CN116589761A - Environment-friendly sole material and preparation method thereof - Google Patents
Environment-friendly sole material and preparation method thereof Download PDFInfo
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- CN116589761A CN116589761A CN202310569751.4A CN202310569751A CN116589761A CN 116589761 A CN116589761 A CN 116589761A CN 202310569751 A CN202310569751 A CN 202310569751A CN 116589761 A CN116589761 A CN 116589761A
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- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 54
- 239000005060 rubber Substances 0.000 claims abstract description 54
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 17
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 16
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 16
- 229920001194 natural rubber Polymers 0.000 claims abstract description 16
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008117 stearic acid Substances 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 14
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 9
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims description 35
- 239000003921 oil Substances 0.000 claims description 29
- 235000019198 oils Nutrition 0.000 claims description 29
- 238000004513 sizing Methods 0.000 claims description 29
- 235000007164 Oryza sativa Nutrition 0.000 claims description 22
- 235000009566 rice Nutrition 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 19
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 13
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 5
- 239000008158 vegetable oil Substances 0.000 claims description 5
- PIBIAJQNHWMGTD-UHFFFAOYSA-N 1-n,3-n-bis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(NC=2C=CC(C)=CC=2)=C1 PIBIAJQNHWMGTD-UHFFFAOYSA-N 0.000 claims description 4
- 244000226021 Anacardium occidentale Species 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- 235000020226 cashew nut Nutrition 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012990 dithiocarbamate Substances 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical group C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 2
- VWNMIDRTNPTBJH-UHFFFAOYSA-N 4-n-(2-methylphenyl)benzene-1,4-diamine Chemical compound CC1=CC=CC=C1NC1=CC=C(N)C=C1 VWNMIDRTNPTBJH-UHFFFAOYSA-N 0.000 claims description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical group C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical group [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 241000209094 Oryza Species 0.000 description 21
- 238000002156 mixing Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 12
- 235000006708 antioxidants Nutrition 0.000 description 12
- 239000013501 sustainable material Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 11
- 235000020238 sunflower seed Nutrition 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 8
- 239000004170 rice bran wax Substances 0.000 description 8
- 235000019384 rice bran wax Nutrition 0.000 description 8
- 238000009472 formulation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000010903 husk Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000010074 rubber mixing Methods 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- A—HUMAN NECESSITIES
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses an environment-friendly sole material and a preparation method thereof, wherein the environment-friendly sole material comprises the following raw materials in parts by weight: 20-60 parts of natural rubber, 20-60 parts of butadiene rubber, 5-50 parts of styrene-butadiene rubber, 0-50 parts of processing oil, 10-50 parts of reinforcing agent, 1-6 parts of coupling agent, 1-5 parts of dispersing agent, 10-50 parts of rubber powder, 0.5-6 parts of tackifier, 1-5 parts of anti-aging agent, 1-4 parts of vulcanizing agent, 1-5 parts of accelerator, 0.5-5 parts of stearic acid and 1-5 parts of zinc oxide. The invention enables the formula to be more environment-friendly and reduces carbon by selecting the bio-based material and the reclaimed material on the premise of not losing the performance of the product.
Description
Technical Field
The invention relates to a sole material, in particular to an environment-friendly sole material and a preparation method thereof.
Background
With the rapid development of socioeconomic performance, there is an increasing demand for footwear products. Early consumers were purchasing footwear primarily concerned whether the footwear was sturdy and durable. With the progress of society and the improvement of the living standard of people, consumers are gradually concerned about the quality and performance of shoes, and the safety and comfort of the shoes are the development targets of the whole shoe making industry. The data show that the sole material is about 50% of the total shoe weight.
With the aim of 'double carbon', the sustainable material (Sustainable Material) is taken as an emerging industry, can reduce carbon emission in the production process of products, and has received great attention from China for industry development. The sustainable materials mainly comprise Bio-based materials and recyclable materials, and have wide application fields and huge industrial development potential. As the green consumer concept continues to go deep, sustainable materials will be increasingly favored by consumers.
In order to solve the climate and environmental problems faced at present, a sole material with excellent performance and high sustainable material content needs to be developed, so that the market demand is met.
