CN111777835A - Inflation-free tire material and preparation method thereof - Google Patents
Inflation-free tire material and preparation method thereof Download PDFInfo
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- CN111777835A CN111777835A CN201910271041.7A CN201910271041A CN111777835A CN 111777835 A CN111777835 A CN 111777835A CN 201910271041 A CN201910271041 A CN 201910271041A CN 111777835 A CN111777835 A CN 111777835A
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- inflation
- tire material
- hydrogenated
- free tire
- sebs
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 40
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 37
- 239000005060 rubber Substances 0.000 claims abstract description 32
- 238000005859 coupling reaction Methods 0.000 claims abstract description 27
- 230000008878 coupling Effects 0.000 claims abstract description 26
- 238000010168 coupling process Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000011049 filling Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004606 Fillers/Extenders Substances 0.000 claims description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 2
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 238000013016 damping Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 13
- 239000000806 elastomer Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an inflation-free tire material and a preparation method thereof, wherein the inflation-free tire material comprises coupling SEBS, hydrogenated S-B (S) -S, rubber filling oil, plastics, an anti-aging agent, an anti-ultraviolet agent, an anti-wear agent and other auxiliary materials. The preparation method comprises the steps of uniformly mixing hydrogenated S-B (S) -S and coupling SEBS with rubber filling oil, then melting and extruding the mixture together with other auxiliary materials, and granulating to obtain the rubber filling oil. The tire prepared from the inflation-free tire material for the vehicle has excellent wet skid resistance, and good damping effect and riding comfort.
Description
Technical Field
The invention relates to an inflation-free tire material, in particular to a composite inflation-free tire material for improving the slip resistance and riding comfort of a tire by using a hydrogenated S-B (S) -S and coupling SEBS mixture, belonging to the technical field of modified rubber.
Background
Bicycle tires are classified into non-pneumatic tires and pneumatic tires. The inflation-free tire is limited in application because of large weight, poor damping effect and poor riding comfort. However, with the improvement of processing technology and new material technology and the wide-scale release of shared bicycles in China, the non-inflatable tire is adopted as the bicycle tire, so that the manual damage can be reduced, the inflation and maintenance cost can be reduced, and the service life of the tire can be prolonged.
Elastomers commonly used in bicycle tires include natural rubber, styrenic elastomers, ethylene-propylene-diene terpolymers EPDM (i.e., ethylene-propylene-diene terpolymer rubber), ethylene-propylene copolymers EP, polyisoprene NR, polychloroprene, butylene-diene copolymers (isoprene or other diene monomer), polyurethane PU, and other vulcanizable copolymer synthetic rubbers.
At present, the bicycle non-inflatable tire materials with excellent performance and widely adopted comprise two main types of polyurethane elastomers and hydrogenated styrene elastomers. Patents of polyurethane elastomers used as tires, such as CN102212180A, CN104497252A, CN104693401A, CN105330811A and CN106189198A, all provide a method for preparing polyurethane for non-pneumatic tires, which has good wear resistance, high tear strength and strong bearing capacity. But all have the problems of various additives, large processing environmental odor, high requirement on equipment, complex waste material recovery process and the like.
The existing hydrogenated styrene elastomer SEBS has good rebound resilience of rubber at normal temperature, shows the fluidity of resin at high temperature, can be directly processed and molded without vulcanization, and has simple processing technology. The leftover bits and pieces can be recycled, the waste material can be recycled, the manufacturing cost is reduced, and the environment is protected. The solubility of the SEBS and the blending property of the filler are good, the processing performance of the blend can be improved, the use temperature of the blend can be increased, and the riding difficulty of the tire in the summer use process can be avoided. And the SEBS filling rubber material has excellent outdoor insolation resistance. SEBS becomes a more preferred material for the bicycle pneumatic tire. However, the bicycle non-pneumatic tire prepared from the hydrogenated styrene elastomer SEBS still has the problems of poor slip resistance, poor damping comfort and the like in the using process.
Disclosure of Invention
Aiming at the problems of the polyurethane elastomer and hydrogenated styrene elastomer bicycle inflation-free tire materials in the prior art, the first purpose of the invention is to provide a bicycle inflation-free tire material which uses hydrogenated S-B (S) -S polymer and coupling SEBS as main raw materials, and the tire prepared from the bicycle inflation-free tire material has excellent wet skid resistance, shock absorption effect and riding comfort.
The invention also aims to provide a method for preparing the inflation-free tire material for the bicycle, which has the advantages of simple process, no need of vulcanization, recyclable leftover materials, safety, environmental protection and low cost.
In order to achieve the technical purpose, the invention provides an inflation-free tire material which comprises coupling SEBS, hydrogenated S-B (S) -S and auxiliary materials.
