CN117247610B - Vegetarian leather sole material and preparation method thereof - Google Patents
Vegetarian leather sole material and preparation method thereof Download PDFInfo
- Publication number
- CN117247610B CN117247610B CN202311306550.1A CN202311306550A CN117247610B CN 117247610 B CN117247610 B CN 117247610B CN 202311306550 A CN202311306550 A CN 202311306550A CN 117247610 B CN117247610 B CN 117247610B
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- parts
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- temperature
- sole material
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- 239000000463 material Substances 0.000 title claims abstract description 111
- 239000010985 leather Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 71
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 71
- 150000003505 terpenes Chemical class 0.000 claims abstract description 56
- 235000007586 terpenes Nutrition 0.000 claims abstract description 56
- 229920001971 elastomer Polymers 0.000 claims abstract description 33
- -1 compatilizer Substances 0.000 claims abstract description 26
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000806 elastomer Substances 0.000 claims abstract description 21
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 17
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 238000004073 vulcanization Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000005060 rubber Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 11
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 9
- UXRBHEQFVKYHRG-UHFFFAOYSA-N triethoxy(3-fluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCF UXRBHEQFVKYHRG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 6
- 238000006065 biodegradation reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000223 polyglycerol Polymers 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004156 Azodicarbonamide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 4
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 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 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 241001330002 Bambuseae Species 0.000 claims description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 239000000835 fiber Substances 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
- 238000005086 pumping Methods 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 229930006722 beta-pinene Natural products 0.000 claims 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims 2
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 11
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000243 solution Substances 0.000 description 11
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
- 229940037312 stearamide Drugs 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 210000004207 dermis Anatomy 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- OMKXXAROSIKIPU-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-5-propan-2-ylcyclohexa-1,3-diene Chemical compound C(C)(C)(C)OOC1(CC=C(C=C1)OOC(C)(C)C)C(C)C OMKXXAROSIKIPU-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2309/06—Copolymers with styrene
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- 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
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- 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
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- C08J2423/08—Copolymers of ethene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a sole material for a diatom shoe and a preparation method thereof in the field of sole materials, wherein the sole material comprises the following components in parts by weight: solution polymerized styrene butadiene rubber, modified TPU, SEBS-POE blend, modified terpene resin, biological degradation auxiliary agent, compatilizer, reinforcing agent, coupling agent, accelerator, anti-aging agent, cross-linking agent, foaming agent, wear-resistant reinforcing agent and plasticizer. According to the invention, the modified terpene resin is added into the solution polymerized styrene-butadiene rubber, and the diphenylmethane diisocyanate and the hydroxyl-terminated polydimethylsiloxane are added into the thermoplastic polyurethane elastomer, so that the hydrophobicity of the solution polymerized styrene-butadiene rubber, the crosslinking density of the TPU and the compatibility of the solution polymerized styrene-butadiene rubber and the thermoplastic elastomer are improved, the technical effects of moisture resistance, skid resistance, wear resistance and tear resistance of the diatomic leather sole material are realized, the air permeability of the sole material is enhanced, and the appearance has the leather texture effect.
Description
Technical Field
The invention belongs to the technical field of sole materials, and particularly relates to a vegetarian leather sole material and a preparation method thereof.
Background
Shoes are indispensable living single products of people, along with the improvement of living standard of people, the requirements for footwear products are continuously improved, and shoes with the qualities of wear resistance, tear resistance, moisture resistance, skid resistance, comfort, high performance price ratio, environmental protection and the like are pursued from the initial pursuit of protection and warmth retention to the current pursuit of people.
The sole material is made of leather, synthetic rubber, plastic, thermoplastic elastomer and the like, and most of leather currently used in the market is made of animal leather, so that the sole material is not beneficial to environmental protection and is high in price, and is rarely used in recent years; the sole materials commonly used in the market at present are synthetic rubber, plastic and thermoplastic elastomer, and the synthetic material has the performances of wear resistance, moisture resistance and skid resistance, but the rubber material has high specific gravity, so that the comfort of the shoes is not high; plastics have cheap and easily available properties, but have poor wear resistance, moisture and skid resistance and comfort; the thermoplastic elastomer has the characteristics of environmental protection, no toxicity and safety, has strong wear resistance, weather resistance and tear resistance, and higher comfort level, and the thermoplastic elastomer has higher price, but the recycling capability of the thermoplastic elastomer can greatly reduce the cost, can be formed by secondary injection molding and can be formed independently, so that the thermoplastic elastomer has a great development prospect in the current market.