Disclosure of Invention
The invention mainly aims to provide an environment-friendly sole material with improved sustainable material content on the premise of ensuring performance without loss.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an environment-friendly sole material comprises the following raw materials in parts by weight: 20-60 parts of natural rubber, 20-60 parts of butadiene rubber, 5-50 parts of styrene-butadiene rubber, 0-50 parts of processing oil, 10-50 parts of reinforcing agent, 1-6 parts of coupling agent, 1-5 parts of dispersing agent, 10-50 parts of rubber powder, 0.5-6 parts of tackifier, 1-5 parts of anti-aging agent, 1-4 parts of vulcanizing agent, 1-5 parts of accelerator, 0.5-5 parts of stearic acid and 1-5 parts of zinc oxide.
The processing oil is vegetable oil, and the vegetable oil is at least one selected from soybean oil, palm oil, rapeseed oil, sunflower seed oil, coconut oil and cashew nut shell oil.
The reinforcing agent is rice hull ash white carbon black.
The coupling agent is selected from at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide (Si 69), bis- [ gamma- (triethoxysilane) propyl ] disulfide (Si 75), 3-mercaptopropyl-ethoxy-bis (tridecyl-pentaethoxy-siloxane) (Si 747) and gamma-aminopropyl triethoxysilane (KH 550).
The dispersing agent is at least one selected from polyethylene glycol (PEG), polypropylene glycol (PPG) and fatty alcohol ethoxylate.
The rubber powder is rubber sole or tire reclaimed rubber powder, and the particle size of the rubber powder is at least 200 meshes.
The tackifier is rosin resin; the vulcanizing agent is sulfur.
The antioxidant is at least one of 2, 6-di-tert-butyl-p-methylphenol (BHT), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (6 PPD), N' -bis (methylphenyl) -1, 4-phenylenediamine (DTPD), 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), vinyl phenol (SP) and wax;
the accelerator is at least one selected from thiazoles, sulfenamides, guanidine, thiurams and dithiocarbamates.
The thiazole is dibenzothiazyl disulfide MBT;
the sulfenamides are N-cyclohexyl-2-benzothiazole sulfenamide CBS and N-tertiary butyl-2-benzothiazole sulfenamide TBBS;
the guanidine is diphenylguanidine DPG;
the thiurams are tetramethylthiuram disulfide TMTD;
the dithiocarbamate is zinc dimethyldithiocarbamate PZ.
The invention also provides a preparation method of the environment-friendly sole material, which comprises the following steps:
s1, weighing raw materials according to a formula;
s2, setting the rotating speed of an internal mixer to be 60-80rpm, adding all raw materials except a vulcanizing agent and an accelerator into the internal mixer, keeping for at least 30 seconds, then adjusting the rotating speed to be 70-90rpm, keeping for 60-180 seconds at the temperature of 120-160 ℃, discharging glue to obtain a glue stock, and standing the glue stock for at least two minutes;
s3, rotating the internal mixer to 60-80rpm, adding sizing material into the internal mixer, reducing the rotating speed to 40-60rpm when the temperature of the sizing material is 150 ℃, keeping the temperature of the sizing material between 150-160 ℃ for at least 60 seconds, discharging the sizing material to obtain master batch, and cooling the master batch to room temperature;
s4, setting the rotating speed of the internal mixer to 55-75rpm, adding the cooled masterbatch, then adding the vulcanizing agent and the accelerator, increasing the rotating speed to 70-80rpm, and discharging the rubber when the time reaches 180 seconds or the temperature reaches 150 ℃ to obtain the sole material.
By means of the technical scheme, the invention has at least the following advantages:
the processing oil adopted by the invention is vegetable oil, preferably sunflower seed oil. The sunflower seed oil can reduce the mixing time of about 1 minute, improve the production efficiency, and improve the flexibility of the sizing material at low temperature, thereby improving the wet skid resistance and the snowfield skid resistance of the sole.
