WO2023281527A1 - Elastomeric tire nanocomposite with polymer coated carbon nanotubes and method thereof - Google Patents
Elastomeric tire nanocomposite with polymer coated carbon nanotubes and method thereof Download PDFInfo
- Publication number
- WO2023281527A1 WO2023281527A1 PCT/IN2022/050610 IN2022050610W WO2023281527A1 WO 2023281527 A1 WO2023281527 A1 WO 2023281527A1 IN 2022050610 W IN2022050610 W IN 2022050610W WO 2023281527 A1 WO2023281527 A1 WO 2023281527A1
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- WIPO (PCT)
- Prior art keywords
- phr
- rubber
- cnt
- nanocomposite
- present
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 153
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 152
- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 128
- 239000005060 rubber Substances 0.000 claims abstract description 117
- 239000006229 carbon black Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims description 114
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 45
- 229920003052 natural elastomer Polymers 0.000 claims description 31
- 229920001194 natural rubber Polymers 0.000 claims description 31
- 244000043261 Hevea brasiliensis Species 0.000 claims description 30
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 28
- 229920002857 polybutadiene Polymers 0.000 claims description 28
- 239000012763 reinforcing filler Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 239000010692 aromatic oil Substances 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical group C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000004614 Process Aid Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 3
- 239000004200 microcrystalline wax Substances 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims description 3
- 238000010923 batch production Methods 0.000 claims description 2
- 239000008380 degradant Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 24
- 239000006185 dispersion Substances 0.000 abstract description 23
- 230000035699 permeability Effects 0.000 abstract description 13
- 239000011324 bead Substances 0.000 abstract description 4
- 230000036961 partial effect Effects 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 61
- 239000002174 Styrene-butadiene Substances 0.000 description 33
- 239000000377 silicon dioxide Substances 0.000 description 28
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 238000005299 abrasion Methods 0.000 description 10
- 229910021392 nanocarbon Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 150000003505 terpenes Chemical class 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012802 nanoclay Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- -1 silane modified CNT Chemical class 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- 241001441571 Hiodontidae Species 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 229960004050 aminobenzoic acid Drugs 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229920003244 diene elastomer Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 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 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 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 description 2
- HWPRFMCKSFTMHQ-UHFFFAOYSA-N 2-(1-thiophen-2-ylethenyl)thiophene Chemical compound C=1C=CSC=1C(=C)C1=CC=CS1 HWPRFMCKSFTMHQ-UHFFFAOYSA-N 0.000 description 1
- LMCBMHKLKJQVNI-UHFFFAOYSA-N 2-cyclohexyl-1,1-bis(sulfanylidene)-1,3-benzothiazole Chemical compound N=1C2=CC=CC=C2S(=S)(=S)C=1C1CCCCC1 LMCBMHKLKJQVNI-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 241000907230 Mahatha Species 0.000 description 1
- 241000254043 Melolonthinae Species 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000950638 Symphysodon discus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical group C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- MECFLMNXIXDIOF-UHFFFAOYSA-L zinc;dibutoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([S-])(=S)OCCCC.CCCCOP([S-])(=S)OCCCC MECFLMNXIXDIOF-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/10—Tyres specially adapted for particular applications for motorcycles, scooters or the like
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to the field of polymer technology. More particularly, it relates to the field of high performance tire tread composition and its method of preparation.
- Carbon black has been used to improve abrasion resistance and tensile strength in tire tread. Recently, carbon nano-materials (carbon nanotube (CNT), carbon nanoclay) is increasing used to improve the reinforcement properties of the material.
- CNT carbon nanotube
- Carbon nano tubes are a cylindrical tube-shaped material with a diameter of several tens of nanometers with an electron orbit Sp2 electron arrangement.
- Tanoso nanotubes As a new material formed on the cathode of graphite, Tanoso nanotubes (CNT) have an elastic modulus of 1 to 2 TPa.
- Carbon nano tubes act as carbon reinforcing agents that can improve stable heat generation, fatigue properties, and tensile strength under rough driving conditions, which are essential performances of tire, treads, and reduce rolling resistance and increase fuel economy through weight reduction of the rubber composition.
- KR101914387 relates to a rubber composition for tire tread, containing, as reinforcing filler, carbon nanotube whose surface is modified by a silane group thereby increasing dispersibility of carbon nanotube in rubber.
- the rubber composition for tire tread of the present invention uses different reinforcing fillers in addition to carbon nanotubes modified on the surface of the silane group (Silane group).
- This patent discusses the use of carbon nanotube modified by a silane group whereas present invention discusses the use of polymer coated CNT in rubber composition.
- This patent uses silane modified CNT to improve bonding force with raw rubber, tensile properties, fatigue resistance, wear resistance and reduce beat-emission properties whereas present invention discusses the use of polymer coated CNT in tire tread to improve the mechanical and thermal properties.
- US2013281612 relates to carbon nanotubes as fillers in composites with materials such as elastomers, thermosets and thermoplastics.
- a further feature of this invention relates to the development of a concentrate of carbon nanotubes that can be diluted with an elastomer and other polymers and fillers using conventional melt mixing.
- the tire has a tread wherein the concentration of discrete nanotubes is in the range of 0.7 vol. % and 30 vol. %.
- This patent discussed about the use of CNT in tires, its dosage and its mixing process whereas present invention discusses the usage of CNT in tire tread to improve the mechanical and thermal properties.
- CN111333060 relates to a wet compounding method of graphene oxide/carbon nanotube and carbon nano carbon black.
- Wet compounding has the advantages that the manufacturing cost is lowered; after the modified carbon nano composite material is applied to the tire tread.
- the optimal definite elongation strength of the tire can be increased by 20%, and the shore hardness is increased by 6-9 degrees.
- the shore hardness of the tire tread is 71.1 degrees, and the 100% constant tensile stress is 3.66 MPa, 300% constant elongation stress is 15.22 MPa.
- This patent discusses the method of compounding CNT and the improvement in properties like EB, Tensile strength, Hardness whereas present invention discusses the use of polymer coated CNT in tire tread to improve the mechanical and thermal properties.
- CN109897249 relates to a preparation method of a CNT (Carbon Nanotube)-containing rubber composition with high tensile strength, good abrasion resistance and low rolling resistance for a tire tread.
- This patent discusses the method of preparation of rubber composition containing CNT whereas present invention discusses the use of polymer coated CNT in tire tread.
- This patent discusses improvement in properties like tensile strength, abrasion resistance and rolling resistance whereas present invention discusses improvement in modulus, thermal conductivity, gas permeability and dispersion.
- CN 109897245 relates to the strong-oxidizing acid and polyalcohol adopted for performing hydroxylation treatment on the surfaces of carbon nanotubes; then an unsaturated acrylate polar monomer and a dithienylethene monomer are adopted for pre-emulsification treatment; an in-situ polymerization method is utilized to prepared high-dispersion type carbon nanotubes; and finally, the high-dispersion type carbon nanotubes and styrene- butadiene rubber latex are mixed and condensed to prepare a styrene -butadiene rubber composition with high tensile strength, good wear resistance and low rolling resistance.
- This patent discusses the mixing of CNT in SBR rubber latex whereas present invention uses addition
- This patent improves tensile strength wear resistance and rolling resistance whereas present invention discusses improvement in modulus, thermal conductivity, gas permeability and dispersion.
- CN107674252 relates to a preparation method for graphene oxide, graphene oxide prepared by using the preparation method, and a manufacturing method for a tire using graphene/carbon nanotube master batch from the graphene oxide, carbon nanotubes, rubber master batch and an auxiliary agent; subjecting the graphene/carbon nanotube master batch, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulfur and an vulcanization accelerator to mixing and processing so as to obtain a tread compound; and subjecting the tread compound to vulcanizing and molding so as to obtain the tire tread.
- KR101703626 relates to a rubber composition for a tire tread, a method for manufacturing the same, and a tire manufactured by using the method.
- the rubber composition for the tire tread comprises 100 wt% of a rubber polymer, 52-150 wt % of filler, and 4.5-12.5 wt% of an addictive with respect to 100 wt% of the rubber polymer.
- the rubber composition for the tire tread includes a master batch, and the master batch includes a carbon nanotube, and the carbon nanotube included in the master batch is more than 0.02 wt% and less than 1.2 wt% with respect to 100 wt% of the rubber polymer.
- This patent uses single walled CNT in its composition whereas present invention uses multi -walled CNT in its composition.
- KR101661155 relates to the tire tread rubber composition
- a carbon nanotube comprises 1-15 parts by weight of liquid isoprene rubber condensed and polymerized with a carbon nanotube having a surface modified with a carboxylic group, based on 100 parts by weight of raw rubber.
- the components of the manufacturing process have excellent dispersibility, thereby enhancing tensile properties, fatigue resistance, and abrasion resistance of the manufactured rubber.
- the liquid isoprene rubber is easily mixed with carbon nanotubes, and can be used as a wet master batch to uniformly and stably mix carbon nanotubes when mixed with tire tread raw rubber.
- This patent relates to rubber composition using liquid isoprene as base polymer whereas present invention relates to the use of SBR as base polymer.
