WO2021124807A1 - Low-residue siloxane compound, and lubricating oil composition and lubricant using this - Google Patents
Low-residue siloxane compound, and lubricating oil composition and lubricant using this Download PDFInfo
- Publication number
- WO2021124807A1 WO2021124807A1 PCT/JP2020/043615 JP2020043615W WO2021124807A1 WO 2021124807 A1 WO2021124807 A1 WO 2021124807A1 JP 2020043615 W JP2020043615 W JP 2020043615W WO 2021124807 A1 WO2021124807 A1 WO 2021124807A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lubricating oil
- silicone
- group
- siloxane compound
- molecular weight
- Prior art date
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- -1 siloxane compound Chemical class 0.000 title claims abstract description 150
- 239000010687 lubricating oil Substances 0.000 title claims description 77
- 239000000203 mixture Substances 0.000 title claims description 64
- 239000000314 lubricant Substances 0.000 title claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 150000002430 hydrocarbons Chemical class 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003963 antioxidant agent Substances 0.000 claims description 24
- 230000003078 antioxidant effect Effects 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000005461 lubrication Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 description 94
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 69
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 68
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 65
- 239000004721 Polyphenylene oxide Substances 0.000 description 45
- 229920000570 polyether Polymers 0.000 description 45
- 238000005160 1H NMR spectroscopy Methods 0.000 description 38
- 239000000126 substance Substances 0.000 description 30
- 125000006353 oxyethylene group Chemical group 0.000 description 28
- 239000003054 catalyst Substances 0.000 description 26
- 229910052697 platinum Inorganic materials 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
- 239000010703 silicon Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 16
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000010696 ester oil Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 230000008034 disappearance Effects 0.000 description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 11
- 229920002545 silicone oil Polymers 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000013558 reference substance Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000002199 base oil Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229940069096 dodecene Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000000415 inactivating effect Effects 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000005956 Cosmos caudatus Nutrition 0.000 description 2
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
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- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- CXYRUNPLKGGUJF-OZVSTBQFSA-M pamine Chemical compound [Br-].C1([C@@H](CO)C(=O)OC2C[C@@H]3[N+]([C@H](C2)[C@@H]2[C@H]3O2)(C)C)=CC=CC=C1 CXYRUNPLKGGUJF-OZVSTBQFSA-M 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/76—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing silicon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/50—Lubricating compositions characterised by the base-material being a macromolecular compound containing silicon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/04—Working-up used lubricants to recover useful products ; Cleaning aqueous emulsion based
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
Definitions
- the present invention relates to a low-residue siloxane compound and a lubricating oil composition and a lubricant using the same.
- Lubricating oils and lubricating oil compositions are used to reduce friction and wear between moving parts and moving surfaces of various mechanical devices.
- a lubricating oil having a high viscosity index (VI) small change in viscosity with respect to temperature change
- a lubricating oil having a high VI has a low viscosity at a low temperature, and the energy loss due to the viscous resistance of the lubricating oil itself is small, so that it is excellent in terms of energy saving (energy saving).
- the viscosity does not become excessively low as compared with the lubricating oil having a low VI, so that the oil film necessary for lubrication can be retained on the lubricating surface, and the appropriate viscosity is maintained. Therefore, the scattering of lubricating oil is suppressed and the surroundings are less likely to be contaminated.
- the siloxane compound has a problem that sludge (SiO 2 ) remains as a residue after oxidative deterioration, which causes pipe clogging and filter clogging. Therefore, existing lubricants containing a siloxane compound as a main component have restrictions on their uses. Therefore, in order to expand into a wider range of fields, it is required to further improve the lubricity and reduce the residue that becomes a bottleneck in the lubricant field.
- polyalkylene glycol and ester oil are synthetic oils with less thickening and less sludge formation after deterioration, respectively. Therefore, it is considered that the lubricant composition also has a slight thickening and sludge formation after deterioration.
- the VI of these mixed base oils is insufficient, and the VI improver (high molecular weight). Additives) need to be added.
- the VI improver not only causes an increase in low-temperature viscosity, but also has a problem that it is affected by a shearing force in an environment in which the lubricating oil is used and impairs the initial lubricating oil characteristics (a decrease in viscosity occurs).
- the object of the present invention is to solve the above-mentioned problems. That is, it is an object of the present invention to provide a siloxane compound having excellent lubricity and a high viscosity index (VI) and low residual property, and a lubricating oil composition using the same.
- a siloxane compound having excellent lubricity and a high viscosity index (VI) and low residual property, and a lubricating oil composition using the same.
- siloxane compound according to one aspect of the present invention is characterized by being represented by the following formula (1).
- X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
- Y is an alkylene group having 2 to 12 carbon atoms.
- Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
- p is an integer of 0 to 13
- q and r are integers of 0 to 16, respectively
- n is an integer of 2 to 4
- a is an integer of 0 to 11.
- Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
- X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
- m is an integer of 2 to 4, and
- b is an integer of 1 to 10.
- FIG. 1 is NMR data of silicone A-2 synthesized in Examples.
- FIG. 2 is the NMR data of the silicone A-4 synthesized in the example.
- FIG. 3 is NMR data of the silicone A-5 synthesized in the examples.
- FIG. 4 is the NMR data of the silicone A-9 synthesized in the example.
- FIG. 5 is NMR data of the silicone A-10 synthesized in the example.
- FIG. 6 is NMR data of the silicone molecule double-ended hydrodimethylsiloxy group-blocking dimethylsiloxane / hexylene copolymer synthesized in the examples.
- FIG. 7 is the NMR data of the silicone A-13 synthesized in the example.
- siloxane compound of the present embodiment is characterized by being represented by the following formula (1).
- siloxane compound of the present embodiment has both a high viscosity index and low residue property, it can be used as a lubricant or the like in a wide range of fields.
- X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
- X 2 represents hydrogen or an alkyl group having 1 to 12 carbon atoms.
- the alkyl group having 1 to 12 carbon atoms in X 1 and X 2 may be cyclic or straight or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, a nonyl group and a dodecyl group. Alone or in these functional groups in the structure, it may contain a combination of two or more in X 1.
- the carbon number of X 1 and X 2 is preferably 1 to 12, more preferably 1 to 10, and particularly preferably 1 to 8 from the viewpoint of maintaining a low viscosity at a low temperature. If the number of carbon atoms of X 1 and X 2 exceeds 12, the low temperature characteristics are significantly deteriorated, which makes it difficult to use the lubricating oil composition in a low temperature range.
- Z 1 and Z 2 are divalent organic groups bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
- the structure of the divalent organic group in Z 1 and Z 2 is not particularly limited, and for example, -R-, -R-CO-, -R-NHCO-, -R-NHCONH-R 2- NHCO-,- R-OOCNH-R 2 -NHCO- (wherein R is, for example, ethylene, propylene, a divalent alkylene group such as butylene, R 2 is, for example -C 6 H 4 -, - C 6 H 4 -C 6 H 4 -, - C 6 H 4 -CH (CH 3) 2 -C 6 H 4 -. a divalent arylene group, such as suitably R 2 is a phenylene group). More preferably, Z 1 and Z 2 are divalent alkylene groups, especially
- Y is an alkylene group having 2 to 12 carbon atoms.
- the structure of Y is not particularly limited, and may be linear, branched, or cyclic.
- an alkylene group such as an ethylene group, a propylene group, a butylene group, and a hexylene group can be mentioned.
- These functional groups may be contained in the structure alone or in combination of two or more.
- the number of carbon atoms of the alkylene group in Y is preferably 2 to 12, more preferably 2 to 10, and particularly preferably 2 to 8 from the viewpoint of maintaining a low viscosity at a low temperature. If the number of carbon atoms of the alkylene group in Y exceeds 12, the low temperature characteristics may be significantly deteriorated.
- the number of repeating units of the polyoxyalkylene group is preferably 1 to 11 from the viewpoint of obtaining the viscosity required for the lubricating oil. If the number of repeating units exceeds 11, the proportion of the siloxane portion in the molecular structure may become small and the viscosity index may decrease.
- p is an integer of 0 to 13. If the p exceeds 13, the amount of residue after thermal deterioration may increase.
- q and r are the same or different integers of 0 to 16, respectively, but if these values exceed 16, the viscosity of the lubricating oil may become too high and energy saving may be lacking. ..
- n is an integer of 2 to 4.
- the polyoxyalkylene compound is polyoxyethylene, polyoxypropylene, polyoxybutylene, mixed polyoxyethylene-oxypropylene, etc.
- m is an integer of 2 to 4.
- b is an integer of 1 to 10. If b exceeds 10, the proportion of the siloxane portion in the molecular structure becomes small, and the viscosity index may decrease.
- the mass average molecular weight of the siloxane compound of the present embodiment is not particularly limited, but is preferably 500 to 11000. If the mass average molecular weight is less than 500, the amount of evaporation may increase. Further, if the mass average molecular weight exceeds 11000, the viscosity of the lubricating oil becomes too high and energy saving is lacking, which is not preferable.
- the mass average molecular weight of the siloxane compound in this embodiment is a value measured by 1 H-NMR as shown in Examples described later. In the following, the mass average molecular weight is also simply referred to as "average molecular weight”.
- the siloxane compound of the present embodiment has a viscosity index of 200 or more, and the amount of residue after heating at 140 ° C. for 100 hours and then at 250 ° C. for 700 hours is 20% or less. Is preferable.
- the viscosity index (VI) of the siloxane compound in this embodiment is preferably 200 or more in order to obtain a lubricating oil composition having a high VI. More preferably, it is 240 or more.
- VI is a value measured and calculated based on JIS K 2283 (2000).
- the method for synthesizing the siloxane compound as described above is not particularly limited, but some production examples show, for example, the presence of a platinum catalyst in a hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and a divinyl ether of polyalkylene glycol.
- the siloxane compound (silicone oil) of the present embodiment can be obtained by hydrosilylation reaction underneath.
- a siloxane is obtained by hydrosilylating a hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and a divinyl ether of a polyalkylene glycol in the presence of a platinum catalyst, and then hydrosilylating the olefin compound in the presence of a platinum catalyst.
- a compound (silicone oil) can be obtained.
