WO2022134121A1 - 一种环保型再生橡胶制备方法 - Google Patents
一种环保型再生橡胶制备方法 Download PDFInfo
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- WO2022134121A1 WO2022134121A1 PCT/CN2020/139765 CN2020139765W WO2022134121A1 WO 2022134121 A1 WO2022134121 A1 WO 2022134121A1 CN 2020139765 W CN2020139765 W CN 2020139765W WO 2022134121 A1 WO2022134121 A1 WO 2022134121A1
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- parts
- reclaimed rubber
- activator
- rubber
- temperature
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000011069 regeneration method Methods 0.000 claims abstract description 36
- 230000008929 regeneration Effects 0.000 claims abstract description 35
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 20
- 230000023556 desulfurization Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000010920 waste tyre Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000012190 activator Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 28
- -1 amine compound Chemical class 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 230000003712 anti-aging effect Effects 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000010692 aromatic oil Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- BWQPMWNSLVMCLS-UHFFFAOYSA-N 2-methoxy-n-[4-(trifluoromethyl)phenyl]benzamide Chemical compound COC1=CC=CC=C1C(=O)NC1=CC=C(C(F)(F)F)C=C1 BWQPMWNSLVMCLS-UHFFFAOYSA-N 0.000 claims description 7
- 239000011280 coal tar Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- JHJHDEZWUNCTQO-UHFFFAOYSA-N 2-prop-2-enylsulfanyl-1h-benzimidazole Chemical compound C1=CC=C2NC(SCC=C)=NC2=C1 JHJHDEZWUNCTQO-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical compound [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 claims description 3
- BIIYNBBOZKYDQE-UHFFFAOYSA-N ethyl 2-(1h-benzimidazol-2-ylsulfanyl)propanoate Chemical compound C1=CC=C2NC(SC(C)C(=O)OCC)=NC2=C1 BIIYNBBOZKYDQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract description 2
- 239000008158 vegetable oil Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 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 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 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 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/26—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L17/00—Compositions of reclaimed rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the invention relates to the field of rubber material preparation, in particular to a preparation method of environmentally friendly recycled rubber.
- CN101220178A provides a method for preparing recycled rubber which can improve the tensile strength of recycled rubber and can effectively remove its unpleasant smell. It is made by crushing waste vulcanized rubber and separating it by magnetic separation to obtain rubber powder, which is then dynamically desulfurized and refined. During the dynamic desulfurization step, 12.3-15.0g of tall oil, 6.6-8.1g of coal tar pitch, and 100g of rubber powder are added to each 100g of rubber powder. De-Link additive 0.53-0.64g, rosin 1.64-2.0g, water 9.8-12.0g, steam pressure 0.6-1.0MPa, holding time 20-40 minutes.
- CN104629137A discloses a preparation method of reclaimed rubber, which relates to the technical field of reclaimed rubber production.
- the preparation method of the reclaimed rubber of the present invention is as follows: cleaning waste rubber, drying, cutting rubber, pulverizing, passing through a molecular sieve to obtain rubber powder; mixing a certain quality of N-methyldiethanolamine and a benzene series compound uniformly, then adding iron oxide, Heat preservation to obtain a desulfurizing agent; transfer the rubber powder into an ultrasonic extractor, then add a desulfurizing agent and a softening agent dropwise, stir evenly, ultrasonically assisted desulfurization, and press the obtained product into tablets to obtain reclaimed rubber.
- the invention adopts the method of ultrasonic-assisted desulfurizer for desulfurization, which has a low action temperature, avoids the shortcomings that high temperature easily breaks carbon-carbon bonds and reduces the performance of reclaimed rubber, and has short desulfurization time, good desulfurization effect and excellent reclaimed rubber performance.
- CN107417964A discloses a method for preparing reclaimed rubber, which comprises uniformly mixing 98-102 parts by weight of waste tire rubber powder, 4-8 parts by weight of regeneration activator, 6-12 parts by weight of paraffin oil and 1-4 parts by weight of anti-aging agent, Add to the reaction kettle for reaction, the reaction temperature is 120-160 °C, and the reaction time is 2-4 hours; then banburying is carried out, the banburying temperature is 130-190 °C, the time is 8-12 minutes, and the rotation speed is 60-100 rpm /minute.
