CN113861576A - Method for recycling waste rubber powder containing low-unsaturation rubber - Google Patents
Method for recycling waste rubber powder containing low-unsaturation rubber Download PDFInfo
- Publication number
- CN113861576A CN113861576A CN202111123768.4A CN202111123768A CN113861576A CN 113861576 A CN113861576 A CN 113861576A CN 202111123768 A CN202111123768 A CN 202111123768A CN 113861576 A CN113861576 A CN 113861576A
- Authority
- CN
- China
- Prior art keywords
- rubber
- parts
- rubber powder
- powder
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 276
- 239000005060 rubber Substances 0.000 title claims abstract description 276
- 239000000843 powder Substances 0.000 title claims abstract description 93
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000004064 recycling Methods 0.000 title claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 116
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 38
- 239000006229 carbon black Substances 0.000 claims description 29
- 235000021355 Stearic acid Nutrition 0.000 claims description 19
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 19
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 19
- 239000008117 stearic acid Substances 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 229920005549 butyl rubber Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920003052 natural elastomer Polymers 0.000 claims description 12
- 229920001194 natural rubber Polymers 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000010692 aromatic oil Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 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 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 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 2
- -1 accelerators Substances 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000001238 wet grinding Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 26
- 239000000126 substance Substances 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000003313 weakening effect Effects 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 description 27
- 238000001816 cooling Methods 0.000 description 23
- 238000007599 discharging Methods 0.000 description 21
- 239000002775 capsule Substances 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 6
- 239000010920 waste tyre Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004200 microcrystalline wax Substances 0.000 description 3
- 235000019808 microcrystalline wax Nutrition 0.000 description 3
- 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 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 241000255925 Diptera Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000008427 organic disulfides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for recycling waste rubber powder, which is used for preparing rubber powder filled rubber materials with excellent performance by blending and vulcanizing rubber powder containing low-unsaturation rubber and rubber, and weakening or eliminating the modulus gradient between the rubber powder and a matrix material by adjusting the modulus of the matrix material. The method does not need to carry out physical, chemical or biological modification on rubber powder, and is favorable for preparing the high-performance waste rubber powder filled rubber material at low cost. The specific operation is that firstly, rubber powder consisting of low-unsaturation rubber is selected; secondly, the rubber powder and the matrix material are blended and vulcanized, and the preparation of the rubber powder filled rubber product with the performance meeting the requirements is realized by adjusting one or more of the raw rubber component, the type and the content of the filler, the type and the content of the crosslinking assistant and the content of the plasticizer in the matrix material.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to a method for recycling waste rubber powder containing low-unsaturation rubber.
Background
Because of its unique viscoelasticity, rubber is widely used in the fields of transportation, aerospace, medical treatment, agriculture and the like, and is an important strategic resource. At present, China is the largest rubber consuming country and is also the largest waste rubber generating country. In 2019, the amount of waste tires produced is about 3.3 million, which is equivalent to over 1000 million tons, and the amount of waste tires produced by annual scrapping is increasing at a rate of 6% to 8%. The waste rubber is difficult to degrade in natural environment due to the stable chemical structure of the waste rubber. If the mosquito is discarded or buried, the mosquito is easy to breed and has fire hazard; meanwhile, the additive in the waste rubber can diffuse and pollute the environment.
The rubber powder is an important way for recycling the waste rubber, can be prepared by crushing the waste rubber at normal temperature, low temperature or a wet method, has the advantage of low cost, and is often blended and used with other materials. However, the addition of rubber powder to the material generally reduces the material performance, mainly because the three-dimensional network structure inside the rubber powder restricts the movement of molecular chains in the rubber powder, which makes it difficult to bond well with the matrix. Therefore, physical (microwave, ultrasonic, shearing, etc.), chemical (thiol, organic disulfide, etc.) or biological methods are commonly used at present to open up the three-dimensional network structure of the gelatine powder and enhance the adhesion thereof to the substrate (Progress in Polymer science 2000,25(7), 909-948; Industrial & Engineering Chemistry Research 2012,51(10), 3975; Journal of Materials Processing Technology 1995,48, 619-625; Polymer Degradation and Stability 2017,143, 186-195; Green Chemistry 2020,22(1), 94-102; Rubber Chemistry and Technology 2012,85(3), 408-449; U.S. patent 4264481; U.S. patent 10227421; CN 105646932; CN 102816343; CN 3531, 31 (47-54), 004-54); however, the above means can change the internal structure and composition of the rubber powder, which is not favorable for preparing rubber powder filling materials with excellent performance. Meanwhile, the modified rubber powder also increases the rubber recovery cost. In addition to the above problem of adhesion between the interface of the rubber powder and the substrate, the inventor recently found that a modulus gradient exists between the interface of the rubber powder and the substrate, which is likely to cause stress concentration, is another main factor causing the reduction of the material performance, and the material performance can be obviously improved by repairing the modulus gradient of the interface. However, this study uses organic bases to eliminate the interfacial modulus gradient, which results in too fast a rubber cure rate, too high a crosslink density and a low elongation at break (ACS Applied Materials & Interfaces,2(42): 47957-.