- the siloxane compound of the present embodiment can be used as it is alone as various lubricants, but it is lubricated by combining a hydrocarbon-based lubricating oil as described later with at least one of an antioxidant and an extreme pressure agent. It may be used as an oil composition.
- the lubricating oil composition of the present embodiment contains (A) the above-mentioned siloxane compound, (B) a hydrocarbon-based lubricating oil, (C) an extreme pressure agent, and (D) at least one of an antioxidant. Is characterized by containing at least.
- the viscosity index (VI) of the lubricating oil composition of this embodiment is preferably 180 or more. More preferably, it is 200 or more, and further preferably 250 or more.
- the content of the siloxane compound (A) with respect to the entire composition is 30 to 95% by mass from the viewpoint of viscosity index and lubricity. In particular, it is preferably 50 to 90% by mass, and more preferably 60 to 90% by mass. Even if the content of the component (A) is less than 30% by mass, it is possible to improve the viscosity index when the lubricating oil composition is used, but the effect of improving the viscosity index is poor, and the upper limit is set. There is no particular limitation, and as described above, 100% by mass may be a siloxane compound.
- the lubricating oil composition of the present embodiment has a hydrocarbon-based lubricating oil.
- the hydrocarbon-based lubricating oil that can be used is not particularly limited as long as it is compatible with the above-mentioned (A) siloxane compound (silicone oil), but specifically, for example, ester oil, ether oil, and the like. Examples thereof include poly ⁇ -olefin (PAO) oil and mineral oil.
- ester oil examples include esters of monohydric alcohols or polyhydric alcohols with monobasic acids or polybasic acids.
- Examples of the monohydric alcohol or polyhydric alcohol include monohydric alcohols or polyhydric alcohols having a hydrocarbon group having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms. ..
- Specific examples of the multivalent alcohols include trimethylolpropane, pentaerythritol, and dipentaerythritol.
- Examples of the monobasic acid or polybasic acid include monobasic acids or polybasic acids having a hydrocarbon group having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms. Be done.
- the hydrocarbon group referred to here may be a straight chain or a branched chain, and for example, an alkyl group, an alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group.
- an alkyl group an alkenyl group
- a cycloalkyl group an alkylcycloalkyl group
- an alkylcycloalkyl group an alkylcycloalkyl group
- an aryl group an alkylaryl group
- arylalkyl group such as hydrocarbon groups.
- ester oil when used as the component (B) in the present embodiment, the above-mentioned ester oil may be used alone or in combination of two or more.
- ester oil a dibasic acid ester or a polyhydric alcohol fatty acid ester having a flash point of 200 ° C. or higher and a pour point of ⁇ 40 ° C. or lower can be used.
- a polyhydric alcohol fatty acid ester such as a fatty acid ester of trimethylolpropane or a fatty acid ester of pentaerythritol is more preferable.
- ether oil examples include polyoxy ether, dialkyl ether, aromatic ether and the like.
- poly- ⁇ -olefin oil examples include polymers of ⁇ -olefins having 2 to 15 carbon atoms such as polybutene, 1-octene oligomer, and 1-decene oligomer, or hydrides thereof.
- the mineral oil is an atmospheric residual oil obtained by atmospheric distillation of crude oils such as paraffinic, naphthenic and intermediate base oils; a distillate obtained by vacuum distillation of the atmospheric residual oil; the distillate.
- Mineral oil refined by performing one or more treatments such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc., for example, light neutral oil, medium neutral.
- the above-mentioned hydrocarbon-based lubricating oil can be used alone, or two or more kinds can be used in combination.
- the content of the (B) hydrocarbon-based lubricating oil in the lubricating oil composition of the present embodiment is 0 to 70% by mass with respect to the entire composition from the viewpoint of lubricity and viscosity index. In particular, it is preferably 10 to 50% by mass, and even more preferably 10 to 20% by mass. If the content of the hydrocarbon-based lubricating oil is less than 10% by mass, it becomes difficult to obtain sufficient lubricity, and if it exceeds 70% by mass, the content of the (A) siloxane compound in the lubricating oil composition is contained. This is not preferable because the amount is small and the viscosity index of the lubricating oil composition is low.
- the lubricating oil composition of the present embodiment further improves the lubricity of the lubricating oil composition by containing 10% by mass or more of ester oil as the (B) hydrocarbon-based lubricating oil. That is, as a preferred embodiment, it is desirable that the (B) hydrocarbon-based lubricating oil contains 10 to 50% by mass of an ester oil.
- the lubricating oil composition of the present embodiment contains at least one of (C) an extreme pressure agent and (D) an antioxidant described later.
- the lubricating oil composition of the present embodiment contains (C) an extreme pressure agent
- the lubricating oil composition of the present embodiment has an advantage that the lubricity and wear resistance can be further improved.
- Examples of the (C) extreme pressure agent that can be used in the present embodiment include thiaxazole compounds, polysulfides, thiocarbamate compounds, sulfide fats and oils, sulfide olefins, sulfide esters, sulfide fatty acids, thiophosphate esters, thiophosphate, thiophosphite, and di.
- Sulfur-based extreme pressure agents such as molybdenum alkylthiocarbamate, molybdenum dialkyldithiophosphate, zinc dialkylthiocarbamate, and zinc dialkylthiophosphate can be preferably used. These may be used alone or in combination of two or more.
- At least one selected from thiophosphate ester, dithiocarbamate, olefin sulfide, and dimercaptothiadiazole-based compound is preferable to use at least one selected from thiophosphate ester, dithiocarbamate, olefin sulfide, and dimercaptothiadiazole-based compound as the (C) extreme pressure agent.
- the content thereof is 0.5 to 10.0% by mass with respect to the entire composition from the viewpoint of obtaining sufficient wear resistance. Degree.
- an antioxidant generally used for lubricating oil can be used without particular limitation.
- phenolic compounds, amine compounds, phosphorus compounds and the like can be mentioned.
- alkylphenols such as 2,6-di-tert-butyl-4-methylphenol, methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol).
- alkylphenols such as 2,6-di-tert-butyl-4-methylphenol, methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol).
- alkylphenols such as 2,6-di-tert-butyl-4-methylphenol, methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol).
- naphthylamines such as phenyl- ⁇ -naphthylamine, dialkyldiphenylamines, phosphite esters and the like.
- phosphorus-based compounds such as phosphoric acid esters, phosphite esters, acidic phosphoric acid esters, and phosphonic acid esters.
- the lubricating oil composition of the present embodiment uses two or more kinds of (D) antioxidants in combination.
- D a phenol-based compound or an amine-based compound that functions as a primary antioxidant in combination with a secondary antioxidant such as a phosphorus-based compound.
- the content of the (D) antioxidant in the entire composition is 0.5 to 10 from the viewpoint of suppressing oxidation and reducing evaporation. It is set to 0.0% by mass. More preferably, it is 2.0 to 7.0% by mass.
- the lubricating oil composition of the present embodiment contains the metal inactivating agent, as long as the effects of the present invention are not impaired, in order to further improve its performance or, if necessary, to impart further performance.
- Various additives such as defoaming agents, thickeners, and colorants may be blended alone or in combination of two or more.
- metal inactivating agent examples include benzotriazole-based, tolyltriazole-based, and imidazole-based compounds.
- defoaming agent examples include polysiloxane, polyacrylate, styrene ester polymer and the like.
- thickener examples include metal soap (for example, lithium soap), silica, expanded graphite, polyurea, clay (for example, hectorite or bentonite) and the like.
- the amount of the additives added is 0.0 to 10.0% by mass or 0 with respect to the entire lubricating oil composition (total mass). It can be used in an amount of about 1 to 5% by mass.
- the thickener for producing grease using the lubricating oil composition of the present embodiment can be used in an amount of 5 to 25% by mass with respect to the entire lubricating grease composition (total mass).
- the method for preparing the lubricating oil composition of the present embodiment is not particularly limited, and for example, (A) a siloxane compound, (B) a hydrocarbon-based oil, (C) an extreme pressure agent, and (D) an antioxidant. It can be adjusted by heating at least one of them or other additives to 100 ° C. and mixing them.
- the lubricating oil composition of the present embodiment is stable for a long period of time and can be used at a wide range of temperatures, it can be used as various lubricants.
- it is suitably used as a lubricant for turbo machines, a lubricant for compressors, a lubricant for hydraulic equipment, a lubricant for machine tools, a grease base oil, a refrigerating machine oil, a plasticizer and the like.
- the amount of residue when heated and burned is smaller than before, it is less likely that pipe blockage or filter clogging due to the residue occurs, and it is suitable for applications in which a lubricant is used in a circulation system.
- the siloxane compound according to one aspect of the present invention is characterized by being represented by the following formula (1).
- X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
- Y is an alkylene group having 2 to 12 carbon atoms.
- Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
- p is an integer of 0 to 13
- q and r are integers of 0 to 16, respectively
- n is an integer of 2 to 4
- a is an integer of 0 to 11.
- Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
- X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
- m is an integer of 2 to 4, and
- b is an integer of 1 to 10.
- the siloxane compound has a viscosity index of 200 or more, and the amount of residue after heating at 140 ° C. for 100 hours and then at 250 ° C. for 700 hours is 20% or less. Thereby, it is considered that the above-mentioned effect can be obtained more reliably.
- the lubricating oil composition according to another aspect of the present invention includes (A) the siloxane compound according to claim 1 or 2, (B) a hydrocarbon-based lubricating oil, (C) an extreme pressure agent, and (D). ) It is characterized by containing at least one of the antioxidants. With such a configuration, it is possible to provide a lubricating oil composition having very excellent lubricity and low residue property.
- the lubricant according to still another aspect of the present invention is characterized by using the above-mentioned siloxane compound or lubricating oil composition. Further, the present invention includes the above-mentioned siloxane compound, a lubricating composition or lubricant using the same, greases and emulsions using them, and a lubrication method using them.
- Silicone A-1 is 1,1,3,3-tetramethyldisiloxane manufactured by Tokyo Chemical Industry Co., Ltd. (average molecular weight 134, average number of dimethyl units (p in the above formula (1) is 0)). ..
- the silicone A-2 has an average molecular weight of 529 and an average number of dimethyl units (p in the above formula (1)) of 5. It was found that the number of silicones A-3 was 1154, and the average number of dimethyl units (p in the above formula (1)) was 13.8.
