CN101312982A - 有机硅化合物及使用其的橡胶组合物 - Google Patents
有机硅化合物及使用其的橡胶组合物 Download PDFInfo
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- CN101312982A CN101312982A CNA2006800438325A CN200680043832A CN101312982A CN 101312982 A CN101312982 A CN 101312982A CN A2006800438325 A CNA2006800438325 A CN A2006800438325A CN 200680043832 A CN200680043832 A CN 200680043832A CN 101312982 A CN101312982 A CN 101312982A
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- 229920001971 elastomer Polymers 0.000 title claims description 47
- 239000005060 rubber Substances 0.000 title claims description 47
- 239000000203 mixture Substances 0.000 title claims description 10
- 150000003377 silicon compounds Chemical class 0.000 title 1
- 239000011256 inorganic filler Substances 0.000 claims abstract description 24
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 229960001866 silicon dioxide Drugs 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 229920003051 synthetic elastomer Polymers 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 239000005061 synthetic rubber Substances 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 6
- 150000003961 organosilicon compounds Chemical class 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- -1 isobutyl- Chemical group 0.000 description 17
- 150000008117 polysulfides Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000005077 polysulfide Substances 0.000 description 9
- 229920001021 polysulfide Polymers 0.000 description 9
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- GPYKQOCYDCMGOA-UHFFFAOYSA-N CCCCCC[O] Chemical compound CCCCCC[O] GPYKQOCYDCMGOA-UHFFFAOYSA-N 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000005968 1-Decanol Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FPVPDSGTVXBUBG-UHFFFAOYSA-N CCCCCCCCCC[O] Chemical compound CCCCCCCCCC[O] FPVPDSGTVXBUBG-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供一种有机硅化合物,其可抑制在与无机填充剂反应时产生的挥发性醇的放出,同时与无机填充剂的反应性高,其为下述通式所示的有机硅化合物。在此,R1为甲基或乙基,R2为碳原子数3~8的直链或支链的饱和或不饱和脂肪族烃基,n以平均组成计为0.5~2.5,R3为选自-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH(CH3)-、-CH2CH(CH2)-、-C(CH3)2-、-CH(C2H5)-、-CH2CH2CH(CH3)-以及-CH2CH(CH3)CH2-中的二价烃基。X选自S、S(C=O)-R4、SH以及NH(3-p),X为S的情况下,p=2且m=1~10,X为S(C=O)-R4的情况下,p=1且m=1,X为SH的情况下,p=1且m=1,X为NH(3-p)的情况下,p=1~3且m=1。R4为碳原子数1~30的直链或支链的饱和或不饱和脂肪族烃基。
