CN117844129A - Low-Mooney-viscosity butyl regenerated rubber and preparation method thereof - Google Patents
Low-Mooney-viscosity butyl regenerated rubber and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 121
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 50
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 44
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008117 stearic acid Substances 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000007670 refining Methods 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 31
- 239000002699 waste material Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003483 aging Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 125000003172 aldehyde group Chemical group 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 150000003904 phospholipids Chemical group 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 description 36
- 238000007599 discharging Methods 0.000 description 16
- 241001441571 Hiodontidae Species 0.000 description 10
- 238000010008 shearing Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- -1 shearing off patches Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-Mooney viscosity butyl regenerated rubber and a preparation method thereof, wherein calcium carbonate powder is used as a sacrificial template, silicon dioxide grows on the surface of the low-Mooney viscosity butyl regenerated rubber, then the calcium carbonate powder is etched through acid liquor to obtain hollow silicon dioxide microspheres, and the silicon dioxide microspheres are added in a banburying process to form a microsphere effect in the mixture, so that the mixture has higher fluidity, the Mooney viscosity of the rubber is quickly reduced, the plasticating effect of the regenerated rubber can be improved, and meanwhile, the energy consumption can be reduced; the surfactant stearic acid is adopted to modify the silica microspheres, so that the fluidity of the silica microspheres in the mixture is enhanced, meanwhile, the stearic acid can also lubricate the chain between butyl rubber molecular chains, inhibit the reactions of functional groups such as phospholipid groups, aldehyde groups and the like, and delay the cross-linking between rubber hydrocarbon macromolecules, thereby further reducing the Mooney viscosity of the rubber.
Description
Technical Field
The invention relates to the technical field of vulcanized rubber regeneration, in particular to low-Mooney-viscosity butyl regenerated rubber and a preparation method thereof.
Background
The production of the regenerated rubber is a main force army for comprehensive recycling of the waste rubber in China, the regenerated rubber also has good cost performance, and the method is a very effective method for turning waste rubber into wealth. The butyl rubber has good air tightness and water tightness, and is widely used for manufacturing various rubber products such as inner tubes of automobiles, sound insulation materials, building waterproof coiled materials and the like. The butyl regenerated rubber is a recycling resource for recycling and reprocessing butyl rubber, reserves certain plasticity and physical properties, is easy to mix with raw rubber, has good processing property, can replace or partially replace butyl rubber in rubber products, reduces the cost of rubber materials, improves the processing technical properties of the rubber materials, relieves the gap of domestic requirements for butyl rubber, and also plays a role in treating the environmental pollution of waste butyl rubber. In recent years, with the change of market demands, automobile inner tubes are gradually banned by vacuum inner tubes, part of butyl regenerated rubber is changed into materials for manufacturing inner liners of the automobile inner tubes, and the Mooney requirement range of the butyl regenerated rubber is changed from 50+/-10 to 30+/-10. The substantial reduction in the required range of mooney values becomes a significant difficulty in the production process of butyl reclaimed rubber. The industry of comprehensive recycling of waste rubber is constantly exploring and developing novel equipment and technology to produce low-Mooney (range 30+/-10) butyl reclaimed rubber products. The double screw extruder can produce butyl regenerated rubber with low Mooney (range 30+/-10) products, but has great defects at present.
The existing production technical scheme of the butyl regenerated rubber product is a high-temperature dynamic regeneration method, and mainly uses high temperature and strong shearing to break the chain of the waste butyl rubber under the action of heat and mechanical force, so as to achieve the purpose of regeneration. The process mainly comprises the following steps: selecting high-quality waste butyl inner tube, finishing, washing rubber, coarse crushing and granulating, high-temperature regenerating (plasticizing), banburying, refining, filtering rubber and forming.
The production mode of the butyl regenerated rubber controls the rubber material Mooney through plasticizing temperature adjustment in the high-temperature regeneration step. When the temperature is higher, the Mooney of the plasticized sizing material is lower, and the physical property index of the sizing material is seriously damaged. The temperature and the physical property balance of the sizing material are required to be achieved, the temperature is 220 ℃ to 250 ℃ generally, so that qualified sizing material physical property indexes can be preserved, but the Mooney value is 50 to 60. Through the subsequent refining thin pass, the rubber material Mooney can only be reduced by about 3, and the low Mooney (30+/-10) product requirement of the butyl rubber can not be met.