- FIG. 1 shows the NMR data of silicone A-2.
- the 1 H-NMR analysis method for the hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain shown in Silicones A-2 to A-3 is as follows. a (chemical shift 0.05 to 0.10 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane. b (chemical shift 0.17 to 0.22 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
- the average molecular weight and the average number of dimethyl units were calculated from the following formulas based on the integrated values (ratio) of the peaks of the above a and b, respectively.
- Average number of dimethyl units 2a ⁇ b
- Average molecular weight average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrodimethylsiloxy groups at both ends of the molecular chain
- the filtrate was placed in a 200 mL separable flask, heated and depressurized to remove the residual hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain from the reaction product, and the hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecule.
- 51 g of a polyether copolymer (silicone A-4) was obtained.
- the silicone A-4 has an average molecular weight of 3546, an average number of dimethyl units (p in the above formula (1)) of 4.6, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.1, and the number of repeating units of oxyethylene (a in the above formula (1)) was 10.1.
- FIG. 2 shows the NMR data of silicone A-4.
- the 1 H-NMR analysis method for silicone A-4 and the hydrodimethylsiloxy group-blocking dimethylsiloxane / polyether copolymer at both ends of the molecule shown in silicones A-7, A-8, and A-12, which will be described later, is as follows. It's a street. a (chemical shift 0.01 to 0.10 ppm) indicates a peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether. b (chemical shift 0.16 to 0.21 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
- c (chemical shift 0.40 to 1.10 ppm) indicates the peak of hydrogen derived from CH 2 next to silicon in the polyether portion bonded to silicon.
- d (chemical shift 3.30 to 3.70 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
- the average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are based on the integrated values (ratio) of the peaks of a, b, c, and d. In addition, it was calculated from the following formulas.
- Average molecular weight (repeated number of oxyethylene x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon part connecting polyether part and silicon + connecting via polyether part and hydrocarbon part (Molecular weight of silicon part) x average number of repeating units of dimethylsiloxane / polyether + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon siloxy groups at both ends of the molecular chain
- the silicone A-5 has an average molecular weight of 739 and an average number of dimethyl units (p in the above formula (1)) of 5.1. I understood it.
- FIG. 3 shows the NMR data of Silicone A-5.
- the 1 H-NMR analysis method for silicone A-5 and the molecular double-ended alkyldimethylsiloki group-blocking dimethylsiloxane shown in silicone A-6 described later is as follows.
- a (chemical shift 0.06 to 0.12 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane.
- b (chemical shift 0.45 to 0.72 ppm) indicates the peak of hydrogen derived from CH 2 next to the silicon of the alkyl group bonded to silicon.
- the average molecular weight and the average number of dimethyl units were calculated from the following formulas based on the integrated values (ratio) of the peaks a and b.
- Average number of dimethyl units 2a ⁇ 3b
- Average molecular weight average number of dimethyl units x molecular weight of dimethyl units + molecular weight of alkyldimethylsiloxy groups at both ends of the molecular chain
- the silicone A-6 has an average molecular weight of 677 and an average number of dimethyl units (p in the above formula (1)) of 5.1. I understood it.
- the mixed solution was heated and aged at 60 ° C. for 5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
- the silicone A-7 has an average molecular weight of 1470, an average number of dimethyl units (p in the above formula (1)) of 4.9, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 1.4, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.1.
- the silicone A-8 has an average molecular weight of 2760, an average number of dimethyl units (p in the above formula (1)) of 4.6, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.5, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.0.
- the dropping speed was adjusted so as to keep the liquid temperature at 65 to 75 ° C.
- the mixed solution of 1-hexene and platinum catalyst it was aged at 65 ° C. for 5.5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual 1-hexene and toluene from the reaction product to obtain 52 g of a dimethylsiloxane-polyether copolymer (silicone A-9) having both ends of the molecule sealed with a hexyldimethylsiloki group.
- the silicone A-9 has an average molecular weight of 2772, an average number of dimethyl units (p in the above formula (1)) of 4.4, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.3, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.1.
- FIG. 4 shows the NMR data of Silicone A-9.
- the 1 H-NMR analysis method for silicone A-9 and the molecular double-ended alkyldimethylsiloki group-blocking dimethylsiloxane / polyether copolymer shown in silicone A-11, which will be described later, is as follows.
- a (chemical shift 0.01 to 0.15 ppm) is a peak of hydrogen derived from the methyl group of the dimethylsiloxane repeating unit, the methyl group of the dimethylsiloxane unit bonded to the polyether, and the methyl group of the dimethylsiloxane unit bonded to the alkyl group.
- b (chemical shift 0.80 to 0.95 ppm) indicates the peak of hydrogen derived from CH 3 at the terminal of the alkyl group bonded to silicon.
- c shows a peak of hydrogen from CH 2 next to the CH 2 next to the silicon polyether portion bonded to silicon.
- d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
- the average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are also the integrated values (ratio) of the peaks of a, b, c, and d. And, each was calculated from the following formulas.
- Silicone A-8 was heated, and after the liquid temperature reached 30 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 80 ° C. for 22 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual alphamethylstyrene (AMS) and toluene used as a solvent from the reaction product, and a 2-phenylpropyldimethylsiloki group-blocking dimethylsiloxane-polyether copolymer (silicone) at both ends of the molecule. A-10) 24 g was obtained.
- AMS alphamethylstyrene
- silicone 2-phenylpropyldimethylsiloki group-blocking dimethylsiloxane-polyether copolymer
- the silicone A-10 has an average molecular weight of 3933, an average number of dimethyl units (p in the above formula (1)) of 4.7, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 4.8, and the number of repeating units of oxyethylene (a in the above formula (1)) was 2.9.
- FIG. 5 shows the NMR data of Silicone A-10.
- the 1 H-NMR analysis method of the 2-phenylpropyldimethylsiloki group-blocking dimethylsiloxane / polyether copolymer shown at both ends of the molecule shown in Silicone A-10 is as follows. a (chemical shift 0.01 to 0.15 ppm) indicates a peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether. b (chemical shift 0.99 to 1.05 ppm) shows the peak of hydrogen derived from CH 2 next to silicon in the polyether portion bonded to silicon.
- c (chemical shift 2.85 to 3.00 ppm) indicates the peak of hydrogen derived from CH of the aralkyl group bonded to silicon.
- d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
- the average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are the integrated values (ratio) of the peaks of a, b, c, and d. Based on this, each was calculated from the following formulas.
- the mixed solution was heated, and after the liquid temperature reached 30 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 85 ° C. for 16 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual 1-dodecene and toluene used as a solvent from the reaction product, and 27 g of a dimethylsiloxane-polyether copolymer (silicone A-11) with both ends of the molecule dodecene dimethylshiroki group-blocked Obtained.
- a dimethylsiloxane-polyether copolymer silicone A-11
- the silicone A-11 has an average molecular weight of 2865, an average number of dimethyl units (p in the above formula (1)) of 4.4, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.2, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.0.
- the silicone A-12 has an average molecular weight of 10572, an average number of dimethyl units (p in the above formula (1)) of 4.1, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 16.2, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.0.
- the mixed solution was heated and aged at 80 ° C. for 5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
- the filtrate was placed in a 100 mL eggplant flask, heated and depressurized to remove the residual hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and toluene used as a solvent, and the hydrodimethylsiloxy at both ends of the molecule. 14 g of a base-sealed dimethylsiloxane / hexylene copolymer was obtained. 1 As a result of analyzing the copolymer obtained by using H-NMR, the copolymer had an average molecular weight of 1201, an average number of dimethyl units (p in the above formula (1)) of 5.3, and dimethylsiloxane. It was found that the number of repeating units of hexylene (q in the above formula (1)) was 1.1.
- FIG. 6 shows NMR data of the hydrodimethylsiloxy group-blocking dimethylsiloxane / hexylene copolymer at both ends of the molecule.
- the 1 H-NMR analysis method of the hydrodimethylsiloxy group-blocked dimethylsiloxane / hexylene copolymer at both ends of the molecule is as follows.
- a (chemical shift 0.01 to 0.11 ppm) indicates the peak of hydrogen derived from the methyl group of the dimethylsiloxane unit bonded to the hexylene group and the methyl group of the repeating unit of dimethylsiloxane.
- b (chemical shift 0.17 to 0.21 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
- c (chemical shift 0.45 to 0.60 ppm) indicates the peak of hydrogen derived from CH 2 next to the silicon of the hexylene group bonded to silicon.
- the average molecular weight, the average number of dimethyl units, and the average number of repeating units of dimethylsiloxane / hexylene were calculated by the following formulas based on the integrated values (ratio) of the peaks a, b, and c above. ..
- the mixed solution was heated, and after the liquid temperature reached 35 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 75 ° C. for 23 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, distilled water and hexane were added to the obtained reaction solution, the hexane layer was recovered, hexane and toluene used as solvents were removed, and both ends of the molecule were polyoxyalkyldimethylsiloki group-blocked dimethylsiloxane / hexylene co-weight. 4 g of coalesced (silicone A-13) was obtained.
- the silicone A-13 has an average molecular weight of 1897, an average number of dimethyl units (p in the above formula (1)) of 4.6, and dimethyl. It was found that the number of repeating units of siloxane / hexylene (q in the above formula (1)) was 1.4, and the number of repeating units of oxyethylene at the molecular terminal (b in the above formula (2)) was 6.0. ..
- FIG. 7 shows the NMR data of Silicone A-13.
- the 1 H-NMR analysis method of the molecular double-ended polyoxyalkyldimethylsiloxy group-blocking dimethylsiloxane / alkylene copolymer shown in Silicone A-13 is as follows.
- a (chemical shift 0.01 to 0.15 ppm) is the peak of hydrogen derived from the methyl group of the dimethylsiloxane unit bonded to the methyl group of the dimethylsiloxane repeating unit and the methyl group of the dimethylsiloxane unit bonded to the polyether group.
- b (chemical shift 1.20 to 1.40 ppm) shows the peak of hydrogen derived from CH 2 of the hexylene group not bonded to silicon.