Description
技术领域
本发明涉及提高在橡胶中所配合的无机填充剂的补强性的有机硅化合物、包含它的橡胶组合物以及使用该橡胶组合物而形成的充气轮胎。
背景技术
近年来,大量提出了用于胎面的各种橡胶组合物:在作为橡胶成分的天然橡胶和/或合成橡胶等二烯系橡胶中配合二氧化硅等无机填充剂,由此同时兼备低燃费性和湿润路面上的抓着性。
使用二氧化硅等无机填充剂的情况下,与以往的使用炭黑的情况相比的话,无机填充剂-橡胶成分的结合比炭黑-橡胶成分的结合弱。
因此,配合了二氧化硅等的橡胶组合物为了补强无机填充剂-橡胶成分的结合,通常使用有机硅化合物、即硅烷偶联剂。也就是说,硅烷偶联剂强化无机填充剂-橡胶成分的结合并提高胎面的耐磨耗性。尤其是其分子内含有烷氧基甲硅烷基和硫双方的有机硅化合物即硅烷偶联剂,由于容易使二氧化硅等无机填充剂和橡胶成分通过硫化反应结合,因此适宜使用。
但是,其分子内具有烷氧基甲硅烷基的有机硅化合物即硅烷偶联剂在与二氧化硅等无机填充剂反应时,产生醇。产生的醇在橡胶中挥发,因此产生如下问题:在挤压成形的未硫化橡胶的内部发泡,使尺寸稳定性和生产率降低。另外,从生产者和消费者的健康方面的缘故以及环境方面的顾虑出发,期望减少挥发性醇的放出。
为了解决这样的问题,提出了减少醇的放出的有机硅化合物即各种硅烷偶联剂。(参照专利文献1~3)但是,在这些化合物中,不能充分兼顾减少挥发性醇的放出和确保与二氧化硅等无机填充剂的反应性。
专利文献1:日本特开2002-275311号公报
专利文献2:日本特表2005-500420号公报
专利文献3:日本特开2005-35889号公报
专利文献4:日本特开2000-103794号公报
发明内容
发明要解决的课题
本发明的课题在于提供一种有机硅化合物,其可抑制在与无机填充剂反应时产生的挥发性醇的放出,同时与无机填充剂的反应性高。
解决课题的方法
本发明人为了解决上述课题进行反复深入研究,结果发现,通过使有机硅化合物的至少一个烷氧基的烃部分为特定范围的长度,可实现该目的。
本发明是基于该见解完成的。
即,本发明是具有下述通式所示的结构的有机硅化合物。
上述通式中,R1为甲基或乙基,R2为碳原子数3~8的直链或支链的饱和或不饱和脂肪族烃基,n以平均组成计为0.5~2.5,R3为选自-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH(CH3)-、-CH2CH(CH3)-、-C(CH3)2-、-CH(C2H5)-、-CH2CH2CH(CH3)-以及-CH2CH(CH3)CH2-中的二价烃基,X选自S、S(C=O)-R4、SH以及NH(3-p),X为S的情况下,p=2且m=1~10,X为S(C=O)-R4的情况下,p=1且m=1,X为SH的情况下,p=1且m=1,X为NH(3-p)的情况下,p=1~3且m=1。R4为碳原子数1~30的直链或支链的饱和或不饱和脂肪族烃基。
发明的效果
根据本发明,可提供一种有机硅化合物,其可抑制在与无机填充剂反应时产生的挥发性醇的放出,同时与无机填充剂的反应性高,以及提供包含该有机硅化合物的橡胶组合物和使用该橡胶组合物而形成的充气轮胎。
具体实施方式
在上述通式中,R2所示的碳原子数3~8的直链或支链的饱和或不饱和脂肪族烃基优选为碳原子数3~7的直链或支链的饱和或不饱和脂肪族烃基,更优选为碳原子数5~7的直链或支链的饱和或不饱和脂肪族烃基,特别优选为碳原子数6~7的直链或支链的饱和或不饱和脂肪族烃基。碳原子数为1或2时,挥发性醇的放出量变多,不能达到本发明的目的。另一方面,碳原子数为9以上的话,与无机填充剂的反应性降低。不能充分发挥作为硅烷偶联剂的功能。
另外,前述脂肪族烃基还包含环状脂肪族烃基。R2的具体例子可列举出正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、环戊基、正己基、异己基、环己基、正庚基、异庚基、正辛基、2-乙基己基、异辛基、丙烯基、烯丙基、各种丁烯基、各种戊烯基、环戊烯基、各种己烯基、环己烯基、各种庚烯基、各种辛烯基等。这些当中,尤其优选正己基、异己基、环己基、正庚基、异庚基、各种己烯基、环己烯基、各种庚烯基。
而且,上述通式中,R3所表示的二价烃基中,从制造方面的观点出发,优选-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-。
另外,在上述通式所表示的有机硅化合物中,X中优选可通过m的数值适度控制S(硫)与橡胶的反应性的基团。在该S的情况下,m为1~10的范围。m大的话,与橡胶的反应性变高。将m为1的有机硅化合物作为硅烷偶联剂使用时,需要在橡胶组合物中配合适当量的硫。
