CN118256029B - A method for preparing natural rubber composite from recycled rubber powder of waste tire with controllable molecular weight - Google Patents
A method for preparing natural rubber composite from recycled rubber powder of waste tire with controllable molecular weight Download PDFInfo
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- CN118256029B CN118256029B CN202410393212.4A CN202410393212A CN118256029B CN 118256029 B CN118256029 B CN 118256029B CN 202410393212 A CN202410393212 A CN 202410393212A CN 118256029 B CN118256029 B CN 118256029B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 134
- 239000005060 rubber Substances 0.000 title claims abstract description 134
- 239000000843 powder Substances 0.000 title claims abstract description 128
- 239000010920 waste tyre Substances 0.000 title claims abstract description 68
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 44
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 44
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 21
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 21
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 21
- 238000010008 shearing Methods 0.000 claims abstract description 21
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 15
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 230000002522 swelling effect Effects 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 13
- 238000011069 regeneration method Methods 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000004132 cross linking Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000010907 mechanical stirring Methods 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000003313 weakening effect Effects 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- 230000009471 action Effects 0.000 description 12
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000004064 recycling Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 3
- -1 sulfur radicals Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开一种可控分子量废轮胎再生胶粉复合天然橡胶的制备方法，其特点是利用一定浓度的天然胶乳和碳酸氢铵溶液作为绿色溶剂，在机械搅拌和高温加热作用下对废轮胎胶粉进行充分渗透、溶胀，减弱胶粉分子链间作用力，增加塑性；将处理后的废轮胎胶粉和无机金属盐在密炼机进行机械强剪切作用，胶粉交联网络断裂产生的硫自由基可与金属盐发生配位作用，一方面阻止其再参与硫化交联反应，另一方面抑制硫自由基进攻胶粉分子主链不饱和键，减弱再生过程中对胶粉分子主链结构的影响，通过控制剪切温度、转速和剪切时间来调控废轮胎再生胶粉的分子量大小；将获得的不同分子量的废轮胎再生胶粉与天然橡胶和其他助剂在开炼机上混炼加工，实现废旧胶粉的良好分散，热压硫化制备废轮胎再生胶粉复合天然橡胶复合材料，发挥废旧胶粉的增强作用。该制备工艺简便，绿色环保，有利于工业化生产。
The invention discloses a method for preparing a composite natural rubber of waste tire recycled rubber powder with controllable molecular weight. The method is characterized in that natural latex and ammonium bicarbonate solution of a certain concentration are used as green solvents to fully penetrate and swell the waste tire rubber powder under mechanical stirring and high-temperature heating, so as to weaken the force between the molecular chains of the rubber powder and increase the plasticity; the treated waste tire rubber powder and inorganic metal salt are subjected to mechanical strong shearing in an internal mixer, and the sulfur free radicals generated by the rupture of the cross-linked network of the rubber powder can coordinate with the metal salt, on the one hand, preventing the free radicals from participating in the vulcanization cross-linking reaction again, and on the other hand, inhibiting the sulfur free radicals from attacking the unsaturated bonds of the main chain of the rubber powder molecule, and weakening the influence on the main chain structure of the rubber powder molecule during the regeneration process; the molecular weight of the waste tire recycled rubber powder is regulated by controlling the shearing temperature, rotation speed and shearing time; the obtained waste tire recycled rubber powder with different molecular weights is mixed with natural rubber and other additives on an open mixer to achieve good dispersion of the waste rubber powder, and hot pressing vulcanization is performed to prepare a composite material of waste tire recycled rubber powder and natural rubber, so as to exert the reinforcing effect of the waste rubber powder. The preparation process is simple, green and environmentally friendly, and is conducive to industrial production.
Description
Technical Field
The invention relates to a preparation method of a compound natural rubber of reclaimed rubber powder of a waste tire with controllable molecular weight, belonging to the field of reclaimed preparation of waste rubber powder.
Background
With the continuous improvement of the automobile industry and the manufacturing industry, the number of junked tires is increasing. The main component of the tire is vulcanized rubber, belongs to thermosetting materials, and the discarded tire causes serious black pollution. Therefore, the waste tires are treated by a reasonable method, and the recycling is very urgent. However, before recycling, the desulfurization and regeneration problems of the waste tires need to be solved, at present, methods such as microwave desulfurization, radiation desulfurization, mechanical desulfurization, chemical regeneration reagent desulfurization and the like are mainly adopted to realize the regeneration of the waste tires, and the essence of the method is that the cross-linking bonds of the tires are broken through energy to change the cross-linking bonds into linear molecules, so that the compatibility with other polymers and the melt fluidity are improved.