The reinforcing agent adopted by the invention is white carbon black extracted from rice hull ash, and is rice hull ash white carbon black. The traditional preparation method of the white carbon black mainly uses quartz sand as a raw material, and is smelted with sodium carbonate at 1400 ℃ to form sodium silicate. And dissolving the obtained sodium silicate in water to obtain sodium silicate solution (water glass), precipitating by using acid, and drying to obtain the white carbon black product. The invention adopts rice hull ash white carbon black to replace the traditional white carbon black. The rice husk ash white carbon black adopts ash after rice husk and straw combustion power generation as raw materials. Compared with the traditional white carbon black preparation process, the rice hull ash white carbon black is more environment-friendly and carbon-reducing, and only needs to burn rice hulls, and does not need to be as high as Wen Yerong. Compared with the traditional white carbon black preparation process, the biomass process can reduce about 0.5 ton of CO per 1 ton of rice husk ash white carbon black 2 About 0.5 ton of coal and about sand2.5 tons. According to the invention, rice hull white carbon black is used for replacing traditional white carbon black, the overall performance of the sizing material is not lost, and the rebound resilience at room temperature is slightly improved.
The reinforcing agent used in the invention is white carbon black, so that the wear resistance and wet skid resistance of the sizing material can be improved. However, white carbon black is not easy to disperse in the product processing process, and aggregates are easy to form, so that the product performance is affected. Therefore, the invention uses the environment-friendly coupling agent Si69 to generate silanization reaction with the white carbon black, promotes the dispersion of the white carbon black and improves the performance of the product. In order to ensure that the silylation reaction proceeds adequately, a heat treatment step is added during the kneading stage, typically at a temperature of 150℃to 160℃for 2 minutes. In addition, the invention uses polyethylene glycol as a dispersing agent to improve the dispersion of the coupling agent in the sizing material, so that the coupling agent and the white carbon black have more complete effect.
One of the antioxidants used in the present invention is a vegetable wax, such as rice bran wax, instead of the conventionally used microcrystalline wax. The rice bran wax can migrate to the surface of the sizing material to form a layer of wax film, so that ozone is prevented from penetrating into the product, and a good protection effect is achieved.
The content of sustainable materials in the sole material manufactured by the technical scheme of the invention can be greatly increased to more than 60% and up to 75% on the premise of ensuring the performance not to be lost. Sustainable materials refer to materials made from renewable/bio-based raw materials or from recycling of materials, in the present invention rubber powders, vegetable oils, rice hull ash carbon black, rosin resins, rice bran waxes and natural rubber.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a plot of the mixing of a section A of the batch of the present invention in example 1;
FIG. 2 is a plot of heat treatment B-stage mixing of the invention for example 1;
FIG. 3 is a final mix curve of example 1 of the present invention;
FIG. 4 is a plot of the mixing of a section A of comparative example 1 of the present invention;
FIG. 5 is a plot of the mixing of a section A of comparative example 3 of the present invention;
FIG. 6 is a heat treatment B-stage mixing curve of comparative example 3 of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the invention, the following detailed description refers to the specific implementation, structure, characteristics and effects of the invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
Referring to fig. 1-6, the graphs include speed, pressure, temperature and power curves. As can be seen from comparing the mixing curves of example 1 and comparative example 1, the use of sunflower seed oil instead of the conventionally used petrochemical oil can reduce the mixing time by at least 1 half, thus improving the production efficiency, and can improve the flexibility of the rubber at low temperature, thereby improving the wet skid resistance and the snowfield skid resistance of the sole.
The invention enables the formula to be more environment-friendly and reduces carbon by selecting the bio-based material and the reclaimed material on the premise of not losing the performance of the product.
The invention is further illustrated by the following specific examples and comparative examples:
example 1.
Weighing the following raw materials in parts by weight:
50kg of natural rubber, 25kg of butadiene rubber, 25kg of styrene-butadiene rubber, 30kg of sunflower seed oil, 45kg of rice hull ash white carbon black, 4.5kg,PEG 400 4.5kg kg of Si69 coupling agent, 30kg of rubber powder, 3kg of rosin resin, 0.5kg of antioxidant 6PPD, 0.5kg of antioxidant RD, 1.5kg of rice bran wax, 1.5kg of sulfur, 2kg of accelerator DPG, 1.5kg of accelerator CBS, 5kg of stearic acid and 1.5kg of zinc oxide.