本发明的有机硅化合物可使用各种已知的反应方法进行制造。例如,在专利文献4中公开了得到具有多硫化合物结构的高纯度的含硫有机硅化合物的方法,其不需要高温处理、真空下的处理,是简化的方法。例如,用乙醇或甲醇与碳原子数3~8的长链醇的混合物将3-氯代丙基三氯硅烷酯化,然后通过与无水硫化碱反应,可得到本发明的有机硅化合物的一种即含硫有机硅化合物。
另外,使乙醇或甲醇与碳原子数3~8的长链醇的混合物与三氯硅烷反应得到酯的混合物,然后使烯丙基卤化物进行氢化硅烷化,与无水硫化碱反应,由此也可得到本发明的有机硅化合物。
而且,也可以如专利文献3所公开的那样,使烷氧基为短链(甲氧基和/或乙氧基)的硅烷化合物与长链醇进行酯交换反应,通过蒸馏使生成的短链醇与反应混合物连续地分离,从而制造本发明的有机硅化合物。
配合本发明的有机硅化合物的橡胶组合物含有二烯系橡胶、即天然橡胶和/或合成橡胶中的至少一种作为橡胶成分。作为合成橡胶,可列举出异戊二烯橡胶(IR)、丁二烯橡胶(BR)、苯乙烯-丁二烯共聚物橡胶(SBR)、乙烯-丙烯-二烯三元共聚物橡胶(EPDM)、丁基橡胶(IIR)、卤代丁基橡胶、丁腈橡胶(NBR)等。如上所述,可以仅单独使用这些中的1种,也可以将2种以上组合使用。
作为本发明的橡胶组合物中所使用的无机填充剂,可使用含硅酸的无机填充剂,例如二氧化硅、铝硅酸盐、沸石、粘土、在表面等固定二氧化硅的炭黑等、或者使用氢氧化铝等。这些当中,优选二氧化硅和氢氧化铝。例示的无机填充剂可以仅单独使用1种,也可以组合2种以上使用。
相对于100质量份含有天然橡胶和/或合成橡胶中的至少一种的橡胶成分、优选以天然橡胶和/或合成橡胶中的至少一种为主而形成的橡胶成分,无机填充剂的配合量优选为1~150质量份,更优选为3~130质量份,进一步优选为3~90质量份。只要在该范围,就可以发挥本发明的效果、即充分的补强性和操作性。另外,无机填充剂的配合量过少时,出现补强性缺乏的倾向。另外,无机填充剂的配合量过多时,出现操作性降低的倾向。
作为本发明的橡胶组合物中所使用的二氧化硅,优选使用通过沉降法得到的二氧化硅。二氧化硅的BET比表面积优选为40~350m2/g、进一步优选为70~300m2/g。作为这样的二氧化硅,可列举NIPPON SILICA KOGYO Co.,Ltd.,生产的“NIPSILAQ”;DEGUSSA Company生产的“Ultrasil VN3”;RHODIACompany生产的“Zeosil 1165MP”、“Zeosil 165GR”以及“Zeosil175P”;以及PPG Company生产的“Hisil 233”、“Hisil 210”以及“Hisil 255”等,但并不限于这些。
本发明的橡胶组合物中所使用的氢氧化铝优选昭和电工(株)生产的商标名“HIGILITE”微粒物或细粒物。在本发明中,将表面等具有氢氧化铝的矾土也看作氢氧化铝的一种。
本发明的有机硅化合物的配合量相对于前述无机填充剂优选为1~30质量%,更优选为5~20质量%。
本发明的橡胶组合物除了上述成分以外,可以适当配合橡胶组合物中通常所使用的各种添加剂,例如硫等硫化剂、硫化促进剂、防老剂、氧化锌、硬脂酸等。
实施例
下面,使用实施例具体说明本发明。另外,本实施例仅为例示,不解释成限制本发明。
另外,按照下述方法测定孔隙率和拉伸试验。
1.孔隙率
将切成5×5×20mm的尺寸的未硫化橡胶片在125℃的烘箱中加热30分钟,比较孔隙率。计算方法根据下式。值越小越优异。
孔隙率(%)={(加热前比重/加热后比重)-1}×100
2.拉伸试验
基于JIS K6301,测定破坏时伸长(EB1)、破坏强度(TB)、50%、100%以及300%拉伸模量以及韧性(TF)。韧性是求出应力-变形曲线在到达破坏时的积分值。将比较例1的数据作为100,以指数表示这些数值。
制造例1:有机硅化合物B[双(3-二乙氧基己基氧基甲硅烷基丙基)多硫化合物]的合成
在室温下,向200ml茄形瓶中加入45g双(3-三乙氧基甲硅烷基丙基)多硫化合物(在上述通式中,n=3、R1=R2=乙基、R3=-CH2CH2CH2-、X=S、p=2、m=2.5。以下,称有机硅化合物A。)、9.3g 1-己醇、0.5g对甲苯磺酸,然后在100~105℃将所得到的红色溶液加热到不产生气泡为止。接着,通过滴液漏斗,用30分钟滴加9.3g 1-己醇,然后用旋转蒸发仪在85℃以及6000Pa下除去乙醇,得到双(3-二乙氧基己基氧基甲硅烷基丙基)多硫化合物(在上述通式中,n=2、R1=乙基、R2=C6H13、R3=-CH2CH2CH2-、X=S、p=2、m=2.5)。
制造例2:有机硅化合物C[双(3-二乙氧基丙基氧基甲硅烷基丙基)多硫化合物]的合成
在室温下,向200ml茄形瓶中加入45g有机硅化合物A、5.5g1-丙醇、0.5g对甲苯磺酸,然后在100~105℃下将所得到的红色溶液加热到不产生气泡为止。接着,通过滴液漏斗,用30分钟滴加5.5g 1-丙醇,然后用旋转蒸发仪在85℃以及6000Pa下除去乙醇,得到双(3-二乙氧基丙基氧基甲硅烷基丙基)多硫化合物(在上述通式中,n=2、R1=乙基、R2=C3H7、R3=-CH2CH2CH2-、X=S、p=2、m=2.5)。