Based on the research background, the invention adopts the rubber powder containing low-unsaturation rubber, and utilizes the advantages of low activity and less change of the internal structure and the composition of the rubber powder in the co-vulcanization process with the matrix material, thereby avoiding the technical route of the prior art focusing on rubber powder modification, finally realizing the preparation of the rubber powder filling material with excellent performance by regulating and controlling the modulus of the matrix material to solve the interface modulus gradient of the rubber powder and the matrix, and achieving the purpose of efficiently recycling the waste rubber powder.
Through the above analysis, the problems and defects of the prior art are as follows: the prior art focuses on modifying rubber powder, and the means can change the internal structure and composition of the rubber powder. Meanwhile, the modified rubber powder can increase the rubber recovery cost.
The difficulty in solving the above problems and defects is: the rubber powder modified by the prior art is difficult to prepare a high-performance rubber powder filling material, and is not beneficial to realizing the high added value of the waste rubber.
The significance of solving the problems and the defects is as follows: the waste rubber powder is efficiently recycled, resources are saved, the environment is protected, and carbon neutralization is realized.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for efficiently recycling waste rubber powder, the raw materials involved in the method comprise raw rubber components, the waste rubber powder, fillers, resin, sulfur, accelerators, activators (zinc oxide, stearic acid and the like), plasticizers, anti-aging agents and the like, and the method is characterized in that: in rubber products filled with rubber powder, the rubber powder containing rubber with low unsaturation degree is blended and vulcanized with the rubber, the weak reaction activity of the rubber with low unsaturation degree in the rubber powder is utilized, during the co-vulcanization, the reaction degree of the rubber powder and a crosslinking assistant in a matrix is small, but the rubber powder and the matrix interface are bonded sufficiently, and meanwhile, the modulus of the rubber powder is not greatly changed.
The raw rubber component is common rubber, and comprises the following components: 50-150 parts of one or more of isoprene rubber, natural rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene propylene rubber and the like, preferably 90-110 parts.
The waste rubber powder comprises low-unsaturation rubber, such as ethylene propylene rubber, butyl rubber and the like, preferably butyl rubber, wherein the low-unsaturation rubber means that the double bond content of a rubber main chain is lower than 15 percent (mol percent), the waste rubber powder is prepared by normal-temperature, low-temperature or wet grinding, preferably low-temperature grinding, and the size of the waste rubber powder is 20-200 meshes, preferably 40-100 meshes.
The filler is carbon black, silica or the like which is generally used in industry, and the addition amount thereof is 20 to 80 parts, preferably 40 to 60 parts.
The resin is vulcanized resin, such as phenolic resin SP-1045, SP-1055, etc., and its addition amount is 1-30 parts, preferably 10-20 parts.
The addition amount of the sulfur is 1-10 parts, preferably 0.5-5 parts, the accelerator of claim 1 is common accelerator, such as promoting M, promoting DM, promoting TMTD, etc., and the addition amount is 0.5-8 parts, preferably 1-4 parts.
The plasticizer is common plasticizer, such as paraffin, environment-friendly aromatic oil, rosin, coumarone and the like, and the addition amount of the plasticizer is 1-20 parts, preferably 2-10 parts.
The antioxidant is common amine and phenol antioxidants, and the addition amount of the antioxidant is 0.5-5 parts, preferably 1-3 parts.