In a preferred scheme, the coupling SEBS is a hydrogenated multi-arm star-shaped styrene-butadiene copolymer; wherein the single arm is hydrogenated styrene-butadiene block copolymer or hydrogenated styrene-butadiene-styrene block polymer, and the number of arms is 3-8. Most preferably 4 arms. The coupling SEBS is prepared by coupling a styrene-butadiene block copolymer or a styrene-butadiene-styrene block copolymer by adopting a coupling agent commonly used in the field to obtain a star polymer and then hydrogenating by using a cyclopentadienyl titanium catalytic system. Coupling agents such as silicon tetrachloride and the like.
Preferably, the number average molecular weight of the coupling SEBS is 150000-300000.
In a preferable scheme, the mass percentage content of the styrene block in the coupling SEBS is 25-40%.
In a preferred embodiment, the hydrogenated S-B (S) -S is a hydrogenated styrene-random styrene/butadiene-styrene block polymer. The hydrogenated S-B (S) -S is a hydrogenation product of a styrene-random styrene/butadiene-styrene triblock polymer through a titanocene catalytic system.
In a preferred embodiment, the hydrogenated S-B (S) -S has a number average molecular weight of 50000 to 100000.
Preferably, the mass percent content of the styrene block in the hydrogenated S-B (S) -S is 30-50%, and the mass percent content of the styrene block in the random styrene/butadiene block is not more than 30%.
In a preferred scheme, the auxiliary materials comprise rubber filling oil, plastics, an anti-aging agent, an anti-ultraviolet agent and an anti-wear agent.
In a preferred scheme, the inflation-free tire material comprises the following components in parts by weight: coupling type SEBS: 20-50 parts of a solvent; rubber extender oil: 20-50 parts of a solvent; hydrogenation of S-B (S) -S: 5-20 parts of a solvent; plastic: 5-30 parts of a solvent; an anti-aging agent: 0.1-1 part; 0.1-0.5 part of anti-ultraviolet agent; 0.5-2 parts of an anti-wear agent.
Preferably, the rubber extender oil comprises a naphthenic rubber oil and/or a paraffinic rubber oil.
Preferably, the plastic comprises at least one of polypropylene, polyethylene and polystyrene. Wherein the polypropylene comprises homo-polypropylene and/or co-polypropylene.
Preferably, the antioxidant comprises at least one of octadecyl beta (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (antioxidant 1076), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant TH-24), and dilauryl thiodipropionate (antioxidant DLTP).
Preferably, the uvioresistant agent comprises at least one of 2-hydroxy-4-n-octyloxybenzophenone (uv531), (2-hydroxy-4-methoxyphenyl) phenyl ketone (uv9), 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (uv326), and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate (uv2908), preferably uv 531.
Preferably, the wear-resistant agent includes silicone master batch.
The coupling SEBS and the hydrogenated S-B (S) -S are obtained by anion polymerization base rubber and selective hydrogenation by using a titanium catalyst, and specifically comprise the following steps:
synthesis of coupling type SEBS:
(1) synthesis of a coupling SEBS (1) base adhesive: injecting cyclohexane solvent into a polymerization kettle, and adding a regulator and an initiator; and (2) adding styrene at the temperature of 60-65 ℃ in a polymerization kettle, initiating a first-stage reaction by n-butyllithium, adding a butadiene monomer at the temperature of 60-80 ℃ for second-stage polymerization, and finally adding silicon tetrachloride for coupling reaction to obtain the base adhesive through polymerization.
(2) Hydrogenation of the base rubber: pressing the base rubber into a hydrogenation kettle, carrying out a passivation reaction with a cocatalyst dimethyl phthalate at 70-75 ℃, and carrying out a hydrogenation reaction with a main catalyst dicyclopentadiene titanium dichloride under hydrogen, wherein the hydrogenation degree of a polybutadiene section is more than or equal to 98%, and the hydrogenation degree of a benzene ring is less than or equal to 5%; obtaining the coupling SEBS.
Hydrogenation of S-B (S) -S Synthesis:
(1) hydrogenated S-B (S) -S (1) base gum synthesis: injecting cyclohexane solvent into a polymerization kettle, and adding a regulator and an initiator; and (2) adding styrene into the polymerization kettle at the temperature of 60-65 ℃, initiating a first-stage reaction by n-butyllithium, adding a mixed monomer of styrene and butadiene at the temperature of 60-80 ℃, carrying out second-stage polymerization, finally adding styrene to carry out third-stage polymerization reaction, and polymerizing to obtain the base adhesive.
(2) Hydrogenation of the base rubber: pressing the base rubber into a hydrogenation kettle, carrying out passivation reaction with a cocatalyst dimethyl phthalate at 70-75 ℃, and carrying out hydrogenation reaction with a main catalyst dicyclopentadiene titanium dichloride under the hydrogen pressure of 1.5Mpa for 2 hours; wherein, the hydrogenation degree of the polybutadiene section is more than or equal to 98 percent, and the hydrogenation degree of the benzene ring is less than or equal to 5 percent; obtaining hydrogenated S-B (S) -S.