Zhang Shibo et al, china plastics, 2023, 37 (9): 83-89, preparing low temperature desulphurized rubber powder with naphthenic oil as desulphurized solvent and 2,2' -dibenzoylaminobenzene disulfide and zinc oxide as catalyst; li Miao et al, rubber and plastic technology and equipment, 2015, 41 (13): 11-15, uniformly mixing rubber powder and an activating agent in a high-temperature stirring kettle. The stirring temperature is 140 ℃, 150 ℃, 160 ℃, 170 ℃ respectively, and then the regeneration is carried out by utilizing a Haake torque rheometer, so that the influence of a regeneration process is studied; chinese patent CN202180069584.6 discloses a method for preparing styrene-butadiene rubber containing recycled rubber powder, which comprises preparing suspension from rubber powder, water and surfactant, mixing with seed styrene-butadiene latex, and flocculating to prepare composite rubber; sedan et al, high molecular materials science and engineering, 2012, 28 (2): 96-100, explored the effect of activators on promoting desulfurization and inhibiting crosslinking by adding activators (alkylphenol polysulfides). The preparation method has the advantages of low regeneration desulfurization efficiency, high energy consumption and complex preparation process, if a higher desulfurization effect is to be obtained, the reaction temperature needs to be increased, the problems of pollution and damage to the mechanical properties of rubber are generally existed in the use of a small molecular solvent and a regeneration reagent, and meanwhile, the molecular weight of reclaimed rubber powder and the influence of the molecular weight on the properties of composite rubber are not fully considered.
According to the invention, the environment-friendly natural latex and ammonium bicarbonate solution are used as media, the coordination effect of sulfur radicals generated by the fracture of inorganic metal salt and rubber powder is utilized to destroy a crosslinking network, the reaction conditions are controlled through the mechanical shearing effect, the preparation of the regenerated rubber powder with different molecular weights is realized, the preparation process is simple and convenient, the environment is protected, and the method has important significance for the regeneration preparation and the recycling of the waste tire rubber powder.
Disclosure of Invention
The invention aims to provide a preparation method of a compound natural rubber of reclaimed rubber powder of a controllable molecular weight waste tire, aiming at the defects of the prior art, and is characterized in that firstly, natural latex and ammonium bicarbonate solution with certain concentration are used as green solvents, and the waste tire rubber powder is fully permeated and swelled under the mechanical stirring and high-temperature heating effects, so that the acting force among rubber powder molecular chains is weakened, and the plasticity is increased; mechanically strong shearing action is carried out on the treated waste tire rubber powder and inorganic metal salt in an internal mixer, sulfur free radicals generated by fracture of a rubber powder crosslinking network under the action of shearing force can coordinate with the metal salt, so that the sulfur free radicals are prevented from participating in vulcanization crosslinking reaction, the sulfur free radicals are prevented from attacking unsaturated bonds of a rubber powder molecular main chain, the influence on the rubber powder molecular main chain structure in the regeneration process is weakened, and the molecular weight of the regenerated rubber powder of the waste tire is regulated and controlled by controlling the shearing temperature, the rotating speed and the shearing time; mixing the obtained waste tire reclaimed rubber powder, natural rubber and other auxiliary agents on an open mill, so as to realize good dispersion of the waste rubber powder, prepare the waste tire reclaimed rubber powder composite natural rubber composite material through hot pressing and vulcanization, and play a role in reinforcing the waste rubber powder.
The aim of the invention is achieved by the following technical scheme, wherein the raw material fractions are mass fractions except for special descriptions.
The preparation method of the composite natural rubber of the reclaimed rubber powder of the scrap tire with the controllable molecular weight is characterized in that the main raw materials comprise the following components in parts by mass:
20-80 parts of waste tyre rubber powder
100 Parts of natural latex
75 Parts of natural rubber
Ammonium bicarbonate 5-15 parts
Inorganic metal salt 2-12 parts
Wherein the mesh number of the waste tire rubber powder is 30-100 meshes;
The inorganic metal salt is any one or two of zinc chloride, zinc acetate, zinc oxide, zinc sulfate, copper chloride and ferric chloride.