- KR20140069584 relates to a rubber composition for a silica tire tread to improve electric conductivity and abrasion resistance by applying carbon nanotubes, which has a high aspect ratio and low density, to a rubber composition filled with silica.
- a rubber composition for a silica tire tread comprises silica and comprises 0.5 -1.0 parts by weight of a multi-wall carbon nanotubes based on 100.0 parts by weight of a raw material natural or synthetic rubber The aspect ratio of the carbon nanotubes is 12,000 or more, the length is 120 micron and the density is 0.01 g/cm A 3.
- a carbon nanotubes aggregate is aligned in a long line and the diameter is 50 micron or less.
- This patent uses silica as filler while present invention uses Carbon black as filler.
- This patent uses 0.1 - l.Ophr of CNT while present invention uses 1.0-5.0 phr of CNT.
- This patent uses CNT of diameter upto 50 microns whereas present invention uses CNT of diameter 1-30 nanometer.
- This patent uses CNT material of length 120 microns whereas present invention uses CNT material of length 50 nanometer to 500 micrometers
- KR20120055247 relates to a rubber composition to cause initial quick heating of tire tread at high speed driving, thereby improving grip performance, to increase the time for physical property degradation of the rubber composition, and to remarkably increase time for durability and abrasion resistance degradation.
- a rubber composition for tire tread comprises ultrafine carbon black surface-treated amino-benzoic acid.
- the ultrafine carbon black is carbon nanotube.
- the average length of the carbon nanotube is l-100pm, and the average diameter of the carbon nanotube is 30-300nm. 100 parts by weight of the carbon nanotube is surface-treated by 5-90 parts by weigh of the amino-benzoic acid.
- the rubber composition for a tire tread may be prepared through a conventional two-step continuous manufacturing process.
- the rubber composition for the tire tread is not limited to the tread (tread cap and tread base) and may be included in various rubber components constituting the tire.
- This patent relates to a rubber composition for tire tread comprising ultrafine carbon nanotube surface-treated with amino benzoic acid whereas present invention discusses the application of polymer coated CNT in tread compound to improve the mechanical and thermal properties.
- This patent uses CNT of diameter 30-300 nm while present invention uses CNT of diameter 1-30 nm.
- KR20120050818 relates to a manufacturing method of silica coated carbon nanotube and use thereof to enhance wear resistance, rotation resistance property, and braking power on wet road of the tire tread by coating silica on surface of surface modified carbon nanotube.
- the invention also relates to a tire tread rubber composition comprising carbon nanotubes coated with silica on a surface thereof and carbon nanotubes coated with silica prepared by the method.
- This patent refers to silica coated CNT whereas present invention relates to polymer coated CNT.
- This patent uses CNT to improve the wear resistance, rotation resistance property, and braking power on wet road of the tire tread whereas present invention uses polymer coated CNT to improve the dispersion, mechanical and thermal properties.
- KR20120133258 relates to a rubber composition for a silica tire tread to improve electric conductivity and abrasion resistance by applying carbon nanotubes, which has a high aspect ratio and low density, to a rubber composition filled with silica.
- a rubber composition for a silica tire tread comprises silica and comprises 0.5 -1.0 parts by weight of a multi-wall carbon nanotubes based on 100.0 parts by weight of a raw material rubber which contains one or more selected from 100.0 parts by weight of a raw rubber which contains one or more selected from a natural rubber and synthetic rubber.
- the aspect ratio of the carbon nanotubes is 12,000 or more, the length is 120 micron and the density is 0.01 g/cm A 3.
- a carbon nanotubes aggregate is aligned in a long line and the diameter is 50 micron or less.
- This patent refers to a rubber composition having silica as a filler to make a silica tire tread whereas present invention uses Carbon black as the reinforcing filler.
- US2020071507 relates to the resin coated silica composition.
- the covered silica composition comprising a silica core and a resin covering the silica core, wherein the resin is not chemically bonded to the silica core.
- the silica core is covered with the resin by mixing slurry comprising silica core with a mixture containing the resin as a solution, an aqueous dispersion; or a solution by dissolving the resin in a solvent.
- the resin is selected from a rosin-based resin, a terpene -based resin, a C5-C9 resin, a hydrogenated resin, a polymerization-modified rosin resin, a styrenated terpene resin, a polyterpene resin, a phenolic terpene resin, a resin dispersion, an a-methyl styrene monomer resin, an a-methyl styrene phenolic resin, and combinations thereof.
- This patent uses resin coated silica composition to form the tire tread whereas present invention uses Carbon black and polymer coated CNT as the fillers.
- EP 1255787 relates to elastomeric compositions containing at least one elastomer and a polymer coated modified carbon product wherein the polymer at least partially coats the modified carbon product.
- the modified product preferably has at least one organic group attached to the carbon product and the organic group is preferably substituted with an ionic, ionizable, or polar group for preparation in polar or aqueous based media.
- Methods of making the polymer coated modified carbon product are also described, such as by aqueous-based or solvent free polymerization methods, organic solvent based polymerization methods, or solution coating methods.
- Polymeric products and master batches containing the polymer coated modified carbon products are also described as well as methods to improve properties such as impact properties and tensile properties.
- This patent relates to elastomeric composition that uses polymer coated carbon product and the carbon product used is carbon black whereas present invention uses polymer coated CNT in its composition to make the tire tread.
- US2017260340 relates to the nanocarbon-reinforced styrene -butadiene rubber (SBR) master batch composition comprising less than 5pphr (parts by weight per hundred parts by weight of SBR) of nanocarbon, wherein the nanocarbon has not been subjected to an acid treatment before incorporation into the SBR, wherein the composition is a liquid composition obtained by combining a liquid dispersion of the nanocarbon and liquid SBR in the form of a latex, and wherein the combined nanocarbon dispersion and SBR latex mixture is masticated.
- the nanocarbon is present as carbon nanotubes (CNT), and as CNTs having a length of less than 50 pm and/or an outer diameter of less than 20nm.
- This patent uses liquid SBR in the form of latex in which CNT is dispersed whereas present invention uses SBR polymer and polymer coated CNT is used as a filler along with carbon black.
- US2014228478 tire with a circumferential rubber tread of a rubber composition which comprises, based upon parts by weight per 100 parts by weight rubber (phr): lOOphr of at least one diene -based elastomer, rubber reinforcing filler comprised of precipitated silica, together with silica coupler for the precipitated silica having a moiety reactive with hydroxyl groups on the precipitated silica and another, different, moiety interactive with said diene-based elastomer (s), (C) about 0.5 to about 30 phr of carbon nanotubes having an average diameter in a range of from about 5 to about 20 nanometers and an L/D dimensional ratio in a range of from about 100 to about 1000; wherein said tread rubber composition contains less than 30 phr of rubber reinforcing carbon black, and wherein the carbon nanotubes are functionalized with a carbon nanotube coupler having moiety containing a pi electron network.
- This patent uses precipitated silica as fill
- US2011146859 is directed to a method of conducting static electricity in a pneumatic tire, comprising the steps of mixing a rubber compound comprising at least one diene based rubber, from 60 to 150phr of precipitated silica, less than 40phr of carbon black, and from 1 to lOphr of carbon nanotubes having a length of at least 5 microns; forming a tire tread from the rubber compound; and including the tire tread in the tire.
- This patent relates to an elastomeric composition that uses precipitated silica as filler whereas present invention dies not use silica in its composition.
- WO2015172915 relates to a sulfur-cross linkable rubber mixture, in particular for treads of vehicle tires, and to a vehicle tire.
- the rubber mixture contains at least the following components: at least one diene rubber and 10 to 200 phr of at least one silicic acid and 2 to 20 phr of at least one silane.
- This patent uses a tire tread composition with silica as reinforcing filler and silane whereas present invention uses carbon black and polymer coated CNT as the reinforcing filler.
- CA2770878 relates to a tire having a rubber tread containing homogeneous compositional distribution containing elastomeric nanocomposites having nanoclay as the nanofiller.
- This patent uses a tire tread composition where the nanofiller used is silicate whereas present invention uses polymer coated CNT as the nanofiller.
- CN 109843942 relates to a composition for use in a number of applications including tires.
- the composition comprises a blend of a rubber component, reinforcing particulate fillers, and based on lOOparts by weight (phr) of the rubber component; from about 5phr to about 70phr of a terpene phenol resin
- the terpene phenol resin has a number average molecular weight of from about 700Da to about 790Da, a weight average molecular weight of from about 930Da to about 1090Da, and a poly-dispersity index of from about 1.25 to about 1.45.
- This patent uses a tire tread composition where one of the fillers can be carbon nanotube which is not surface modified whereas present invention uses polymer coated CNT as the nanofiller.
- KR101703626 relates to a rubber composition for a tire tread, a method for manufacturing the same, and a tire manufactured by using the method.
- the rubber composition for the tire tread comprises 100 wt% of a rubber polymer, 52-150 wt% of filler, and 4.5-12.5 wt% of an addictive with respect to 100 wt% of the rubber polymer.