The invention also provides a preparation method of the inflation-free tire material, which comprises the steps of uniformly mixing the hydrogenated S-B (S) -S and the coupling SEBS with the rubber filling oil, melting and extruding the mixture together with other auxiliary materials, and granulating the mixture to obtain the inflation-free tire material.
In the preferred scheme, a double-screw extruder is adopted in the melt extrusion process, and the temperature of each section of the double-screw extruder is 180-185 ℃, 190-200 ℃ and the head temperature is 200-210 ℃ from a feeding port in sequence.
The preparation method of the bicycle inflation-free tire material comprises the following specific steps:
1) weighing the raw materials in parts
2) Mixing: the mixture of hydrogenated S-B (S) -S and star SEBS fully absorbs the rubber filling oil, and then is added into a stirrer together with other auxiliary components to be uniformly mixed.
3) And (3) granulation: extruding and granulating by using a double-screw extruder with forced feeding, and finally drying and packaging; in the step, the temperature of each section of the double-screw extruder is from a feed inlet to 180-185 ℃, 190-200 ℃ and the head temperature is 200-210 ℃ in sequence.
Compared with the prior art, the invention has the beneficial effects that:
the key point of the material for the bicycle inflation-free tire is that two thermoplastic elastomers of hydrogenated S-B (S) -S and coupling SEBS are adopted at the same time, wherein the hydrogenated S-B (S) -S can improve the compatibility of the elastomer with plastics and inorganic fillers and reduce the dynamic internal consumption; the coupling SEBS has good resilience and strength, and the coupling SEBS have synergistic effect, so that the bicycle inflation-free tire material with good comprehensive performance is obtained, for example, the bicycle inflation-free tire material has good wear resistance, excellent resilience and riding comfort, and the defects existing in hydrogenated styrene elastomers, polyurethane elastomers and the like serving as the bicycle inflation-free tire material in the prior art are well overcome.
The preparation method of the bicycle inflation-free tire material can utilize the existing processing method of the bicycle inflation-free tire material, has simple process, does not need vulcanization, can recycle leftover materials, is safe and environment-friendly, has low cost, and is beneficial to industrial production.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention as claimed.
In the following examples, the coupling SEBS is a hydrogenated multi-arm star-shaped styrene-butadiene copolymer, the number of arms is 4, the number average molecular weight is about 200000, and the mass percent content of the styrene block is 30%. Hydrogenated S-B (S) -S has a number average molecular weight of about 80000, a styrene block content of 40% by mass, and a styrene block content of about 15% by mass in the random styrene/butadiene block.
The preparation method of the bicycle inflation-free tire material in the following embodiment comprises the following specific steps:
1) weighing the raw materials in parts
2) Mixing: the mixture of hydrogenated S-B (S) -S and star SEBS fully absorbs the rubber filling oil, and then is added into a stirrer together with other auxiliary components to be uniformly mixed.
3) And (3) granulation: extruding and granulating by using a double-screw extruder with forced feeding, and finally drying and packaging; in the step, the temperature of each section of the double-screw extruder is from a feed inlet to 180-185 ℃, 190-200 ℃ and the head temperature is 200-210 ℃ in sequence.
Example 1
Weighing the following raw materials: 45 parts of star SEBS; 45 parts of paraffin-based rubber oil; 10 parts of PP; LDPE10 parts by weight; 0.4 part by weight of antioxidant; and 1.5 parts of an auxiliary agent. Mixing, granulating and measuring the performance. See Table 1
Example 2
Weighing the following raw materials: 30 parts of star SEBS; hydrogenated S-B (S) -S15 parts by weight; 45 parts of paraffin-based rubber oil; 10 parts of PP; LDPE10 parts by weight; 0.4 part by weight of antioxidant; and 1.5 parts of an auxiliary agent. Mixing, granulating and measuring the performance. See Table 1
Example 3
Weighing the following raw materials: 27 parts of star SEBS; hydrogenated S-B (S) -S18 parts by weight; 45 parts of paraffin-based rubber oil; 10 parts of PP; LDPE10 parts by weight; 0.4 part by weight of antioxidant; and 1.5 parts of an auxiliary agent. Mixing, granulating and measuring the performance. See Table 1
Example 4
Weighing the following raw materials: 22.5 parts of star SEBS; hydrogenated S-B (S) -S22.5 parts by weight; 45 parts of paraffin-based rubber oil; 10 parts of PP; LDPE10 parts by weight; 0.4 part by weight of antioxidant; and 1.5 parts of an auxiliary agent. Mixing, granulating and measuring the performance. See Table 1
Table 1 physical property test results
Note: melt index MFR is the melt index loaded at 5Kg, 200 ℃.