The preparation method of the environment-friendly sole material comprises the following steps: after weighing all materials, setting the rotating speed of an internal mixer to 70rpm, adding natural rubber, styrene-butadiene rubber, sunflower seed oil, rice hull ash white carbon black, si69 coupling agent, polyethylene glycol PEG 400, rubber powder with the particle size of 300 meshes recovered from rubber soles, rosin resin, an anti-aging agent 6PPD, an anti-aging agent RD, rice bran wax, stearic acid and zinc oxide into the internal mixer, keeping for 30 seconds, then adjusting the rotating speed to 80rpm, keeping for 120 seconds at the temperature of 140 ℃, discharging rubber to obtain a rubber material, and standing the rubber material for 3 minutes; this stage was a batch A, and the mixing curve is shown in FIG. 1.
Rotating the internal mixer to 70rpm, adding sizing material into the internal mixer, reducing the rotating speed to 50rpm when the temperature of the sizing material is 150 ℃, keeping the temperature of the sizing material between 150 and 160 ℃ for 120 seconds, discharging the sizing material again to obtain master batch, and naturally cooling the master batch to room temperature; this stage was a B-stage mixing, and the mixing curves are shown in FIG. 2.
Setting the rotation speed of an internal mixer to 65rpm, adding cooled masterbatch, adding sulfur, accelerator DPG and accelerator CBS, increasing the rotation speed to 70rpm, and discharging rubber when the temperature reaches 150 ℃ to obtain the sole material. This stage is the final mix, and the mixing curve is shown in FIG. 3.
Example 2.
Weighing the following raw materials in parts by weight:
20kg of natural rubber, 60kg of butadiene rubber, 5kg of styrene-butadiene rubber, 30kg of soybean oil, 20kg of cashew shell oil, 50kg of rice hull ash white carbon black, 4kg of Si75 coupling agent, 2kg of KH550 coupling agent, 5kg of dispersing agent PPG, 10kg of rubber powder, 6kg of rosin resin, 3kg of antioxidant DTPD, 2kg of antioxidant SP, 4kg of sulfur, 5kg of accelerator TBBS, 3kg of stearic acid and 1kg of zinc oxide.
The preparation method of the environment-friendly sole material comprises the following steps: after weighing all materials, setting the rotating speed of an internal mixer to be 60rpm, adding rubber powder with the particle size of 200 meshes, rosin resin, an anti-aging agent DTPD, an anti-aging agent SP, stearic acid and zinc oxide, which are obtained by recycling rubber soles, into the internal mixer, and then, adjusting the rotating speed to 90rpm, keeping the temperature at 120 ℃ for 180 seconds, discharging rubber to obtain rubber material, and standing the rubber material for 2 minutes; this stage is the A-stage rubber mixing.
Rotating the internal mixer to 80rpm, adding sizing material into the internal mixer, reducing the rotating speed to 40rpm when the temperature of the sizing material is 150 ℃, keeping the temperature of the sizing material between 150 and 160 ℃ for 60 seconds, discharging the sizing material again to obtain master batch, and naturally cooling the master batch to room temperature; this stage is a B-stage rubber mixing.
Setting the rotation speed of an internal mixer to 75rpm, adding cooled masterbatch, adding sulfur and a accelerator TBBS, increasing the rotation speed to 80rpm, and discharging rubber when the temperature reaches 150 ℃ to obtain the sole material. This stage is the final mix.
Example 3.
Weighing the following raw materials in parts by weight:
60kg of natural rubber, 20kg of butadiene rubber, 20kg of styrene-butadiene rubber, 10kg of rice hull ash white carbon black, 1kg,PEG 400 4kg,PPG 0.5kg kg of Si747 coupling agent, 0.5kg of fatty alcohol ethoxylate, 50kg of rubber powder, 0.5kg of rosin resin, 1kg of anti-aging agent BHT, 1.8kg of sulfur, 1.2kg of accelerator CBS, 1.5kg of accelerator TBBS, 0.5kg of stearic acid and 5kg of zinc oxide.
The preparation method of the environment-friendly sole material comprises the following steps: after weighing all materials, setting the rotating speed of an internal mixer to 80rpm, adding natural rubber, styrene-butadiene rubber, soybean oil, palm oil, cashew shell oil, rice hull ash white carbon black, si747 coupling agent, polyethylene glycol PEG 400, PPG, fatty alcohol ethoxylate, rubber powder with the particle size of 300 meshes obtained by recycling waste tires, rosin resin, an anti-aging agent BHT, stearic acid and zinc oxide into the internal mixer, keeping for 50 seconds, then adjusting the rotating speed to 70rpm, keeping for 60 seconds at 160 ℃, discharging rubber to obtain rubber material, and standing the rubber material for 4 minutes; this stage was a batch A, and the mixing curve is shown in FIG. 1.