- the rubber composition for the tire tread includes a master batch, and the master batch includes a carbon nanotube, and the carbon nanotube included in the master batch is more than 0.02 wt% and less than 1.2 wt% with respect to 100 wt% of the rubber polymer.
- This patent uses single walled CNT whereas present invention uses multi-walled CNT as the filler.
- KR100635604 provides a tire tread rubber composition which is improved in the dispersion of a reinforcing agent and is excellent in abrasion resistance, and a tire containing the tread comprising the composition.
- the tire tread rubber composition comprises 10-40 phr of a carbon nanotube; and l-3phr of sodium dioctyl sulfosuccinate for improving the dispersion of the carbon nanotube, based on lOOphr of a rubber material.
- the carbon nanotube is a single-wall carbon nanotube or a multi-wall carbon nanotube.
- the rubber material is selected from a natural rubber, a synthetic rubber or a mixture of a natural rubber and a synthetic rubber in a ratio of 1:9 to 9: 1.
- This patent uses dioctyl sulpho succinate to improve the dispersibility of the CNT in the polymer whereas present invention used polymer coated CNT to improve the dispersion in the compound.
- This patent uses CNT to improve the mechanical properties like tensile strength, abrasion resistance, elongation and modulus whereas present invention uses CNT to improve the thermal properties, modulus and dispersion of the compound.
- US2020079935 discloses rubber composition.
- the composition comprises a blend based on 100 parts by weight (phr) of diene elastomers: 5 to 95 phr of a first diene elastomer, 5 to 50 phr of a hydrogenated styrenic block copolymer (HSBC), 50 to 200 phr of a filler, up to 25 phr of a plasticizer.
- the composition does not comprise a resin, a plasticizer, or comprises a resin or a plasticizer in an amount of less than 20 phr.
- This patent does not use CNT in it composition whereas present invention uses CNT as nanofiller in its composition.
- CN 109843942 relates to a composition for use in a number of applications including tires.
- the composition comprises a blend of a rubber component, reinforcing particulate fillers, and based on lOOparts by weight (phr) of the rubber component; from about 5 phr to about 70 phr of a terpene phenol resin.
- This patent does not use CNT in it composition whereas present invention uses CNT as nanofiller in its composition.
- CA2770878 relates copolymer is formed from an isoolefin having from 4 to 7 carbon atoms and an alkyl styrene.
- the copolymer has a substantially homogeneous compositional distribution.
- the copolymer may in elastomeric nanocomposites.
- At least one cure accelerator is selected from the group consisting of mercaptobenzothiazole disulfide, mercaptobenzothiazole, cyclohexyl benzothiazole disulfide, dibutyl thiourea, tetramethylthiuram disulfide, 4-4-dithiodimropholine, zinc dimethyldithiocarbamate, and zinc dibutyl phosphorodithiate.
- This patent uses nanoclay as the nanofiller composition whereas present invention uses CNT as a nanofiller in its composition.
- WO2017190859 discloses an artillery shell-shaped information gathering device.
- the present invention comprises: a body part; a gas storage part which is installed in the body part and stores gas; a variable volume part which is installed in the body part and has a volume varying according to the amount of gas disposed in and supplied from the gas storage part; a photographing part which is installed in the body part and moves along the body part; and a movement channel part which is installed in the body part and supplies gas in the variable volume part to the photographing part to move the photographing part.
- This patent refers to artilery diaphragm as the product whereas present invention discusses about tire tread compound.
- US2020062933 relates to a tire for vehicle wheels comprising at least one structural element comprising a cross-linked elastomeric material obtained by cross-linking a cross- linkable elastomeric composition comprising carbon nanotubes, wherein said carbon nanotubes are obtained with iron oxides and/or aluminum oxides based catalyst substantially free of Co, Ni and Mo.
- This patent does not use polymer coated CNT whereas present invention uses polymer coated CNT.
- This patent uses CNT to improve the dynamic mechanical properties whereas present invention uses CNT to improve the mechanical and thermal properties.
- US2017260340 relates to the use of nanocarbon (carbon nanotubes and/or carbon nanofibers) in the preparation of reinforced (filled) styrene -butadiene rubber (SBR). Furthermore, the present invention relates to a method of preparing reinforced SBR master batches having nanocarbon as reinforcing agent wherein the nanocarbon is uniformly pre dispersed within the SBR, as well reinforced rubber compositions containing said reinforced SBR which have nanocarbon and carbon black as reinforcing agents, and to uses thereof.
- This patent uses CNT reinforced SBR latex whereas present invention uses polymer coated CNT as nanofiller in its compound.
- US2019023083 provides a pneumatic tire in which an electric resistance can be reduced without adversely affecting other performances such as tire durability or manufacturing processes even when low loss of a rubber member of the tire is attempted.
- the pneumatic tire includes a belt layer 2 provided at an outer side of a crown portion of a carcass 1 in a tire radial direction, and a rubber chafer 4 is provided at an outer surface of a bead portion in a tire width direction.
- This patent discuses a chaffer compound and its electrical resistance property whereas present invention discusses about tire tread compound and improvement of its mechanical and thermal properties using CNT.
- the present invention aims to provide high performance tire tread composition with superior thermal stability, high modulus, and low gas permeability and its method of preparation.
- the invention uses polymer coated CNT as a nanofiller to improve the gas impermeability and thermal stability along with conventional black in a cured elastomeric composite.
- CNT polymer coated carbon nano tubes
- a cured elastomeric nanocomposite comprising of: elastomeric matrix or elastomeric blend- 100 phr; a reinforcing filler - 50-69 phr; nanofiller - 1-20 phr; process aid - 28-32 phr; anti-degradants- 1 -3 phr; cure activators - 2-5 phr; vulcanization agent -1.20 - 1.5 phr; accelerator -1.2 - 1.5 phr; and pre-vulcanization inhibitor - 0.1 - 0.3 phr, wherein the nanofiller is polymer coated carbon nano tube having a diameter of 1 - 30 nm, and length 50 nm to 500 pm, and wherein the elastomeric matrix or elastomeric blend is non oil extended styrene butadiene rubber (SBR), natural rubber (NR) and polybutadiene rubber (PBR) in
- nanofiller is styrene butadiene rubber coated multi-walled carbon nano tubes in a weight ratio of 10:90.
- IAN Iodine absorption number
- OFAN Oil absorption number
- N2SA value ranges between 86 and 96 m 2 /gm.
- the anti-degradants comprises 6PPD [N-(l,3-dimethylbutyl)-N’- phenyl-p-phenylenediamine and Microcrystalline wax (MC wax) in a weight ratio of 2:1.
- the present invention relates to the high performance tire tread composition.
- the present invention provides an elastomeric nanocomposite comprising polymer coated carbon nanotubes (CNT) in bead form as nanofiller that offers superior thermal stability, high modulus, and low gas permeability.
- the polymer coated CNT provides excellent dispersion of the fillers in the rubber compound.
- the present invention provides high- performance nanocomposites with partial replacement of carbon black filler by a small dosage of polymer coated CNT in carbon black filled system.
- the invention uses 1.0-20.0 phr of CNT of diameter up to 1- 30 nm; length 50 nanometer to 500 micrometers.
- the elastomer can be a single or blend of two or more elastomers.
- Elastomer(s) in the 5 nanocomposite can be natural rubbers and its grades, epoxidized natural rubbers and its grades, polyisoprene rubber, styrene butadiene rubber (SBR) and its grades, polybutadiene rubber and its grades.
- SBR styrene butadiene rubber
- the new elastomeric composition constituting polymer coated CNT as nanofiller offers0 ⁇ high modulus
- the present invention relates to high performance tyre tread elastomeric nano composite5 capable of providing better dry grip, high modulus, low gas permeability, high thermal stability and better processing properties.
- the high performance tire tread elastomeric nanocomposite according to the present invention comprising tri blend polymer system of 50 phr of non oil extended styrene0 butadiene rubber (SBR 1502), 30 phr of natural rubber (RSS 5 grade) and 20 phr of Polybutadiene rubber (PBR 1220).
- the other ingredients selected for the present invention is based on high performance tire tread elastomeric nanocomposite containing activators zinc oxide and stearic acid, antidegradant 6PPD (N-(l,3-dimethylbutyl)-N’ -phenyl -p-phenylenediamine) and0 microcrystalline wax along with aromatic oil as processing aid.
- Cure chemicals selected for the present invention are TBBS N-tert-butyl-2-benzothiazole sulfenamide as primary accelerator and sulphur as vulcanizing agent.
- Table 1 Rubber Composition in Phr 1.
- SBR 1502 Non- oil extended emulsion based styrene butadiene rubber with the Mooney viscosity, ML (1+4) at 100 deg C is 43.3 MU from Reliance Industries limited, India.
- PBR 1220 - 96% high cis 1,4 configuration with the Mooney viscosity, ML (1+4) at 100 deg C is 45 MU from Reliance Industries limited, India.
- IAN Iodine adsorption number
- OAN Oil Absorption number
- N2SA value ranges between 86 to 96 m 2 /gm from Continental carbon India Ghaziabad.
- Stearic Acid It is a process aid . Also, zinc oxide reacts with stearic acid forming zinc stearate which is essential for improving the efficiency of crosslinking from 3F Industries, Andhra Pradesh.