If the synthetic rubber, plastic or thermoplastic elastomer is used alone to prepare the sole material, the sole material with strong comprehensiveness cannot be prepared, and the various requirements of people on the sole cannot be met, so that various materials are required to be blended to prepare the composite sole material with excellent comprehensive performance, however, the composite sole material at present has some problems, mainly including poor moisture and skid resistance and wear resistance, poor tearing resistance, poor leather texture effect and high price.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a vegetarian leather sole material, and aims to solve the problems of poor moisture and skid resistance, poor wear resistance and high price, the invention provides a manner of adding modified terpene resin into solution polymerized styrene-butadiene rubber, so that the hydrophobicity of the solution polymerized styrene-butadiene rubber is improved, the technical effect of moisture and skid resistance of the sole material is realized, the crosslinking density of the thermoplastic polyurethane elastomer is improved by adding diphenylmethane diisocyanate and hydroxyl-terminated polydimethylsiloxane into the thermoplastic polyurethane elastomer, the technical effect of wear resistance and tear resistance of the sole material is realized, the formation of crystallization is promoted by using a plasticizer, the foaming rate of the thermoplastic elastomer is improved, the technical effect of comfort and good air permeability of the sole material is realized, the polyurethane thermoplastic elastomer leather has the dermis texture effect, the dermis texture effect can be realized without adopting animal dermis, the environment is protected, the cost is saved, the rubber and the thermoplastic elastomer are blended, the defects of the respective performances are overcome, the prepared sole material can be recycled, the performance is high, and the sustainable development concept is met.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a vegetarian leather sole material which comprises the following components in parts by weight: 50-60 parts of solution polymerized styrene butadiene rubber, 20-40 parts of modified TPU, 20-40 parts of SEBS-POE blend, 8-10 parts of modified terpene resin, 5-8 parts of biological degradation auxiliary agent, 5-10 parts of compatilizer, 10-12 parts of reinforcing agent, 2-8 parts of coupling agent, 1-3 parts of accelerator, 1-2 parts of anti-aging agent, 2-4 parts of cross-linking agent, 2-4 parts of foaming agent, 2-6 parts of wear-resistant reinforcing agent and 2-4 parts of plasticizer;
Preferably, the modified TPU specifically comprises the following components in parts by weight: 8-10 parts of thermoplastic polyurethane elastomer, 1-2 parts of diphenylmethane diisocyanate and 3-5 parts of hydroxyl-terminated polydimethylsiloxane;
preferably, the preparation method of the modified TPU specifically comprises the following steps:
A. Drying thermoplastic polyurethane elastomer in a constant temperature drying box at 100 ℃ for 4-6 hours, drying diphenylmethane diisocyanate in a blast drying box at 100 ℃ for 0.5-1 hour to a flowing state, weighing the dried thermoplastic polyurethane elastomer and the flowing diphenylmethane diisocyanate according to parts by weight, uniformly mixing in an internal mixer at 180-200 ℃ at the rotating speed of 50r/min for 5-8 minutes, and cooling to room temperature to obtain long-chain TPU;
B. Weighing long-chain TPU and hydroxyl-terminated polydimethylsiloxane according to parts by weight, putting into an internal mixer at 150-160 ℃ for uniform mixing, rotating at 60r/min for 10-15min, and cooling to room temperature to obtain the modified TPU.
Preferably, in the modified terpene resin, the terpene resin consists of (alpha+beta) pinene and divinylbenzene in a mass ratio of 4:1-2; the modified terpene resin comprises 3-4wt% of 3-fluoropropyl triethoxysilane;
preferably, the preparation method of the modified terpene resin specifically comprises the following steps:
① Adding 100mL of toluene into a four-neck flask with a thermometer and a stirrer, placing the flask into a low-temperature bath, starting the stirrer, reducing the temperature to 0 to-5 ℃, adding a catalyst, respectively dropwise adding (alpha+beta) pinene and divinylbenzene, controlling the dropping speed to 100d/min, stirring at 200r/min, reacting at-5 to-15 ℃ for 4-5h, adding water with the temperature of 80-85 ℃ into the system after the reaction is finished, extracting, taking an upper organic phase, distilling under normal pressure, and removing the solvent to obtain a resin intermediate;
② The temperature of the system is increased to 80-85 ℃, 3-fluoropropyl triethoxysilane is firstly added, then sodium hydroxide is added, the temperature is controlled to be unchanged, the reaction time is 10-12h, water is added into the system for extraction after the reaction is finished, an upper organic phase is taken and put into a three-neck flask, a vacuum device is connected, oligomers are distilled out under the condition of reduced pressure, the final distillation temperature is controlled to be 250 ℃, the vacuum degree is 100KPa, when the temperature of the three-neck flask is reduced to be lower than 200 ℃, the vacuum pumping is stopped, and distillate is recovered to obtain modified terpene resin;
Preferably, in step ①, the volume ratio of toluene to terpene resin is 0.5-1:1-1.2;
preferably, in step ①, the catalyst is AlCl 3, and the addition amount of the catalyst is 5-7% of the mass of the terpene resin;
Preferably, in step ②, the sodium hydroxide is added in an amount of 0.3 to 0.5% by mass of the resin intermediate;
preferably, the volume ratio of water to reactants during extraction is 1-2:1.
Preferably, the biological degradation auxiliary comprises the following components in parts by weight: 10-12 parts of polybutylene succinate-butylene terephthalate copolymer, 5-8 parts of SEBS-POE blend, 0.5-1 part of coupling agent, 1-2 parts of compatilizer and 1-3 parts of salicylic acid;
Preferably, the compatibilizer comprises at least one of ethylene-octene copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride, and polypropylene grafted maleic anhydride;
preferably, the reinforcing agent comprises at least one of kaolin, bentonite, white carbon black, montmorillonite, reclaimed rubber and bamboo fiber;
preferably, the coupling agent comprises at least one of Si-69, si-75, KH-550, KH-560 and KH-570;
Preferably, the accelerator comprises the following components in parts by weight: 1-1.5 parts of stearic acid, 2-3 parts of nano zinc oxide and 1.5-2 parts of polyglycerol;
Preferably, the anti-aging agent includes at least one of an anti-aging agent RD, an anti-aging agent MB, and an anti-aging agent 4010 NA;
Preferably, the crosslinking agent comprises at least one of 1, 4-bis-tert-butylperoxycumene, dicumyl peroxide and cumene hydroperoxide;
preferably, the foaming agent comprises at least one of azodicarbonamide and azodiisobutyronitrile;
preferably, the wear-resistant reinforcing agent is modified nano CaCO 3;
Preferably, the preparation method of the modified nano CaCO 3 specifically comprises the following steps:
Ultrasonically oscillating nano CaCO 3, a silane coupling agent and acetone in a mass ratio of 5:1.5-2:10-15 for 30min at 60 ℃, adding 0.1-0.5 part of an accelerator, uniformly stirring and mixing, ultrasonically oscillating for 30min to obtain a nano CaCO 3 filter cake, washing with acetone, and placing in a constant-temperature drying box at 100 ℃ for drying for 2-3h to obtain modified nano CaCO 3;
Preferably, the plasticizer comprises the following components in parts by weight: 5-10 parts of methyl stearate, 3-4 parts of dioctyl phthalate and 10-12 parts of stearamide.