Rotating the internal mixer to 60rpm, adding sizing material into the internal mixer, reducing the rotating speed to 60rpm when the temperature of the sizing material is 150 ℃, keeping the temperature of the sizing material between 150 and 160 ℃ for 130 seconds, discharging the sizing material again to obtain master batch, and naturally cooling the master batch to room temperature; this stage is a B-stage rubber mixing.
Setting the rotation speed of an internal mixer to 55rpm, adding cooled masterbatch, adding sulfur, a promoter CBS and a promoter TBBS, increasing the rotation speed to 75rpm, and discharging rubber when the temperature reaches 150 ℃ to obtain the sole material. This stage is the final mix.
Comparative example 1.
Weighing the following raw materials in parts by weight:
50kg of natural rubber, 25kg of butadiene rubber, 25kg of styrene-butadiene rubber, 30kg of naphthenic oil, 45kg of rice hull ash white carbon black, 4.5kg,PEG 400 4.5kg kg of Si69 coupling agent, 30kg of rubber powder, 3kg of rosin resin, 1kg of antioxidant 6PPD, 0.5kg of antioxidant RD, 1kg of rice bran wax, 1.5kg of sulfur, 2kg of accelerator DPG, 1.5kg of accelerator CBS, 5kg of stearic acid and 1.5kg of zinc oxide.
The method for preparing the environment-friendly sole material by using the traditional raw materials comprises the following steps: after weighing all materials, adding natural rubber, styrene-butadiene rubber, naphthenic oil, traditional white carbon black, si69 coupling agent, PEG 400, rubber powder with particle size of 300 meshes recovered from rubber soles, C9 resin, anti-aging agent 6PPD, anti-aging agent RD, paraffin, stearic acid and zinc oxide into an internal mixer for mixing, keeping the rotating speed at 70rpm for 60 seconds, then reducing the rotating speed to 60rpm, keeping the rotating speed at 160 ℃ for 270 seconds, discharging rubber to obtain rubber material, standing the rubber material for 3 minutes, wherein the mixing curve is shown in figure 4.
Rotating the internal mixer to 70rpm, adding sizing material into the internal mixer, reducing the rotating speed to 50rpm when the temperature of the sizing material is 160 ℃, keeping the temperature of the sizing material between 150 and 160 ℃ for 120 seconds, discharging the sizing material again to obtain master batch, and naturally cooling the master batch to room temperature;
setting the rotation speed of an internal mixer to 65rpm, adding cooled masterbatch, adding sulfur, accelerator DPG and accelerator CBS, increasing the rotation speed to 70rpm, and discharging rubber when the temperature reaches 150 ℃ to obtain the sole material.
Comparative example 2.
Weighing the following raw materials in parts by weight:
50kg of natural rubber, 25kg of butadiene rubber, 25kg of styrene-butadiene rubber, 30kg of sunflower seed oil, 45kg of rice hull ash white carbon black, 4.5kg,PEG 400 4.5kg kg of Si69 coupling agent, 60kg of rubber powder, 3kg of rosin resin, 1kg of antioxidant 6PPD, 0.5kg of antioxidant RD, 1kg of rice bran wax, 1.5kg of sulfur, 2kg of accelerator DPG, 1.5kg of accelerator CBS, 5kg of stearic acid and 1.5kg of zinc oxide.
The preparation method of the sole material of this comparative example using a large amount of reclaimed rubber powder was the same as that of example 1.
Comparative example 3.
Weighing the following raw materials in parts by weight:
20kg of natural rubber, 40kg of styrene-butadiene rubber, 40kg of sunflower seed oil, 5kg of rice hull ash carbon black, 400 kg of PEG (polyethylene glycol) 400, 20kg of rubber powder, 2.5kg of rosin resin, 0.5kg of antioxidant SP-P, 1kg of antioxidant RD, 2kg of sulfur, 2kg of accelerator TBBS, 2.5kg of stearic acid and 2.5kg of zinc oxide.