- c shows a peak of hydrogen from CH 2 next to the CH 2 next to the silicon polyoxyethylene alkyl group attached to silicon.
- d shows the peak of hydrogen derived from the repeating portion of ethylene in the polyoxyalkyl moiety.
- the average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are the integrated values (ratio) of the peaks of a, b, c, and d. Based on this, each was calculated from the following formulas.
- Average number of dimethyl units (4a-6b-18c) ⁇ 3b
- Average number of repeating units of dimethylsiloxane / hexylene b / 2c
- Number of repetitions of oxyethylene d ⁇ 2c
- Average molecular weight (average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hexylene + molecular weight of silicon part connected to hexylene part) x average number of repeating units of dimethylsiloxane / hexylene + average number of dimethyl units x dimethyl units
- the amount of residue (% by weight) in the table was measured by the method described later.
- silicone oils shown in Table 1 for silicone A-3, the value of p in the formula (1) exceeds 13, so it is considered that the amount of residue has increased.
- -PAO oil poly- ⁇ -olefin manufactured by Chevron Phillips, product name: Synfluid PAO 6 cSt (40 ° C. kinematic viscosity: 30.5 mm 2 / s, 100 ° C. kinematic viscosity: 5.9 mm 2 / s, VI: 137)
- -Ether oil Alkyl diphenyl ether "Moresco High Lube LB-100" manufactured by MORESCO Co., Ltd.
- kinematic viscosity 12.6mm 2 / s, 100 °C kinematic viscosity: 2.9mm 2 / s, VI: 56) -PAG (Polyalkylene Glycol): "New Pole HB50-660" manufactured by Sanyo Chemical Industries, Ltd. (40 ° C. kinematic viscosity: 130.1 mm 2 / s, 100 ° C. kinematic viscosity: 20.1 mm 2 / s, VI: 178)
- ((C) Extreme pressure agent) Sulfur-based extreme pressure agent: isobutylene sulfide, manufactured by Rhein Chemie, "RC 2545” -Sulfur-phosphorus extreme pressure agent: Thiophosphate ester, made by LUBRIZOL "LUBRIZOL IC9AW31” -Phosphorus-based extreme pressure agent: Amin salt of fatty acid phosphate, "NA-LUBE AW-6400FG” manufactured by Kingindustries
- (D) Antioxidant) -Primary antioxidant BASF's aromatic amine compound, "IRGANOX L-57” -Primary antioxidant: BASF's phenolic compound, "IRGANOX L-135" -Secondary antioxidant: Johoku Chemical Industry "JP-310", a phosphite ester compound manufactured by Co., Ltd.
- (Other) -Metal inactivating agent Vanderbilt's benzotriazole compound "CUVAN303" -Silicone used in the comparative test 1: Methylphenyl silicone, "SH-550” manufactured by Toray Dow Corning Co., Ltd. (40 ° C kinematic viscosity: 75.3 mm 2 / s, 100 ° C kinematic viscosity: 20.1 mm 2 / s , VI: 291) -Silicone used in the comparative test: Alkylic silicone, "KF-4917” manufactured by Shin-Etsu Chemical Co., Ltd. (40 ° C kinematic viscosity: 13.8 mm 2 / s, 100 ° C kinematic viscosity: 4.6 mm 2 / s, VI : 292)
- Examples 1 to 22 and Comparative Examples 1 to 6 For Examples 1 to 10, various siloxane compounds (silicone oils) obtained in the above synthesis examples shown in Table 2 were used as they were. In Examples 11 to 22 and Comparative Examples 1 to 6, the respective components were blended in proportions (% by mass) shown in Tables 2 and 3 below, and (A) silicone oil and (B) hydrocarbons were blended. Each lubricating oil composition was prepared by heating the system oil, (C) extreme pressure agent, (D) antioxidant, and other additives to 100 ° C. and mixing them.
- Viscosity index The viscosity index (VI) was measured and calculated according to JIS K 2283 (2000). The evaluation criteria are as follows.
- Residue ratio (% by weight) is 10% or less ⁇ Residue ratio (% by weight) is more than 10% to 20% or less ⁇ Residue ratio (% by weight) exceeds 20% ⁇
- the above results are shown in Tables 2 and 3.
- Examples 11 to 22 it was shown that even if the siloxane compound of the present invention is used as a composition together with other components, a high viscosity index and a low residual property can be achieved at the same time.
- the larger the amount of the siloxane compound blended the smaller the residue after heating.
- the larger the amount of the siloxane compound blended the better the viscosity index.
- the siloxane compound and the lubricating oil composition of the present invention can be used as a lubricating oil having excellent lubricity, they can be used as lubricants for various purposes, for example, lubricants for turbo machinery, lubricants for compressors, and hydraulic equipment. It can be suitably used as a lubricant, a lubricant for machine tools, a grease base oil, a refrigerating machine oil, a plasticizer and the like. Especially suitable for high load applications.
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Abstract
The present invention relates to the siloxane compound represented by formula (1).
Description
本発明は、低残渣シロキサン化合物並びにそれを用いた潤滑油組成物及び潤滑剤に関する。
The present invention relates to a low-residue siloxane compound and a lubricating oil composition and a lubricant using the same.
潤滑油や潤滑油組成物は、様々な機械装置などの可動部や可動面間の摩擦や摩耗を低減するために用いられる。
Lubricating oils and lubricating oil compositions are used to reduce friction and wear between moving parts and moving surfaces of various mechanical devices.
最近では、輸送機器の使用環境の拡大、過酷化により、機械装置の高度化、小型化が進んでいる。機械装置の高度化、小型化に伴い、幅広い温度範囲で使用できる粘度指数（ＶＩ）が高い（温度変化に対する粘度変化が小さい）潤滑油が求められている。ＶＩが高い潤滑油は、低温での粘度が低く、潤滑油自体の粘性抵抗によるエネルギー損失が小さいことから省エネルギー性（省エネ性）の点で優れている。また、高温環境下においては、ＶＩの低い潤滑油と比較し、過度に低粘度化することがないため、潤滑面で潤滑に必要な油膜を保持することができ、また適度な粘性を保持することから潤滑油の飛散が抑えられ周囲を汚染することが少ない。
Recently, due to the expansion and harshness of the usage environment of transportation equipment, the sophistication and miniaturization of mechanical devices are progressing. With the sophistication and miniaturization of mechanical devices, there is a demand for a lubricating oil having a high viscosity index (VI) (small change in viscosity with respect to temperature change) that can be used in a wide temperature range. A lubricating oil having a high VI has a low viscosity at a low temperature, and the energy loss due to the viscous resistance of the lubricating oil itself is small, so that it is excellent in terms of energy saving (energy saving). Further, in a high temperature environment, the viscosity does not become excessively low as compared with the lubricating oil having a low VI, so that the oil film necessary for lubrication can be retained on the lubricating surface, and the appropriate viscosity is maintained. Therefore, the scattering of lubricating oil is suppressed and the surroundings are less likely to be contaminated.
これまでは、一般に炭化水素系の潤滑油の粘度指数を高くする方法として、ポリメタクリル酸エステルやポリブテンなどの高分子化合物がＶＩ向上剤として使用されてきた（特許文献１および２）。
Until now, polymer compounds such as polymethacrylic acid ester and polybutene have been generally used as VI improvers as a method for increasing the viscosity index of hydrocarbon-based lubricating oils (Patent Documents 1 and 2).
近年では、ＶＩが高い潤滑油として知られるシリコーン油（以下、Ｓｉ油とも称す）等のシロキサン化合物を潤滑油基材とした潤滑油組成物が提案されている（特許文献３および４）。
In recent years, lubricating oil compositions using a siloxane compound such as silicone oil (hereinafter, also referred to as Si oil) known as a lubricating oil having a high VI as a lubricating oil base material have been proposed (Patent Documents 3 and 4).
しかし、シロキサン化合物は、酸化劣化後にスラッジ（ＳｉＯ２）が残渣として残る問題があり、配管閉塞やフィルター詰まりの原因となるため、既存のシロキサン化合物を主剤とする潤滑剤は用途に制約がある。よって、更に幅広い分野に展開するためには、更なる潤滑性の向上や潤滑剤分野でネックとなる残渣を少なくすることが求められている。
However, the siloxane compound has a problem that sludge (SiO 2 ) remains as a residue after oxidative deterioration, which causes pipe clogging and filter clogging. Therefore, existing lubricants containing a siloxane compound as a main component have restrictions on their uses. Therefore, in order to expand into a wider range of fields, it is required to further improve the lubricity and reduce the residue that becomes a bottleneck in the lubricant field.
これまでに、耐熱性に優れる潤滑油に使用可能な共重合体として、ポリシロキサンとビスフェノール構造を含有するポリエーテルとからなるポリシロキサン・ポリエーテルブロック共重合体が報告されている（特許文献５）。また、低残渣性（スラッジ抑制効果が高い）を有するポリアルキレングリコールとポリオールエステルとを基油とリン系およびアミン系の酸化防止剤からなる潤滑油組成物も報告されている（特許文献６）。
So far, as a copolymer that can be used for a lubricating oil having excellent heat resistance, a polysiloxane / polyether block copolymer composed of a polysiloxane and a polyether containing a bisphenol structure has been reported (Patent Document 5). ). Further, a lubricating oil composition containing a polyalkylene glycol having a low residual property (high sludge suppressing effect) and a polyol ester as a base oil and a phosphorus-based and amine-based antioxidant is also reported (Patent Document 6). ..
しかしながら、特許文献５記載の共重合体は、ポリシロキサンを含む構造であるため、劣化に伴う増粘、スラッジの生成が問題となる。
However, since the copolymer described in Patent Document 5 has a structure containing polysiloxane, thickening and sludge formation due to deterioration become problems.