The invention also provides a preparation method of the vegetarian leather sole material, which specifically comprises the following steps:
S1, preparing master batch: adding the solution polymerized styrene-butadiene rubber and the modified terpene resin into an internal mixer at 180-200 ℃ according to parts by weight, and banburying for 10-15min to a molten state at the rotating speed of 50 r/min; adding the modified TPU and SEBS-POE blend into the internal mixer, controlling the temperature and the rotating speed to be unchanged, and carrying out internal mixing for 8-10min to obtain master batch;
s2, preparation of a mixed material: sequentially adding a biodegradation auxiliary agent, a compatilizer, a reinforcing agent, a coupling agent, an accelerator, an anti-aging agent, a crosslinking agent, a foaming agent, an abrasion-resistant reinforcing agent and a plasticizer into the internal mixer containing the master batch in the step S1 according to parts by weight, controlling the temperature and the rotating speed unchanged, continuously mixing for 5-10min, cooling to room temperature to obtain a mixed material, and granulating the mixed material in a granulator to obtain a sample;
S3, vulcanization molding: and (3) putting the sample obtained in the step (S2) into a vulcanization molding machine, controlling the vulcanization temperature to be 150-160 ℃ and the vulcanization time to be 3-4h, cooling to room temperature after vulcanization, and taking out the vulcanized material from the vulcanization molding machine to obtain the vegetarian leather sole material.
The beneficial effects obtained by the invention are as follows:
The invention provides a novel composite sole material with excellent comprehensive performance, which is prepared by blending synthetic rubber and a thermoplastic elastomer, wherein the novel composite sole material is prepared by reacting pinene and divinylbenzene in a solvent by using Lewis acid to obtain modified terpene resin, and TPU is modified by adding hydroxyl-terminated polydimethylsiloxane and diphenylmethane diisocyanate, so that the moisture and skid resistance, wear resistance and tear resistance of the material are improved, and the leather texture effect is realized.
1. The modified terpene resin is obtained by dropwise adding resin raw materials (alpha+beta) pinene and divinylbenzene into a solvent in the presence of a catalyst to carry out polymerization reaction and electrophilic substitution reaction, has excellent compatibility, hydrophobicity, ageing resistance, thermal stability and other performances, and is widely used as a compatilizer and applied to rubber and plastic industries; the terpene resin is subjected to polymerization reaction with divinylbenzene through double bond addition to form a cross structure, so that the crosslinking density of the terpene resin is improved, the wear resistance and weather resistance of the material are improved, the modified terpene resin is prepared by adding 3-fluoropropyl triethoxysilane, the compatibility of rubber and resin can be improved, and the hydrophobicity of the rubber can be improved by introducing a large amount of fluoropropyl groups, so that the moisture-proof and skid-proof performances of the material are improved; the solution polymerized styrene-butadiene rubber, the thermoplastic elastomer and the modified terpene resin are blended, so that a cross-linked three-dimensional structure is easy to form, and the interaction between molecular chains can be increased, thereby improving the tear resistance of the material;
2. Adding diphenylmethane diisocyanate into the thermoplastic elastomer for blending, introducing a long-chain branch structure, increasing the length of a molecular chain, and carrying out an affinity addition reaction on carbamate in the TPU and diisocyanate in the diphenylmethane diisocyanate, so that a silicon-oxygen chain segment of hydroxyl-terminated polydimethylsiloxane is introduced into the thermoplastic polyurethane elastomer, the crosslinking density of the thermoplastic polyurethane elastomer is improved, the hydroxyl-terminated polydimethylsiloxane is also blended with SEBS to form a compact co-crosslinking network structure, and the wear resistance and tear resistance of the material are further improved;
3. The plasticizer is added into the rubber and the thermoplastic elastomer, polar groups in the plasticizer can form hydrogen bonds with carbonyl groups of the thermoplastic elastomer, ordered arrangement of molecular chains is facilitated, and formation of crystals is promoted, so that the foaming rate of the thermoplastic elastomer is improved, and the sole material has the characteristics of comfort and ventilation;
4. the auxiliary biodegradable substances are added into the rubber and the thermoplastic elastomer, so that the composite material is easy to degrade, and the environmental pollution is reduced; the thermoplastic elastomer can be recycled, so that the cost can be reduced, and energy-saving, environment-friendly and green production can be realized;
In conclusion, the vegetarian leather shoe sole material prepared by the invention has the advantages of good moisture and skid resistance, strong tearing resistance and wear resistance, good air permeability, high comfort level, high cost performance, less environmental pollution and leather texture effect.
Drawings
FIG. 1 is a graph showing the results of moisture resistance measurements of the vegetarian leather sole materials made in examples 1-3 and comparative examples 1-4 of the present invention;
FIG. 2 is a graph showing the IR spectrum of the modified terpene resin obtained in example 1 of the present invention;
FIG. 3 is a graph showing the IR spectrum of the modified TPU obtained in example 1 of this invention;
FIG. 4 is a graph showing the scanning result of an electron microscope at 50 times magnification of the surface of the modified TPU prepared in example 1 of the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the 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.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials used in the examples described below, unless otherwise specified, were all commercially available; the parts are weight parts.
Example 1
A vegetarian leather sole material, which comprises the following components in parts by weight: 50 parts of solution polymerized styrene-butadiene rubber, 20 parts of TPU, 20 parts of SEBS-POE blend, 8 parts of modified terpene resin, 5 parts of biological degradation auxiliary agent, 5 parts of compatilizer, 10 parts of reinforcing agent, 2 parts of coupling agent, 1 part of accelerator, 1 part of anti-aging agent RD, 2 parts of 1, 4-di-tert-butyl peroxyisopropyl benzene, 2 parts of azodicarbonamide, 3 parts of modified nano CaCO and 2 parts of plasticizer;
The modified TPU specifically comprises the following components in parts by weight: 8 parts of thermoplastic polyurethane elastomer, 1 part of diphenylmethane diisocyanate and3 parts of hydroxyl-terminated polydimethylsiloxane;
the preparation method of the modified TPU specifically comprises the following steps:
A. Drying a thermoplastic polyurethane elastomer in a constant-temperature drying box at 100 ℃ for 4 hours, drying diphenylmethane diisocyanate in a blast drying box at 100 ℃ for 0.5 hour to a flowing state, weighing the dried thermoplastic polyurethane elastomer and the flowing diphenylmethane diisocyanate according to parts by weight, putting the materials into an internal mixer at 180 ℃ for uniform mixing at the rotating speed of 50r/min for 5min, and cooling to room temperature to obtain a long-chain TPU;
B. Weighing long-chain TPU and hydroxyl-terminated polydimethylsiloxane according to parts by weight, putting into an internal mixer at 150 ℃ for uniform mixing, wherein the rotating speed is 60r/min, the time is 10min, and cooling to room temperature to obtain the modified TPU.