According to the defect improvement of the original production mode, a double-screw extruder for producing low-Mooney products of butyl regenerated rubber appears on the market, the equipment uses the double-screw extruder to further heat and shear the rubber after the rubber is regenerated (plasticized) at high temperature, so that C-S bonds and S-S bonds of the rubber are further broken to improve the fluidity of the rubber, the effect of reducing the Mooney of the product is achieved, however, the physical properties of the rubber are further damaged due to the further heating of the rubber by the equipment, and the physical indexes of the rubber are unqualified after the Mooney value is reduced. The method has the defects of high equipment cost, high energy consumption, low yield, poor physical property indexes of products, the requirement of adding the original rubber (butyl rubber) to improve the physical property indexes of the products and the like.
At present, no better technology is available for producing low-Mooney (30+/-10) butyl regenerated rubber, if the defect can be solved, the technology breaks through the butyl regenerated rubber industry greatly, and the technology adds power for recycling economy of waste rubber and relieves the gap of the demand of China for butyl rubber.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the low-Mooney-viscosity butyl regenerated rubber and the preparation method thereof, and the Mooney viscosity of the butyl regenerated rubber is effectively reduced on the premise of ensuring the physical properties of the butyl regenerated rubber.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the low-Mooney viscosity butyl regenerated rubber comprises the steps of taking a waste butyl rubber inner tube as a raw material, washing rubber, crushing, plasticizing, banburying, refining, filtering, forming and metering and packaging to obtain the butyl regenerated rubber, and adding auxiliary agent modified silicon dioxide into the plasticized waste butyl rubber inner tube rubber material in the banburying process.
Preferably, the preparation method of the modified silicon dioxide comprises the following steps:
s1, dispersing nano calcium carbonate in an ethanol solvent, then adding an ethyl orthosilicate solution into the ethanol solvent, stirring the mixture uniformly, then adding an ammonia water solution, adjusting the pH of the solution to 8.5-10, stirring the mixture for 3-5 hours, standing the mixture for ageing, and filtering, washing and drying the mixture to obtain white powder;
s2, immersing the white powder into a dilute nitric acid solution, stirring for 30-60min, filtering, washing and drying to obtain hollow silica microspheres;
and S3, mixing the hollow silica microspheres with stearic acid, and then placing the mixture in a ball mill for ball milling, and obtaining the modified silica after ball milling is finished.
Preferably, in the step S1, the mass ratio of the nano calcium carbonate to the ethanol to the tetraethyl orthosilicate solution is 1-2:60-80:40-60.
Preferably, in the step S1, the mass ratio of the ethyl orthosilicate, the ethanol and the water in the ethyl orthosilicate solution is 20-40:40-50:20-30.
Preferably, in step S3, the mass ratio of hollow silica microspheres to stearic acid is 20-30:1-2.
Preferably, the mass ratio of the plasticized waste butyl rubber inner tube rubber material to the modified silicon dioxide is 100:1-5.
Preferably, the waste butyl rubber inner tube is ground and crushed into colloidal particles with the granularity of 0.18-0.425cm by a crusher.
Preferably, the banburying temperature is 100-180 ℃ and the banburying time is 20-40min.
Preferably, in the glue filtering process, a glue filter is adopted for filtering, and the size of a sieve hole of a filter screen on the glue filter is 0.15-0.18mm.
The invention also provides the low-Mooney-viscosity butyl reclaimed rubber prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the calcium carbonate powder is used as a sacrificial template, silicon dioxide grows on the surface of the silicon dioxide powder, then the calcium carbonate powder is etched through acid liquor to obtain hollow silicon dioxide microspheres, the surfaces of the silicon dioxide microspheres are rich in silicon hydroxyl groups, the silicon hydroxyl groups and carboxyl groups in stearic acid are combined through hydrogen bonds, stearic acid is further loaded on the surfaces and pore structures of the silicon dioxide microspheres, and the silicon dioxide microspheres are added in a banburying process to form a microsphere effect in the mixture, so that the mixture has higher fluidity, the Mooney viscosity of the rubber is quickly reduced, the plasticating effect of the reclaimed rubber can be improved, and the effect of reducing energy consumption can be played.
(2) According to the invention, the surfactant stearic acid is adopted to modify the silica microspheres, so that the fluidity of the silica microspheres in the mixture is enhanced, meanwhile, the stearic acid can also lubricate the chain connection between butyl rubber molecular chains, inhibit the reactions of functional groups such as phospholipid groups, aldehyde groups and the like, and delay the cross-linking between rubber hydrocarbon macromolecules, thereby further reducing the Mooney viscosity of the rubber.
(3) The invention changes the original production principle of the butyl regenerated rubber industry, breaks through a plurality of defects of the original production principle, saves energy, can improve the yield of the butyl regenerated rubber, and plays a role in promoting the recycling of waste butyl rubber.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
The particle size of the nano calcium carbonate used in the invention is 20-40nm.