制造例3:有机硅化合物D[双(3-二乙氧基癸基氧基甲硅烷基丙基)多硫化合物]的合成
在室温下,向200ml茄形瓶中加入45g有机硅化合物A、14.5g 1-癸醇、0.5g对甲苯磺酸,然后在100~105℃下将所得到的红色溶液加热到不产生气泡为止。接着,通过滴液漏斗,用30分钟滴加14.5g 1-癸醇,然后用旋转蒸发仪在85℃以及6000Pa下除去乙醇,得到双(3-二乙氧基己基氧基甲硅烷基丙基)多硫化合物(在上述通式中,n=2、R1=乙基、R2=C10H21、R3=-CH2CH2CH2-、X=S、p=2、m=2.5)。
制造例4:有机硅化合物E[双(3-三己基氧基甲硅烷基丙基)多硫化合物]的合成
在室温下,向200ml茄形瓶中加入45g有机硅化合物A、28.1g 1-己醇、0.5g对甲苯磺酸,然后在100~105℃下将所得到的红色溶液加热到不产生气泡为止。接着,通过滴液漏斗,用30分钟滴加28.1g 1-己醇,然后用旋转蒸发仪在85℃以及6000Pa下除去乙醇,得到双(3-二乙氧基己基氧基甲硅烷基丙基)多硫化合物(在上述通式中,n=0、R2=C6H13、R3=-CH2CH2CH2-、X=S、p=2、m=2.5)。
实施例1~6以及比较例1~8
根据表1所示的配合内容,在通常的混炼条件下,制备14种橡胶组合物,对未硫化橡胶组合物测定孔隙率,对硫化橡胶组合物进行拉伸试验。结果在表1中示出。
注)有机硅化合物B、C、D以及E是相对于有机硅化合物A以等摩尔的量置换。
*1:JSR Co.,Ltd.,制造,乳液聚合SBR#1500
*2:ASAHI CARBON Co.,Ltd.,制造、#80
*3:NIPPON SILICA KOGYO Co.,Ltd.,制造、NIPSIL AQ
*4:昭和电工(株)制造、HIGILITE微粒品
*5:N-(1,3-二甲基丁基)-N’-苯基-对苯二胺、大内新兴化学工业(株)制造、NOCRAC 6C
*6:2,2,4-三甲基-1,2,-二羟基喹啉的聚合物、大内新兴化学工业(株)制造、NOCRAC 224
*7:二苯胍、三新化学工业(株)制造、SANCELOR D
*8:二硫化二苯并噻唑
*9:N-叔丁基-2-苯并噻唑基亚磺酰胺、三新化学工业(株)制造、SANCELOR NS
分别将表1所记载的实施例1和5与比较例1的橡胶组合物、实施例2和6与比较例2的橡胶组合物、实施例3与比较例3的橡胶组合物、实施例4与比较例4的橡胶组合物进行比较,由此可知,实施例1~6所使用的本发明的有机硅化合物保持与比较例1~4所使用的有机硅化合物同等的硫化物性,并且显著降低孔隙率。
另外,像比较例5和6所示那样,R2的碳链变长的话,立体障碍变大,阻碍硅烷-二氧化硅间的反应,拉伸模量和破坏强度降低。另外,像比较例7和8那样,n=0时,同样立体障碍变大,阻碍硅烷-二氧化硅间的反应,拉伸模量和破坏强度降低。
工业上的可利用性
本发明的有机硅化合物适合作为小汽车用、小型卡车用、轻型小汽车用、轻型卡车用以及大型车辆用等各种充气轮胎、尤其适合作为充气子午线轮胎的胎面用等的无机填充剂配合橡胶组合物的硅烷偶联剂使用。
Claims (4)
1.具有下述通式所示的结构的有机硅化合物。
(式中,R1为甲基或乙基,R2为碳原子数3~8的直链或支链的饱和或不饱和脂肪族烃基,n以平均组成计为0.5~2.5,R3为选自-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH(CH3)-、-CH2CH(CH3)-、-C(CH3)2-、-CH(C2H5)-、-CH2CH2CH(CH3)-以及-CH2CH(CH3)CH2-中的二价的烃基。X选自S、S(C=O)-R4、SH以及NH(3-p),X为S的情况下,p=2且m=1~10,X为S(C=O)-R4的情况下,p=1且m=1,X为SH的情况下,p=1且m=1,X为NH(3-p)的情况下,p=1~3且m=1。R4为碳原子数1~30的直链或支链的饱和或不饱和脂肪族烃基。)
2.橡胶组合物,其特征在于,相对于100质量份含有天然橡胶和/或合成橡胶中至少一种的橡胶成分,包含1~150质量份无机填充剂,并且相对于该无机填充剂,包含1~30质量%权利要求1所述的有机硅化合物。
3.根据权利要求2所述的橡胶组合物,其中,无机填充剂为二氧化硅和/或氢氧化铝。
4.充气轮胎,其使用权利要求2或3所述的橡胶组合物而形成。
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JPH1036513A (ja) * | 1996-07-30 | 1998-02-10 | Bayer Corp | キヤツプ付きシラン類および織物基質に対するそれらの適用 |