- Aromatic oil - Elasto 710 grade It helps in improving the dispersion of fillers and flow characteristics of the rubber compound during processing from Indian oil corporation Ltd, Tamilnadu.
- CTP N-(cyclohexylthio) phthalimide (CTP) for the diene based accelerated sulphur cured compounds from NOCIL limited, Mumbai.
- Rubber compositions are prepared by a thermomechanical process. To demonstrate the method of preparation, mixing process is carried out in 2 litre capacity Banbury mixer with the tangential rotors.
- Step I Masterbatch Mixing has been done with the head temperature of the Banbury mixer maintained between 65 to 75 °C and the unloaded rotor speed maintained between 58 rpm to 62 rpm.
- the mixing cycle is to be followed as: a) Mixing chamber has been charged with rubbers SBR, NR & PBR and allowed to mix for 10 to 40 seconds b) and further carbon nanotubes (CNT), carbon black, rubber chemicals 6PPD, MC wax, aromatic oil, and PVI are added and allowed to mix for 210 to 230 seconds, c) sweeping has been done in the orifice and allowed to mix for another 80 to 120 seconds, the rubber compound has been dumped at the temperature in the range of 140°C to 145°C and sheeted out in the two roll mill.
- CNT carbon nanotubes
- Step II Masterbatch Add the step I master batch in the Lab Banbury Mixer and allowed to mix it for 120 seconds to 180 seconds and the rubber compound has been dumped at the temperature in the range of 110°C to 125°C and sheeted out in the two roll mill.
- the Mooney Scorch measurements are carried out with a Mooney Viscometer (MV 2000 Alpha technologies, USA) according to ASTM D1646. MV indicates the minimum viscosity, ts indicates the time to scorch (MV+5) which indicates the processing properties (process safety).
- MV indicates the minimum viscosity
- ts indicates the time to scorch (MV+5) which indicates the processing properties (process safety).
- b. Dispersion Rating of the Rubber Vulcanizate Dispersion analysis of the rubber vulcanizates are carried out with a Dispergrader, Model DGAV SR (Alpha technologies, USA) according to ASTM D 7723 for rubber vulcanizates. It indicates the macro dispersion of fillers in the rubber matrix.
- Shore A Hardness of the rubber vulcanizates are measured in accordance with ASTM D 2240.
- Visco elastic properties of the Rubber Vulcanizates are measured on a dynamic mechanical analyzer (DMA Metravib +1000) with a 0.3% dynamic strain, 0.6% static strain%, temperature -40 deg C to +80 deg C, and 10Hz frequency as per ASTM D5992.
- Tan delta at 25 deg C is commonly used as predictor for dry grip of the rubber vulcanizate. Also, higher the tan delta value at 25 deg C, better the dry grip. M5: Gas permeability of the Rubber Vulcanizate
- the present invention provides a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nanotubes (CNT) gave process safety, t5 value improved by 1.21% and the dispersion of filler improved by 2.41% when compared to SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
- the present invention also relates to a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nanotubes (CNT) gave higher shore A hardness improved by 5% , 100% modulus and 200% modulus of the rubber vulcanizate is improved by 41.29 % & 11.57% respectively when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
- the present invention also relates to a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nano tubes (CNT) provides dry grip and it is improved by 3.39% when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
- the present invention also relates to a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nano tubes (CNT) provides lower gas permeability and it is lowered by 2.22 % when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
- polymer coated carbon nano tubes (CNT) containing SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black provides better dry grip, high modulus, high hardness, high thermal stability, low gas permeability along with better processing properties when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition along with reinforcing filler carbon black.
Abstract
The present invention provides an elastomeric nanocomposite for tire tread comprising polymer coated carbon nanotubes (CNT) in bead form as nanofiller that offers superior thermal stability, high modulus, and low gas permeability. The polymer coated CNT provides excellent dispersion of the fillers in the rubber compound. The present invention provides high-performance nanocomposites with partial replacement of carbon black filler by a small dosage of polymer coated CNT in carbon black filled system. The invention uses 1.0-20.0 phr of CNT of diameter upto 1- 30 nm; length 50 nanometer to 500 micrometers.
Description
ELASTOMERIC TIRE NANOCOMPOSITE WITH POLYMER COATED CARBON NANOTUBES AND METHOD THEREOF
FIELD OF THE INVENTION
The present invention relates to the field of polymer technology. More particularly, it relates to the field of high performance tire tread composition and its method of preparation.
BACKGROUND OF THE INVENTION
Due to advancements in automobile technology and diversified requirements of consumer, the need for high performance tires is increasing. The performance parameters like vehicle movement, braking etc. are directly affected by the tire tread that contacts the ground.
Carbon black has been used to improve abrasion resistance and tensile strength in tire tread. Recently, carbon nano-materials (carbon nanotube (CNT), carbon nanoclay) is increasing used to improve the reinforcement properties of the material.
Carbon nano tubes are a cylindrical tube-shaped material with a diameter of several tens of nanometers with an electron orbit Sp2 electron arrangement. As a new material formed on the cathode of graphite, Tanoso nanotubes (CNT) have an elastic modulus of 1 to 2 TPa.
Carbon nano tubes act as carbon reinforcing agents that can improve stable heat generation, fatigue properties, and tensile strength under rough driving conditions, which are essential performances of tire, treads, and reduce rolling resistance and increase fuel economy through weight reduction of the rubber composition.
Reference may be made to the following:
KR101914387 relates to a rubber composition for tire tread, containing, as reinforcing filler, carbon nanotube whose surface is modified by a silane group thereby increasing dispersibility of carbon nanotube in rubber. Thus, bonding force with raw rubber, tensile properties, fatigue resistance, wear resistance are enhanced while keeping heat-emission
properties low. The rubber composition for tire tread of the present invention, uses different reinforcing fillers in addition to carbon nanotubes modified on the surface of the silane group (Silane group). This patent discusses the use of carbon nanotube modified by a silane group whereas present invention discusses the use of polymer coated CNT in rubber composition. This patent uses silane modified CNT to improve bonding force with raw rubber, tensile properties, fatigue resistance, wear resistance and reduce beat-emission properties whereas present invention discusses the use of polymer coated CNT in tire tread to improve the mechanical and thermal properties.
US2013281612 relates to carbon nanotubes as fillers in composites with materials such as elastomers, thermosets and thermoplastics. A further feature of this invention relates to the development of a concentrate of carbon nanotubes that can be diluted with an elastomer and other polymers and fillers using conventional melt mixing. The tire has a tread wherein the concentration of discrete nanotubes is in the range of 0.7 vol. % and 30 vol. %. This patent discussed about the use of CNT in tires, its dosage and its mixing process whereas present invention discusses the usage of CNT in tire tread to improve the mechanical and thermal properties.
CN111333060 relates to a wet compounding method of graphene oxide/carbon nanotube and carbon nano carbon black. Wet compounding has the advantages that the manufacturing cost is lowered; after the modified carbon nano composite material is applied to the tire tread. The optimal definite elongation strength of the tire can be increased by 20%, and the shore hardness is increased by 6-9 degrees. The shore hardness of the tire tread is 71.1 degrees, and the 100% constant tensile stress is 3.66 MPa, 300% constant elongation stress is 15.22 MPa. This patent discusses the method of compounding CNT and the improvement in properties like EB, Tensile strength, Hardness whereas present invention discusses the use of polymer coated CNT in tire tread to improve the mechanical and thermal properties.
CN109897249 relates to a preparation method of a CNT (Carbon Nanotube)-containing rubber composition with high tensile strength, good abrasion resistance and low rolling
resistance for a tire tread. This patent discusses the method of preparation of rubber composition containing CNT whereas present invention discusses the use of polymer coated CNT in tire tread. This patent discusses improvement in properties like tensile strength, abrasion resistance and rolling resistance whereas present invention discusses improvement in modulus, thermal conductivity, gas permeability and dispersion.
CN 109897245 relates to the strong-oxidizing acid and polyalcohol adopted for performing hydroxylation treatment on the surfaces of carbon nanotubes; then an unsaturated acrylate polar monomer and a dithienylethene monomer are adopted for pre-emulsification treatment; an in-situ polymerization method is utilized to prepared high-dispersion type carbon nanotubes; and finally, the high-dispersion type carbon nanotubes and styrene- butadiene rubber latex are mixed and condensed to prepare a styrene -butadiene rubber composition with high tensile strength, good wear resistance and low rolling resistance. This patent discusses the mixing of CNT in SBR rubber latex whereas present invention uses addition This patent improves tensile strength wear resistance and rolling resistance whereas present invention discusses improvement in modulus, thermal conductivity, gas permeability and dispersion.