The waste rubber powder and the matrix material are blended by adopting a conventional blending device, such as an internal mixer, an open mill or a screw extruder, and the blending temperature is 20-160 ℃, and preferably 40-120 ℃. The vulcanization temperature of the rubber powder and the base material blend is between 130 ℃ and 200 ℃, and preferably between 150 ℃ and 180 ℃.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects: the invention adopts rubber powder containing low-unsaturation rubber and rubber to be blended and vulcanized, and weakens or eliminates the modulus gradient between the rubber powder and the matrix material by adjusting the modulus of the matrix material, thereby preparing the rubber powder filling material with excellent performance. The method does not need to carry out physical, chemical or biological modification on the rubber powder, and is favorable for preparing the high-performance waste rubber powder filling material at low cost.
Drawings
FIG. 1 is a stress-strain graph of vulcanizates 1a and 1 b.
Fig. 2 is a stress-strain graph of vulcanizates 2a,2b,2c and 2 d.
Fig. 3 is a stress-strain graph of vulcanizates 2a,2b,2e and 2 f.
Fig. 4 is a stress-strain graph of vulcanizates 3a and 3 b.
FIG. 5 is a stress-strain graph of the vulcanizates 4a-4 d.
Fig. 6 is a stress-strain graph of vulcanizates 5a,5b and 5 c.
FIG. 7 is a butyl rubber based formulation.
FIG. 8 is a formulation based on carbon black filled natural rubber.
FIG. 9 is a schematic representation of a carbon black/white carbon based blend natural rubber formulation.
FIG. 10 vulcanizate 2a,2c,4a,4c stress-strain curves
FIG. 11 is a graph of the physical and mechanical properties of the vulcanizate.
Detailed Description
The technical solution of the present patent will now be described in detail with reference to specific embodiments, but the described embodiments are only for the purpose of facilitating understanding of the present invention and do not limit the present invention. In the case of the invention, the used capsule powder is derived from waste vulcanized capsules; the waste tire rubber powder is from waste truck tires. The size of the rubber powder is 40-60 meshes.
Reference example 1A
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 20 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. And secondly, cooling the internal mixer to 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing and thinly passing the film on the open mill for 50 times, discharging the film, and naturally cooling the film to room temperature. And vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 1 a.
Example 1B
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 20 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes for rubber discharge to obtain an internal mixed rubber sheet, and the rubber discharge temperature is 120 ℃. Setting the temperature of the internal mixer to be 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing the rubber sheets on the open mill, adding 34 parts of waste capsule rubber powder, thinly passing for 50 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And secondly, vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 1 b. In a 14 mass percent carbon black filled system, 20 mass percent of waste rubber powder is added into the system by taking vulcanized rubber 1a as reference, and the tensile strength of the material is improved, as shown in figure 1.
Reference example 2A
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 50 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. And secondly, cooling the internal mixer to 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing and thinly passing the film on the open mill for 50 times, discharging the film, and naturally cooling the film to room temperature. And vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 2 a.
Example 2B
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 50 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. Setting the temperature of the internal mixer to be 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing the rubber sheets on the open mill, adding 34 parts of waste capsule rubber powder, thinly passing for 50 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And secondly, vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 2 b.
Example 2C
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 50 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. Setting the temperature of the internal mixer to be 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 20 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing the rubber sheets on the open mill, adding 34 parts of waste capsule rubber powder, thinly passing for 50 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And secondly, vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 2 c.
Example 2D
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 50 parts of carbon black, 1 part of stearic acid, 5 parts of zinc oxide and 10 parts of environment-friendly aromatic oil are added for internal mixing for 8 minutes, and rubber is discharged to obtain an internal mixing rubber sheet, wherein the rubber discharging temperature is 120 ℃. Setting the temperature of the internal mixer to be 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing the rubber sheets on the open mill, adding 34 parts of waste capsule rubber powder, thinly passing for 50 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. Secondly, vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 2 d.
Example 2E
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 50 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. Setting the temperature of the internal mixer to be 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing the rubber sheets on the open mill, adding 19 parts of waste capsule rubber powder, thinly passing for 50 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And secondly, vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 2 e.
Example 2F
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 50 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. Setting the temperature of the internal mixer to be 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing the rubber sheets on the open mill, adding 110 parts of waste capsule rubber powder, thinly passing for 50 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And secondly, vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 2 f.
The addition of 20% by mass fraction rubber powder to material 2b in a vulcanization system containing 30% by mass fraction carbon black, in comparison to the stress-strain curves of vulcanizates 2a and 2b (fig. 2), contributes to an improvement in the 100% and 300% stress at elongation of the material, but leads to a reduction in its elongation at break and tensile strength. To optimize the physical and mechanical properties of the material 2b, the tensile strength of the material was first increased by increasing the content of the vulcanization aid SP-1055 in the system (2b vs 2c, see FIG. 2). Secondly, the elongation at break of the material is improved by adding plasticizer and environment-friendly aromatic oil into the system (2b vs 2d, as shown in figure 2).