The preparation method of the sole material comprises the following steps: after weighing all materials, adding natural rubber, styrene-butadiene rubber, naphthenic oil, traditional white carbon black, PEG 400, rubber powder, C9 resin, an anti-aging agent SP-P, an anti-aging agent RD, stearic acid and zinc oxide into an internal mixer for mixing, keeping the mixture for 30 seconds at a rotating speed of 70rpm, then reducing the rotating speed to 65rpm, discharging rubber when the waiting time reaches 360 seconds, and standing the obtained master batch for 5 minutes; this stage was a batch A, and the mixing curve is shown in FIG. 5.
The internal mixer was set at 65rpm, and the above master batch, sulfur and accelerator were charged, and the rotational speed was increased to 70rpm, and when the time reached 180 seconds, rubber was discharged to obtain a sole material, which was a B-stage rubber batch, and the kneading curve was as shown in FIG. 6.
The formulations for the above examples are summarized in Table 1, with performance versus Table 2.
The invention aims to solve the problems of climate and environment faced by the prior art, and breaks through the application precedent of sustainable materials, especially biological base materials, in sole formulations. In example 1, the total sustainable material content of the formulation is up to 75% (reference to the conventional formulation of comparative example 1, 58% of the total sustainable material content of the formulation) by using bio-based materials including natural rubber, rice hull ash carbon black, sunflower seed oil, rosin resin, rice bran wax, etc., so that the material properties are not changed. The present invention has found that the use of sunflower oil instead of naphthenic oil can reduce the mixing time by about one and a half minutes. The rice husk ash white carbon black is used for replacing the traditional white carbon black, the performance of the material is kept unchanged, and the rebound resilience is slightly improved. Moreover, the glass transition temperature of the sunflower seed oil is lower, namely-100 ℃, which is far lower than that of naphthenic oil (-50 ℃), so that the low-temperature flexibility and the wet skid resistance of the material are slightly improved, and the sunflower seed oil has the advantages of short processing time and high anti-skid coefficient. In example 3, a large amount of rubber powder was used, although the physical properties thereof were slightly degraded, and the M300 modulus value was not obtained (sample fracture was earlier than 300% strain). However, by adding a large amount of rubber powder, the cost of this embodiment is greatly reduced. Meanwhile, because the rubber powder has residual processing oil and anti-aging agent, the dosage of the anti-aging agent in the embodiment can be correspondingly reduced, and the processing oil can not be added independently.
The reinforcing agent of comparative example 3 was added in a small amount, the sustainable material content was small, and no coupling agent was used, although the coupling reaction was reduced by one step (two minutes time) in the process, the physical properties of the product were significantly lower than in the other examples, only slightly better rebound resilience due to the small filler content of the sample and the large rubber content.
TABLE 1
| Raw materials | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Natural rubber | 50 | 20 | 60 | 50 | 50 | 20 |
| Butadiene rubber | 25 | 60 | 20 | 25 | 25 | 40 |
| Styrene-butadiene rubber | 25 | 5 | 20 | 25 | 25 | 40 |
| White carbon black | 45 | 50 | 10 | 45 | 45 | 5 |
| Coupling agent | 4.5 | 6 | 1 | 4.5 | 4.5 | 0 |
| Dispersing agent | 4.5 | 5 | 5 | 4.5 | 4.5 | 1 |
| Processing oil | 30 | 50 | - | 30 | 30 | 40 |
| Rubber powder | 30 | 10 | 50 | 30 | 60 | 20 |
| Stearic acid | 5 | 3 | 0.5 | 5 | 5 | 2.5 |
| Zinc oxide | 1.5 | 1 | 5 | 1.5 | 1.5 | 2.5 |
| Resin composition | 3 | 6 | 0.5 | 3 | 3 | 2.5 |
| Anti-aging agent | 2.5 | 5 | 1 | 2.5 | 2.5 | 1.5 |
| S | 1.5 | 4 | 1.8 | 1.5 | 1.5 | 2 |
| DPG | 2 | - | - | 2 | 2 | - |
| CBS | 1.5 | - | 1.2 | 1.5 | 1.5 | - |
| TBBS | - | 5 | 1.5 | - | - | 2 |
| Totals to | 231.0 | 230.0 | 177.5 | 231.0 | 261.0 | 179.0 |
TABLE 2
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (10)
1. An environment-friendly sole material is characterized by comprising the following raw materials in parts by weight: 20-60 parts of natural rubber, 20-60 parts of butadiene rubber, 5-50 parts of styrene-butadiene rubber, 0-50 parts of processing oil, 10-50 parts of reinforcing agent, 1-6 parts of coupling agent, 1-5 parts of dispersing agent, 10-50 parts of rubber powder, 0.5-6 parts of tackifier, 1-5 parts of anti-aging agent, 1-4 parts of vulcanizing agent, 1-5 parts of accelerator, 0.5-5 parts of stearic acid and 1-5 parts of zinc oxide.