- the method for preparing the reclaimed rubber of the invention has the advantages of low cost and high recycling rate, and the reclaimed rubber obtained by the method has excellent anti-aging properties and mechanical properties.
- reclaimed rubber occupies an important position in the raw rubber formulation system. Although the addition of reclaimed rubber will reduce the physical and mechanical properties of raw rubber, it can provide characteristics that raw rubber does not have. The addition of reclaimed rubber can shorten the mixing time and increase the feeding speed of extrusion and calendering. During vulcanization, the reclaimed rubber can act as an anti-aging agent.
- the main regeneration methods such as water-oil method and dynamic continuous desulfurization method have large pollution, long time and high energy consumption.
- the widely used regeneration activator such as polyalkylphenol disulfide has certain toxicity. Regardless of the global development trend or the carrying capacity of the ecological environment, my country cannot continue to rely on this extensive method to achieve efficient resource utilization and recycling.
- the present invention provides an environment-friendly method for preparing recycled rubber.
- a kind of environment-friendly reclaimed rubber preparation method, its concrete scheme is as follows:
- the parts by mass 100-120 parts of waste tire rubber powder and 0.5-1.1 parts of peptizer are mixed uniformly, and then added to the reaction kettle for reaction, the reaction temperature is 100-130 °C, and the reaction time is 60-120min; After completion, the cooling water is cooled, and the temperature of the material in the reaction kettle is lowered to 60-80 ° C, and then 6-12 parts of regeneration activator, 0.2-5 parts of aromatic oil, 0.8-2.4 parts of zinc oxide, 0.3-1.2 parts of regenerating activator are added.
- organic acid, 0.2-0.6 part of amine compound and 0.4-0.7 part of anti-aging agent are stirred at 80-200 r/min for 5-10 minutes; after mixing evenly, they are added to the internal mixer for internal mixing and desulfurization.
- the internal mixing temperature is 150-175° C.
- the time is 5-15 min
- the speed of the internal mixer is 80-140 rpm. After completion, the environment-friendly reclaimed rubber can be obtained.
- Described regeneration activator is a kind of environment-friendly regeneration activator, and its preparation method is:
- the activator is 2-(allylthio)benzimidazole or 2-(thiobenzimidazole)acetic acid or ethyl 2-(benzimidazol-2-ylthio)propionate.
- the catalyst is copper chloride or zinc stearate or copper methacrylate.
- the organic acid is oxalic acid or malic acid or tartaric acid.
- the amine compound is hexamethylenetetramine or triethanolamine or diphenylguanidine.
- the present invention firstly reacts a small amount of peptizer with waste tire rubber powder to increase the fluidity of the rubber and its compatibility with the activating regenerating agent to achieve a better activation effect , greatly reduces the desulfurization time and desulfurization temperature, reduces energy consumption, and achieves the purpose of rapid desulfurization;
- the main component of an environmentally friendly regeneration activator provided by the present invention is natural vegetable oil, and no solvent is added during the preparation process, and waste water and waste gas are discharged.
- the activator used is also a non-toxic product, which meets the requirements of green, low-carbon and environmental protection.
- the regenerated rubber sol prepared by the method has high content, high regeneration degree, low Mooney viscosity of the product, significantly improved processing performance, and improved overall comprehensive performance. .
- Tensile strength performance test According to the "National Standard GB/T528-2009", the test is carried out with an electronic tensile testing machine, the tensile speed is 500mm/min, and the test temperature is room temperature.
- Sol content Weigh 10g of reclaimed rubber samples with a thickness of less than 2mm, wrap them with filter paper, put them in a Soxhlet extractor, extract them with acetone for 12 hours, take them out in a vacuum drying box, and dry them at 60°C to constant weight.