The invention further considers the influence of the rubber powder addition amount on the material performance, firstly, the rubber powder content (2b vs 2e, as shown in figure 3) in the rubber is reduced, the tensile strength of the vulcanized rubber 2e is improved by about 9 percent compared with 2b, the elongation at break and 100 percent stress at definite elongation are similar to those of the vulcanized rubber 2a without rubber powder filling, but the tensile strength and 300 percent stress at definite elongation are slightly reduced compared with 2 a; secondly, the addition amount of rubber powder in the rubber is increased (2b vs 2f, as shown in figure 3), and the 100% and 300% stress at definite elongation of the vulcanized rubber 2f has no obvious influence compared with 2b, but the tensile strength and the elongation at break are reduced.
Reference example 3A
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 80 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. And secondly, cooling the internal mixer to 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing and thinly passing the film on the open mill for 50 times, discharging the film, and naturally cooling the film to room temperature. And vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 3 a.
Example 3B
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of butyl rubber is added into an internal mixer for internal mixing for one minute, then 80 parts of carbon black, 1 part of stearic acid and 5 parts of zinc oxide are added for internal mixing for 8 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. Setting the temperature of the internal mixer to be 80 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 10 parts of resin SP-1055, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 50 ℃, mixing the rubber sheets on the open mill, adding 34 parts of waste capsule rubber powder, thinly passing for 50 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. Secondly, vulcanizing the rubber sheet at 180 ℃ for 40min to obtain vulcanized rubber 3 b. In a system filled with 40% of carbon black by mass fraction (3a vs 3b, as shown in figure 4), the addition of rubber powder has no obvious influence on the tensile strength of the material, the stress at definite elongation of 100% and 300% of the material is improved, and the elongation at break is reduced.
Reference example 4A
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of natural rubber is added into an internal mixer for internal mixing for one minute, then 60 parts of carbon black, 2.5 parts of stearic acid and 7.5 parts of zinc oxide are added for internal mixing for 6 minutes, and rubber is discharged to obtain an internal mixing rubber sheet, wherein the rubber discharging temperature is 120 ℃. Secondly, the internal mixer is cooled to 60 ℃, the internal mixing rubber sheet is put into the internal mixer again for mixing, 2.3 parts of sulfur, 0.4 part of accelerator M and 0.8 part of accelerator DM are added, and the mixture is mixed for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 40 ℃, mixing and thinly passing the film on the open mill for 30 times, and naturally cooling the film to room temperature. And vulcanizing the rubber sheet at 143 ℃ for 17min to obtain vulcanized rubber 4 a.
Reference example 4B
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 80 parts of natural rubber and 20 parts of brominated butyl rubber are added into an internal mixer for internal mixing for one minute, then 60 parts of carbon black, 2.5 parts of stearic acid and 7.5 parts of zinc oxide are added, internal mixing is carried out for 6 minutes, and rubber discharge is carried out to obtain an internal mixing rubber sheet, wherein the rubber discharge temperature is 120 ℃. Secondly, the internal mixer is cooled to 60 ℃, the internal mixing rubber sheet is put into the internal mixer again for mixing, 2.3 parts of sulfur, 0.4 part of accelerator M and 0.8 part of accelerator DM are added, and the mixture is mixed for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 40 ℃, mixing and thinly passing the film on the open mill for 30 times, and naturally cooling the film to room temperature. And vulcanizing the rubber sheet at 143 ℃ for 30min to obtain vulcanized rubber 4 b.
Example 4C
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of natural rubber is added into an internal mixer for internal mixing for one minute, then 60 parts of carbon black, 2.5 parts of stearic acid and 7.5 parts of zinc oxide are added for internal mixing for 6 minutes, and rubber is discharged to obtain an internal mixing rubber sheet, wherein the rubber discharging temperature is 120 ℃. Secondly, the internal mixer is cooled to 60 ℃, the internal mixing rubber sheet is put into the internal mixer again for mixing, 2.3 parts of sulfur, 0.4 part of accelerator M and 0.8 part of accelerator DM are added, and the mixture is mixed for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 40 ℃, mixing the rubber sheets on the open mill, adding 43 parts of waste capsule rubber powder, thinly passing for 30 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And vulcanizing the rubber sheet at 143 ℃ for 27min to obtain vulcanized rubber 4 c.