The preparation method of the composite natural rubber of the reclaimed rubber powder of the scrap tire with the controllable molecular weight comprises the following steps:
preparing the reclaimed rubber powder of the waste tires with controllable molecular weight:
diluting 100 parts of natural latex (solid content is 25%) with deionized water to 3-10wt%, adding 5-15 parts of ammonium bicarbonate, stirring to dissolve completely, adding 20-80 parts of 30-100 mesh waste tire rubber powder, fully stirring at 80 ℃ for reaction of 5-18 h, fully penetrating and swelling the rubber powder by using the swelling effect of the natural latex and the swelling effect of gas generated by decomposing the ammonium bicarbonate at low temperature, and vacuum drying at 60 ℃ for 6-h; and (3) carrying out mechanical strong shearing action on the treated rubber powder and 2-12 parts of inorganic metal salt in an internal mixer, wherein the internal mixing temperature is 150-240 ℃, the internal mixing rotating speed is 30-80 r/min, the internal mixing time is 8-60 min, and after the internal mixing is finished, naturally cooling to obtain the reclaimed rubber powder of the waste tires with different molecular weights.
Preparing the waste tire reclaimed rubber powder composite natural rubber:
Mixing the prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 1-3 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 0.5-2 parts of sulfur uniformly on an open mill, realizing good dispersion of the waste rubber powder, and hot-pressing at 140-180 ℃ and 15 MPa for 8-40 min to obtain the natural rubber composite material.
The invention has the following advantages:
According to the invention, the natural latex and the ammonium bicarbonate solution are used as environment-friendly solution media, the natural latex is used for fully swelling the waste tire rubber powder, ammonia gas and carbon dioxide generated by decomposing the ammonium bicarbonate are utilized for penetrating the rubber powder, so that the distance between rubber molecular chains is increased, the entanglement of the molecular chains is weakened, meanwhile, the plasticity of the rubber molecular chains is increased, and the subsequent desulfurization regeneration is promoted; the polar sulfur free radical has strong activity, the sulfur free radical generated by breaking the crosslinking network of the rubber powder under the mechanical shearing action can coordinate with metal salt to prevent the re-crosslinking reaction after desulfurization, and meanwhile, the influence on the molecular main chain structure of the rubber powder in the regeneration process is weakened, and the regenerated rubber powder with different molecular weights is obtained by regulating and controlling the reaction conditions and processes of the mechanical shearing temperature, the rotating speed and the time. The natural rubber composite material with enhanced mechanical properties is prepared by mixing and processing the reclaimed rubber powder with different molecular weights and the natural rubber, so that the high-value recycling of the waste tire rubber powder is realized. The preparation method is simple and convenient, mild in condition and high in efficiency, and is beneficial to industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of a brittle fracture section of a reclaimed rubber powder composite natural rubber of a scrap tire
The reclaimed rubber powder of the waste tire is well dispersed in the natural rubber matrix, has better interface combination and has no obvious phase separation phenomenon.
Detailed Description
The invention is further described below by means of specific examples, which are given herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous modifications and adaptations of the invention will occur to those skilled in the art upon consideration of the foregoing disclosure.
Examples
Diluting 100 parts of natural latex (solid content 25%) with deionized water to a concentration of 10wt%, adding 4 parts of ammonium bicarbonate, stirring to dissolve completely, adding 20 parts of 50-mesh waste tire rubber powder, stirring at 80 ℃ to react for 6 h, fully swelling the rubber powder, filtering, and vacuum drying at 60 ℃ for 6 h; and (3) carrying out mechanical strong shearing action on the treated rubber powder and 4 parts of zinc chloride in an internal mixer, wherein the internal mixing temperature is 170 ℃, the internal mixing rotating speed is 50r/min, the internal mixing time is 25 min, and after the internal mixing is finished, naturally cooling to obtain the reclaimed rubber powder of the waste tire. Cyclohexane is used as a solvent, the content of sol is tested to be 58%, dimethylbenzene is used as a mobile phase, and the relative molecular weight of the regenerated rubber powder sol is tested to be 9.3 ten thousand by gel permeation chromatography.
The prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 3 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 1.2 parts of sulfur are uniformly mixed on an open mill, so that good dispersion of the waste rubber powder is realized, and the natural rubber composite material is obtained by hot-pressing 20 min at 145 ℃ and 15 MPa. The tensile strength was measured to be 6.4 MPa and the elongation at break was measured to be 479%.