The preparation method of the modified terpene resin specifically comprises the following steps:
① Adding 100mL of toluene into a four-neck flask with a thermometer and a stirrer, placing the flask into a low-temperature bath, starting the stirrer, reducing the temperature to 0 ℃, adding AlCl 3 catalyst accounting for 5% of the mass of terpene resin, respectively dripping (alpha+beta) pinene and divinylbenzene with the mass ratio of 4:1, controlling the dripping speed to 100d/min, stirring at 200r/min, reacting at-5 ℃ for 4h, adding water with the temperature of 80 ℃ into the system after the reaction is finished, extracting, taking an upper organic phase, distilling under normal pressure, and removing the solvent to obtain a resin intermediate;
② The temperature of the system is increased to 80 ℃, 3-fluoropropyl triethoxysilane accounting for 3 percent of the mass of the resin intermediate is firstly added, then sodium hydroxide accounting for 0.3 percent of the mass of the resin intermediate is added, the temperature is controlled to be unchanged, the reaction time is 10 hours, water is added into the system for extraction after the reaction is finished, an upper organic phase is taken and put into a three-neck flask, a vacuum device is connected, oligomers are distilled off under the condition of reduced pressure, the final distillation temperature is controlled to be 250 ℃, the vacuum degree is 100KPa, when the temperature of the three-neck flask is reduced to be below 200 ℃, vacuum pumping is stopped, and distillate is recovered to obtain modified terpene resin;
In step ①, the volume ratio of toluene to terpene resin is 0.5:1;
In the extraction process, the volume ratio of water to reactants is 1:1.
The biological degradation auxiliary agent comprises 10 parts of polybutylene succinate-butylene terephthalate copolymer, 5 parts of SEBS-POE blend, 0.5 part of coupling agent, 1 part of compatilizer and 1 part of salicylic acid;
The compatilizer comprises a blend of ethylene-octene copolymer grafted maleic anhydride and ethylene-vinyl acetate copolymer grafted maleic anhydride in a mass ratio of 1:1;
The reinforcing agent comprises a mixture of kaolin and white carbon black in a mass ratio of 1:1.5;
The coupling agent comprises a mixture of Si-69 and KH-550 in a mass ratio of 1.2:1;
the accelerator comprises 1 part of stearic acid, 2 parts of nano zinc oxide and 1.5 parts of polyglycerol;
The preparation method of the modified nano CaCO 3 specifically comprises the following steps:
Ultrasonically oscillating nano CaCO 3, a silane coupling agent and acetone in a mass ratio of 5:1.5:10 for 30min at 60 ℃, adding 0.1 part of stearic acid accelerator, uniformly stirring and mixing, ultrasonically oscillating for 30min to obtain a nano CaCO 3 filter cake, washing with acetone, and drying in a drying box at 100 ℃ for 2h to obtain modified nano CaCO 3;
the plasticizer includes 5 parts of methyl stearate, 3 parts of dioctyl phthalate and 10 parts of stearamide.
The embodiment provides a preparation method of a vegetarian leather sole material, which specifically comprises the following steps:
S1, preparing master batch: adding solution polymerized styrene-butadiene rubber and modified terpene resin into an internal mixer at 180 ℃ according to parts by weight, and banburying for 10min to a molten state at the rotating speed of 50 r/min; adding the modified TPU and SEBS-POE blend into the internal mixer, controlling the temperature and the rotating speed to be unchanged, and carrying out internal mixing for 8min to obtain master batch;
S2, preparation of a mixed material: sequentially adding a biodegradation assisting product, a compatilizer, a reinforcing agent, a coupling agent, an accelerator, an anti-aging agent, a crosslinking agent, a foaming agent, an abrasion-resistant reinforcing agent and a dry plasticizer into the internal mixer containing the master batch in the step S1 according to parts by weight, controlling the temperature and the rotating speed unchanged, continuously mixing for 5min, cooling to room temperature to obtain a mixed material, and granulating the mixed material in a granulator to obtain a sample;
S3, vulcanization molding: and (3) putting the sample obtained in the step (S2) into a vulcanization molding machine, controlling the vulcanization temperature to be 150 ℃ and the vulcanization time to be 3 hours, cooling to room temperature after vulcanization, and taking out the vulcanized material from the vulcanization molding machine to obtain the vegetarian leather sole material.
Example 2
A vegetarian leather sole material, which comprises the following components in parts by weight: 60 parts of solution polymerized styrene-butadiene rubber, 30 parts of TPU, 30 parts of SEBS-POE blend, 9 parts of modified terpene resin, 7 parts of biological degradation auxiliary agent, 8 parts of compatilizer, 11 parts of reinforcing agent, 5 parts of Si-69 coupling agent, 2 parts of accelerator, 1.5 parts of antioxidant MB, 3 parts of dicumyl peroxide, 3 parts of azodiisobutyronitrile, 3 parts of modified nano CaCO and 3 parts of plasticizer;
The modified TPU specifically comprises the following components in parts by weight: 9 parts of thermoplastic polyurethane elastomer, 1.5 parts of diphenylmethane diisocyanate and 4 parts of hydroxyl-terminated polydimethylsiloxane;
the preparation method of the modified TPU specifically comprises the following steps:
A. drying a thermoplastic polyurethane elastomer in a constant-temperature drying box at 100 ℃ for 5 hours, drying diphenylmethane diisocyanate in a blast drying box at 100 ℃ for 0.8 hour to a flowing state, weighing the dried thermoplastic polyurethane elastomer and the flowing diphenylmethane diisocyanate according to parts by weight, putting the materials into an internal mixer at 190 ℃ for uniform mixing at the rotating speed of 50r/min for 6 minutes, and cooling to the room temperature to obtain a long-chain TPU;
B. Weighing long-chain TPU and hydroxyl-terminated polydimethylsiloxane according to parts by weight, putting into an internal mixer at 155 ℃ for uniform mixing, wherein the rotating speed is 60r/min, the time is 12min, and cooling to room temperature to obtain the modified TPU.