Example 4D
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of natural rubber is added into an internal mixer for internal mixing for one minute, then 60 parts of carbon black, 2.5 parts of stearic acid and 7.5 parts of zinc oxide are added for internal mixing for 6 minutes, and rubber is discharged to obtain an internal mixing rubber sheet, wherein the rubber discharging temperature is 120 ℃. Secondly, the internal mixer is cooled to 60 ℃, the internal mixing rubber sheet is put into the internal mixer again for mixing, 2.3 parts of sulfur, 0.4 part of accelerator M and 0.8 part of accelerator DM are added, and the mixture is mixed for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 40 ℃, mixing the rubber sheet on the open mill, adding 43 parts of waste tire rubber powder, thinly passing for 30 times, discharging the rubber sheet, and naturally cooling the rubber sheet to room temperature. And vulcanizing the rubber sheet at 143 ℃ for 27min to obtain vulcanized rubber 4 d. When the base material is changed from butyl rubber to natural rubber with high unsaturation degree, taking the vulcanized rubber 4a and 4b as reference, the tensile strength of the vulcanized rubber 4c containing rubber powder is close to 4a and 4b, the 100% and 300% stress at definite elongation are slightly reduced, but the elongation at break is improved (as shown in figure 5). In order to further clarify the advantages of the rubber powder containing low unsaturation degree, the invention adopts the system 4d of the waste tire rubber powder containing high unsaturation degree rubber as a reference, and researches the influence on the material performance, as shown in fig. 5, the performance of the system 4d is obviously reduced compared with that of the system 4 c.
Reference example 5A
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of natural rubber is added into an internal mixer for internal mixing for one minute, and then 33 parts of carbon black, 25 parts of white carbon black, 2.5 parts of silane coupling agent, 2 parts of stearic acid, 3.5 parts of zinc oxide, 1 part of age inhibitor 6PPD, 0.5 part of age inhibitor TMQ and 2 parts of microcrystalline wax are added for internal mixing for 6 minutes, and rubber is discharged to obtain an internal mixed rubber sheet, wherein the rubber discharging temperature is 150 ℃. And secondly, cooling the internal mixer to 60 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 1.4 parts of sulfur and 2.1 parts of accelerating agent TBBS, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 40 ℃, mixing and thinly passing the film on the open mill for 30 times, and naturally cooling the film to room temperature. And vulcanizing the rubber sheet at 150 ℃ for 20min to obtain vulcanized rubber 5 a.
Example 5B
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of natural rubber is added into an internal mixer for internal mixing for one minute, and then 33 parts of carbon black, 25 parts of white carbon black, 2.5 parts of silane coupling agent, 2 parts of stearic acid, 3.5 parts of zinc oxide, 1 part of age inhibitor 6PPD, 0.5 part of age inhibitor TMQ and 2 parts of microcrystalline wax are added for internal mixing for 6 minutes, and rubber is discharged to obtain an internal mixed rubber sheet, wherein the rubber discharging temperature is 150 ℃. And secondly, cooling the internal mixer to 60 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 1.4 parts of sulfur and 2.1 parts of accelerating agent TBBS, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 40 ℃, mixing the rubber sheets on the open mill, adding 43 parts of waste capsule rubber powder, thinly passing for 30 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And vulcanizing the rubber sheet at 150 ℃ for 20min to obtain vulcanized rubber 5 b.
Example 5C
The initial temperature of the internal mixer was set at 50 ℃ and the rotation speed was 55 rpm. Firstly, 100 parts of natural rubber is added into an internal mixer for internal mixing for one minute, and then 33 parts of carbon black, 25 parts of white carbon black, 2.5 parts of silane coupling agent, 2 parts of stearic acid, 3.5 parts of zinc oxide, 1 part of age inhibitor 6PPD, 0.5 part of age inhibitor TMQ and 2 parts of microcrystalline wax are added for internal mixing for 6 minutes, and rubber is discharged to obtain an internal mixed rubber sheet, wherein the rubber discharging temperature is 150 ℃. And secondly, cooling the internal mixer to 60 ℃, putting the internal mixing rubber sheet into the internal mixer again for mixing, adding 1.8 parts of sulfur and 2.1 parts of accelerating agent TBBS, and mixing for 4 minutes to discharge rubber. Adjusting the roll temperature of the open mill to 40 ℃, mixing the rubber sheets on the open mill, adding 43 parts of waste capsule rubber powder, thinly passing for 30 times, discharging the rubber sheets, and naturally cooling the rubber sheets to room temperature. And vulcanizing the rubber sheet at 150 ℃ for 20min to obtain vulcanized rubber 5 c. According to the invention, the vulcanized rubber 5a using carbon black/white carbon black as a reference is added into the system, so that the tensile strength of the vulcanized rubber and the stress at elongation of 100% and 300% are reduced (5a vs 5b, as shown in figure 6). On the basis of the above, the invention further improves the tensile strength of the vulcanized rubber and the stress at definite elongation of 100% and 300% by increasing the sulfur content in the vulcanized rubber (5b vs 5c, as shown in fig. 6).