また、特許文献６記載の技術においては、ポリアルキレングリコールやエステル油はそれぞれ劣化後の増粘、スラッジの生成が少ない合成油である。そのため、潤滑剤組成物としても劣化後に増粘、スラッジの生成は軽微であると考えられる。しかし、昨今の潤滑剤のトレンドである幅広い温度域で使用できる（粘度指数が高い）組成物とするためには、これらの混合基油ではＶＩが不十分であり、ＶＩ向上剤（高分子の添加剤）の添加が必要となる。ＶＩ向上剤は、低温粘度の上昇を引き起こすのみでなく、潤滑油の使用環境下において、せん断力の影響を受け、初期の潤滑油特性を損なう（粘度低下が起こる）問題がある。
Further, in the technique described in Patent Document 6, polyalkylene glycol and ester oil are synthetic oils with less thickening and less sludge formation after deterioration, respectively. Therefore, it is considered that the lubricant composition also has a slight thickening and sludge formation after deterioration. However, in order to obtain a composition that can be used in a wide temperature range (high viscosity index), which is the trend of lubricants in recent years, the VI of these mixed base oils is insufficient, and the VI improver (high molecular weight). Additives) need to be added. The VI improver not only causes an increase in low-temperature viscosity, but also has a problem that it is affected by a shearing force in an environment in which the lubricating oil is used and impairs the initial lubricating oil characteristics (a decrease in viscosity occurs).
本発明の課題は、上述したような問題点を解決することにある。すなわち、優れた潤滑性と高い粘度指数（ＶＩ）を兼ね備え、かつ、低残渣性を有する、シロキサン化合物並びにそれを用いた潤滑油組成物を提供することを目的とする。
The object of the present invention is to solve the above-mentioned problems. That is, it is an object of the present invention to provide a siloxane compound having excellent lubricity and a high viscosity index (VI) and low residual property, and a lubricating oil composition using the same.
本発明者は、上記課題を解決すべく鋭意研究した結果、下記構成によって、上記目的を達することを見出し、この知見に基づいて更に検討を重ねることによって本発明を完成した。
As a result of diligent research to solve the above problems, the present inventor has found that the above object is achieved by the following configuration, and has completed the present invention by further studies based on this finding.
すなわち、本発明の一局面に係るシロキサン化合物は、下記式（１）で示されることを特徴とする。
That is, the siloxane compound according to one aspect of the present invention is characterized by being represented by the following formula (1).
［式（１）中、
Ｘ１は、同一または異なって、水素、炭素数１～１２のアルキル基または下記式（２）で示されるポリオキシアルキル基であり、
Ｙは、炭素数２～１２のアルキレン基であり、
Ｚ１は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
ｐは０～１３の整数、ｑおよびｒはそれぞれ０～１６の整数、ｎは２～４の整数、ａは０～１１の整数である。
（式（２）中、
Ｚ２は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
Ｘ２は、水素もしくは炭素数１～１２のアルキル基であり、
ｍは２～４の整数、ｂは１～１０の整数である。）］ [In equation (1),
X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
Y is an alkylene group having 2 to 12 carbon atoms.
Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
p is an integer of 0 to 13, q and r are integers of 0 to 16, respectively, n is an integer of 2 to 4, and a is an integer of 0 to 11.
(In equation (2),
Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
m is an integer of 2 to 4, and b is an integer of 1 to 10. )]
Ｘ１は、同一または異なって、水素、炭素数１～１２のアルキル基または下記式（２）で示されるポリオキシアルキル基であり、
Ｙは、炭素数２～１２のアルキレン基であり、
Ｚ１は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
ｐは０～１３の整数、ｑおよびｒはそれぞれ０～１６の整数、ｎは２～４の整数、ａは０～１１の整数である。
Ｚ２は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
Ｘ２は、水素もしくは炭素数１～１２のアルキル基であり、
ｍは２～４の整数、ｂは１～１０の整数である。）］ [In equation (1),
X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
Y is an alkylene group having 2 to 12 carbon atoms.
Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
p is an integer of 0 to 13, q and r are integers of 0 to 16, respectively, n is an integer of 2 to 4, and a is an integer of 0 to 11.
Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
m is an integer of 2 to 4, and b is an integer of 1 to 10. )]
以下、本発明の実施形態について詳細に説明するが、本発明はこれらに限定されるものではない。
Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.
（（Ａ）シロキサン化合物）
本実施形態のシロキサン化合物は、下記式（１）で示されることを特徴とする。 ((A) Siloxane compound)
The siloxane compound of the present embodiment is characterized by being represented by the following formula (1).
本実施形態のシロキサン化合物は、下記式（１）で示されることを特徴とする。 ((A) Siloxane compound)
The siloxane compound of the present embodiment is characterized by being represented by the following formula (1).
このような本実施形態のシロキサン化合物は、高い粘度指数と、低残渣性を兼ね備えるため、幅広い分野で潤滑剤などとして使用することが可能である。
Since such a siloxane compound of the present embodiment has both a high viscosity index and low residue property, it can be used as a lubricant or the like in a wide range of fields.
すなわち、上記構成によれば、非常に優れた潤滑性を有し、かつ、低残渣性を有する、シロキサン化合物並びにそれを用いた潤滑油組成物を提供することができる。
That is, according to the above configuration, it is possible to provide a siloxane compound having very excellent lubricity and low residual property, and a lubricating oil composition using the same.
上記式（１）において、Ｘ１は、同一または異なって、水素、炭素数１～１２のアルキル基または下記式（２）で示されるポリオキシアルキル基である。
上記式（２）において、Ｘ２は、水素または炭素数１～１２のアルキル基を示す。
In the above formula (1), X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
In the above formula (2), X 2 represents hydrogen or an alkyl group having 1 to 12 carbon atoms.
上記式（１）および式（２）において、Ｘ１およびＸ２における炭素数１～１２のアルキル基の構造については特に限定はなく、直鎖でも分枝鎖でも環状でもよい。具体的には、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、オクチル基、ノニル基、ドデシル基などが挙げられる。これらの官能基を構造中に１種単独または、Ｘ１においては２種以上を組み合わせて含んでいてもよい。
In the above formula (1) and (2), no particular limitation is imposed upon the structure of the alkyl group having 1 to 12 carbon atoms in X 1 and X 2, may be cyclic or straight or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, a nonyl group and a dodecyl group. Alone or in these functional groups in the structure, it may contain a combination of two or more in X 1.
Ｘ１およびＸ２の炭素数としては、低温で低粘度を維持するという観点から１～１２が好ましく、１～１０がより好ましく、１～８が特に好ましい。Ｘ１およびＸ２の炭素数が１２を超えると、低温特性が著しく悪化するため、潤滑油組成物とした場合に低温度域での使用が困難となる。
The carbon number of X 1 and X 2 is preferably 1 to 12, more preferably 1 to 10, and particularly preferably 1 to 8 from the viewpoint of maintaining a low viscosity at a low temperature. If the number of carbon atoms of X 1 and X 2 exceeds 12, the low temperature characteristics are significantly deteriorated, which makes it difficult to use the lubricating oil composition in a low temperature range.
また、上記式（１）および式（２）において、Ｚ１およびＺ２は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表す。Ｚ１およびＺ２における２価の有機基の構造については特に限定はなく、例えば、－Ｒ－、－Ｒ－ＣＯ－、－Ｒ－ＮＨＣＯ－、－Ｒ－ＮＨＣＯＮＨ－Ｒ２－ＮＨＣＯ－、－Ｒ－ＯＯＣＮＨ－Ｒ２－ＮＨＣＯ－（式中Ｒは、例えばエチレン、プロピレン、ブチレンなどの２価のアルキレン基であり、Ｒ２は、例えば－Ｃ６Ｈ４－、－Ｃ６Ｈ４－Ｃ６Ｈ４－、－Ｃ６Ｈ４－ＣＨ（ＣＨ３）２－Ｃ６Ｈ４－などの２価のアリレン基である。好適にはＲ２はフェニレン基である）などが挙げられる。より好ましくは、Ｚ１およびＺ２は、２価のアルキレン基、特にエチレン、プロピレンである。
Further, in the above formulas (1) and (2), Z 1 and Z 2 are divalent organic groups bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom. Represents. The structure of the divalent organic group in Z 1 and Z 2 is not particularly limited, and for example, -R-, -R-CO-, -R-NHCO-, -R-NHCONH-R 2- NHCO-,- R-OOCNH-R 2 -NHCO- (wherein R is, for example, ethylene, propylene, a divalent alkylene group such as butylene, R 2 is, for example -C 6 H 4 -, - C 6 H 4 -C 6 H 4 -, - C 6 H 4 -CH (CH 3) 2 -C 6 H 4 -. a divalent arylene group, such as suitably R 2 is a phenylene group). More preferably, Z 1 and Z 2 are divalent alkylene groups, especially ethylene and propylene.
上記式（１）において、Ｙは、炭素数２～１２のアルキレン基である。Ｙの構造は特に限定はなく、直鎖でも分枝鎖でも環状でもよい。
In the above formula (1), Y is an alkylene group having 2 to 12 carbon atoms. The structure of Y is not particularly limited, and may be linear, branched, or cyclic.
具体的には、例えば、エチレン基、プロピレン基、ブチレン基、へキシレン基等のアルキレン基が挙げられる。これらの官能基を構造中に１種単独または２種以上を組み合わせて含んでいてもよい。
Specifically, for example, an alkylene group such as an ethylene group, a propylene group, a butylene group, and a hexylene group can be mentioned. These functional groups may be contained in the structure alone or in combination of two or more.
Ｙにおけるアルキレン基の炭素数としては、低温で低粘度を維持するという観点から２～１２が好ましく、２～１０がより好ましく２～８が特に好ましい。Ｙにおけるアルキレン基の炭素数が１２を超えると、低温特性が著しく悪化する可能性がある。
The number of carbon atoms of the alkylene group in Y is preferably 2 to 12, more preferably 2 to 10, and particularly preferably 2 to 8 from the viewpoint of maintaining a low viscosity at a low temperature. If the number of carbon atoms of the alkylene group in Y exceeds 12, the low temperature characteristics may be significantly deteriorated.
また、ポリオキシアルキレン基の繰り返しユニット数としては、潤滑油として必要な粘性を得るという観点から１～１１が好ましい。前記繰り返しユニット数が１１を超えると、分子構造中のシロキサン部が占める割合が小さくなり粘度指数が低下するおそれがある。
The number of repeating units of the polyoxyalkylene group is preferably 1 to 11 from the viewpoint of obtaining the viscosity required for the lubricating oil. If the number of repeating units exceeds 11, the proportion of the siloxane portion in the molecular structure may become small and the viscosity index may decrease.