2. The environmentally friendly sole material of claim 1 wherein the processing oil is a vegetable oil selected from at least one of soybean oil, palm oil, rapeseed oil, sunflower oil, coconut oil and cashew nut shell oil.
3. The environmentally friendly sole material of claim 1 wherein the reinforcing agent is rice hull ash carbon black.
4. An environmentally friendly sole material according to claim 1, wherein the coupling agent is selected from at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide (Si 69), bis- [ gamma- (triethoxysilane) propyl ] disulfide (Si 75), 3-mercaptopropyl-ethoxy-bis (tridecyl-pentaethoxy-siloxane) (Si 747) and gamma-aminopropyl triethoxysilane (KH 550).
5. The environmentally friendly sole material of claim 1 wherein the dispersant is selected from at least one of polyethylene glycol (PEG), polypropylene glycol (PPG) and fatty alcohol ethoxylate.
6. The environmentally friendly sole material according to claim 1, wherein the rubber powder is rubber sole or tire reclaimed rubber powder, and the particle size of the rubber powder is at least 200 meshes.
7. The environmentally friendly sole material of claim 1 wherein the tackifier is rosin resin; the vulcanizing agent is sulfur.
8. The environmentally friendly sole material according to claim 1, wherein the anti-aging agent is at least one of 2, 6-di-t-butyl-p-methylphenol (BHT), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (6 PPD), N' -bis (methylphenyl) -1, 4-phenylenediamine (DTPD), 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), vinylated phenol (SP) and wax;
the accelerator is at least one selected from thiazoles, sulfenamides, guanidine, thiurams and dithiocarbamates.
9. The environmentally friendly sole material according to claim 8, wherein the thiazole is dibenzothiazyl disulfide MBT;
the sulfenamides are N-cyclohexyl-2-benzothiazole sulfenamide CBS and N-tertiary butyl-2-benzothiazole sulfenamide TBBS;
the guanidine is diphenylguanidine DPG;
the thiurams are tetramethylthiuram disulfide TMTD;
the dithiocarbamate is zinc dimethyldithiocarbamate PZ.
10. A method for preparing the environment-friendly sole material according to any one of claims 1 to 9, comprising the steps of:
s1, weighing raw materials according to a formula;
s2, setting the rotating speed of an internal mixer to be 60-80rpm, adding all raw materials except a vulcanizing agent and an accelerator into the internal mixer, keeping for at least 30 seconds, then adjusting the rotating speed to be 70-90rpm, keeping for 60-180 seconds at the temperature of 120-160 ℃, discharging glue to obtain a glue stock, and standing the glue stock for at least two minutes;
s3, rotating the internal mixer to 60-80rpm, adding sizing material into the internal mixer, reducing the rotating speed to 40-60rpm when the temperature of the sizing material is 150 ℃, keeping the temperature of the sizing material between 150-160 ℃ for at least 60 seconds, discharging the sizing material to obtain master batch, and cooling the master batch to room temperature;
s4, setting the rotating speed of the internal mixer to 55-75rpm, adding the cooled masterbatch, then adding the vulcanizing agent and the accelerator, increasing the rotating speed to 70-80rpm, and discharging the rubber when the time reaches 180 seconds or the temperature reaches 150 ℃ to obtain the sole material.
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| CN117887153B (en) * | 2024-01-31 | 2024-11-08 | 广州市政鑫橡塑有限公司 | Environment-friendly sole rubber composition and preparation method thereof |
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