling agent.
Preferably, the kneading apparatus is a hydraulic upper ram.
The beneficial effects of the invention are as follows:
(1) According to the invention, the EVA waste rubber powder is effectively and physically de-crosslinked through the high-temperature high-pressure shearing action, and the de-crosslinking efficiency and the de-crosslinking degree of EVA are effectively improved under the action of the peptizer, so that the compatibility between the de-crosslinked EVA waste rubber powder and the rubber matrix is improved, and the reinforcing action of the EVA composite material is further improved.
(2) The invention also adds superfine inorganic filler, organic modifier and dispersant, etc. together, and makes the organic modifier and dispersant uniformly coat the surface of superfine inorganic filler and decrosslinked EVA rubber powder through strong blending and heat treatment, and react with the surface group, thus improving the active group on the surface and the compatibility between EVA rubber powder and inorganic filler, thus promoting the dispersibility of waste rubber powder, improving the chemical adsorption effect with rubber molecular chain in the mixing process, participating in the rubber vulcanization reaction, and further improving the mechanical property of vulcanized rubber.
(3) According to the invention, the cross-linking agent is introduced to enable the cross-linked EVA material to carry out secondary cross-linking, so that not only is the mechanical property of the EVA material improved, but also an interpenetrating network structure with stronger effect is formed between the EVA material and the rubber matrix, and the compatibility between the EVA material and the rubber matrix is further improved.
(4) The process of the invention has simple operation, reduces dust pollution in the production process by closed operation, and simultaneously provides a production technology process with high efficiency, energy conservation, environmental protection and low operation cost.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The method for preparing the rubber composite pre-dispersion master batch by using the EVA waste rubber powder comprises the following steps:
s1, throwing waste rubber powder into a storage bin cache tank for standby through a ton package disassembly station;
s2, conveying the waste rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, adding a peptizer, mixing for 5-60 min, conveying into a hopper of a double-screw extruder, heating to 200-250 ℃ to soften the waste rubber powder mixture by heating, and spreading and crushing the waste rubber powder under the action of a screw shearing element.
The high-speed stirring equipment is one of a high-speed mixer, a coulter mixer and a ribbon mixer. The frequencies of the mixer include, but are not limited to, 10Hz, 20Hz, 30Hz, 40Hz, 50Hz.
Mixing times include, but are not limited to, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min.
The primary temperature of the twin screw extruder includes, but is not limited to, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃.
S3, injecting the plasticized waste rubber powder in the S2 into a double-screw extruder again, establishing internal pressure in a machine barrel of the double-screw extruder under the action of a screw shearing element, simultaneously increasing the heating temperature, controlling the temperature to be 280-400 ℃ so that the temperature and the pressure in the double-screw extruder are higher than the critical temperature and the pressure of the waste rubber powder in uncrosslinking, selectively opening crosslinking bonds with weaker bond energy at the moment, and accelerating the uncrosslinking reaction under the action of thermal shearing of the double screws, thereby enabling the crosslinking bonds of the thermosetting waste rubber powder to rapidly complete uncrosslinking, converting the thermosetting waste rubber powder into thermoplastic elastomer materials, and cooling the thermoplastic elastomer materials by cooling equipment and then crushing the thermoplastic elastomer materials to obtain the uncrosslinked rubber powder.
The secondary temperature of the twin screw extruder includes, but is not limited to, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃.
S4, conveying the uncrosslinked rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, and setting the temperature to be 100-200 ℃. After the temperature is reached, adding compatilizer, inorganic filler, dispersant, cross-linking agent and modifier in the stirring process, and fully mixing for 10-60 min.
The high-speed stirring equipment is one of a high-speed mixer, a coulter mixer and a ribbon mixer. The frequencies of the mixer include, but are not limited to, 10Hz, 20Hz, 30Hz, 40Hz, 50Hz.
The high speed stirring device temperature includes, but is not limited to, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃.
Mixing times include, but are not limited to, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min.
And S5, continuously mixing the mixture by conveying the mixture in the step S4 to mixing equipment.
And S6, extruding and molding the rubber material subjected to mixing and plasticizing in the step S5 through a screw extruder at the molding temperature of 100-200 ℃, connecting a discharge port of the screw extruder with an air cooling machine, cooling and hardening the extruded and molded material through the air cooling machine, and finally granulating, shaping and packaging.
The molding temperature of the screw extrusion includes, but is not limited to, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃.