また、上記式（１）において、ｐは０～１３の整数である。前記ｐが１３を超えると、熱劣化後の残渣量が多くなるおそれがある。
Further, in the above equation (1), p is an integer of 0 to 13. If the p exceeds 13, the amount of residue after thermal deterioration may increase.
上記式（１）において、ｑおよびｒはそれぞれ同一または異なって０～１６の整数であるが、これらの値が１６を超えると、潤滑油として粘性が高くなりすぎて省エネルギー性に欠けるおそれがある。
In the above formula (1), q and r are the same or different integers of 0 to 16, respectively, but if these values exceed 16, the viscosity of the lubricating oil may become too high and energy saving may be lacking. ..
さらに、上記式（１）において、ポリオキシアルキレン化合物はポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン、混合ポリオキシエチレン-オキシプロピレン等であるため、ｎは２～４の整数である。
Further, in the above formula (1), since the polyoxyalkylene compound is polyoxyethylene, polyoxypropylene, polyoxybutylene, mixed polyoxyethylene-oxypropylene and the like, n is an integer of 2 to 4.
また、上記式（２）において、ポリオキシアルキレン化合物はポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン、混合ポリオキシエチレン-オキシプロピレン等であるため、ｍは２～４の整数である。
Further, in the above formula (2), since the polyoxyalkylene compound is polyoxyethylene, polyoxypropylene, polyoxybutylene, mixed polyoxyethylene-oxypropylene, etc., m is an integer of 2 to 4.
さらに、上記式（２）において、ｂは１～１０の整数である。ｂが１０を超えると、分子構造中のシロキサン部が占める割合が小さくなり粘度指数が低下するおそれがある。
Further, in the above equation (2), b is an integer of 1 to 10. If b exceeds 10, the proportion of the siloxane portion in the molecular structure becomes small, and the viscosity index may decrease.
本実施形態のシロキサン化合物の質量平均分子量は、特に限定はされないが、５００～１１０００であることが好ましい。質量平均分子量が５００を下回ると、蒸発量が多くなるおそれがある。また、質量平均分子量が１１０００を超えると、潤滑油として粘性が高くなりすぎて省エネルギー性に欠けるので好ましくない。
The mass average molecular weight of the siloxane compound of the present embodiment is not particularly limited, but is preferably 500 to 11000. If the mass average molecular weight is less than 500, the amount of evaporation may increase. Further, if the mass average molecular weight exceeds 11000, the viscosity of the lubricating oil becomes too high and energy saving is lacking, which is not preferable.
なお、本実施形態におけるシロキサン化合物の質量平均分子量とは、後述の実施例に示すように、１Ｈ－ＮＭＲを用いて測定した値である。なお、以下では質量平均分子量を単に「平均分子量」とも称す。
The mass average molecular weight of the siloxane compound in this embodiment is a value measured by 1 H-NMR as shown in Examples described later. In the following, the mass average molecular weight is also simply referred to as "average molecular weight".
具体的には、本実施形態のシロキサン化合物は、その粘度指数が２００以上であり、かつ、１４０℃で１００時間加熱後、２５０℃で７００時間加熱した後の残渣量が２０％以下であることが好ましい。
Specifically, the siloxane compound of the present embodiment has a viscosity index of 200 or more, and the amount of residue after heating at 140 ° C. for 100 hours and then at 250 ° C. for 700 hours is 20% or less. Is preferable.
本実施形態におけるシロキサン化合物の粘度指数（ＶＩ）は、ＶＩが高い潤滑油組成物を得るために、２００以上であることが好ましい。より好ましくは２４０以上であることが好ましい。本明細書において、ＶＩとは、ＪＩＳ Ｋ ２２８３（２０００年）に基づいて測定・算出した値である。
The viscosity index (VI) of the siloxane compound in this embodiment is preferably 200 or more in order to obtain a lubricating oil composition having a high VI. More preferably, it is 240 or more. In the present specification, VI is a value measured and calculated based on JIS K 2283 (2000).
上述したようなシロキサン化合物を合成する方法は特に限定されないが、いくつかの製造例を示すと、例えば、分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンとポリアルキレングリコールのジビニルエーテルとを白金触媒存在下でヒドロシリル化反応することによって、本実施形態のシロキサン化合物（シリコーン油）を得ることができる。あるいは、分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンとポリアルキレングリコールのジビニルエーテルとを白金触媒存在下でヒドロシリル化反応させた後に、オレフィン化合物と白金触媒存在下でヒドロシリル化反応することによって、シロキサン化合物（シリコーン油）を得ることができる。
The method for synthesizing the siloxane compound as described above is not particularly limited, but some production examples show, for example, the presence of a platinum catalyst in a hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and a divinyl ether of polyalkylene glycol. The siloxane compound (silicone oil) of the present embodiment can be obtained by hydrosilylation reaction underneath. Alternatively, a siloxane is obtained by hydrosilylating a hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and a divinyl ether of a polyalkylene glycol in the presence of a platinum catalyst, and then hydrosilylating the olefin compound in the presence of a platinum catalyst. A compound (silicone oil) can be obtained.
本実施形態のシロキサン化合物は、そのまま単独で、各種潤滑剤として使用することもできるが、後述するような炭化水素系潤滑油と、酸化防止剤および極圧剤のうち少なくとも一つと、組み合わせて潤滑油組成物として使用してもよい。
The siloxane compound of the present embodiment can be used as it is alone as various lubricants, but it is lubricated by combining a hydrocarbon-based lubricating oil as described later with at least one of an antioxidant and an extreme pressure agent. It may be used as an oil composition.
すなわち、本実施形態の潤滑油組成物は、（Ａ）上述のシロキサン化合物と、（Ｂ）炭化水素系潤滑油と、（Ｃ）極圧剤および（Ｄ）酸化防止剤のうち少なくとも一つと、を少なくとも含むことを特徴とする。
That is, the lubricating oil composition of the present embodiment contains (A) the above-mentioned siloxane compound, (B) a hydrocarbon-based lubricating oil, (C) an extreme pressure agent, and (D) at least one of an antioxidant. Is characterized by containing at least.
本実施形態の潤滑油組成物の粘度指数（ＶＩ）は、１８０以上であることが好ましい。より好ましくは２００以上、さらには２５０以上であることが好ましい。
The viscosity index (VI) of the lubricating oil composition of this embodiment is preferably 180 or more. More preferably, it is 200 or more, and further preferably 250 or more.
本実施形態の潤滑油組成物において、組成物全体に対する前記（Ａ）シロキサン化合物の含有量は、粘度指数及び潤滑性の観点から３０～９５質量％である。特に５０～９０質量％であることが好ましく、６０～９０質量％であることがさらに好ましい。（Ａ）成分の含有量が３０質量％未満であっても潤滑油組成物とした場合に粘度指数を向上させることは可能であるが、粘度指数を向上させる効果が乏しく、また、上限については特に限定はなく、上記したように１００質量％がシロキサン化合物であってもよい。
In the lubricating oil composition of the present embodiment, the content of the siloxane compound (A) with respect to the entire composition is 30 to 95% by mass from the viewpoint of viscosity index and lubricity. In particular, it is preferably 50 to 90% by mass, and more preferably 60 to 90% by mass. Even if the content of the component (A) is less than 30% by mass, it is possible to improve the viscosity index when the lubricating oil composition is used, but the effect of improving the viscosity index is poor, and the upper limit is set. There is no particular limitation, and as described above, 100% by mass may be a siloxane compound.
以下、本実施形態の潤滑油組成物における、シロキサン化合物以外の成分について説明する。
Hereinafter, components other than the siloxane compound in the lubricating oil composition of the present embodiment will be described.
（（Ｂ）炭化水素系潤滑油）
本実施形態の潤滑油組成物は、炭化水素系潤滑油を有する。使用できる炭化水素系潤滑油としては、上述した（Ａ）シロキサン化合物（シリコーン油）との相溶性があるものであれば特に限定はされないが、具体的には、例えば、エステル油、エーテル油、ポリαオレフィン（ＰＡＯ）油、鉱油等が挙げられる。 ((B) Hydrocarbon-based lubricating oil)
The lubricating oil composition of the present embodiment has a hydrocarbon-based lubricating oil. The hydrocarbon-based lubricating oil that can be used is not particularly limited as long as it is compatible with the above-mentioned (A) siloxane compound (silicone oil), but specifically, for example, ester oil, ether oil, and the like. Examples thereof include poly α-olefin (PAO) oil and mineral oil.
本実施形態の潤滑油組成物は、炭化水素系潤滑油を有する。使用できる炭化水素系潤滑油としては、上述した（Ａ）シロキサン化合物（シリコーン油）との相溶性があるものであれば特に限定はされないが、具体的には、例えば、エステル油、エーテル油、ポリαオレフィン（ＰＡＯ）油、鉱油等が挙げられる。 ((B) Hydrocarbon-based lubricating oil)
The lubricating oil composition of the present embodiment has a hydrocarbon-based lubricating oil. The hydrocarbon-based lubricating oil that can be used is not particularly limited as long as it is compatible with the above-mentioned (A) siloxane compound (silicone oil), but specifically, for example, ester oil, ether oil, and the like. Examples thereof include poly α-olefin (PAO) oil and mineral oil.
前記エステル油としては、具体的には、１価アルコール類または多価アルコールと１塩基酸または多塩基酸とのエステルが挙げられる。
Specific examples of the ester oil include esters of monohydric alcohols or polyhydric alcohols with monobasic acids or polybasic acids.
前記１価アルコールまたは多価アルコールとしては、炭素数１～３０、好ましくは炭素数４～２０、より好ましくは炭素数６～１８の炭化水素基を有する１価アルコールまたは多価アルコール類が挙げられる。前記多価アルコール類としては、具体的には、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等が挙げられる。
Examples of the monohydric alcohol or polyhydric alcohol include monohydric alcohols or polyhydric alcohols having a hydrocarbon group having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms. .. Specific examples of the multivalent alcohols include trimethylolpropane, pentaerythritol, and dipentaerythritol.