Example 1
The preparation method of the low-Mooney-viscosity butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer, 1 part of auxiliary agent modified silicon dioxide is added into 100 parts of butyl rubber inner tube rubber powder in the banburying process, the banburying temperature is 160 ℃, the banburying time is 30min, the rubber powder is refined twice by a refiner after the banburying is finished, the refining thickness of the first refining time is 0.25mm, and the refining thickness of the second refining time is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; discharging and shaping the filtered sizing material by a sheet discharging machine to obtain the low-Mooney-viscosity butyl regenerated rubber;
the preparation method of the modified silicon dioxide comprises the following steps:
s1, dispersing 1g of nano calcium carbonate in 60g of ethanol solvent, then adding 40g of tetraethoxysilane solution (the mass ratio of tetraethoxysilane to ethanol to water is 30:40:30), uniformly stirring, then adding 25wt% ammonia water solution, adjusting the pH of the solution to 9.0, stirring for 4 hours, standing and aging for 24 hours, and filtering, washing and drying to obtain white powder;
s2, immersing the white powder into a dilute nitric acid solution with the concentration of 0.5mol/L, stirring for 60min, filtering, washing and drying to obtain hollow silica microspheres;
s3, mixing 20g of hollow silica microspheres with 1g of stearic acid, and then placing the mixture into a ball mill for ball milling, wherein the ball milling speed is 600r/min, the ball milling time is 3h, and the modified silica is obtained after the ball milling is finished.
Example 2
The preparation method of the low-Mooney-viscosity butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer, in the banburying process, 2 parts of auxiliary agent modified silicon dioxide is added into 100 parts of butyl rubber inner tube rubber powder, the banburying temperature is 160 ℃, the banburying time is 30min, the rubber powder is refined twice by a refiner after the banburying is finished, the refining thickness of the first refining time is 0.25mm, and the refining thickness of the second refining time is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; discharging and shaping the filtered sizing material by a sheet discharging machine to obtain the low-Mooney-viscosity butyl regenerated rubber;
the preparation method of the modified silicon dioxide comprises the following steps:
s1, dispersing 1g of nano calcium carbonate in 60g of ethanol solvent, then adding 40g of tetraethoxysilane solution (the mass ratio of tetraethoxysilane to ethanol to water is 30:40:30), uniformly stirring, then adding 25wt% ammonia water solution, adjusting the pH of the solution to 9.0, stirring for 4 hours, standing and aging for 24 hours, and filtering, washing and drying to obtain white powder;
s2, immersing the white powder into a dilute nitric acid solution with the concentration of 0.5mol/L, stirring for 60min, filtering, washing and drying to obtain hollow silica microspheres;
s3, mixing 20g of hollow silica microspheres with 1g of stearic acid, and then placing the mixture into a ball mill for ball milling, wherein the ball milling speed is 600r/min, the ball milling time is 3h, and the modified silica is obtained after the ball milling is finished.
Example 3
The preparation method of the low-Mooney-viscosity butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer, 3 parts of auxiliary agent modified silicon dioxide is added into 100 parts of butyl rubber inner tube rubber powder in the banburying process, the banburying temperature is 160 ℃, the banburying time is 30min, the rubber powder is refined twice by a refiner after the banburying is finished, the refining thickness of the first refining time is 0.25mm, and the refining thickness of the second refining time is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; discharging and shaping the filtered sizing material by a sheet discharging machine to obtain the low-Mooney-viscosity butyl regenerated rubber;
the preparation method of the modified silicon dioxide comprises the following steps:
s1, dispersing 1g of nano calcium carbonate in 60g of ethanol solvent, then adding 40g of tetraethoxysilane solution (the mass ratio of tetraethoxysilane to ethanol to water is 30:40:30), uniformly stirring, then adding 25wt% ammonia water solution, adjusting the pH of the solution to 9.0, stirring for 4 hours, standing and aging for 24 hours, and filtering, washing and drying to obtain white powder;
s2, immersing the white powder into a dilute nitric acid solution with the concentration of 0.5mol/L, stirring for 60min, filtering, washing and drying to obtain hollow silica microspheres;
s3, mixing 20g of hollow silica microspheres with 1g of stearic acid, and then placing the mixture into a ball mill for ball milling, wherein the ball milling speed is 600r/min, the ball milling time is 3h, and the modified silica is obtained after the ball milling is finished.