- a kind of environment-friendly reclaimed rubber preparation method, its concrete scheme is as follows:
- Described regeneration activator is a kind of environment-friendly regeneration activator, and its preparation method is:
- the activator is 2-(allylthio) benzimidazole.
- the catalyst is copper chloride.
- the organic acid is oxalic acid.
- the amine compound is hexamethylenetetramine.
- a kind of environment-friendly reclaimed rubber preparation method, its concrete scheme is as follows:
- Described regeneration activator is a kind of environment-friendly regeneration activator, and its preparation method is:
- the activator is 2-(thiobenzimidazole)acetic acid.
- the catalyst is zinc stearate.
- the organic acid is malic acid.
- the amine compound is triethanolamine.
- a kind of environment-friendly reclaimed rubber preparation method, its concrete scheme is as follows:
- Described regeneration activator is a kind of environment-friendly regeneration activator, and its preparation method is:
- the activator is ethyl 2-(benzimidazol-2-ylthio)propionate.
- the catalyst is copper methacrylate.
- the organic acid is tartaric acid.
- the amine compound is diphenylguanidine.
- a kind of environment-friendly reclaimed rubber preparation method, its concrete scheme is as follows:
- the activator is 2-(allylthio) benzimidazole.
- the catalyst is copper chloride.
- the organic acid is oxalic acid.
- the amine compound is hexamethylenetetramine.
- a kind of environment-friendly reclaimed rubber preparation method, its concrete scheme is as follows:
- Described regeneration activator is a kind of environment-friendly regeneration activator, and its preparation method is:
- the activator is 2-(allylthio) benzimidazole.
- the catalyst is copper chloride.
- the amine compound is hexamethylenetetramine.