Wherein the EVA waste rubber powder is at least one of sole waste rubber powder, photovoltaic rubber waste rubber powder, battery adhesive waste rubber powder and coating product waste rubber powder, and the mesh number of the superfine inorganic filler is more than 40 meshes. The weight parts of EVA waste rubber powder include, but are not limited to, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts and 70 parts.
The peptizer is at least one of polyvinylpyrrolidone, polypropylene wax, unsaturated fatty acid zinc, polyoxyethylene wax, polyvinyl alcohol and polyethylene wax, and the weight parts of the peptizer comprise, but are not limited to, 0.1 part, 0.5 part, 1.0 part, 1.5 parts and 2.0 parts.
The compatilizer is at least one of maleic anhydride grafted polyethylene wax, maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted ethylene-vinyl acetate copolymer, ethylene-vinyl acetate hot melt adhesive, polyglycidyl methacrylate and polyethylene octene copolymer, and the compatilizer comprises, by weight, but is not limited to, 0.1 part, 0.5 part, 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts and 5.0 parts.
The inorganic filler is at least one of cracking carbon black, silicon aluminum carbon black, superfine clay, superfine kaolin, nano calcium carbonate, superfine mica powder, superfine sepiolite and superfine montmorillonite, the mesh number of the superfine inorganic filler is more than 800 meshes, and the weight parts of the inorganic filler comprise, but are not limited to, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts and 40 parts.
The dispersing agent is at least one of polyethylene glycol, paraffin oil, zinc stearate, sodium stearate, stearic acid and zinc acrylate, and the weight parts of the dispersing agent comprise, but are not limited to, 0.1 part, 0.5 part, 1.0 part, 1.5 part, 2.0 parts, 2.5 parts and 3.0 parts.
The cross-linking agent is at least one of dicumyl peroxide, alpha-bis (tert-butylperoxyisopropyl) isopropyl benzene, bis (tert-butylperoxyisopropyl) benzene, tert-butyl hydroperoxide, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate and polytriallyl isocyanurate, and the weight parts of the cross-linking agent comprise but are not limited to 0.1 part, 0.5 part, 1.0 part, 1.5 parts and 2.0 parts.
The modifier is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, gamma-glycidoxypropyl trimethoxysilane, triisostearoyl isopropyl titanate, isopropyl dioleoyl (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate, chelate of bis (dioctyl pyrophosphate acyloxy) ethylene titanate and triethanolamine, bis (dioctyl pyrophosphate oxy) ethylene titanate, pyrophosphoric acid type monoalkoxy titanate, distearoyl isopropyl aluminate, pyrophosphite aluminate coupling agent and boric acid ester coupling agent. The weight parts of the modifier include, but are not limited to, 0.1 part, 0.5 part, 1.0 part, 1.5 part, 2.0 parts, 2.5 parts, 3.0 parts.
Example 1:
a method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder comprises the following components in parts by weight: 65 parts of waste sole rubber powder, 1.2 parts of polyvinylpyrrolidone, 5 parts of ethylene-vinyl acetate hot melt adhesive, 25.5 parts of 1250-mesh pyrolysis carbon black, 1.3 parts of polyethylene glycol, 1 part of dicumyl peroxide and 1 part of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide.
Example 2:
a method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder comprises the following components in parts by weight: 55 parts of waste sole rubber powder, 1.5 parts of unsaturated fatty acid zinc, 4 parts of maleic anhydride grafted polyethylene wax, 35 parts of 800-mesh sepiolite, 1.5 parts of zinc acrylate, 1 part of dicumyl peroxide and 2 parts of diisopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate.
Example 3:
a method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder comprises the following components in parts by weight: 70 parts of battery adhesive waste rubber powder, 1.5 parts of polyoxyethylene wax, 3.0 parts of polyglycidyl methacrylate, 20 parts of 800-mesh silicon-aluminum carbon black, 2.0 parts of polyethylene glycol, 0.5 part of triallyl isocyanurate, 1.5 parts of dicumyl peroxide and 1.5 parts of chelate of bis (dioctyl pyrophosphoric acid acyloxy) ethylene titanate and triethanolamine.
Example 4:
a method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder comprises the following components in parts by weight: 50 parts of photovoltaic rubber waste rubber powder, 0.8 part of polyvinylpyrrolidone, 4.5 parts of ethylene-vinyl acetate hot melt adhesive, 40 parts of 800-mesh clay, 1.5 parts of paraffin, 1.7 parts of alpha, alpha-bis (tert-butylperoxyisopropyl) isopropylbenzene and 1.5 parts of distearoyl oxyisopropyl aluminate.