The test results show that: as the addition amount of hydrogenated S-B (S) -S increases, the permanent deformation becomes significantly smaller. Indicating that the resilience of the material becomes better.
Example 5
Weighing the following raw materials: 30 parts of star SEBS; hydrogenated S-B (S) -S20 parts by weight; 45 parts of paraffin-based rubber oil; 15 parts of PP; 0.4 part by weight of antioxidant; and 1.5 parts of an auxiliary agent. Mixing, granulating and measuring the performance.
The master batches prepared in the examples 2 and 5 were pressed into tablets on a vulcanizing machine, and the dynamic mechanical properties of the materials were measured. The test condition is a stretching mode, the frequency is 5Hz, the strain is 7 +/-0.25%, the temperature scanning range is-50-80 ℃, and the temperature rise speed is 2 ℃/min. The test results are shown in Table 2
TABLE 2 DMA test results
The test results from table 2 show that: the large addition amount of hydrogenated S-B (S) -S results in small Tan, which indicates that the internal consumption of the material is reduced, the damping is small, the riding comfort is good, and the wear resistance is also good.
Claims (16)
1. An inflation-free tire material is characterized in that: comprises coupling SEBS, hydrogenated S-B (S) -S and auxiliary materials.
2. An inflation-free tire material as claimed in claim 1, wherein: the coupling SEBS is a hydrogenated multi-arm star-shaped styrene-butadiene copolymer; wherein the single arm is hydrogenated styrene-butadiene block copolymer or hydrogenated styrene-butadiene-styrene block polymer, and the number of arms is 3-8.
3. An inflation-free tire material as claimed in claim 2, wherein: the number average molecular weight of the coupling SEBS is 150000-300000.
4. A non-pneumatic tire material as in claim 3, wherein: the mass percentage content of the styrene block in the coupling SEBS is 25-40%.
5. An inflation-free tire material as claimed in claim 1, wherein: the hydrogenated S-B (S) -S is a hydrogenated styrene-random styrene/butadiene-styrene block polymer.
6. An inflation-free tire material as claimed in claim 5, wherein: the hydrogenated S-B (S) -S has a number average molecular weight of 50000-100000.
7. An inflation-free tire material as claimed in claim 6, wherein: the mass percent content of the styrene block in the hydrogenated S-B (S) -S is 30-50%, and the mass percent content of the styrene block in the random styrene/butadiene block is not more than 30%.
8. An inflation-free tire material as claimed in claim 1, wherein: the auxiliary materials comprise rubber filling oil, plastics, an anti-aging agent, an anti-ultraviolet agent and an anti-wear agent.
9. An inflation-free tire material as claimed in any one of claims 1 to 8, wherein:
the paint comprises the following components in parts by weight:
coupling type SEBS: 20-50 parts of a solvent;
rubber extender oil: 20-50 parts of a solvent;
hydrogenation of S-B (S) -S: 5-20 parts of a solvent;
plastic: 5-30 parts of a solvent;
an anti-aging agent: 0.1-1 part;
0.1-0.5 part of anti-ultraviolet agent;
0.5-2 parts of an anti-wear agent.
10. An inflation-free tire material as claimed in claim 9, wherein: the rubber extender oil comprises a naphthenic rubber oil and/or a paraffin-based rubber oil.
11. An inflation-free tire material as claimed in claim 9, wherein: the plastic comprises at least one of polypropylene, polyethylene and polystyrene.
12. An inflation-free tire material as claimed in claim 9, wherein: the anti-aging agent comprises at least one of octadecyl beta (4-hydroxy-3, 5-di-tert-butylphenyl) propionate, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and dilauryl thiodipropionate.
13. An inflation-free tire material as claimed in claim 9, wherein: the uvioresistant agent comprises at least one of 2-hydroxy-4-n-octoxybenzophenone, (2-hydroxy-4-methoxyphenyl) phenyl ketone, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole and 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl.
14. An inflation-free tire material as claimed in claim 9, wherein: the wear-resistant agent comprises silicone master batch.
15. A method for preparing an inflation-free tire material as claimed in any one of claims 1 to 14, wherein: uniformly mixing hydrogenated S-B (S) -S and coupling SEBS with rubber filling oil, melting and extruding the mixture together with other auxiliary materials, and granulating to obtain the rubber filling material.
16. The method for preparing a non-pneumatic tire material as claimed in claim 15, wherein: the melt extrusion process adopts a double-screw extruder, the temperature of each section of the double-screw extruder is from a charging opening to 180-185 ℃, 190-200 ℃ and the head temperature is 200-210 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112606628A (en) * | 2021-01-21 | 2021-04-06 | 广东云韬新材料科技有限公司 | Double-color injection-molded TPE (thermoplastic elastomer) plastic elastomer inflation-free tire and manufacturing process thereof |
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