Examples
Diluting 100 parts of natural latex (solid content is 25%) with deionized water to a concentration of 8wt%, adding 5 parts of ammonium bicarbonate, stirring to dissolve completely, adding 30 parts of 80-mesh waste tire rubber powder, stirring at 80 ℃ to react for 6h, fully swelling the rubber powder, filtering, and vacuum drying at 60 ℃ for 6 h; and (3) carrying out mechanical strong shearing action on the treated rubber powder and 6 parts of zinc oxide in an internal mixer, wherein the internal mixing temperature is 170 ℃, the internal mixing rotating speed is 70 r/min, the internal mixing time is 30min, and after the internal mixing is finished, naturally cooling to obtain the reclaimed rubber powder of the waste tire. The content of sol is tested to be 52% by taking cyclohexane as a solvent, and the relative molecular weight of the regenerated rubber powder sol is tested to be 8.4 ten thousand by taking dimethylbenzene as a mobile phase through gel permeation chromatography.
Uniformly mixing the prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 3 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 2 parts of sulfur on an open mill, realizing good dispersion of the waste rubber powder, and hot-pressing at 155 ℃ and 15 MPa for 23: 23 min to obtain the natural rubber composite material. The tensile strength was measured to be 6.9 MPa and the elongation at break was measured to be 424%.
Examples
Diluting 100 parts of natural latex (solid content 25%) with deionized water to a concentration of 6wt%, adding 6 parts of ammonium bicarbonate, stirring to dissolve completely, adding 35 parts of 100-mesh waste tire rubber powder, stirring at 80 ℃ to react 8 h, swelling the rubber powder sufficiently, filtering, and vacuum drying at 60 ℃ to 6 h; and (3) carrying out mechanical strong shearing action on the treated rubber powder and 8 parts of zinc acetate in an internal mixer, wherein the internal mixing temperature is 165 ℃, the internal mixing rotating speed is 55 r/min, the internal mixing time is 35 min, and after the internal mixing is finished, naturally cooling to obtain the reclaimed rubber powder of the waste tire. The content of sol is tested to be 79% by taking cyclohexane as a solvent, and the relative molecular weight of the regenerated rubber powder sol is tested to be 11.9 ten thousand by taking dimethylbenzene as a mobile phase through gel permeation chromatography.
The prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 2 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 1.5 parts of sulfur are uniformly mixed on an open mill, so that good dispersion of the waste rubber powder is realized, and the natural rubber composite material is obtained by hot-pressing 28 min at 160 ℃ and 15 MPa. The tensile strength was measured to be 10.1 MPa and the elongation at break was measured to be 527%.
Examples
Diluting 100 parts of natural latex (solid content 25%) with deionized water to a concentration of 6wt%, adding 6 parts of ammonium bicarbonate, stirring to dissolve completely, adding 35 parts of 100-mesh waste tire rubber powder, stirring at 80 ℃ to react 8 h, swelling the rubber powder sufficiently, filtering, and vacuum drying at 60 ℃ to 6 h; and (3) carrying out mechanical strong shearing action on the treated rubber powder and 8 parts of copper chloride in an internal mixer, wherein the internal mixing temperature is 165 ℃, the internal mixing rotating speed is 55 r/min, the internal mixing time is 35 min, and after the internal mixing is finished, naturally cooling to obtain the reclaimed rubber powder of the waste tire. The content of sol is tested to be 72% by taking cyclohexane as a solvent, and the relative molecular weight of the regenerated rubber powder sol is tested to be 10.8 ten thousand by taking dimethylbenzene as a mobile phase through gel permeation chromatography.
The prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 2 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 1.5 parts of sulfur are uniformly mixed on an open mill, so that good dispersion of the waste rubber powder is realized, and the natural rubber composite material is obtained by hot-pressing 28 min at 160 ℃ and 15 MPa. The tensile strength was measured to be 9.2 MPa and the elongation at break was measured to be 548%.
Examples
Diluting 100 parts of natural latex (solid content 25%) with deionized water to a concentration of 6wt%, adding 6 parts of ammonium bicarbonate, stirring to dissolve completely, adding 35 parts of 100-mesh waste tire rubber powder, stirring at 80 ℃ to react 8 h, swelling the rubber powder sufficiently, filtering, and vacuum drying at 60 ℃ to 6 h; and (3) carrying out mechanical strong shearing action on the treated rubber powder and 8 parts of ferric chloride in an internal mixer, wherein the internal mixing temperature is 165 ℃, the internal mixing rotating speed is 55 r/min, the internal mixing time is 35 min, and after the internal mixing is finished, naturally cooling to obtain the reclaimed rubber powder of the waste tire. Cyclohexane is used as a solvent, the sol content is tested to be 67%, dimethylbenzene is used as a mobile phase, and the relative molecular weight of the regenerated rubber powder sol is tested to be 10.1 ten thousand by gel permeation chromatography.
The prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 2 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 1.5 parts of sulfur are uniformly mixed on an open mill, so that good dispersion of the waste rubber powder is realized, and the natural rubber composite material is obtained by hot-pressing 28 min at 160 ℃ and 15 MPa. The tensile strength was measured to be 9.5 MPa and the elongation at break was measured to be 488%.
Examples
Diluting 100 parts of natural latex (solid content 25%) with deionized water to 3wt%, adding 12 parts of ammonium bicarbonate, stirring to dissolve completely, adding 80 parts of 60-mesh waste tire rubber powder, stirring at 80deg.C for reaction 15h to make the rubber powder swell sufficiently, filtering, and vacuum drying at 60deg.C for 6 h; and (3) carrying out mechanical strong shearing action on the treated rubber powder, 4 parts of zinc chloride and 8 parts of zinc acetate in an internal mixer, wherein the internal mixing temperature is 190 ℃, the internal mixing rotating speed is 60 r/min, the internal mixing time is 40 min, and naturally cooling after the internal mixing is finished to obtain the reclaimed rubber powder of the waste tire. The content of the sol is tested to be 64% by taking cyclohexane as a solvent, and the relative molecular weight of the regenerated rubber powder sol is tested to be 12.6 ten thousand by taking dimethylbenzene as a mobile phase through gel permeation chromatography.
The prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 2 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 1.8 parts of sulfur are uniformly mixed on an open mill, so that good dispersion of the waste rubber powder is realized, and the natural rubber composite material is obtained by hot-pressing 35 min at 175 ℃ and 15 MPa. The tensile strength was measured to be 13.8 MPa and the elongation at break was measured to be 579%.
Examples
Diluting 100 parts of natural latex (solid content 25%) with deionized water to 3wt%, adding 12 parts of ammonium bicarbonate, stirring to dissolve completely, adding 80 parts of 60-mesh waste tire rubber powder, stirring at 80deg.C for reaction 15h to make the rubber powder swell sufficiently, filtering, and vacuum drying at 60deg.C for 6 h; and (3) carrying out mechanical strong shearing action on the treated rubber powder, 4 parts of zinc oxide and 8 parts of copper chloride in an internal mixer, wherein the internal mixing temperature is 190 ℃, the internal mixing rotating speed is 60 r/min, the internal mixing time is 40 min, and naturally cooling after the internal mixing is finished to obtain the reclaimed rubber powder of the waste tire. Cyclohexane is used as a solvent, the content of sol is tested to be 60 percent, dimethylbenzene is used as a mobile phase, and the relative molecular weight of the regenerated rubber powder sol is tested to be 11.1 ten thousand by gel permeation chromatography.
The prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 2 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 1.8 parts of sulfur are uniformly mixed on an open mill, so that good dispersion of the waste rubber powder is realized, and the natural rubber composite material is obtained by hot-pressing 35 min at 175 ℃ and 15 MPa. The tensile strength was measured to be 13.2 MPa and the elongation at break was measured to be 601%.
Comparative example 1
Directly carrying out mechanical strong shearing action on 20 parts of 50-mesh waste tire rubber powder in an internal mixer, wherein the internal mixing temperature is 170 ℃, the internal mixing rotating speed is 50 r/min, the internal mixing time is 25 min, and naturally cooling after finishing to obtain the waste tire reclaimed rubber powder. The content of sol is tested to be 29% by taking cyclohexane as a solvent, and the relative molecular weight of the regenerated rubber powder sol is tested to be 6.4 ten thousand by taking dimethylbenzene as a mobile phase through gel permeation chromatography.
The prepared waste tire reclaimed rubber powder, 75 parts of natural rubber, 3 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 1.2 parts of sulfur are uniformly mixed on an open mill, so that good dispersion of the waste rubber powder is realized, and the natural rubber composite material is obtained by hot-pressing 20 min at 145 ℃ and 15 MPa. The tensile strength was measured to be 4.1 MPa and the elongation at break was measured to be 337%.