Example 5:
a method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder comprises the following components in parts by weight: 61 parts of waste rubber powder for soles, 2.0 parts of polyvinyl alcohol, 5.0 parts of ethylene-vinyl acetate hot melt adhesive, 25 parts of 1250-mesh pyrolysis carbon black, 2.0 parts of polyethylene glycol, 0.5 part of trimethylolpropane trimethacrylate, 1.5 parts of bis (tert-butylperoxyisopropyl) benzene and 3 parts of isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate.
Example 6:
a method for preparing rubber composite pre-dispersion master batch by using EVA waste rubber powder comprises the following components in parts by weight: 65 parts of coating product waste rubber powder, 0.5 part of polyvinylpyrrolidone, 1.2 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer, 30 parts of 1250-mesh light calcium carbonate, 0.8 part of polyethylene glycol, 0.5 part of triallyl isocyanurate, 1.0 part of bis (tert-butylperoxyisopropyl) benzene and 1.0 part of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide.
Comparative example 1:
comparative example 1 reference example 1, except that polyvinylpyrrolidone was not added.
Comparative example 2:
comparative example 2 referring to example 1, except that the ethylene-vinyl acetate hot melt adhesive was not added.
Comparative example 3:
comparative example 3 reference example 1 except that zinc acrylate was not added.
Comparative example 4:
comparative example 4 reference example 1, except that dicumyl peroxide was not added.
Comparative example 5:
comparative example 5 reference example 1, except that bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide was not added.
Comparative example 6:
commercially available N660 from Dragon chemical Co., ltd.
The preparation method of the above embodiment comprises the following steps:
1) Putting the waste rubber powder into a storage bin cache tank for standby through a ton package disassembly station;
2) Conveying the waste rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, adding peptizer, mixing for 5-60 min, conveying into a hopper of a double-screw extruder, heating to 200-250 ℃ to soften the waste rubber powder mixture by heating, and spreading and crushing the waste rubber powder under the action of a screw shearing element.
3) And (2) injecting the waste rubber powder after plasticization in the step (S2) into a double-screw extruder again, establishing internal pressure in a machine barrel of the double-screw extruder under the action of a screw shearing element, simultaneously increasing the heating temperature, controlling the temperature to be 280-400 ℃ so that the temperature and the pressure in the double-screw extruder are higher than the critical temperature and the pressure of the waste rubber powder for crosslinking, selectively opening crosslinking bonds with weaker bond energy at the moment, and accelerating the crosslinking reaction under the action of thermal shearing of the double screws, thereby enabling the crosslinking bonds of the thermosetting waste rubber powder to rapidly complete crosslinking, converting the crosslinking bonds into thermoplastic elastomer materials, and cooling the thermoplastic elastomer materials by cooling equipment and then crushing the thermoplastic elastomer materials to obtain the crosslinked rubber powder.
4) And conveying the uncrosslinked rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, and setting the temperature to be 100-200 ℃. After the temperature is reached, adding compatilizer, inorganic filler, dispersant, cross-linking agent and modifier in the stirring process, and fully mixing for 10-60 min.
5) The mixture in step S4 is continuously kneaded by feeding the mixture into a kneading apparatus.
6) Extruding and molding the rubber material subjected to mixing and plasticizing in the step S5 by a screw extruder at the molding temperature of 100-200 ℃, connecting a discharge port of the screw extruder with an air cooling machine, cooling and hardening the extruded and molded material by the air cooling machine, and finally granulating, shaping and packaging.
Experimental example 1
In order to comparatively illustrate the influence of the pre-dispersed fillers obtained in different examples on the rubber properties, the mechanical properties and the like of the rubber are tested after the pre-dispersed fillers in different examples are respectively applied to the rubber according to the following method, and the test results are shown in table 1.
The specific raw materials are mixed according to the following components in parts by weight: 100 parts of natural rubber, 50 parts of pre-dispersed filler (N660), 3 parts of stearic acid, 5 parts of zinc oxide, 0.6 part of accelerator DM and 2.5 parts of sulfur.