The preparation method of the modified terpene resin specifically comprises the following steps:
① Adding 100mL of toluene into a four-neck flask with a thermometer and a stirrer, placing the flask into a low-temperature bath, starting the stirrer, reducing the temperature to-3 ℃, adding AlCl 3 catalyst accounting for 6% of the mass of terpene resin, respectively dropwise adding (alpha+beta) pinene and divinylbenzene with the mass ratio of 4:1.5, controlling the dripping speed to be 100d/min, stirring at 200r/min, reacting at-10 ℃ for 4.5h, adding water with the temperature of 82 ℃ into the system after the reaction is finished, extracting, taking an upper organic phase, distilling under normal pressure, and removing the solvent to obtain a resin intermediate;
② The temperature of the system is increased to 82 ℃, 3-fluoropropyl triethoxysilane which is 3.5 percent of the mass of the resin intermediate is firstly added, then sodium hydroxide which is 0.4 percent of the mass of the resin intermediate is added, the temperature is controlled to be unchanged, the reaction time is 11h, water is added into the system for extraction after the reaction is finished, an upper organic phase is taken and put into a three-neck flask, a vacuum device is connected, oligomers are distilled off under the condition of reduced pressure, the final distillation temperature is controlled to 250 ℃, the vacuum degree is 100KPa, when the temperature of the three-neck flask is reduced to be below 200 ℃, vacuumizing is stopped, and distillate is recovered to obtain modified terpene resin;
In step ①, the volume ratio of toluene to terpene resin is 0.7:1.1;
During the extraction, the volume ratio of water to reactants was 1.5:1.
The biological degradation auxiliary agent comprises 11 parts of polybutylene succinate-butylene terephthalate copolymer, 7 parts of SEBS-POE blend, 0.8 part of coupling agent, 1.5 parts of compatilizer and 2 parts of salicylic acid;
the compatilizer comprises a blend of ethylene-vinyl acetate copolymer grafted maleic anhydride and polypropylene grafted maleic anhydride in a mass ratio of 1:1.2;
The reinforcing agent comprises a mixture of white carbon black, montmorillonite and reclaimed rubber in a mass ratio of 1.2:1:1.5;
the accelerator comprises 1.2 parts of stearic acid, 2.5 parts of nano zinc oxide and 1.8 parts of polyglycerol;
The preparation method of the modified nano CaCO 3 specifically comprises the following steps:
ultrasonically oscillating nano CaCO 3, a silane coupling agent and acetone in a mass ratio of 5:1.8:12 for 30min at 60 ℃, adding 0.3 part of nano zinc oxide accelerator, uniformly stirring and mixing, ultrasonically oscillating for 30min to obtain a nano CaCO 3 filter cake, washing with acetone, and drying in a drying box at 100 ℃ for 2.5h to obtain modified nano CaCO 3;
the plasticizer included 8 parts of methyl stearate, 3.5 parts of dioctyl phthalate and 11 parts of stearamide.
The embodiment provides a preparation method of a vegetarian leather sole material, which specifically comprises the following steps:
S1, preparing master batch: adding the solution polymerized styrene-butadiene rubber and the modified terpene resin into an internal mixer with the temperature of 190 ℃ according to parts by weight, and banburying for 12min to a molten state at the rotating speed of 50 r/min; adding the modified TPU and SEBS-POE blend into the internal mixer, controlling the temperature and the rotating speed to be unchanged, and carrying out internal mixing for 9min to obtain master batch;
S2, preparation of a mixed material: sequentially adding a biodegradation assisting substance, a compatilizer, a reinforcing agent, a coupling agent, an accelerator, an anti-aging agent, a crosslinking agent, a foaming agent, an abrasion-resistant reinforcing agent and a dry plasticizer into the internal mixer containing the master batch in the step S1 according to parts by weight, controlling the temperature and the rotating speed unchanged, continuously mixing for 8min, cooling to room temperature to obtain a mixed material, and granulating the mixed material in a granulator to obtain a sample;
S3, vulcanization molding: and (3) putting the sample obtained in the step (S2) into a vulcanization molding machine, controlling the vulcanization temperature to be 155 ℃ and the vulcanization time to be 3.5h, cooling to room temperature after vulcanization, and taking out the vulcanized material from the vulcanization molding machine to obtain the vegetarian leather sole material.
Example 3
A vegetarian leather sole material, which comprises the following components in parts by weight: 60 parts of solution polymerized styrene-butadiene rubber, 40 parts of TPU, 40 parts of SEBS-POE blend, 10 parts of modified terpene resin, 8 parts of biological degradation auxiliary agent, 10 parts of compatilizer, 12 parts of reinforcing agent, 8 parts of KH-560 coupling agent, 3 parts of accelerator, 2 parts of antioxidant 4010NA, 4 parts of cumene hydroperoxide, 4 parts of azodicarbonamide, 3 parts of modified nano CaCO and 4 parts of plasticizer;
The modified TPU specifically comprises the following components in parts by weight: 10 parts of thermoplastic polyurethane elastomer, 2 parts of diphenylmethane diisocyanate and 5 parts of hydroxyl-terminated polydimethylsiloxane;
the preparation method of the modified TPU specifically comprises the following steps:
A. Drying a thermoplastic polyurethane elastomer in a constant-temperature drying box at 100 ℃ for 6 hours, drying diphenylmethane diisocyanate in a blast drying box at 100 ℃ for 1 hour to a flowing state, weighing the dried thermoplastic polyurethane elastomer and the flowing diphenylmethane diisocyanate according to parts by weight, putting the materials into an internal mixer at 200 ℃ for uniform mixing, wherein the rotating speed is 50r/min, the time is 8min, and cooling to room temperature to obtain long-chain TPU;
B. Weighing long-chain TPU and hydroxyl-terminated polydimethylsiloxane according to parts by weight, putting into an internal mixer at 160 ℃ for uniform mixing, rotating at 60r/min for 15min, and cooling to room temperature to obtain the modified TPU.