Example 4
The preparation method of the low-Mooney-viscosity butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer, in the banburying process, 4 parts of auxiliary agent modified silicon dioxide is added into 100 parts of butyl rubber inner tube rubber powder, the banburying temperature is 160 ℃, the banburying time is 30min, the rubber powder is refined twice by a refiner after the banburying is finished, the refining thickness of the first refining time is 0.25mm, and the refining thickness of the second refining time is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; discharging and shaping the filtered sizing material by a sheet discharging machine to obtain the low-Mooney-viscosity butyl regenerated rubber;
the preparation method of the modified silicon dioxide comprises the following steps:
s1, dispersing 1g of nano calcium carbonate in 60g of ethanol solvent, then adding 40g of tetraethoxysilane solution (the mass ratio of tetraethoxysilane to ethanol to water is 30:40:30), uniformly stirring, then adding 25wt% ammonia water solution, adjusting the pH of the solution to 9.0, stirring for 4 hours, standing and aging for 24 hours, and filtering, washing and drying to obtain white powder;
s2, immersing the white powder into a dilute nitric acid solution with the concentration of 0.5mol/L, stirring for 60min, filtering, washing and drying to obtain hollow silica microspheres;
s3, mixing 20g of hollow silica microspheres with 1g of stearic acid, and then placing the mixture into a ball mill for ball milling, wherein the ball milling speed is 600r/min, the ball milling time is 3h, and the modified silica is obtained after the ball milling is finished.
Example 5
The preparation method of the low-Mooney-viscosity butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer, in the banburying process, 5 parts of auxiliary agent modified silicon dioxide is added into 100 parts of butyl rubber inner tube rubber powder, the banburying temperature is 160 ℃, the banburying time is 30min, the rubber powder is refined twice by a refiner after the banburying is finished, the refining thickness of the first refining time is 0.25mm, and the refining thickness of the second refining time is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; discharging and shaping the filtered sizing material by a sheet discharging machine to obtain the low-Mooney-viscosity butyl regenerated rubber;
the preparation method of the modified silicon dioxide comprises the following steps:
s1, dispersing 1g of nano calcium carbonate in 60g of ethanol solvent, then adding 40g of tetraethoxysilane solution (the mass ratio of tetraethoxysilane to ethanol to water is 30:40:30), uniformly stirring, then adding 25wt% ammonia water solution, adjusting the pH of the solution to 9.0, stirring for 4 hours, standing and aging for 24 hours, and filtering, washing and drying to obtain white powder;
s2, immersing the white powder into a dilute nitric acid solution with the concentration of 0.5mol/L, stirring for 60min, filtering, washing and drying to obtain hollow silica microspheres;
s3, mixing 20g of hollow silica microspheres with 1g of stearic acid, and then placing the mixture into a ball mill for ball milling, wherein the ball milling speed is 600r/min, the ball milling time is 3h, and the modified silica is obtained after the ball milling is finished.
Comparative example 1
A preparation method of butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer at 160 ℃ for 30min, and is refined twice by the refiner after the banburying is finished, wherein the refining thickness of the first refining is 0.25mm, and the refining thickness of the second refining is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; and (5) discharging the filtered sizing material from a sheet discharging machine for forming to obtain the butyl regenerated rubber.
Comparative example 2
A preparation method of butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer, 3 parts of auxiliary agent modified silicon dioxide is added into 100 parts of butyl rubber inner tube rubber powder in the banburying process, the banburying temperature is 160 ℃, the banburying time is 30min, the rubber powder is refined twice by a refiner after the banburying is finished, the refining thickness of the first refining time is 0.25mm, and the refining thickness of the second refining time is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; discharging and shaping the filtered sizing material by a sheet discharging machine to obtain butyl regenerated rubber;
the preparation method of the modified silicon dioxide comprises the following steps:
s1, dispersing 1g of nano calcium carbonate in 60g of ethanol solvent, then adding 40g of tetraethoxysilane solution (the mass ratio of tetraethoxysilane to ethanol to water is 30:40:30), uniformly stirring, then adding 25wt% ammonia water solution, adjusting the pH of the solution to 9.0, stirring for 4 hours, standing and aging for 24 hours, and filtering, washing and drying to obtain white powder;
s2, immersing the white powder into a 0.5mol/L dilute nitric acid solution, stirring for 60min, filtering, washing and drying to obtain the modified silicon dioxide.