In conclusion, the invention prepares the rubber powder filling material meeting different performance requirements by reasonably regulating and controlling the modulus of the matrix material on the premise of not modifying the rubber powder, and the performance is excellent, which is shown in detail in fig. 10 and fig. 11.
Claims (9)
1. The invention aims to provide a method for recycling waste rubber powder efficiently, the raw materials involved in the method comprise raw rubber components, waste rubber powder, filler, resin, sulfur, accelerators, activators (zinc oxide, stearic acid and the like), plasticizers, anti-aging agents and the like, and the method is characterized in that: in the rubber product filled with rubber powder, the rubber powder containing rubber with low unsaturation degree is blended and vulcanized with rubber, and the weaker reaction activity of the rubber with low unsaturation degree in the rubber powder is utilized, so that the rubber powder cannot bring large change to the self modulus due to the small reaction degree of the rubber powder and the crosslinking assistant in the matrix in the co-vulcanization process, but the rubber powder can be sufficiently adhered to the matrix interface, on the basis, the modulus of the matrix material is regulated and controlled, such as the raw rubber component, the type and the content of the filler, the type and the content of the crosslinking assistant, the content of the plasticizer and the like in the matrix material are changed, so that the modulus gradient between the rubber powder and the matrix material is weakened or eliminated, and the rubber product filled with the rubber powder and having the required performance is prepared.
2. The green rubber component of claim 1 is a conventional rubber comprising: 50-150 parts of one or more of isoprene rubber, natural rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene propylene rubber and the like, preferably 90-110 parts.
3. The waste rubber powder as claimed in claim 1 contains low unsaturation degree rubber, such as ethylene propylene rubber, butyl rubber, etc., preferably butyl rubber, wherein the low unsaturation degree means that the double bond content of the rubber main chain is less than 15% (mol%), the waste rubber powder can be prepared by normal temperature, low temperature or wet grinding, preferably low temperature grinding, and the size of the waste rubber powder is 20-200 meshes, preferably 40-100 meshes.
4. The filler of claim 1 is carbon black, silica or the like which is generally used in industry, and is added in an amount of 20 to 80 parts, preferably 40 to 60 parts.
5. The resin according to claim 1 is a vulcanized resin, such as phenol resin SP-1045, SP-1055, etc., and is added in an amount of 1 to 30 parts, preferably 10 to 20 parts.
6. The addition amount of sulfur related to claim 1 is between 1 and 10 parts, preferably between 0.5 and 5 parts, and the accelerator related to claim 1 is a common accelerator such as M accelerator, DM accelerator, TMTD accelerator and the like, and the addition amount is between 0.5 and 8 parts, preferably between 1 and 4 parts.
7. The plasticizer according to claim 1 is a common plasticizer, such as paraffin, environmentally friendly aromatic oil, rosin, coumarone, etc., and the addition amount thereof is 1 to 20 parts, preferably 2 to 10 parts.
8. The antioxidant according to claim 1 is a commonly used amine-based or phenol-based antioxidant, and is added in an amount of 0.5 to 5 parts, preferably 1 to 3 parts.