The preparation method of the modified terpene resin specifically comprises the following steps:
① Adding 100mL of toluene into a four-neck flask with a thermometer and a stirrer, placing the flask into a low-temperature bath, starting the stirrer, reducing the temperature to-5 ℃, adding AlCl 3 catalyst accounting for 7% of the mass of terpene resin, respectively dropwise adding (alpha+beta) pinene copolymer and divinylbenzene with the mass ratio of 4:2, controlling the dripping speed to be 100d/min, stirring at 200r/min, reacting at-15 ℃ for 5h, adding water with the temperature of 85 ℃ into the system after the reaction is finished, extracting, taking an upper organic phase, distilling at normal pressure, and removing the solvent to obtain a resin intermediate;
② The method comprises the steps of raising the temperature of a system to 85 ℃, firstly adding 3-fluoropropyl triethoxysilane accounting for 4% of the mass of a resin intermediate, then adding sodium hydroxide accounting for 0.5% of the mass of the resin intermediate, controlling the temperature to be unchanged, enabling the reaction time to be 12h, adding water into the system for extraction after the reaction is finished, taking an upper organic phase, putting the upper organic phase into a three-neck flask, connecting a vacuum device, evaporating an oligomer under a reduced pressure condition, controlling the final distillation temperature to be 250 ℃ and the vacuum degree to be 100KPa, stopping vacuumizing when the temperature of the three-neck flask is reduced to be lower than 200 ℃, and recycling distillate to obtain modified terpene resin;
In step ①, the volume ratio of toluene to terpene resin is 1:1.2;
During the extraction, the volume ratio of water to reactants was 2:1.
The biological degradation auxiliary agent comprises 12 parts of polybutylene succinate-butylene terephthalate copolymer, 8 parts of SEBS-POE blend, 1 part of coupling agent, 2 parts of compatilizer and 3 parts of salicylic acid;
the compatilizer comprises ethylene-octene copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride and polypropylene grafted maleic anhydride which are mixed according to the mass ratio of 1.5:1:2;
the reinforcing agent comprises montmorillonite, reclaimed rubber and bamboo fiber mixture with the mass ratio of 0.5:1.2:2;
the accelerator comprises 1.5 parts of stearic acid, 3 parts of nano zinc oxide and 2 parts of polyglycerol;
The preparation method of the modified nano CaCO 3 specifically comprises the following steps:
Ultrasonically oscillating nano CaCO 3, a silane coupling agent and acetone in a mass ratio of 5:2:15 for 30min at 60 ℃, adding 0.5 part of polyglycerol accelerator, uniformly stirring and mixing, ultrasonically oscillating for 30min to obtain a nano CaCO 3 filter cake, washing with acetone, and drying in a constant-temperature drying box at 100 ℃ for 3h to obtain modified nano CaCO 3;
the plasticizer comprises 10 parts of methyl stearate, 4 parts of dioctyl phthalate and 12 parts of stearamide.
The embodiment provides a preparation method of a vegetarian leather sole material, which specifically comprises the following steps:
S1, preparing master batch: adding the solution polymerized styrene-butadiene rubber and the modified terpene resin into an internal mixer with the temperature of 200 ℃ according to parts by weight, and banburying for 15min to a molten state at the rotating speed of 50 r/min; adding the modified TPU and SEBS-POE blend into the internal mixer, controlling the temperature and the rotating speed to be unchanged, and carrying out internal mixing for 10min to obtain master batch;
S2, preparation of a mixed material: sequentially adding a biodegradation assisting product, a compatilizer, a reinforcing agent, a coupling agent, an accelerator, an anti-aging agent, a crosslinking agent, a foaming agent, an abrasion-resistant reinforcing agent and a dry plasticizer into the internal mixer containing the master batch in the step S1 according to parts by weight, controlling the temperature and the rotating speed unchanged, continuously mixing for 10 minutes, cooling to room temperature to obtain a mixed material, and granulating the mixed material in a granulator to obtain a sample;
s3, vulcanization molding: and (2) putting the sample obtained in the step (S2) into a vulcanization molding machine, controlling the vulcanization temperature to 160 ℃, controlling the vulcanization time to 4 hours, cooling to room temperature after vulcanization, and taking out the vulcanized material from the vulcanization molding machine to obtain the vegetarian leather sole material.
Comparative example 1
This comparative example provides a vegetarian leather sole material which differs from example 1 only in that the terpene resin is not modified and the remaining components, component contents, and preparation methods are the same as in example 1.
Comparative example 2
This comparative example provides a vegetarian leather sole material which differs from example 1 only in that no terpene resin is added to the sole material, and the remaining components, component contents, and preparation methods are the same as in example 1.
Comparative example 3
This comparative example provides a vegetarian leather sole material which differs from example 1 only in that the TPU has not been modified and the remaining components, component contents, and method of preparation are the same as in example 1.
Experimental example 1
The hydrophobic property of the vegetarian leather sole material described in the examples and comparative examples is determined in this experimental example, and the specific method is as follows: the samples of the literacy leather sole materials prepared in examples 1 to 3 and comparative examples 1 to 3, which had a length of 10mm, a width of 8mm and a thickness of 3mm, were taken out, two drops of deionized water were dropped on the surface of each sheet, and after standing for 1min, the samples were tested by using a G-1 type erma angle contact angle tester manufactured by Kyowa corporation, japan, and were measured three times in parallel, and finally, the average value was obtained.