Comparative example 3
A preparation method of butyl regenerated rubber comprises the following steps:
selecting waste butyl rubber inner tubes as raw materials, shearing off patches, copper nozzles and other impurities, cleaning, draining, grinding and crushing into colloidal particles with granularity of 0.2cm by using a crusher, wherein the temperature of a roller of the crusher is controlled at 80 ℃, and the roller spacing is set to be 0.25mm; plasticizing the waste butyl rubber inner tube rubber powder at 240 ℃; the cooled rubber powder is banburying by an internal mixer, 3 parts of auxiliary agent stearic acid is added into 100 parts of butyl rubber inner tube rubber powder in the banburying process, the banburying temperature is 160 ℃, the banburying time is 30min, the rubber powder is refined twice by a refiner after the banburying is finished, the refining thickness of the first refining time is 0.25mm, and the refining thickness of the second refining time is 0.18mm; filtering the refined sizing material by a sizing filter, wherein the size of a filter screen hole adopted by the sizing filter is 0.16mm; and (5) discharging the filtered sizing material from a sheet discharging machine for forming to obtain the butyl regenerated rubber.
The butyl rubber reclaimed rubber prepared in examples 1 to 5 and comparative examples 1 to 3 was subjected to a performance test by referring to GB/T13460-2016, and the test results are shown in the following table:
| mooney viscosity ML100 ℃ (1+4) | Tensile Strength (MPa) | Elongation at break (%) | |
| Example 1 | 44 | 7.9 | 520 |
| Example 2 | 43 | 8.0 | 515 |
| Example 3 | 37 | 7.8 | 503 |
| Example 4 | 36 | 7.8 | 496 |
| Example 5 | 32 | 7.6 | 484 |
| Comparative example 1 | 55 | 8.0 | 533 |
| Comparative example 2 | 53 | 7.9 | 528 |
| Comparative example 3 | 49 | 8.0 | 517 |
Finally, it should be noted that: the above examples are not intended to limit the present invention in any way. Modifications and improvements will readily occur to those skilled in the art upon the basis of the present invention. Accordingly, any modification or improvement made without departing from the spirit of the invention is within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the low-Mooney-viscosity butyl regenerated rubber comprises the steps of taking a waste butyl rubber inner tube as a raw material, and performing rubber washing, crushing, plasticizing, banburying, refining, rubber filtering, forming and metering packaging to obtain the butyl regenerated rubber.
2. The method for preparing the low mooney viscosity butyl reclaimed rubber as claimed in claim 1, wherein the modified silica is prepared by the following steps:
s1, dispersing nano calcium carbonate in an ethanol solvent, then adding an ethyl orthosilicate solution into the ethanol solvent, stirring the mixture uniformly, then adding an ammonia water solution, adjusting the pH of the solution to 8.5-10, stirring the mixture for 3-5 hours, standing the mixture for ageing, and filtering, washing and drying the mixture to obtain white powder;
s2, immersing the white powder into a dilute nitric acid solution, stirring for 30-60min, filtering, washing and drying to obtain hollow silica microspheres;
and S3, mixing the hollow silica microspheres with stearic acid, and then placing the mixture in a ball mill for ball milling, and obtaining the modified silica after ball milling is finished.
3. The method for preparing the low-Mooney-viscosity butyl reclaimed rubber according to claim 2, wherein in the step S1, the mass ratio of the nano calcium carbonate to the ethanol to the tetraethyl orthosilicate solution is 1-2:60-80:40-60.
4. The method for producing a butyl rubber regenerated from low mooney viscosity according to claim 2, characterized in that in step S1, the mass ratio of ethyl orthosilicate, ethanol and water in the ethyl orthosilicate solution is 20-40:40-50:20-30.
5. The method for producing a low mooney viscosity butyl reclaimed rubber as claimed in claim 2, wherein in step S3, the mass ratio of hollow silica microspheres to stearic acid is 20-30:1-2.
6. The method for preparing the low-Mooney-viscosity butyl reclaimed rubber according to claim 1, wherein the mass ratio of the plasticized waste butyl rubber inner tube rubber material to the modified silicon dioxide is 100:1-5.
7. The method for producing a low-mooney-viscosity butyl reclaimed rubber as claimed in claim 1, wherein the waste butyl rubber inner tube is ground and pulverized into colloidal particles having a particle size of 0.18 to 0.425cm by a pulverizer.
8. The method for preparing the low-mooney-viscosity butyl reclaimed rubber according to claim 1, wherein the banburying temperature is 100-180 ℃ and the banburying time is 20-40min.
9. The method for preparing the low-mooney viscosity butyl reclaimed rubber according to claim 1, wherein in the rubber filtering process, a rubber filter is adopted for filtering, and the size of a screen hole of a filter screen on the rubber filter is 0.15-0.18mm.
10. The low mooney viscosity butyl reclaimed rubber produced by the production method according to any one of claims 1 to 9.
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