また、前記１塩基酸または多塩基酸としては、炭素数１～３０、好ましくは炭素数４～２０、より好ましくは炭素数６～１８の炭化水素基を有する１塩基酸または多塩基酸類が挙げられる。
Examples of the monobasic acid or polybasic acid include monobasic acids or polybasic acids having a hydrocarbon group having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms. Be done.
ここでいう炭化水素基は、直鎖であっても分枝鎖であってもよく、例えば、アルキル基、アルケニル基、シクロアルキル基、アルキルシクロアルキル基、アリール基、アルキルアリール基、アリールアルキル基等の炭化水素基が挙げられる。
The hydrocarbon group referred to here may be a straight chain or a branched chain, and for example, an alkyl group, an alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group. Such as hydrocarbon groups.
本実施形態において（Ｂ）成分としてエステル油を使用する場合、上記したようなエステル油を単独で用いても、２種以上を混合して用いてもよい。
When an ester oil is used as the component (B) in the present embodiment, the above-mentioned ester oil may be used alone or in combination of two or more.
好ましい実施形態では、エステル油として、引火点が２００℃以上であり、流動点が－４０℃以下の二塩基酸エステルまたは多価アルコール脂肪酸エステルを使用できる。特に、蒸発性が低いという観点より、トリメチロールプロパンの脂肪酸エステルやペンタエリスリトールの脂肪酸エステルといった多価アルコール脂肪酸エステルであることがより好ましい。
In a preferred embodiment, as the ester oil, a dibasic acid ester or a polyhydric alcohol fatty acid ester having a flash point of 200 ° C. or higher and a pour point of −40 ° C. or lower can be used. In particular, from the viewpoint of low evaporability, a polyhydric alcohol fatty acid ester such as a fatty acid ester of trimethylolpropane or a fatty acid ester of pentaerythritol is more preferable.
前記エーテル油としては、具体的には、ポリオキシエーテルやジアルキルエーテル、芳香族系エーテル等が挙げられる。
Specific examples of the ether oil include polyoxy ether, dialkyl ether, aromatic ether and the like.
また、前記ポリαオレフィン油としては、ポリブテン、１－オクテンオリゴマー、１－デセンオリゴマー等の炭素数２～１５までのαオレフィンの重合物またはその水素化物が挙げられる。
Examples of the poly-α-olefin oil include polymers of α-olefins having 2 to 15 carbon atoms such as polybutene, 1-octene oligomer, and 1-decene oligomer, or hydrides thereof.
前記鉱油としては、パラフィン系、ナフテン系、中間基系等の原油を常圧蒸留して得られる常圧残油；該常圧残油を減圧蒸留して得られた留出油；該留出油を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製等のうちの１つ以上の処理を行って精製した鉱油、例えば、軽質ニュートラル油、中質ニュートラル油、重質ニュートラル油、ブライトストック等、フィッシャー・トロプシュ法等により製造されるワックス（ＧＴＬワックス（Ｇａｓ Ｔｏ Ｌｉｑｕｉｄｓ ＷＡＸ））を異性化することで得られる鉱油等が挙げられる。
The mineral oil is an atmospheric residual oil obtained by atmospheric distillation of crude oils such as paraffinic, naphthenic and intermediate base oils; a distillate obtained by vacuum distillation of the atmospheric residual oil; the distillate. Mineral oil refined by performing one or more treatments such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc., for example, light neutral oil, medium neutral. Examples thereof include oils, heavy neutral oils, bright stocks, and mineral oils obtained by isomerizing waxes (GTL wax (Gas To Liquids WAX)) produced by the Fisher-Tropsch method or the like.
本実施形態では、（Ｂ）成分として、上述したような炭化水素系潤滑油を単独で用いることもできるし、２種以上を組み合わせて使用することもできる。
In the present embodiment, as the component (B), the above-mentioned hydrocarbon-based lubricating oil can be used alone, or two or more kinds can be used in combination.
本実施形態の潤滑油組成物における（Ｂ）炭化水素系潤滑油の含有量は、潤滑性、粘度指数の観点から、組成物全体に対して０～７０質量％である。特に１０～５０質量％であることが好ましく、１０～２０質量％であることがさらに好ましい。炭化水素系潤滑油の含有量が１０質量％未満となると、十分な潤滑性を得ることが困難となり、また、７０質量％を超える場合は、潤滑油組成物中の（Ａ）シロキサン化合物の含有量が少なくなり、潤滑油組成物の粘度指数が低くなるため好ましくない。
The content of the (B) hydrocarbon-based lubricating oil in the lubricating oil composition of the present embodiment is 0 to 70% by mass with respect to the entire composition from the viewpoint of lubricity and viscosity index. In particular, it is preferably 10 to 50% by mass, and even more preferably 10 to 20% by mass. If the content of the hydrocarbon-based lubricating oil is less than 10% by mass, it becomes difficult to obtain sufficient lubricity, and if it exceeds 70% by mass, the content of the (A) siloxane compound in the lubricating oil composition is contained. This is not preferable because the amount is small and the viscosity index of the lubricating oil composition is low.
さらに、本実施形態の潤滑油組成物は、（Ｂ）炭化水素系潤滑油として、エステル油を１０質量％以上含むことによって、潤滑油組成物の潤滑性がさらに向上する。つまり、好ましい実施形態としては、前記（Ｂ）炭化水素系潤滑油として、エステル油を１０～５０質量％含んでいることが望ましい。
Further, the lubricating oil composition of the present embodiment further improves the lubricity of the lubricating oil composition by containing 10% by mass or more of ester oil as the (B) hydrocarbon-based lubricating oil. That is, as a preferred embodiment, it is desirable that the (B) hydrocarbon-based lubricating oil contains 10 to 50% by mass of an ester oil.
（（Ｃ）極圧剤）
本実施形態の潤滑油組成物は、（Ｃ）極圧剤か、後述する（Ｄ）酸化防止剤のうち少なくとも一方を含む。 ((C) Extreme pressure agent)
The lubricating oil composition of the present embodiment contains at least one of (C) an extreme pressure agent and (D) an antioxidant described later.
本実施形態の潤滑油組成物は、（Ｃ）極圧剤か、後述する（Ｄ）酸化防止剤のうち少なくとも一方を含む。 ((C) Extreme pressure agent)
The lubricating oil composition of the present embodiment contains at least one of (C) an extreme pressure agent and (D) an antioxidant described later.
本実施形態の潤滑油組成物が（Ｃ）極圧剤を含む場合、本実施形態の潤滑油組成物は、潤滑性・耐摩耗性をより向上させることができるという利点がある。
When the lubricating oil composition of the present embodiment contains (C) an extreme pressure agent, the lubricating oil composition of the present embodiment has an advantage that the lubricity and wear resistance can be further improved.
本実施形態で使用できる（Ｃ）極圧剤としては、チアジアゾール系化合物、ポリサルファイド、チオカーバメート系化合物、硫化油脂、硫化オレフィン、硫化エステル、硫化脂肪酸、チオリン酸エステル、チオフォスフェート、チオフォスファイト、ジアルキルチオカルバミン酸モリブデン、ジアルキルジチオリン酸モリブデン、ジアルキルチオカルバミン酸亜鉛、ジアルキルチオリン酸亜鉛等の硫黄系極圧剤を好ましく使用できる。これらは単独で使用してもよいし、２種以上を組み合わせて使用することもできる。
Examples of the (C) extreme pressure agent that can be used in the present embodiment include thiaxazole compounds, polysulfides, thiocarbamate compounds, sulfide fats and oils, sulfide olefins, sulfide esters, sulfide fatty acids, thiophosphate esters, thiophosphate, thiophosphite, and di. Sulfur-based extreme pressure agents such as molybdenum alkylthiocarbamate, molybdenum dialkyldithiophosphate, zinc dialkylthiocarbamate, and zinc dialkylthiophosphate can be preferably used. These may be used alone or in combination of two or more.
なかでも、チオリン酸エステル、ジチオカーバメート、硫化オレフィン、及びジメルカプトチアジアゾール系化合物から選択される少なくとも１つを（Ｃ）極圧剤として使用することが好ましい。
Among them, it is preferable to use at least one selected from thiophosphate ester, dithiocarbamate, olefin sulfide, and dimercaptothiadiazole-based compound as the (C) extreme pressure agent.
本実施形態の潤滑油組成物が（Ｃ）極圧剤を含有する場合、その含有量は、十分な耐摩耗性を得るという観点、組成物全体に対して０．５～１０．０質量％程度である。このような含有量で（Ｃ）極圧剤を含有することにより、極圧効果と極圧剤自体の蒸発による潤滑油組成物の蒸発量増加を両立できるという利点がある。
When the lubricating oil composition of the present embodiment contains (C) an extreme pressure agent, the content thereof is 0.5 to 10.0% by mass with respect to the entire composition from the viewpoint of obtaining sufficient wear resistance. Degree. By containing the (C) extreme pressure agent at such a content, there is an advantage that the extreme pressure effect and the increase in the evaporation amount of the lubricating oil composition due to the evaporation of the extreme pressure agent itself can be achieved at the same time.
（（Ｄ）酸化防止剤）
本実施形態の潤滑油組成物が（Ｄ）酸化防止剤を含む場合、それにより、潤滑油組成物の寿命を延長できるという利点がある。 ((D) Antioxidant)
When the lubricating oil composition of the present embodiment contains (D) an antioxidant, there is an advantage that the life of the lubricating oil composition can be extended.
本実施形態の潤滑油組成物が（Ｄ）酸化防止剤を含む場合、それにより、潤滑油組成物の寿命を延長できるという利点がある。 ((D) Antioxidant)
When the lubricating oil composition of the present embodiment contains (D) an antioxidant, there is an advantage that the life of the lubricating oil composition can be extended.
本実施形態に用いられる（Ｄ）酸化防止剤としては、一般的に潤滑油に使用される酸化防止剤を特に限定なく使用することができる。例えば、フェノール系化合物やアミン系化合物、リン系化合物等が挙げられる。
As the (D) antioxidant used in the present embodiment, an antioxidant generally used for lubricating oil can be used without particular limitation. For example, phenolic compounds, amine compounds, phosphorus compounds and the like can be mentioned.