FIG. 1 is a graph showing the results of the hydrophobic properties of the vegetarian leather sole materials prepared in examples 1-3 and comparative examples 1-3 according to the present invention, wherein the water contact angle of the vegetarian leather sole materials in examples 1-3 is 120-130 degrees, which indicates that the vegetarian leather sole materials in examples 1-3 have good hydrophobic properties, i.e., strong moisture resistance; the water contact angle of the vegetarian leather sole material described in comparative example 1 was 80, the hydrophobic property of the basic leather shoe sole material described in the comparative example 1 is general, namely, the moisture resistance is good; the water contact angle of the vegetarian leather sole material described in comparative example 2 was 50, the material of the basic leather shoe base material in the comparative example 2 has poor hydrophobicity, namely weak moisture resistance; the water contact angle of the vegetarian leather sole material of the comparative example 3 is 100-110 degrees, which shows that the vegetarian leather sole material of the comparative example 3 has better hydrophobic performance, namely stronger moisture resistance; the modified terpene resin is used for the vegetarian leather sole material, and a large amount of fluoropropyl groups are introduced, so that the hydrophobic property of the sole material is improved, and the moisture resistance of the sole material is enhanced; the terpene resin added in the vegetarian leather sole material of the comparative example 1 is not modified, and only the terpene resin has the hydrophobicity, so that the sole material hydrophobicity is not obviously improved; the sole material described in comparative example 2 was not added with any terpene resin, and the rubber and thermoplastic elastomer composite was inferior in moisture resistance; the sole material of the diathesis leather in the comparative example 3 does not modify TPU, has little influence on the hydrophobic property of the sole material, and has stronger moisture resistance.
Experimental example 2
In this experimental example, the modified terpene resin described in example 1 was subjected to infrared spectroscopic analysis using a fourier transform infrared spectrometer, and the spectral range was measured to be 500-4000cm -1, and fig. 2 is an infrared spectrogram of the modified terpene resin obtained in example 1.
Experimental example 3
In this experimental example, the modified TPU described in example 1 was subjected to infrared spectroscopic analysis using a fourier transform infrared spectrometer, and the spectral range tested was between 500 and 4000cm -1, and fig. 3 is an infrared spectrum of the modified TPU obtained in example 1, (a) an image was an infrared image of a thermoplastic polyurethane elastomer, (b) an image was an infrared image of a long-chain TPU, and (c) an image was an infrared image of a modified TPU.
Experimental example 4
In this experimental example, the surface of the modified TPU described in example 1 was scanned by an electron microscope, and fig. 4 is a 50-magnification electron microscope scan of the surface of the modified TPU obtained in example 1.
Experimental example 5
This experimental example performs a performance measurement on the sole materials prepared in examples 1 to 3 and comparative examples 1 to 3:
The sole materials prepared in examples 1 to 3 and comparative examples 1 to 3 were sampled, and the following performance test was performed on the sampled products, and the test results are recorded in table 1.
TABLE 1 Performance test results
| Test item and standard | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Shore A hardness GB/T531 | 64 | 63 | 65 | 67 | 66 | 65 |
| Density (g/cm 3) GB/T533 | 0.563 | 0.574 | 0.586 | 0.694 | 0.652 | 0.783 |
| Coefficient of slip resistance (dry) GB/T40910-2021 | 0.91 | 0.90 | 0.93 | 0.75 | 0.51 | 0.82 |
| Coefficient of slip resistance (wet) GB/T40910-2021 | 0.63 | 0.67 | 0.68 | 0.53 | 0.40 | 0.60 |
| Wear resistance/%GB/T5478 | 0.06 | 0.07 | 0.07 | 0.15 | 0.21 | 0.48 |
| Compression set/%GB/T1683 | 8.2 | 8.1 | 8.3 | 9.5 | 15.3 | 16.7 |
| Tensile strength/MPaASTMD 638 | 40 | 38 | 39 | 37 | 36 | 38 |
| Elongation at break/% astm d638 | 500 | 510 | 530 | 420 | 460 | 400 |
| Rebound resilience/%GB/T1681-2009 | 48 | 47 | 50 | 43 | 45 | 34 |
| Ventilation mL/cm 2. HGB/T19786-2021 | 2400 | 2500 | 2450 | 2330 | 2350 | 2300 |
| Biodegradation rate/%GB/T19277 | 95 | 96 | 96 | 94 | 95 | 92 |
Analysis of results:
(1) Comparison of comparative example 1 with example 1 shows that the terpene resin is not modified, the wet and slip resistance of the sole material is reduced, and the abrasion and tear resistance is reduced;
(2) Comparison of comparative example 2 with example 1 shows that the sole material without any terpene resin added is extremely weak in wet and slip resistance and poor in wear resistance;
(3) Comparison of comparative example 3 with example 1 shows that the TPU is not modified, the wear and tear resistance of the sole material is very poor, the rebound rate is reduced, and the material density is increased, making the sole material heavy and uncomfortable.