9. The waste rubber powder and the matrix material are blended by a conventional blending device, such as an internal mixer, an open mill or a screw extruder, and the like, wherein the blending temperature is 20-160 ℃, preferably 40-120 ℃, and the vulcanization temperature of the rubber powder and matrix material blend is 130-200 ℃, preferably 150-180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111123768.4A CN113861576A (en) | 2021-09-24 | 2021-09-24 | Method for recycling waste rubber powder containing low-unsaturation rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111123768.4A CN113861576A (en) | 2021-09-24 | 2021-09-24 | Method for recycling waste rubber powder containing low-unsaturation rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113861576A true CN113861576A (en) | 2021-12-31 |
Family
ID=78993990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111123768.4A Pending CN113861576A (en) | 2021-09-24 | 2021-09-24 | Method for recycling waste rubber powder containing low-unsaturation rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113861576A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10128752A (en) * | 1996-11-05 | 1998-05-19 | Agency Of Ind Science & Technol | Reclamation of used tire rubber |
| CN1528815A (en) * | 2003-09-29 | 2004-09-15 | 华南理工大学 | In situ modified waste rubber powder composite material and preparing method thereof |
| CN104371147A (en) * | 2014-09-11 | 2015-02-25 | 中海油（福建）深冷精细胶粉有限公司 | Tire tread rubber material and production method thereof |
| CN108774363A (en) * | 2018-06-12 | 2018-11-09 | 柳州市大新实业有限公司 | A kind of EPDM rubber formula and preparation method containing rubber powder |
| CN111138771A (en) * | 2020-01-13 | 2020-05-12 | 沈阳化工大学 | Preparation method of butyl inner tube added with butyl rubber powder for heavy truck |
-
2021
- 2021-09-24 CN CN202111123768.4A patent/CN113861576A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10128752A (en) * | 1996-11-05 | 1998-05-19 | Agency Of Ind Science & Technol | Reclamation of used tire rubber |
| CN1528815A (en) * | 2003-09-29 | 2004-09-15 | 华南理工大学 | In situ modified waste rubber powder composite material and preparing method thereof |
| CN104371147A (en) * | 2014-09-11 | 2015-02-25 | 中海油（福建）深冷精细胶粉有限公司 | Tire tread rubber material and production method thereof |
| CN108774363A (en) * | 2018-06-12 | 2018-11-09 | 柳州市大新实业有限公司 | A kind of EPDM rubber formula and preparation method containing rubber powder |
| CN111138771A (en) * | 2020-01-13 | 2020-05-12 | 沈阳化工大学 | Preparation method of butyl inner tube added with butyl rubber powder for heavy truck |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| De et al. | Processing and material characteristics of a reclaimed ground rubber tire reinforced styrene butadiene rubber | |
| Sienkiewicz et al. | Development of methods improving storage stability of bitumen modified with ground tire rubber: A review | |
| EP0931809B1 (en) | Rubber composition and method for producing the same | |
| JP5647128B2 (en) | Tires containing recycled materials | |
| JP2015212377A (en) | Chemically functionalized renewed rubber composition | |
| JPH08503252A (en) | Treatment of rubber to form a bituminous composition | |
| US9902831B2 (en) | Re-processed rubber and a method for producing same | |
| CN105899593B (en) | In the improvement for mixing and processing on the rubber composition containing polar filler | |
| CN101613496B (en) | Method for preparing blended vulcanizate of modified rubber power and rubber | |
| EP0051450A1 (en) | Polymer-carbon black mixing | |
| US6479558B1 (en) | Microbial processing of used rubber | |
| EP2465898B1 (en) | Tire having rubber composition and a rubber component containing short fiber reinforcement with a comptabilizer | |
| CN108774363A (en) | A kind of EPDM rubber formula and preparation method containing rubber powder | |
| MXPA04001194A (en) | Process for regeneration of rubber from scrap. | |
| CN1715318A (en) | Pneumatic tire having an innerliner comprised butyl rubber and dispersion of pre-cured diene-based rubber | |
| CN1086715C (en) | Improvement in and relating to the receiving of naural and synthetic rubber | |
| CN114058097B (en) | High-performance uncrosslinked rubber asphalt and preparation method thereof | |
| CN1100084C (en) | Waste rubber regenerating process and waste rubber regenerant | |
| CN113861576A (en) | Method for recycling waste rubber powder containing low-unsaturation rubber | |
| US6407144B1 (en) | Combination biological and microwave treatments of used rubber products | |
| CN108192168A (en) | A kind of electronic automobile-used cover tire sizing material | |
| CN103865100B (en) | A kind of rubber processing aids and preparation method thereof | |
| Ansarifar et al. | The reinforcement and crosslinking of styrene butadiene rubber with silanized precipitated silica nanofiller | |
| JP4338365B2 (en) | Rubber composition for tire | |
| Chuan et al. | Cure and physical characterizations of natural rubber blended with recycled latex-foam-waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20211231 |