CN107674252 relates to a preparation method for graphene oxide, graphene oxide prepared by using the preparation method, and a manufacturing method for a tire using graphene/carbon nanotube master batch from the graphene oxide, carbon nanotubes, rubber master batch and an auxiliary agent; subjecting the graphene/carbon nanotube master batch, natural rubber, butadiene rubber, vulcanized rubber powder, ZnO, sulfur and an vulcanization accelerator to mixing and processing so as to obtain a tread compound; and subjecting the tread compound to vulcanizing and molding so as to obtain the tire tread. This patent discusses the manufacturing method of CNT, mixing of CNT based tread compound with other chemicals and the final curing process whereas present invention discusses the application of polymer coated CNT in tread compound to improve the mechanical and thermal properties. This patent uses NR and PBR rubber as base polymer whereas present invention uses SBR as base polymer.
KR101703626 relates to a rubber composition for a tire tread, a method for manufacturing the same, and a tire manufactured by using the method. The rubber composition for the tire tread comprises 100 wt% of a rubber polymer, 52-150 wt % of filler, and 4.5-12.5 wt% of an addictive with respect to 100 wt% of the rubber polymer. The rubber composition for the tire tread includes a master batch, and the master batch includes a carbon nanotube, and the carbon nanotube included in the master batch is more than 0.02 wt% and less than 1.2 wt% with respect to 100 wt% of the rubber polymer. This patent uses single walled CNT in its composition whereas present invention uses multi -walled CNT in its composition.
KR101661155 relates to the tire tread rubber composition comprising a carbon nanotube comprises 1-15 parts by weight of liquid isoprene rubber condensed and polymerized with a carbon nanotube having a surface modified with a carboxylic group, based on 100 parts by weight of raw rubber. The components of the manufacturing process have excellent dispersibility, thereby enhancing tensile properties, fatigue resistance, and abrasion resistance of the manufactured rubber. The liquid isoprene rubber is easily mixed with carbon nanotubes, and can be used as a wet master batch to uniformly and stably mix carbon nanotubes when mixed with tire tread raw rubber. This patent relates to rubber composition using liquid isoprene as base polymer whereas present invention relates to the use of SBR as base polymer.
KR20140069584 relates to a rubber composition for a silica tire tread to improve electric conductivity and abrasion resistance by applying carbon nanotubes, which has a high aspect ratio and low density, to a rubber composition filled with silica. A rubber composition for a silica tire tread comprises silica and comprises 0.5 -1.0 parts by weight of a multi-wall carbon nanotubes based on 100.0 parts by weight of a raw material natural or synthetic rubber The aspect ratio of the carbon nanotubes is 12,000 or more, the length is 120 micron and the density is 0.01 g/cmA3. A carbon nanotubes aggregate is aligned in a long line and the diameter is 50 micron or less. This patent uses silica as filler while present invention uses Carbon black as filler. This patent claims for improving the electrical conductivity and abrasion resistance while present invention claims to improve modulus and thermal conductivity. This patent uses 0.1 - l.Ophr of CNT while present
invention uses 1.0-5.0 phr of CNT. This patent uses CNT of diameter upto 50 microns whereas present invention uses CNT of diameter 1-30 nanometer. This patent uses CNT material of length 120 microns whereas present invention uses CNT material of length 50 nanometer to 500 micrometers
KR20120055247 relates to a rubber composition to cause initial quick heating of tire tread at high speed driving, thereby improving grip performance, to increase the time for physical property degradation of the rubber composition, and to remarkably increase time for durability and abrasion resistance degradation. A rubber composition for tire tread comprises ultrafine carbon black surface-treated amino-benzoic acid. The ultrafine carbon black is carbon nanotube. The average length of the carbon nanotube is l-100pm, and the average diameter of the carbon nanotube is 30-300nm. 100 parts by weight of the carbon nanotube is surface-treated by 5-90 parts by weigh of the amino-benzoic acid. The rubber composition for a tire tread may be prepared through a conventional two-step continuous manufacturing process. The rubber composition for the tire tread is not limited to the tread (tread cap and tread base) and may be included in various rubber components constituting the tire. This patent relates to a rubber composition for tire tread comprising ultrafine carbon nanotube surface-treated with amino benzoic acid whereas present invention discusses the application of polymer coated CNT in tread compound to improve the mechanical and thermal properties. This patent uses CNT of diameter 30-300 nm while present invention uses CNT of diameter 1-30 nm.
KR20120050818 relates to a manufacturing method of silica coated carbon nanotube and use thereof to enhance wear resistance, rotation resistance property, and braking power on wet road of the tire tread by coating silica on surface of surface modified carbon nanotube. The invention also relates to a tire tread rubber composition comprising carbon nanotubes coated with silica on a surface thereof and carbon nanotubes coated with silica prepared by the method. This patent refers to silica coated CNT whereas present invention relates to polymer coated CNT. This patent uses CNT to improve the wear resistance, rotation resistance property, and braking power on wet road of the tire tread whereas present
invention uses polymer coated CNT to improve the dispersion, mechanical and thermal properties.
KR20120133258 relates to a rubber composition for a silica tire tread to improve electric conductivity and abrasion resistance by applying carbon nanotubes, which has a high aspect ratio and low density, to a rubber composition filled with silica. A rubber composition for a silica tire tread comprises silica and comprises 0.5 -1.0 parts by weight of a multi-wall carbon nanotubes based on 100.0 parts by weight of a raw material rubber which contains one or more selected from 100.0 parts by weight of a raw rubber which contains one or more selected from a natural rubber and synthetic rubber. The aspect ratio of the carbon nanotubes is 12,000 or more, the length is 120 micron and the density is 0.01 g/cmA3. A carbon nanotubes aggregate is aligned in a long line and the diameter is 50 micron or less. This patent refers to a rubber composition having silica as a filler to make a silica tire tread whereas present invention uses Carbon black as the reinforcing filler.
US2020071507 relates to the resin coated silica composition. The covered silica composition comprising a silica core and a resin covering the silica core, wherein the resin is not chemically bonded to the silica core. The silica core is covered with the resin by mixing slurry comprising silica core with a mixture containing the resin as a solution, an aqueous dispersion; or a solution by dissolving the resin in a solvent. The resin is selected from a rosin-based resin, a terpene -based resin, a C5-C9 resin, a hydrogenated resin, a polymerization-modified rosin resin, a styrenated terpene resin, a polyterpene resin, a phenolic terpene resin, a resin dispersion, an a-methyl styrene monomer resin, an a-methyl styrene phenolic resin, and combinations thereof. This patent uses resin coated silica composition to form the tire tread whereas present invention uses Carbon black and polymer coated CNT as the fillers.
EP 1255787 relates to elastomeric compositions containing at least one elastomer and a polymer coated modified carbon product wherein the polymer at least partially coats the modified carbon product. The modified product preferably has at least one organic group attached to the carbon product and the organic group is preferably substituted with an
ionic, ionizable, or polar group for preparation in polar or aqueous based media. Methods of making the polymer coated modified carbon product are also described, such as by aqueous-based or solvent free polymerization methods, organic solvent based polymerization methods, or solution coating methods. Polymeric products and master batches containing the polymer coated modified carbon products are also described as well as methods to improve properties such as impact properties and tensile properties. This patent relates to elastomeric composition that uses polymer coated carbon product and the carbon product used is carbon black whereas present invention uses polymer coated CNT in its composition to make the tire tread.
US2017260340 relates to the nanocarbon-reinforced styrene -butadiene rubber (SBR) master batch composition comprising less than 5pphr (parts by weight per hundred parts by weight of SBR) of nanocarbon, wherein the nanocarbon has not been subjected to an acid treatment before incorporation into the SBR, wherein the composition is a liquid composition obtained by combining a liquid dispersion of the nanocarbon and liquid SBR in the form of a latex, and wherein the combined nanocarbon dispersion and SBR latex mixture is masticated. The nanocarbon is present as carbon nanotubes (CNT), and as CNTs having a length of less than 50 pm and/or an outer diameter of less than 20nm. This patent uses liquid SBR in the form of latex in which CNT is dispersed whereas present invention uses SBR polymer and polymer coated CNT is used as a filler along with carbon black.
US2014228478 tire with a circumferential rubber tread of a rubber composition which comprises, based upon parts by weight per 100 parts by weight rubber (phr): lOOphr of at least one diene -based elastomer, rubber reinforcing filler comprised of precipitated silica, together with silica coupler for the precipitated silica having a moiety reactive with hydroxyl groups on the precipitated silica and another, different, moiety interactive with said diene-based elastomer (s), (C) about 0.5 to about 30 phr of carbon nanotubes having an average diameter in a range of from about 5 to about 20 nanometers and an L/D dimensional ratio in a range of from about 100 to about 1000; wherein said tread rubber composition contains less than 30 phr of rubber reinforcing carbon black, and wherein the carbon nanotubes are functionalized with a carbon nanotube coupler having moiety
containing a pi electron network. This patent uses precipitated silica as filler while present invention uses Carbon black and CNT as filler.
US2011146859 is directed to a method of conducting static electricity in a pneumatic tire, comprising the steps of mixing a rubber compound comprising at least one diene based rubber, from 60 to 150phr of precipitated silica, less than 40phr of carbon black, and from 1 to lOphr of carbon nanotubes having a length of at least 5 microns; forming a tire tread from the rubber compound; and including the tire tread in the tire. This patent relates to an elastomeric composition that uses precipitated silica as filler whereas present invention dies not use silica in its composition.