- a kind of environment-friendly reclaimed rubber preparation method, its concrete scheme is as follows:
- Described regeneration activator is a kind of environment-friendly regeneration activator, and its preparation method is:
- the activator is 2-(allylthio) benzimidazole.
- the catalyst is copper chloride.
- the organic acid is oxalic acid.
Abstract
涉及橡胶材料制备领域,具体关于一种环保型再生橡胶制备方法;首先将少量的塑解剂与废旧轮胎胶粉反应,增加橡胶的流动性和其与活化再生剂的相容性,达到较好的活化效果,大幅度减少脱硫时间和降低脱硫温度,降低能耗,达到快速脱硫的目的;提供的一种环保再生活化剂主要成分为天然植物油,制备过程中也没有溶剂添加,无废水废气排放,采用的活化剂也属于无毒产品,符合绿色,低碳环保的要求。制备的再生橡胶溶胶含量高,再生程度高,产品的门尼粘度低,加工性能得到显著提高,整体的综合性能得到很好的提高,是一种由工业化前景的环保型再生橡胶制备方法。
Description
本发明涉及橡胶材料制备领域,尤其是一种环保型再生橡胶制备方法。
在天然橡胶资源日趋减少和能源相对紧缺的今天,废旧橡胶资源化研究具有重要的现实意义,生产再生胶是废旧橡胶循环利用的有效手段。
CN101220178A提供一种可以提高再生橡胶抗拉强度并能有效去除其难闻气味的再生橡胶制备方法。其是把废旧硫化橡胶粉碎后进行磁选分离得胶粉,再动态脱硫、精炼而成,动态脱硫步骤时,每100g胶粉中,加入妥尔油12.3-15.0g、煤沥青6.6-8.1g、De-Link助剂0.53-0.64g、松香1.64-2.0g、水9.8-12.0g,蒸汽压力0.6-1.0MPa、保温时间20-40分钟。
CN104629137A公开了一种再生橡胶的制备方法,涉及再生胶生产技术领域。本发明再生橡胶的制备方法为:清洗废旧橡胶,晾干,切胶,粉碎,过分子筛,得到橡胶粉;将一定质量的N-甲基二乙醇胺和苯系物混合均匀,然后加入氧化铁,保温,得到脱硫剂;将橡胶粉转入超声波萃取仪中,然后逐滴加入脱硫剂和软化剂,搅拌均匀,超声波辅助脱硫,将所得产物压片,即得到再生胶。该发明采用超声波辅助脱硫剂的方法进行脱硫,其作用温度低,避免高温易使碳-碳键断裂、使再生胶的性能下降的缺点,脱硫时间短,脱硫效果好、再生胶性能优良。
CN107417964A公开了一种再生橡胶制备方法,将98-102重量份废旧轮胎胶粉、4-8重量份再生活化剂、6-12重量份石蜡油和1-4重量份抗老化剂混合均匀,加入到反应釜中反应,反应温度为120-160℃,反应时间为2-4小时;再进行密炼,密炼温度为130-190℃,时间为8-12分钟,转速为60-100转/分钟。该发明所述再生橡胶制备方法,成本低,回收利用率高,采用该方法得到的再生橡胶具有优良的抗老化性能和力学性能。
再生胶作为填充剂在生胶配方体系中占有重要的地位。再生胶的添加虽然会使得生胶的物理机械性能下降,但却可以提供生胶所没有的特点。再生胶的加入可缩短混炼时间,提高挤出压延的供料速度,在硫化时,再生胶可起到抗老化剂的作用,然而在生产再生胶的过程中也存在很多不足和困难。主要的再生方法如水油法,动态连续脱硫法等生产过程污染大、时间长、耗能高;此外,现在广泛应用的再生活化剂如多烷基苯酚二硫化物等有一定的毒性。无论是从全球发展态势还是生态环境承载能力看,我国都无法继续靠这种粗放式的方法实现资源高效利用和循环利用。
发明内容
为了解决上述问题,本发明提供了一种环保型再生橡胶制备方法。
一种环保型再生橡胶制备方法,其具体方案如下:
按照质量份数,将100-120份的废旧轮胎胶粉与0.5-1.1份的塑解剂混合均匀,然后加入到反应釜中反应,反应温度为100-130℃,反应时间为60-120min;完成后冷却水进行冷却,将反应釜中物料温度降至60-80℃后加入6-12份的再生活化剂,0.2-5份的芳烃油,0.8-2.4份的氧化锌,0.3-1.2份的有机酸,0.2-0.6份的胺类化合物和0.4-0.7份的抗老化剂以80-200转/分的转速搅拌5-10min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为150-175℃,时间为5-15min,密炼机转速为80-140转/分,完成后即可得到所述的一种环保型再生橡胶。
所述的再生活化剂为一种环保再生活化剂,其制备方法为:
按照质量份数,将38-62份的大豆油,5-9份的油烯基硫醇加入到反应釜中,加热升温到80-120℃没加入10-18份的煤焦油,搅拌混合10-30min后加入活化剂和0.01-0.05份的催化剂,在60-100℃下搅拌5-8min后升温到110-130℃,继续搅拌8-15min,然后降温到60-80℃,加入2.1-3.8份的高苯乙烯树脂和0.8-1.6份的(2,7-辛二烯-1-基)琥珀酸酐,保温搅拌10-60min后停止加热,继续搅拌至温度降温到室温后即可得到所述的一种环保再生活化剂。
所述的活化剂2-(烯丙基硫代)苯并咪唑或2-(硫代苯并咪唑)乙酸或2-(苯并咪唑-2-基硫代)丙酸乙酯。
所述的催化剂为氯化铜或硬脂酸锌或甲基丙烯酸铜。
所述的有机酸为草酸或苹果酸或酒石酸。
所述的胺类化合物为六次甲基四胺或三乙醇胺或二苯胍。
本发明的一种环保型再生橡胶制备方法,本发明首先将少量的塑解剂与废旧轮胎胶粉反应,增加橡胶的流动性和其与活化再生剂的相容性,达到较好的活化效果,大幅度减少脱硫时间和降低脱硫温度,降低能耗,达到快速脱硫的目的;本发明提供的一种环保再生活化剂主要成分为天然植物油,制备过程中也没有溶剂添加,物废水废气排放,采用的活化剂也属于无毒产品,符合绿色,低碳环保的要求。本发明制备的再生橡胶溶胶含量高,再生程度高,产品的门尼粘度低,加工性能得到显著提高,整体的综合性能得到很好的提高,是一种由工业化前景的环保型再生橡胶制备方法。
下面通过具体实施例对该发明作进一步说明:
拉伸强度性能测试:按照《国标GB/T528-2009》用电子拉力实验机进行测试,拉伸速度为500mm/min,测试温度为室温。溶胶含量:称量10g厚度小于2mm的再生胶试样用滤纸 包裹,放入索氏提取器中,先用丙酮抽提12小时,取出于真空干燥箱中,在60℃下干燥至恒重,称得质量m
1,然后再用甲苯抽提12h后,取出于真空干燥箱中,在60℃下干燥至恒重,立即称量得质量为m
2;则溶胶含量=(m
1-m
2)/m
1;溶胶含量越大,硫化橡胶三维交联网络结构的破坏程度越大,橡胶的再生程度越高。
实施例1
一种环保型再生橡胶制备方法,其具体方案如下:
按照质量份数,将100kg废旧轮胎胶粉与0.5kg塑解剂混合均匀,然后加入到反应釜中反应,反应温度为100℃,反应时间为60min;完成后冷却水进行冷却,将反应釜中物料温度降至60℃后加入6kg再生活化剂,0.2kg芳烃油,0.8kg氧化锌,0.3kg有机酸,0.2kg胺类化合物和0.4kg抗老化剂以80转/分的转速搅拌5min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为150℃,时间为5min,密炼机转速为80转/分,完成后即可得到所述的一种环保型再生橡胶。
所述的再生活化剂为一种环保再生活化剂,其制备方法为:
kg质量份数,将38kg大豆油,5kg油烯基硫醇加入到反应釜中,加热升温到80℃没加入10kg煤焦油,搅拌混合10min后加入活化剂和0.01kg催化剂,在60℃下搅拌5min后升温到110℃,继续搅拌8min,然后降温到60℃,加入2.1kg高苯乙烯树脂和0.8kg(2,7-辛二烯-1-基)琥珀酸酐,保温搅拌10min后停止加热,继续搅拌至温度降温到室温后即可得到所述的一种环保再生活化剂。
所述的活化剂2-(烯丙基硫代)苯并咪唑。
所述的催化剂为氯化铜。
所述的有机酸为草酸。
所述的胺类化合物为六次甲基四胺。
实施例2
一种环保型再生橡胶制备方法,其具体方案如下:
按照质量份数,将110kg废旧轮胎胶粉与0.8kg塑解剂混合均匀,然后加入到反应釜中反应,反应温度为120℃,反应时间为90min;完成后冷却水进行冷却,将反应釜中物料温度降至70℃后加入9kg再生活化剂,2.5kg芳烃油,1.4kg氧化锌,0.6kg有机酸,0.4kg胺类化合物和0.6kg抗老化剂以120转/分的转速搅拌8min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为165℃,时间为10min,密炼机转速为120转/分,完成后即可得到所述的一种环保型再生橡胶。
所述的再生活化剂为一种环保再生活化剂,其制备方法为:
kg质量份数,将46kg大豆油,7kg油烯基硫醇加入到反应釜中,加热升温到100℃没加入14kg煤焦油,搅拌混合20min后加入活化剂和0.03kg催化剂,在80℃下搅拌7min后升温到120℃,继续搅拌12min,然后降温到70℃,加入2.8kg高苯乙烯树脂和1.2kg(2,7-辛二烯-1-基)琥珀酸酐,保温搅拌30min后停止加热,继续搅拌至温度降温到室温后即可得到所述的一种环保再生活化剂。
所述的活化剂2-(硫代苯并咪唑)乙酸。
所述的催化剂为硬脂酸锌。
所述的有机酸为苹果酸。
所述的胺类化合物为三乙醇胺。
实施例3
一种环保型再生橡胶制备方法,其具体方案如下:
按照质量份数,将120kg废旧轮胎胶粉与1.1kg塑解剂混合均匀,然后加入到反应釜中反应,反应温度为130℃,反应时间为120min;完成后冷却水进行冷却,将反应釜中物料温度降至80℃后加入12kg再生活化剂,5kg芳烃油,2.4kg氧化锌,1.2kg有机酸,0.6kg胺类化合物和0.7kg抗老化剂以200转/分的转速搅拌10min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为175℃,时间为15min,密炼机转速为140转/分,完成后即可得到所述的一种环保型再生橡胶。
所述的再生活化剂为一种环保再生活化剂,其制备方法为:
kg质量份数,将62kg大豆油,9kg油烯基硫醇加入到反应釜中,加热升温到120℃没加入18kg煤焦油,搅拌混合30min后加入活化剂和0.05kg催化剂,在100℃下搅拌8min后升温到130℃,继续搅拌15min,然后降温到80℃,加入3.8kg高苯乙烯树脂和1.6kg(2,7-辛二烯-1-基)琥珀酸酐,保温搅拌60min后停止加热,继续搅拌至温度降温到室温后即可得到所述的一种环保再生活化剂。
所述的活化剂2-(苯并咪唑-2-基硫代)丙酸乙酯。
所述的催化剂为甲基丙烯酸铜。
所述的有机酸为酒石酸。
所述的胺类化合物为二苯胍。
所以上实施例所制备的再生橡胶的质量测试数据如下表所示:
拉伸强度(MPa) | 溶胶含量(%) | |
实施例1 | 8.6 | 21.87 |
实施例2 | 9.2 | 22.46 |
实施例3 | 9.4 | 23.08 |
对比例1
一种环保型再生橡胶制备方法,其具体方案如下:
按照质量份数,将100kg废旧轮胎胶粉与0.5kg塑解剂混合均匀,然后加入到反应釜中反应,反应温度为100℃,反应时间为60min;完成后冷却水进行冷却,将反应釜中物料温度降至60℃后加入6kg再生活化剂,0.2kg芳烃油,0.8kg氧化锌,0.3kg有机酸,0.2kg胺类化合物和0.4kg抗老化剂以80转/分的转速搅拌5min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为150℃,时间为5min,密炼机转速为80转/分,完成后即可得到所述的一种环保型再生橡胶。
所述的活化剂2-(烯丙基硫代)苯并咪唑。
所述的催化剂为氯化铜。
所述的有机酸为草酸。
所述的胺类化合物为六次甲基四胺。
对比例2
一种环保型再生橡胶制备方法,其具体方案如下:
按照质量份数,将100kg废旧轮胎胶粉与0.5kg塑解剂混合均匀,然后加入到反应釜中反应,反应温度为100℃,反应时间为60min;完成后冷却水进行冷却,将反应釜中物料温度降至60℃后加入6kg再生活化剂,0.2kg芳烃油,0.8kg氧化锌,0.2kg胺类化合物和0.4kg抗老化剂以80转/分的转速搅拌5min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为150℃,时间为5min,密炼机转速为80转/分,完成后即可得到所述的一种环保型再生橡胶。
所述的再生活化剂为一种环保再生活化剂,其制备方法为:
kg质量份数,将38kg大豆油,5kg油烯基硫醇加入到反应釜中,加热升温到80℃没加入10kg煤焦油,搅拌混合10min后加入活化剂和0.01kg催化剂,在60℃下搅拌5min后升温到110℃,继续搅拌8min,然后降温到60℃,加入2.1kg高苯乙烯树脂和0.8kg(2,7-辛二烯-1-基)琥珀酸酐,保温搅拌10min后停止加热,继续搅拌至温度降温到室温后即可得到所述的一种环保再生活化剂。
所述的活化剂2-(烯丙基硫代)苯并咪唑。
所述的催化剂为氯化铜。
所述的胺类化合物为六次甲基四胺。
对比例3
一种环保型再生橡胶制备方法,其具体方案如下:
按照质量份数,将100kg废旧轮胎胶粉与0.5kg塑解剂混合均匀,然后加入到反应釜中反应,反应温度为100℃,反应时间为60min;完成后冷却水进行冷却,将反应釜中物料温度降至60℃后加入6kg再生活化剂,0.2kg芳烃油,0.8kg氧化锌,0.3kg有机酸和0.4kg抗老化剂以80转/分的转速搅拌5min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为150℃,时间为5min,密炼机转速为80转/分,完成后即可得到所述的一种环保型再生橡胶。
所述的再生活化剂为一种环保再生活化剂,其制备方法为:
kg质量份数,将38kg大豆油,5kg油烯基硫醇加入到反应釜中,加热升温到80℃没加入10kg煤焦油,搅拌混合10min后加入活化剂和0.01kg催化剂,在60℃下搅拌5min后升温到110℃,继续搅拌8min,然后降温到60℃,加入2.1kg高苯乙烯树脂和0.8kg(2,7-辛二烯-1-基)琥珀酸酐,保温搅拌10min后停止加热,继续搅拌至温度降温到室温后即可得到所述的一种环保再生活化剂。
所述的活化剂2-(烯丙基硫代)苯并咪唑。
所述的催化剂为氯化铜。
所述的有机酸为草酸。
所以上对比例所制备的再生橡胶的质量测试数据如下表所示:
拉伸强度(MPa) | 溶胶含量(%) | |
对比例1 | 6.4 | 14.22 |
对比例2 | 7.5 | 18.63 |
对比例3 | 7.2 | 17.59 |
Claims (6)
- 一种环保型再生橡胶制备方法,其具体方案如下:按照质量份数,将100-120份的废旧轮胎胶粉与0.5-1.1份的塑解剂混合均匀,然后加入到反应釜中反应,反应温度为100-130℃,反应时间为60-120min;完成后冷却水进行冷却,将反应釜中物料温度降至60-80℃后加入6-12份的再生活化剂,0.2-5份的芳烃油,0.8-2.4份的氧化锌,0.3-1.2份的有机酸,0.2-0.6份的胺类化合物和0.4-0.7份的抗老化剂以80-200转/分的转速搅拌5-10min;混合均匀后在加入到密炼机中密炼脱硫,密炼温度为150-175℃,时间为5-15min,密炼机转速为80-140转/分,完成后即可得到所述的一种环保型再生橡胶。
- 根据权利要求1所述的一种环保型再生橡胶制备方法,其特征在于:所述的再生活化剂为一种环保再生活化剂,其制备方法为:按照质量份数,将38-62份的大豆油,5-9份的油烯基硫醇加入到反应釜中,加热升温到80-120℃没加入10-18份的煤焦油,搅拌混合10-30min后加入活化剂和0.01-0.05份的催化剂,在60-100℃下搅拌5-8min后升温到110-130℃,继续搅拌8-15min,然后降温到60-80℃,加入2.1-3.8份的高苯乙烯树脂和0.8-1.6份的(2,7-辛二烯-1-基)琥珀酸酐,保温搅拌10-60min后停止加热,继续搅拌至温度降温到室温后即可得到所述的一种环保再生活化剂。
- 根据权利要求2所述的一种环保型再生橡胶制备方法,其特征在于:所述的活化剂2-(烯丙基硫代)苯并咪唑或2-(硫代苯并咪唑)乙酸或2-(苯并咪唑-2-基硫代)丙酸乙酯。
- 根据权利要求2所述的一种环保型再生橡胶制备方法,其特征在于:所述的催化剂为氯化铜或硬脂酸锌或甲基丙烯酸铜。
- 根据权利要求1所述的一种环保型再生橡胶制备方法,其特征在于:所述的有机酸为草酸或苹果酸或酒石酸。
- 根据权利要求1所述的一种环保型再生橡胶制备方法,其特征在于:所述的胺类化合物为六次甲基四胺或三乙醇胺或二苯胍。
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