TABLE 1 Property test results of different rubbers
| Sample numbering | Hardness of | Tensile Strength (Mpa) | Elongation at break (%) | 300% stretching strength (Mpa) |
| Example 1 | 68 | 22.9 | 509 | 11.9 |
| Example 2 | 69 | 23.8 | 512 | 12.1 |
| Examples3 | 67 | 24.1 | 497 | 12.6 |
| Example 4 | 68 | 21.9 | 485 | 11.8 |
| Example 5 | 66 | 23.4 | 492 | 11.6 |
| Example 6 | 69 | 22.5 | 468 | 12.5 |
| Comparative example 1 | 65 | 20.8 | 562 | 8.8 |
| Comparative example 2 | 64 | 19.5 | 559 | 9.6 |
| Comparative example 3 | 62 | 20.6 | 542 | 10.1 |
| Comparative example 4 | 67 | 21.1 | 571 | 8.2 |
| Comparative example 5 | 66 | 18.5 | 548 | 9.2 |
| Comparative example 6 | 71 | 23.1 | 468 | 12.3 |
From the test results, the pre-dispersed filler reduces dust pollution caused by inorganic filler in the production process of products, and reduces the feeding times and equipment input cost. The modified polyurethane foam is easy to disperse in rubber, has good dispersibility and reinforcing effect, can reduce dust pollution in the use process, and belongs to an environment-friendly product.
The novel rubber environment-friendly reinforcing pre-dispersed filler prepared by the pre-dispersed filler reduces dust pollution caused by inorganic filler in the production process of products in the preparation process, reduces the feeding times and reduces the production cost. The organic modifier and the dispersing agent are uniformly coated on the surface of the superfine inorganic filler through synergistic action of the superfine inorganic filler, the organic modifier and the dispersing agent and through strong blending and heat treatment, and react with surface groups of the superfine inorganic filler, so that active groups on the surface of the superfine inorganic filler are improved, chemical adsorption action with rubber molecular chains is improved in the mixing process, rubber vulcanization reaction is participated, mechanical properties of vulcanized rubber are further improved, reinforcing effect of the inorganic filler in rubber products is improved, N series of carbon black with higher price can be replaced, and production cost of the rubber products is reduced. The process is simple to operate, and dust pollution in the production process is reduced by closed operation. The above description is illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention, but is to be accorded the full scope of the claims.
Claims (9)
1. A method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder is characterized by comprising the following materials in parts by weight: 50 to 70 parts of EVA waste rubber powder, 0.1 to 2 parts of peptizer, 0.1 to 5 parts of compatilizer, 20 to 40 parts of inorganic filler, 0.1 to 3 parts of dispersant, 0.1 to 2 parts of cross-linking agent and 0.1 to 3 parts of modifier;
the preparation method comprises the following steps:
s1, throwing waste rubber powder into a storage bin cache tank for standby through a ton package disassembly station;
s2, conveying the waste rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, adding a peptizer, mixing for 5-60 min, conveying into a hopper of a double-screw extruder, heating to 200-250 ℃ to soften the waste rubber powder mixture by heating, and spreading and crushing the waste rubber powder under the action of a screw shearing element;
s3, injecting the waste rubber powder plasticized in the S2 into a double-screw extruder again, establishing internal pressure in a machine barrel of the double-screw extruder under the action of a screw shearing element, simultaneously increasing the heating temperature, controlling the temperature to be 280-400 ℃ so that the temperature and the pressure in the double-screw extruder are higher than the critical temperature and the pressure of the waste rubber powder for crosslinking, selectively opening crosslinking bonds with weaker bond energy at the moment, accelerating the crosslinking reaction under the action of thermal shearing of the double screw, and thus enabling the crosslinking bonds of the thermosetting waste rubber powder to rapidly complete crosslinking, convert into thermoplastic elastomer materials, and cooling by cooling equipment and then crushing to obtain crosslinked rubber powder;
s4, conveying the uncrosslinked rubber powder into high-speed stirring equipment, starting stirring, setting the frequency to be 10-50 Hz, and setting the temperature to be 100-200 ℃; after the temperature is reached, adding a compatilizer, an inorganic filler, a dispersing agent, a crosslinking agent and a modifying agent in the stirring process, and fully mixing for 10-60 min;
s5, continuously mixing the mixture by conveying the mixture in the step S4 to mixing equipment;
and S6, extruding and molding the rubber material subjected to mixing and plasticizing in the step S5 through a screw extruder at the molding temperature of 100-200 ℃, connecting a discharge port of the screw extruder with an air cooling machine, cooling and hardening the extruded and molded material through the air cooling machine, and finally granulating, shaping and packaging.
2. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the EVA waste rubber powder is at least one of sole waste rubber powder, photovoltaic rubber waste rubber powder, battery adhesive waste rubber powder and coating product waste rubber powder, and the mesh number of the superfine inorganic filler is more than 40 meshes.
3. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the peptizer is at least one of polyvinylpyrrolidone, polypropylene wax, unsaturated fatty acid zinc, polyoxyethylene wax, polyvinyl alcohol and polyethylene wax.
4. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the compatilizer is at least one of maleic anhydride grafted polyethylene wax, maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted ethylene-vinyl acetate copolymer, ethylene-vinyl acetate hot melt adhesive, polyglycidyl methacrylate and polyethylene octene copolymer.
5. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the inorganic filler is at least one of cracking carbon black, silicon aluminum carbon black, superfine clay, superfine kaolin, nano calcium carbonate, superfine mica powder, superfine sepiolite and superfine montmorillonite, and the mesh number of the superfine inorganic filler is more than 800 meshes.
6. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the dispersing agent is at least one of polyethylene glycol, paraffin oil, zinc stearate, sodium stearate, stearic acid and zinc acrylate.
7. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the cross-linking agent is at least one of dicumyl peroxide, alpha-bis (tert-butylperoxyisopropyl) isopropyl benzene, bis (tert-butylperoxyisopropyl) benzene, tert-butyl hydroperoxide, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate and polytriallyl isocyanurate.
8. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the coupling agent is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, gamma-glycidoxypropyl trimethoxysilane, triisostearoyl isopropyl titanate, isopropyl dioleoyl (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate, chelate of bis (dioctyl pyrophosphate acyloxy) ethylene titanate and triethanolamine, bis (dioctyl pyrophosphate oxy) ethylene titanate, pyrophosphoric acid type monoalkoxy titanate, distearoyl isopropyl aluminate, pyrophosphite aluminate coupling agent and boric acid ester coupling agent.
9. The method for preparing rubber composite pre-dispersed master batch by using EVA waste rubber powder according to claim 1, which is characterized in that: the mixing equipment is a hydraulic upper top bolt.
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Citations (6)
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| WO2001014464A1 (en) * | 1999-08-23 | 2001-03-01 | Liu, Guixing | Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom |
| CN110655678A (en) * | 2019-09-29 | 2020-01-07 | 安徽滁州德威新材料有限公司 | Continuous dynamic uncrosslinking recovery method and equipment for thermosetting silane crosslinked polyolefin |
| CN112852049A (en) * | 2021-02-01 | 2021-05-28 | 东莞市东塑高分子材料科技有限公司 | Production process and application of EVA foamed sole regenerated particles |
| CN113308044A (en) * | 2021-06-23 | 2021-08-27 | 上高远大化纤有限公司 | Method for preparing light high-elastic wear-resistant rubber and plastic material by utilizing regenerated EVA |
| CN113502015A (en) * | 2021-07-30 | 2021-10-15 | 陈梓良 | 100% EVA regenerated particle and preparation method and application thereof |
| CN114957824A (en) * | 2022-05-09 | 2022-08-30 | 茂泰(福建)鞋材有限公司 | Rubber foamed sole based on preparation of rubber reclaimed materials |
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| WO2001014464A1 (en) * | 1999-08-23 | 2001-03-01 | Liu, Guixing | Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom |
| CN110655678A (en) * | 2019-09-29 | 2020-01-07 | 安徽滁州德威新材料有限公司 | Continuous dynamic uncrosslinking recovery method and equipment for thermosetting silane crosslinked polyolefin |
| CN112852049A (en) * | 2021-02-01 | 2021-05-28 | 东莞市东塑高分子材料科技有限公司 | Production process and application of EVA foamed sole regenerated particles |
| CN113308044A (en) * | 2021-06-23 | 2021-08-27 | 上高远大化纤有限公司 | Method for preparing light high-elastic wear-resistant rubber and plastic material by utilizing regenerated EVA |
| CN113502015A (en) * | 2021-07-30 | 2021-10-15 | 陈梓良 | 100% EVA regenerated particle and preparation method and application thereof |
| CN114957824A (en) * | 2022-05-09 | 2022-08-30 | 茂泰(福建)鞋材有限公司 | Rubber foamed sole based on preparation of rubber reclaimed materials |
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| 徐海露: "发泡EVA的解交联与填充改性研究", 中国优秀硕士学位论文电子期刊网 工程科技Ⅰ辑, no. 01, 15 January 2018 (2018-01-15), pages 016 - 277 * |
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