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DE10019554A1 (de) * | 2000-04-18 | 2001-10-31 | Degussa | Abmischungen von mindestens einem Füllstoff und Organosiliciumverbindungen, Verfahren zu deren Herstellung und deren Verwendung |
JP2002275311A (ja) * | 2001-01-10 | 2002-09-25 | Bridgestone Corp | ゴム組成物及びタイヤ |
DE50205449D1 (de) | 2001-08-06 | 2006-02-02 | Degussa | Organosiliciumverbindungen |
KR20040030095A (ko) | 2001-08-13 | 2004-04-08 | 소시에떼 드 테크놀로지 미쉐린 | 강화용 충전제로서 특정한 실리콘을 포함하는 타이어용디엔 고무 조성물 |
EP1298163B1 (de) * | 2001-09-26 | 2005-07-06 | Degussa AG | Geblockte Mercaptosilane, Verfahren zu deren Herstellung und die enthaltenden Kautschukmischungen |
US6433206B1 (en) * | 2001-11-05 | 2002-08-13 | Crompton Corporation | Process for preparing silylorganomercaptans |
US6673954B1 (en) * | 2003-02-19 | 2004-01-06 | General Electric Company | Process for the preparation of N-silylorganocarbamates |
US20060025506A1 (en) * | 2004-07-30 | 2006-02-02 | Weller Keith J | Silane compositions, processes for their preparation and rubber compositions containing same |
US7531588B2 (en) * | 2004-07-30 | 2009-05-12 | Momentive Performance Materials Inc. | Silane compositions, processes for their preparation and rubber compositions containing same |
-
2006
- 2006-11-21 EP EP06833031A patent/EP1953167B1/en not_active Expired - Fee Related
- 2006-11-21 CN CN2006800438325A patent/CN101312982B/zh not_active Expired - Fee Related
- 2006-11-21 WO PCT/JP2006/323181 patent/WO2007060934A1/ja active Application Filing
- 2006-11-21 JP JP2007546442A patent/JP5108528B2/ja not_active Expired - Fee Related
- 2006-11-21 US US12/094,562 patent/US7732517B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11673720B2 (en) | 2019-01-03 | 2023-06-13 | Cool Gear International, Llc | Container lid with rotatable sipper and flexible handle |
Also Published As
Publication number | Publication date |
---|---|
WO2007060934A1 (ja) | 2007-05-31 |
JP5108528B2 (ja) | 2012-12-26 |
EP1953167A1 (en) | 2008-08-06 |
EP1953167A4 (en) | 2011-05-04 |
JPWO2007060934A1 (ja) | 2009-05-07 |
US20090247683A1 (en) | 2009-10-01 |
US7732517B2 (en) | 2010-06-08 |
CN101312982B (zh) | 2012-05-09 |
EP1953167B1 (en) | 2012-06-06 |
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