WO2015172915 relates to a sulfur-cross linkable rubber mixture, in particular for treads of vehicle tires, and to a vehicle tire. The rubber mixture contains at least the following components: at least one diene rubber and 10 to 200 phr of at least one silicic acid and 2 to 20 phr of at least one silane. This patent uses a tire tread composition with silica as reinforcing filler and silane whereas present invention uses carbon black and polymer coated CNT as the reinforcing filler.
CA2770878 relates to a tire having a rubber tread containing homogeneous compositional distribution containing elastomeric nanocomposites having nanoclay as the nanofiller. This patent uses a tire tread composition where the nanofiller used is silicate whereas present invention uses polymer coated CNT as the nanofiller.
CN 109843942 relates to a composition for use in a number of applications including tires. The composition comprises a blend of a rubber component, reinforcing particulate fillers, and based on lOOparts by weight (phr) of the rubber component; from about 5phr to about 70phr of a terpene phenol resin In one embodiment, the terpene phenol resin has a number average molecular weight of from about 700Da to about 790Da, a weight average molecular weight of from about 930Da to about 1090Da, and a poly-dispersity index of from about 1.25 to about 1.45. This patent uses a tire tread composition where one of the
fillers can be carbon nanotube which is not surface modified whereas present invention uses polymer coated CNT as the nanofiller.
KR101703626 relates to a rubber composition for a tire tread, a method for manufacturing the same, and a tire manufactured by using the method. The rubber composition for the tire tread comprises 100 wt% of a rubber polymer, 52-150 wt% of filler, and 4.5-12.5 wt% of an addictive with respect to 100 wt% of the rubber polymer. The rubber composition for the tire tread includes a master batch, and the master batch includes a carbon nanotube, and the carbon nanotube included in the master batch is more than 0.02 wt% and less than 1.2 wt% with respect to 100 wt% of the rubber polymer. This patent uses single walled CNT whereas present invention uses multi-walled CNT as the filler.
KR100635604 provides a tire tread rubber composition which is improved in the dispersion of a reinforcing agent and is excellent in abrasion resistance, and a tire containing the tread comprising the composition. The tire tread rubber composition comprises 10-40 phr of a carbon nanotube; and l-3phr of sodium dioctyl sulfosuccinate for improving the dispersion of the carbon nanotube, based on lOOphr of a rubber material. Preferably the carbon nanotube is a single-wall carbon nanotube or a multi-wall carbon nanotube. Preferably the rubber material is selected from a natural rubber, a synthetic rubber or a mixture of a natural rubber and a synthetic rubber in a ratio of 1:9 to 9: 1. This patent uses dioctyl sulpho succinate to improve the dispersibility of the CNT in the polymer whereas present invention used polymer coated CNT to improve the dispersion in the compound. This patent uses CNT to improve the mechanical properties like tensile strength, abrasion resistance, elongation and modulus whereas present invention uses CNT to improve the thermal properties, modulus and dispersion of the compound.
US2020079935 discloses rubber composition. The composition comprises a blend based on 100 parts by weight (phr) of diene elastomers: 5 to 95 phr of a first diene elastomer, 5 to 50 phr of a hydrogenated styrenic block copolymer (HSBC), 50 to 200 phr of a filler, up to 25 phr of a plasticizer. The composition does not comprise a resin, a plasticizer, or comprises a resin or a plasticizer in an amount of less than 20 phr. This patent does not use
CNT in it composition whereas present invention uses CNT as nanofiller in its composition.
CN 109843942 relates to a composition for use in a number of applications including tires. The composition comprises a blend of a rubber component, reinforcing particulate fillers, and based on lOOparts by weight (phr) of the rubber component; from about 5 phr to about 70 phr of a terpene phenol resin. This patent does not use CNT in it composition whereas present invention uses CNT as nanofiller in its composition.
CA2770878 relates copolymer is formed from an isoolefin having from 4 to 7 carbon atoms and an alkyl styrene. The copolymer has a substantially homogeneous compositional distribution. The copolymer may in elastomeric nanocomposites. To obtain a good dispersion of the nanoclay in a formulated compound, at least one cure accelerator is selected from the group consisting of mercaptobenzothiazole disulfide, mercaptobenzothiazole, cyclohexyl benzothiazole disulfide, dibutyl thiourea, tetramethylthiuram disulfide, 4-4-dithiodimropholine, zinc dimethyldithiocarbamate, and zinc dibutyl phosphorodithiate. This patent uses nanoclay as the nanofiller composition whereas present invention uses CNT as a nanofiller in its composition.
WO2017190859 discloses an artillery shell-shaped information gathering device. The present invention comprises: a body part; a gas storage part which is installed in the body part and stores gas; a variable volume part which is installed in the body part and has a volume varying according to the amount of gas disposed in and supplied from the gas storage part; a photographing part which is installed in the body part and moves along the body part; and a movement channel part which is installed in the body part and supplies gas in the variable volume part to the photographing part to move the photographing part. This patent refers to artilery diaphragm as the product whereas present invention discusses about tire tread compound.
US2020062933 relates to a tire for vehicle wheels comprising at least one structural element comprising a cross-linked elastomeric material obtained by cross-linking a cross-
linkable elastomeric composition comprising carbon nanotubes, wherein said carbon nanotubes are obtained with iron oxides and/or aluminum oxides based catalyst substantially free of Co, Ni and Mo. This patent does not use polymer coated CNT whereas present invention uses polymer coated CNT. This patent uses CNT to improve the dynamic mechanical properties whereas present invention uses CNT to improve the mechanical and thermal properties.
US2017260340 relates to the use of nanocarbon (carbon nanotubes and/or carbon nanofibers) in the preparation of reinforced (filled) styrene -butadiene rubber (SBR). Furthermore, the present invention relates to a method of preparing reinforced SBR master batches having nanocarbon as reinforcing agent wherein the nanocarbon is uniformly pre dispersed within the SBR, as well reinforced rubber compositions containing said reinforced SBR which have nanocarbon and carbon black as reinforcing agents, and to uses thereof. This patent uses CNT reinforced SBR latex whereas present invention uses polymer coated CNT as nanofiller in its compound.
US2019023083 provides a pneumatic tire in which an electric resistance can be reduced without adversely affecting other performances such as tire durability or manufacturing processes even when low loss of a rubber member of the tire is attempted. The pneumatic tire includes a belt layer 2 provided at an outer side of a crown portion of a carcass 1 in a tire radial direction, and a rubber chafer 4 is provided at an outer surface of a bead portion in a tire width direction. This patent discuses a chaffer compound and its electrical resistance property whereas present invention discusses about tire tread compound and improvement of its mechanical and thermal properties using CNT.
Thus conventionally, in cured elastomers composites carbon black is used to improve modulus and special grades of conductive black are used to improve thermal conductivity. Hence there needed a composition which has high thermal stability, high modulus, and low gas permeability.
The present invention aims to provide high performance tire tread composition with superior thermal stability, high modulus, and low gas permeability and its method of preparation. The invention uses polymer coated CNT as a nanofiller to improve the gas impermeability and thermal stability along with conventional black in a cured elastomeric composite.
OBJECT OF THE INVENTION
It is main object of the present invention to provide high performance tire tread composition and its method of preparation.
It is another object of the present invention to provide high performance motorcycle tire tread composition.
It is another object of the present invention to provide an elastomeric nanocomposite with superior thermal stability, high modulus, and low gas permeability.
It is another object of the present invention to provide an elastomeric nanocomposite of tyre tread that provides better dry grip. It is another object of the present invention to provide an elastomeric nanocomposite comprising polymer coated carbon nano tubes (CNT) in bead form as nanofiller.
It is yet another object of the present invention to provide SBR:NR:BR tri-blend based tire tread elastomeric nanocomposite along with polymer coated nano tubes CNT as nanofiller having diameter up to 1-30 nm and length 50 nano meter to 500 nano meter.
It is yet another aspect of the present invention to provide a high performance tire elastomeric nanocomposite, by partial replacement of carbon black reinforcing filler with nanofiller polymer coated carbon nano tube (CNT).
SUMMARY OF THE INVENTION
One or more problems of the conventional prior arts may be overcome by various embodiments of the present invention.
It is primary aspect of the present invention to provide a cured elastomeric nanocomposite, comprising of: elastomeric matrix or elastomeric blend- 100 phr; a reinforcing filler - 50-69 phr; nanofiller - 1-20 phr; process aid - 28-32 phr; anti-degradants- 1 -3 phr; cure activators - 2-5 phr; vulcanization agent -1.20 - 1.5 phr; accelerator -1.2 - 1.5 phr; and pre-vulcanization inhibitor - 0.1 - 0.3 phr, wherein the nanofiller is polymer coated carbon nano tube having a diameter of 1 - 30 nm, and length 50 nm to 500 pm, and wherein the elastomeric matrix or elastomeric blend is non oil extended styrene butadiene rubber (SBR), natural rubber (NR) and polybutadiene rubber (PBR) in a weight ratio of 50: 30: 20.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the nanofiller is styrene butadiene rubber coated multi-walled carbon nano tubes in a weight ratio of 10:90.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the reinforcing filler is carbon black.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the carbon black is N339 grade having the Iodine absorption
number (IAN) value ranges between 85 and 95 mg/gm, Oil absorption number (OAN), ranges between 115 and 125 cc/100 gm and N2SA value ranges between 86 and 96 m2/gm.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the process aid is aromatic oil.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the anti-degradants comprises 6PPD [N-(l,3-dimethylbutyl)-N’- phenyl-p-phenylenediamine and Microcrystalline wax (MC wax) in a weight ratio of 2:1.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the cure activator comprises zinc oxide and stearic acid in a weight ratio of 3:2.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the vulcanization agent is sulphur.