In conclusion, the vegetarian leather shoe sole material prepared by the invention has the advantages of good moisture and skid resistance, strong tearing resistance and wear resistance, good air permeability, high comfort level, high cost performance, less environmental pollution and leather texture effect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (6)
1. A vegetarian leather sole material characterized by: the vegetarian leather sole material comprises the following components in parts by weight: 50-60 parts of solution polymerized styrene butadiene rubber, 20-40 parts of modified TPU, 20-40 parts of SEBS-POE blend, 8-10 parts of modified terpene resin, 5-8 parts of biological degradation auxiliary agent, 5-10 parts of compatilizer, 10-12 parts of reinforcing agent, 2-8 parts of coupling agent, 1-3 parts of accelerator, 1-2 parts of anti-aging agent, 2-4 parts of cross-linking agent, 2-4 parts of foaming agent, 2-6 parts of wear-resistant reinforcing agent and 2-4 parts of plasticizer;
the modified TPU specifically comprises the following components in parts by weight: 8-10 parts of thermoplastic polyurethane elastomer, 1-2 parts of diphenylmethane diisocyanate and 3-5 parts of hydroxyl-terminated polydimethylsiloxane;
The preparation method of the modified TPU specifically comprises the following steps:
A. Drying thermoplastic polyurethane elastomer in a constant temperature drying box at 100 ℃ for 4-6 hours, drying diphenylmethane diisocyanate in a blast drying box at 100 ℃ for 0.5-1 hour to a flowing state, weighing the dried thermoplastic polyurethane elastomer and the flowing diphenylmethane diisocyanate according to parts by weight, uniformly mixing in an internal mixer at 180-200 ℃ at the rotating speed of 50r/min for 5-8 minutes, and cooling to room temperature to obtain long-chain TPU;
B. Weighing long-chain TPU and hydroxyl-terminated polydimethylsiloxane according to parts by weight, putting into an internal mixer at 150-160 ℃ for uniform mixing, wherein the rotating speed is 60r/min, the time is 10-15min, and cooling to room temperature to obtain modified TPU; in the modified terpene resin, the terpene resin consists of alpha+beta pinene and divinylbenzene with the mass ratio of 4:1-2; the modified terpene resin comprises 3-4wt% of 3-fluoropropyl triethoxysilane;
The preparation method of the modified terpene resin specifically comprises the following steps:
① Adding 100mL of toluene into a four-neck flask with a thermometer and a stirrer, placing the flask into a low-temperature bath, starting the stirrer, reducing the temperature to 0-5 ℃, adding a catalyst, respectively dropwise adding alpha+beta pinene and divinylbenzene, controlling the dropping speed to 100d/min, stirring at 200r/min, reacting at-5-15 ℃ for 4-5h, adding water with the temperature of 80-85 ℃ into the system after the reaction is finished, extracting, taking an upper organic phase, distilling at normal pressure, and removing the solvent to obtain a resin intermediate;
② The temperature of the system is increased to 80-85 ℃, 3-fluoropropyl triethoxysilane is firstly added, then sodium hydroxide is added, the temperature is controlled to be unchanged, the reaction time is 10-12h, water is added into the system for extraction after the reaction is finished, an upper organic phase is taken and put into a three-neck flask, a vacuum device is connected, oligomers are distilled out under the condition of reduced pressure, the final distillation temperature is controlled to be 250 ℃, the vacuum degree is 100KPa, when the temperature of the three-neck flask is reduced to be lower than 200 ℃, the vacuum pumping is stopped, and distillate is recovered to obtain modified terpene resin;
in step ①, the volume ratio of toluene to terpene resin is 0.5-1:1-1.2;
In the step ①, the catalyst is AlCl3, and the addition amount of the catalyst is 5-7% of the mass of the terpene resin; in the step ②, the addition amount of the sodium hydroxide is 0.3-0.5% of the mass of the resin intermediate;
In the extraction process, the volume ratio of water to reactants is 1-2:1;
The biological degradation auxiliary agent comprises the following components in parts by weight: 10-12 parts of polybutylene succinate-butylene terephthalate copolymer, 5-8 parts of SEBS-POE blend, 0.5-1 part of coupling agent, 1-2 parts of compatilizer and 1-3 parts of salicylic acid;
The wear-resistant reinforcing agent is modified nano CaCO 3;
the preparation method of the modified nano CaCO 3 specifically comprises the following steps:
Ultrasonically oscillating nano CaCO 3, a silane coupling agent and acetone in a mass ratio of 5:1.5-2:10-15 for 30min at 60 ℃, adding 0.1-0.5 part of an accelerator, uniformly stirring and mixing, ultrasonically oscillating for 30min to obtain a nano CaCO 3 filter cake, washing with acetone, and placing in a drying box at 100 ℃ for drying for 2-3h to obtain modified nano CaCO 3.
2. The vegetarian leather sole material of claim 1 wherein: the compatibilizer comprises at least one of ethylene-octene copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride, and polypropylene grafted maleic anhydride.
3. The vegetarian leather sole material of claim 2 wherein: the reinforcing agent comprises at least one of kaolin, bentonite, white carbon black, montmorillonite, reclaimed rubber and bamboo fiber; the coupling agent comprises at least one of Si-69, si-75, KH-550, KH-560 and KH-570; the anti-aging agent comprises at least one of an anti-aging agent RD, an anti-aging agent MB and an anti-aging agent 4010 NA; the cross-linking agent comprises at least one of 1, 4-di-tert-butyl cumene peroxide, diisopropylbenzene peroxide and cumene hydroperoxide; the foaming agent includes at least one of azodicarbonamide and azobisisobutyronitrile.
4. The vegetarian leather sole material of claim 3 wherein: the accelerator comprises the following components in parts by weight: 1-1.5 parts of stearic acid, 2-3 parts of nano zinc oxide and 1.5-2 parts of polyglycerol.
5. The vegetarian leather sole material of claim 4 wherein: the plasticizer comprises the following components in parts by weight: 5-10 parts of methyl stearate, 3-4 parts of dioctyl phthalate and 10-12 parts of stearamide
Parts by weight.
6. A method of making a vegetarian leather sole material according to any one of claims 1 to 5 characterized by: the method specifically comprises the following steps:
S1, preparing master batch: adding the solution polymerized styrene-butadiene rubber and the modified terpene resin into an internal mixer at 180-200 ℃ according to parts by weight, and banburying for 10-15min to a molten state at the rotating speed of 50 r/min; adding the modified TPU and SEBS-POE blend into the internal mixer, controlling the temperature and the rotating speed to be unchanged, and carrying out internal mixing for 8-10min to obtain master batch;
S2, preparation of a mixed material: sequentially adding a biodegradation auxiliary agent, a compatilizer, a reinforcing agent, a coupling agent, an accelerator, an anti-aging agent, a crosslinking agent, an abrasion-resistant reinforcing agent and a plasticizer into the internal mixer containing the master batch in the step S1 according to parts by weight, controlling the temperature and the rotating speed to be unchanged, continuously mixing for 5-10min, cooling to room temperature to obtain a mixed material, and granulating the mixed material in a granulator to obtain a sample;
S3, vulcanization molding: and (3) putting the sample obtained in the step (S2) into a vulcanization molding machine, controlling the vulcanization temperature to be 150-160 ℃ and the vulcanization time to be 3-4h, cooling to room temperature after vulcanization, and taking out the vulcanized material from the vulcanization molding machine to obtain the vegetarian leather sole material.
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