In summary, the embodiment of the invention can obtain the reclaimed rubber powder of the waste tire with controllable molecular weight by changing the concentration of the natural latex and the content of ammonium bicarbonate, regulating and controlling the type and the content of inorganic metal salt and banburying and shearing processes. The mechanical property of the natural rubber is enhanced by mixing the reclaimed rubber powder with different molecular weights with the natural rubber, so that the reclaimed rubber powder of the waste tire is recycled. Through the embodiment 1 and the comparative example 1, the waste tire rubber powder is activated by adopting the natural latex and the ammonium bicarbonate and then reacts with the metal salt, so that the regeneration effect can be obviously improved, the molecular weight of the sol is increased, and the mechanical property of the composite natural rubber is improved.
While the invention has been described in detail with reference to the specific embodiments, it will be understood by those skilled in the art that the invention is not limited thereto, and that equivalents thereof may be substituted and remain within the scope of the invention.
Claims (1)
1. The preparation method of the composite natural rubber of the reclaimed rubber powder of the scrap tire with the controllable molecular weight is characterized in that the main raw materials comprise the following components in parts by mass:
20-80 parts of waste tire rubber powder;
100 parts of natural latex;
75 parts of natural rubber;
5-15 parts of ammonium bicarbonate;
2-12 parts of inorganic metal salt;
Wherein the mesh number of the waste tire rubber powder is 30-100 meshes; the inorganic metal salt is any one or two of zinc chloride, zinc acetate, zinc oxide, zinc sulfate, copper chloride and ferric chloride; the preparation method of the composite natural rubber of the reclaimed rubber powder of the scrap tire with the controllable molecular weight comprises the following steps: preparing the reclaimed rubber powder of the waste tires with controllable molecular weight: diluting 100 parts of natural latex with 25% of solid content by deionized water to 3-10wt% of concentration, adding 5-15 parts of ammonium bicarbonate, stirring until the ammonium bicarbonate is completely dissolved, then adding 20-80 parts of 30-100-mesh waste tire rubber powder, fully stirring at 80 ℃ for reaction of 5-18 h, fully penetrating and swelling the rubber powder by utilizing the swelling effect of the natural latex and the swelling effect of gas generated by low-temperature decomposition of the ammonium bicarbonate, and vacuum drying at 60 ℃ for 6-h; mechanically strong shearing the treated rubber powder and 2-12 parts of inorganic metal salt in an internal mixer, wherein the internal mixing temperature is 150-240 ℃, the internal mixing rotating speed is 30-80 r/min, the internal mixing time is 8-60 min, and after the internal mixing, the rubber powder is naturally cooled to obtain the reclaimed rubber powder of the waste tires with different molecular weights; preparing the waste tire reclaimed rubber powder composite natural rubber: uniformly mixing the prepared reclaimed rubber powder of the waste tire with 75 parts of natural rubber, 1-3 parts of zinc oxide, 0.5 part of stearic acid, 0.5 part of accelerator CZ, 0.3 part of accelerator M and 0.5-2 parts of sulfur on an open mill, realizing good dispersion of the waste rubber powder, and hot-pressing at 140-180 ℃ and 15 MPa for 8-40 min to obtain the natural rubber composite material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101456968A (en) * | 2009-01-09 | 2009-06-17 | 北京化工大学 | Method for reproducing waste rubber by using microorganism |
| CN101817934A (en) * | 2010-04-26 | 2010-09-01 | 南京工业大学 | Process for stress-induced desulfurization reaction of waste tire rubber |
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| KR20030084427A (en) * | 2002-04-26 | 2003-11-01 | 김진국 | The manufacture of shoe outsole using NR and waste tire powder |
| US7250451B2 (en) * | 2004-03-09 | 2007-07-31 | American Rubber Technologies, Inc. | Recycled rubber processing and performance enhancement |
| JP5094135B2 (en) * | 2006-01-20 | 2012-12-12 | 株式会社ブリヂストン | Method for producing natural rubber and / or synthetic isoprene rubber masterbatch using powder rubber and filler |
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| CN101456968A (en) * | 2009-01-09 | 2009-06-17 | 北京化工大学 | Method for reproducing waste rubber by using microorganism |
| CN101817934A (en) * | 2010-04-26 | 2010-09-01 | 南京工业大学 | Process for stress-induced desulfurization reaction of waste tire rubber |
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