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the accelerator is TBBS [N-tert-butyl-2-benzothiazole sulfenamide].
It is another aspect of the present invention to provide the cured elastomeric nanocomposite, wherein the pre-vulcanization inhibitor PVI is CTP [N-(cyclohexylthio) phthalimide].
It is another aspect of the present invention to provide a process for preparation of cured elastomeric nanocomposite, comprising of steps: preparation of master batch comprising of steps: step 1 master batch: mixing of the elastomers comprising non-oil extended styrene butadiene rubber, natural rubber, and polybutadiene rubber for 10 to 40 seconds;
addition of nanofiller, carbon black, rubber chemicals 6PPD, MC wax, aromatic oil and PVI; sweeping off the chemicals from the orifice and mixing for 210 to 230 seconds; mixing for 80-120 seconds and dumping the rubber compound at the temperature in the range of 140-145°C; sheet out in the two-roll mill; step 2 master batch: mixing of step 1 master batch in the Banbury mixer for 120-180 seconds; dumping at the temperature range of 110-125 °C and sheet out in the two roll mill; preparation of final batch comprising of steps: mixing of Step 2 master batch rubber compound and the curatives for 60 to 90 seconds; dumping at the temperature range of 100-115°C; and sheet out the rubber compound in the two roll mill, wherein the nanofiller is polymer coated carbon nano tube having a diameter of 1-30 nm, and length 50 nm to 500 pm.
It is another aspect of the present invention to provide a process for preparation of cured elastomeric nanocomposite, wherein the master batch process parameters includes head temperature of the Banbury mixer maintained between 65 and 75 °C and the unloaded rotor speed maintained between 58 and 62 rpm.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the high performance tire tread composition. The present invention provides an elastomeric nanocomposite comprising polymer coated carbon nanotubes (CNT) in bead form as nanofiller that offers superior thermal stability, high modulus, and low gas permeability. The polymer coated CNT provides excellent dispersion of the fillers in the rubber compound. The present invention provides high- performance nanocomposites with partial replacement of carbon black filler by a small
dosage of polymer coated CNT in carbon black filled system. The invention uses 1.0-20.0 phr of CNT of diameter up to 1- 30 nm; length 50 nanometer to 500 micrometers.
The elastomer can be a single or blend of two or more elastomers. Elastomer(s) in the 5 nanocomposite can be natural rubbers and its grades, epoxidized natural rubbers and its grades, polyisoprene rubber, styrene butadiene rubber (SBR) and its grades, polybutadiene rubber and its grades.
The new elastomeric composition constituting polymer coated CNT as nanofiller offers0 · high modulus,
• high thermal conductivity
• low gas permeability
• high dispersion 5 Addition of the nanofiller improves physical properties like modulus. The thermal conductivity is improved with nanofiller and it does not require special grades of conductive carbon black. The gas impermeability and dispersion is effectively improved in the elastomeric nanocomposite. 0 The small dosages of CNT can act as a partial replacement for conventional carbon black. The developed nanocomposite is used in tires and tire treads in particular.
EXAMPLE
The present invention relates to high performance tyre tread elastomeric nano composite5 capable of providing better dry grip, high modulus, low gas permeability, high thermal stability and better processing properties. High performance tire tread elastomeric nanocomposite according to Table 1, consisting of a) The high performance tire tread elastomeric nanocomposite according to the present invention comprising tri blend polymer system of 50 phr of non oil extended styrene0 butadiene rubber (SBR 1502), 30 phr of natural rubber (RSS 5 grade) and 20 phr of Polybutadiene rubber (PBR 1220).
b) Reinforcing filler, Carbon black of ASTM grade N339 having the Iodine adsorption number (IAN) value ranges between 85 to 95 mg/gm, Oil Absorption number (OAN), ranges between 115 to 125 cc/100 gm and N2SA value ranges between 86 to 96 m2/gm. c) Reinforcing filler, Carbon nanotubes (CNT) is 10 % polymer (SBR) coated and 90 % 5 multiwalled carbon nanotubes of diameter up to 1- 30 nm; length 50 nm to 500 pm (Grade:
Durobeads DRF 4110). d) The other ingredients selected for the present invention is based on high performance tire tread elastomeric nanocomposite containing activators zinc oxide and stearic acid, antidegradant 6PPD (N-(l,3-dimethylbutyl)-N’ -phenyl -p-phenylenediamine) and0 microcrystalline wax along with aromatic oil as processing aid. e) Cure chemicals selected for the present invention are TBBS N-tert-butyl-2-benzothiazole sulfenamide as primary accelerator and sulphur as vulcanizing agent.
Table 1: Rubber Composition in Phr
1. SBR 1502 - Non- oil extended emulsion based styrene butadiene rubber with the Mooney viscosity, ML (1+4) at 100 deg C is 43.3 MU from Reliance Industries limited, Gujarat.
2. RSS 5- Ribbed smoke sheet from Kurian Abraham (P) Ltd, Kanyakumari
3. PBR 1220 - 96% high cis 1,4 configuration with the Mooney viscosity, ML (1+4) at 100 deg C is 45 MU from Reliance Industries limited, Gujarat.
4. N-339 - Reinforcing filler ASTM carbon black N339 having the Iodine adsorption number (IAN) value ranges between 85 to 95 mg/gm, Oil Absorption number (OAN), ranges between 115 to 125 cc/100 gm and N2SA value ranges between 86 to 96 m2/gm from Continental carbon India Ghaziabad.
5. Carbon Nanotubes (CNT) - It is 10 % polymer (SBR) coated and 90 % multiwalled carbon nanotubes of diameter up to 1- 30 nm; length 50 nm to 500 pm , DRF 4110 grade from Mitsubishi corporation, Japan.
6. Zinc oxide - It is an activator added to the rubber compound to activate sulphur vulcanization from Pondy Oxides & chemicals Ltd, Kancheepuram, Tamilnadu.
7. Stearic Acid - It is a process aid . Also, zinc oxide reacts with stearic acid forming zinc stearate which is essential for improving the efficiency of crosslinking from 3F Industries, Andhra Pradesh.
8. Aromatic oil - Elasto 710 grade, It helps in improving the dispersion of fillers and flow characteristics of the rubber compound during processing from Indian oil corporation Ltd, Tamilnadu.
9. MC Wax - It is an antiozonant from Mahatha petroleum private Limited, India.
10. 6PPD - It is an antidegradant from N-(l, 3 -dimethylbutyl)-N’ -phenyl -p- phenylenediamine from NOCIL Limited, Mumbai.
11. Sulphur - It is a vulcanizing agent from The Standard Chemical Co Pvt Ltd, Tamilnadu
12. TBBS - It is a delayed action primary accelerator from NOCIL limited, Mumbai.
13. CTP, PVI - It is a pre vulcanization inhibitor PVI: N-(cyclohexylthio) phthalimide (CTP) for the diene based accelerated sulphur cured compounds from NOCIL limited, Mumbai.
Method for preparation of the rubber compositions:
Rubber compositions are prepared by a thermomechanical process. To demonstrate the method of preparation, mixing process is carried out in 2 litre capacity Banbury mixer with the tangential rotors.
A) Method of preparation of masterbatch consisting of the steps:
Step I Masterbatch: Mixing has been done with the head temperature of the Banbury mixer maintained between 65 to 75 °C and the unloaded rotor speed maintained between 58 rpm to 62 rpm.
The mixing cycle is to be followed as: a) Mixing chamber has been charged with rubbers SBR, NR & PBR and allowed to mix for 10 to 40 seconds b) and further carbon nanotubes (CNT), carbon black, rubber chemicals 6PPD, MC wax, aromatic oil, and PVI are added and allowed to mix for 210 to 230 seconds, c) sweeping has been done in the orifice and allowed to mix for another 80 to 120 seconds, the rubber compound has been dumped at the temperature in the range of 140°C to 145°C and sheeted out in the two roll mill.
Step II Masterbatch: Add the step I master batch in the Lab Banbury Mixer and allowed to mix it for 120 seconds to 180 seconds and the rubber compound has been dumped at the temperature in the range of 110°C to 125°C and sheeted out in the two roll mill.
B) Preparation of Final Batch: Thermo mechanical mixing of final batch mixing is as follows:
Mixing chamber charged with the Step II master batch rubber compound and the curatives, and allowed to mix for 60 to 90 seconds and the compound has been dumped at the temperature in the range of up to the temperature 100°C to 115°C. The final batch sheet out has been done in the two roll mill.
Characterization of Cured Rubber Vulcanizate and Uncured Rubber Compound:
The compound properties are listed in Table 2 below - Measurements and Tests:
Ml. Better processability (Process Requirements) of a Rubber Compound: a. Mooney Scorch Characteristics (pre vulcanization characteristics using large rotor) for processability:
The Mooney Scorch measurements are carried out with a Mooney Viscometer (MV 2000 Alpha technologies, USA) according to ASTM D1646. MV indicates the minimum viscosity, ts indicates the time to scorch (MV+5) which indicates the processing properties (process safety). b. Dispersion Rating of the Rubber Vulcanizate: Dispersion analysis of the rubber vulcanizates are carried out with a Dispergrader, Model DGAV SR (Alpha technologies, USA) according to ASTM D 7723 for rubber vulcanizates. It indicates the macro dispersion of fillers in the rubber matrix.
M2: Hardness of the Rubber Vulcanizate:
Shore A Hardness of the rubber vulcanizates are measured in accordance with ASTM D 2240.
M3: Modulus of the Rubber Vulcanizate:
100 % modulus and 200% modulus of the rubber vulcanizates are measured in accordance with ASTM D 412.
M4: Visco elastic properties of the Rubber Vulcanizate Visco elastic properties of the rubber vulcanizates are measured on a dynamic mechanical analyzer (DMA Metravib +1000) with a 0.3% dynamic strain, 0.6% static strain%, temperature -40 deg C to +80 deg C, and 10Hz frequency as per ASTM D5992.
Tan delta at 25 deg C is commonly used as predictor for dry grip of the rubber vulcanizate. Also, higher the tan delta value at 25 deg C, better the dry grip. M5: Gas permeability of the Rubber Vulcanizate
Gas permeability of the rubber vulcanizate is measured in accordance with ASTM F 1927 M6: Thermal stability of the Rubber Vulcanizate
Thermal stability is measured using an advanced thermogravimetric analyzer machine (model: TGA 8000, PerkinElmer, MA, USA).
Table 2: Compound Properties
RESULTS
The purpose of these tests is to measure the improved properties of the elastomeric nano composite formulation related to the invention against control rubber composition. For this, two rubber compositions Cl & FI prepared based on SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black , Cl (control) and SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nanotubes (CNT), FI (Formulation related to invention).
The present invention provides a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nanotubes (CNT) gave process safety, t5 value improved by 1.21% and the dispersion of filler improved by 2.41% when compared to SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
The present invention also relates to a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nanotubes (CNT) gave higher shore A hardness improved by 5% , 100% modulus and 200% modulus of the rubber vulcanizate is improved by 41.29 % & 11.57% respectively when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
The present invention also relates to a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nano
tubes (CNT) provides dry grip and it is improved by 3.39% when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl. The present invention also relates to a 100 phr of an elastomeric nano composite FI, SBR: NR: PBR (50 phr:30 phr:20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nano tubes (CNT) provides lower gas permeability and it is lowered by 2.22 % when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
Thermal degradation of an elastomeric nano composite FI, SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black and it is replaced with 5 phr of polymer coated carbon nanotubes (CNT) , its initial polymer degradation temperature delayed by 22 deg C and it is improved by 7.09% when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition reinforced with 70 phr of the carbon black, Cl.
Hence, polymer coated carbon nano tubes (CNT) containing SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based elastomeric nano composite along with reinforcing filler carbon black provides better dry grip, high modulus, high hardness, high thermal stability, low gas permeability along with better processing properties when compared to SBR: NR: PBR (50 phr: 30 phr: 20 phr) tri blend based rubber composition along with reinforcing filler carbon black.
Claims
1. A cured elastomeric nanocomposite, comprising of: elastomeric matrix or elastomeric blend- 100 phr; a reinforcing filler - 50-69 phr; nanofiller - 1-20 phr; process aid - 28-32 phr; anti-degradants- 1 -3 phr; cure activators - 2-5 phr; vulcanization agent -1.20 - 1.5 phr; accelerator -1.2 - 1.5 phr; and pre-vulcanization inhibitor - 0.1 - 0.3 phr, wherein the nanofiller is polymer coated carbon nano tube having a diameter of 1 - 30 nm, and length 50 nm to 500 pm, and wherein the elastomeric matrix or elastomeric blend is non oil extended styrene butadiene rubber (SBR), natural rubber (NR) and polybutadiene rubber (PBR) in a weight ratio of 50: 30: 20.
2. The cured elastomeric nanocomposite as claimed in claim 1, wherein the nanofiller is styrene butadiene rubber coated multi-walled carbon nano tubes in a weight ratio of 10:90.
3. The cured elastomeric nanocomposite as claimed in claim 1, wherein the reinforcing filler is carbon black.
4. The cured elastomeric nanocomposite as claimed in claim 3, wherein the carbon black is N339 grade having the Iodine absorption number (IAN) value ranges between 85 and 95 mg/gm, Oil absorption number (OAN), ranges between 115 and 125 cc/100 gm and N2SA value ranges between 86 and 96 m2/gm.
5. The cured elastomeric nanocomposite as claimed in claim 1, wherein the process aid is aromatic oil.
6. The cured elastomeric nanocomposite as claimed in claim 1, wherein the anti-degradants comprises 6PPD [N-(l,3-dimethylbutyl)-N’ -phenyl -p-phenylenediamine and
Microcrystalline wax (MC wax) in a weight ratio of 2: 1.
7. The cured elastomeric nanocomposite as claimed in claim 1, wherein the cure activators comprises zinc oxide and stearic acid in a weight ratio of 3:2.
8. The cured elastomeric nanocomposite as claimed in claim 1, wherein the vulcanization agent is sulphur.
9. The cured elastomeric nanocomposite as claimed in claim 1, wherein the accelerator is TBBS [N-tert-butyl-2-benzothiazole sulfenamide].
10. The cured elastomeric nanocomposite as claimed in claim 1, wherein the pre vulcanization inhibitor PVI is CTP [N-(cyclohexylthio) phthalimide].
11. A process for preparation of cured elastomeric nanocomposite, comprising of steps: preparation of master batch comprising of steps: step 1 master batch: mixing of the elastomers comprising non-oil extended styrene butadiene rubber, natural rubber, and polybutadiene rubber for 10 to 40 seconds; addition of nanofiller, carbon black, rubber chemicals 6PPD, MC wax, aromatic oil and PVI; sweeping off the chemicals from the orifice and mixing for 210 to 230 seconds; mixing for 80-120 seconds and dumping the rubber compound at the temperature in the range of 140-145°C; sheet out in the two-roll mill; step 2 master batch: mixing of step 1 master batch in the Banbury mixer for 120-180 seconds; dumping at the temperature range of 110-125 °C and sheet out in the two roll mill; preparation of final batch comprising of steps:
mixing of Step 2 master batch rubber compound and the curatives for 60 to 90 seconds; dumping at the temperature range of 100-115°C; and sheet out the rubber compound in the two roll mill, wherein the nanofiller is polymer coated carbon nano tube having a diameter of 1-30 nm, and length 50 nm to 500 pm.
12. The process for preparation of cured elastomeric nanocomposite as claimed in claim 11, wherein the master batch process parameters includes head temperature of the Banbury mixer maintained between 65 and 75 °C and the unloaded rotor speed maintained between 58 and 62 rpm.
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PCT/IN2022/050610 WO2023281527A1 (en) | 2021-07-05 | 2022-07-04 | Elastomeric tire nanocomposite with polymer coated carbon nanotubes and method thereof |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117106239A (en) * | 2023-07-28 | 2023-11-24 | 三浦橡胶(无锡)有限公司 | Soft tread rubber and preparation method thereof |
Citations (4)
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WO2001055254A1 (en) * | 2000-01-25 | 2001-08-02 | Cabot Corporation | Elastomeric compositions containing polymer coated carbon products and other pigments |
US20130281612A1 (en) * | 2010-12-14 | 2013-10-24 | Styron Europe Gmbh | Elastomer Formulations |
KR20140069584A (en) * | 2012-11-29 | 2014-06-10 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
WO2020121180A1 (en) * | 2018-12-11 | 2020-06-18 | Pirelli Tyre S.P.A. | Tyre and elastomeric compound for tyre, comprising cross-linked phenolic resins |
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2022
- 2022-07-04 WO PCT/IN2022/050610 patent/WO2023281527A1/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001055254A1 (en) * | 2000-01-25 | 2001-08-02 | Cabot Corporation | Elastomeric compositions containing polymer coated carbon products and other pigments |
US20130281612A1 (en) * | 2010-12-14 | 2013-10-24 | Styron Europe Gmbh | Elastomer Formulations |
KR20140069584A (en) * | 2012-11-29 | 2014-06-10 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
WO2020121180A1 (en) * | 2018-12-11 | 2020-06-18 | Pirelli Tyre S.P.A. | Tyre and elastomeric compound for tyre, comprising cross-linked phenolic resins |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117106239A (en) * | 2023-07-28 | 2023-11-24 | 三浦橡胶(无锡)有限公司 | Soft tread rubber and preparation method thereof |
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