より具体的には、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノールなどのアルキルフェノール類、メチレン－４，４－ビスフェノール（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール）等のビスフェノール類、フェニル－α－ナフチルアミン等のナフチルアミン類、ジアルキルジフェニルアミン類、亜リン酸エステル類等が挙げられる。
More specifically, for example, alkylphenols such as 2,6-di-tert-butyl-4-methylphenol, methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol). Such as bisphenols, naphthylamines such as phenyl-α-naphthylamine, dialkyldiphenylamines, phosphite esters and the like.
これらの中でも、潤滑性のさらなる向上という観点から、リン酸エステル、亜リン酸エステル類、酸性リン酸エステル、ホスホン酸エステル等のリン系化合物を含むことが好ましい。
Among these, from the viewpoint of further improving lubricity, it is preferable to contain phosphorus-based compounds such as phosphoric acid esters, phosphite esters, acidic phosphoric acid esters, and phosphonic acid esters.
さらに、本実施形態の潤滑油組成物は２種以上の（Ｄ）酸化防止剤を併用することが好ましい。例えば、一次酸化防止剤として機能するフェノール系化合物やアミン系化合物と、リン系化合物といった二次酸化防止剤を併用することが特に好ましい。
Further, it is preferable that the lubricating oil composition of the present embodiment uses two or more kinds of (D) antioxidants in combination. For example, it is particularly preferable to use a phenol-based compound or an amine-based compound that functions as a primary antioxidant in combination with a secondary antioxidant such as a phosphorus-based compound.
本実施形態の潤滑油組成物が（Ｄ）酸化防止剤を含む場合、組成物全体に対する前記（Ｄ）酸化防止剤の含有量は、酸化抑制と蒸発量低減の観点から、０．５～１０．０質量％とする。より好ましくは、２．０～７．０質量％である。このような含有量で（Ｄ）酸化防止剤を含有することにより、酸化防止効果と酸化防止剤自体の蒸発による潤滑油組成物の蒸発量増加を両立できるという利点がある。
When the lubricating oil composition of the present embodiment contains (D) an antioxidant, the content of the (D) antioxidant in the entire composition is 0.5 to 10 from the viewpoint of suppressing oxidation and reducing evaporation. It is set to 0.0% by mass. More preferably, it is 2.0 to 7.0% by mass. By containing the (D) antioxidant in such a content, there is an advantage that the antioxidant effect and the increase in the evaporation amount of the lubricating oil composition due to the evaporation of the antioxidant itself can be achieved at the same time.
より潤滑性を高めるという観点からは、上記（Ｃ）極圧剤と（Ｄ）酸化防止剤とを両方含むことが好ましく、その場合、それらの合計量が、組成物全体に対して、０．５～１０．０質量％程度であることが好ましい。
From the viewpoint of further enhancing lubricity, it is preferable to contain both the above-mentioned (C) extreme pressure agent and (D) antioxidant, in which case the total amount thereof is 0. It is preferably about 5 to 10.0% by mass.
（その他の添加剤）
本実施形態の潤滑油組成物には、その性能をさらに向上させる目的で、または、必要に応じてさらなる性能を付与するために、本発明の効果を損なわない範囲で、金属不活性化剤、消泡剤、増粘剤、着色剤等の各種添加剤を単独でまたは複数を組み合わせて配合しても良い。 (Other additives)
The lubricating oil composition of the present embodiment contains the metal inactivating agent, as long as the effects of the present invention are not impaired, in order to further improve its performance or, if necessary, to impart further performance. Various additives such as defoaming agents, thickeners, and colorants may be blended alone or in combination of two or more.
本実施形態の潤滑油組成物には、その性能をさらに向上させる目的で、または、必要に応じてさらなる性能を付与するために、本発明の効果を損なわない範囲で、金属不活性化剤、消泡剤、増粘剤、着色剤等の各種添加剤を単独でまたは複数を組み合わせて配合しても良い。 (Other additives)
The lubricating oil composition of the present embodiment contains the metal inactivating agent, as long as the effects of the present invention are not impaired, in order to further improve its performance or, if necessary, to impart further performance. Various additives such as defoaming agents, thickeners, and colorants may be blended alone or in combination of two or more.
金属不活性化剤としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、及びイミダゾール系化合物等が挙げられる。
Examples of the metal inactivating agent include benzotriazole-based, tolyltriazole-based, and imidazole-based compounds.
消泡剤としては、例えば、ポリシロキサン、ポリアクリレート、及びスチレンエステルポリマー等が挙げられる。
Examples of the defoaming agent include polysiloxane, polyacrylate, styrene ester polymer and the like.
増粘剤としては、例えば、金属石鹸（例えば、リチウム石鹸）、シリカ、膨張黒鉛、ポリ尿素、粘土（例えば、ヘクトライトまたはベントナイト）等が挙げられる。
Examples of the thickener include metal soap (for example, lithium soap), silica, expanded graphite, polyurea, clay (for example, hectorite or bentonite) and the like.
本実施形態に潤滑油組成物に上記したような添加剤を配合する場合、その添加量は、潤滑剤組成物全体（総質量）に対して、０．０～１０．０質量％、あるいは０．１～５質量％程度の量で使用され得る。本実施形態の潤滑油組成物を用いてグリースを生成するための増粘剤は、潤滑剤グリース組成物全体（総質量）に対して、５～２５質量％の量で使用され得る。
When the above-mentioned additives are added to the lubricating oil composition in the present embodiment, the amount of the additives added is 0.0 to 10.0% by mass or 0 with respect to the entire lubricating oil composition (total mass). It can be used in an amount of about 1 to 5% by mass. The thickener for producing grease using the lubricating oil composition of the present embodiment can be used in an amount of 5 to 25% by mass with respect to the entire lubricating grease composition (total mass).
（調製方法）
本実施形態の潤滑油組成物を調製する方法としては、特に限定はなく、例えば、（Ａ）シロキサン化合物と（Ｂ）炭化水素系油、及び（Ｃ）極圧剤と（Ｄ）酸化防止剤のうち少なくとも一つやその他添加剤を１００℃に加熱して混合することによって調整することができる。 (Preparation method)
The method for preparing the lubricating oil composition of the present embodiment is not particularly limited, and for example, (A) a siloxane compound, (B) a hydrocarbon-based oil, (C) an extreme pressure agent, and (D) an antioxidant. It can be adjusted by heating at least one of them or other additives to 100 ° C. and mixing them.
本実施形態の潤滑油組成物を調製する方法としては、特に限定はなく、例えば、（Ａ）シロキサン化合物と（Ｂ）炭化水素系油、及び（Ｃ）極圧剤と（Ｄ）酸化防止剤のうち少なくとも一つやその他添加剤を１００℃に加熱して混合することによって調整することができる。 (Preparation method)
The method for preparing the lubricating oil composition of the present embodiment is not particularly limited, and for example, (A) a siloxane compound, (B) a hydrocarbon-based oil, (C) an extreme pressure agent, and (D) an antioxidant. It can be adjusted by heating at least one of them or other additives to 100 ° C. and mixing them.
（用途）
本実施形態の潤滑油組成物は、長期間安定して、幅広い温度で使用することが可能であるため、各種潤滑剤として使用することができる。例えば、ターボ機械用潤滑剤、圧縮機用の潤滑剤、油圧機器用の潤滑剤、工作機械用の潤滑剤、グリース基油、冷凍機油、可塑剤等として好適に使用される。特に、加熱・燃焼した時の残渣が従来より少ないため、残渣が原因となる配管閉塞やフィルター詰まりが起こりにくく、循環方式で潤滑剤が使用される用途に好適である。 (Use)
Since the lubricating oil composition of the present embodiment is stable for a long period of time and can be used at a wide range of temperatures, it can be used as various lubricants. For example, it is suitably used as a lubricant for turbo machines, a lubricant for compressors, a lubricant for hydraulic equipment, a lubricant for machine tools, a grease base oil, a refrigerating machine oil, a plasticizer and the like. In particular, since the amount of residue when heated and burned is smaller than before, it is less likely that pipe blockage or filter clogging due to the residue occurs, and it is suitable for applications in which a lubricant is used in a circulation system.
本実施形態の潤滑油組成物は、長期間安定して、幅広い温度で使用することが可能であるため、各種潤滑剤として使用することができる。例えば、ターボ機械用潤滑剤、圧縮機用の潤滑剤、油圧機器用の潤滑剤、工作機械用の潤滑剤、グリース基油、冷凍機油、可塑剤等として好適に使用される。特に、加熱・燃焼した時の残渣が従来より少ないため、残渣が原因となる配管閉塞やフィルター詰まりが起こりにくく、循環方式で潤滑剤が使用される用途に好適である。 (Use)
Since the lubricating oil composition of the present embodiment is stable for a long period of time and can be used at a wide range of temperatures, it can be used as various lubricants. For example, it is suitably used as a lubricant for turbo machines, a lubricant for compressors, a lubricant for hydraulic equipment, a lubricant for machine tools, a grease base oil, a refrigerating machine oil, a plasticizer and the like. In particular, since the amount of residue when heated and burned is smaller than before, it is less likely that pipe blockage or filter clogging due to the residue occurs, and it is suitable for applications in which a lubricant is used in a circulation system.
本明細書は、上述したように様々な態様の技術を開示しているが、そのうち主な技術を以下に纏める。
This specification discloses various modes of technology as described above, and the main technologies are summarized below.
本発明の一局面に係るシロキサン化合物は、下記式（１）で示されることを特徴とする。
The siloxane compound according to one aspect of the present invention is characterized by being represented by the following formula (1).
［式（１）中、
Ｘ１は、同一または異なって、水素、炭素数１～１２のアルキル基または下記式（２）で示されるポリオキシアルキル基であり、
Ｙは、炭素数２～１２のアルキレン基であり、
Ｚ１は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
ｐは０～１３の整数、ｑおよびｒはそれぞれ０～１６の整数、ｎは２～４の整数、ａは０～１１の整数である。
（式（２）中、
Ｚ２は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
Ｘ２は、水素もしくは炭素数１～１２のアルキル基であり、
ｍは２～４の整数、ｂは１～１０の整数である。）］ [In equation (1),
X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
Y is an alkylene group having 2 to 12 carbon atoms.
Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
p is an integer of 0 to 13, q and r are integers of 0 to 16, respectively, n is an integer of 2 to 4, and a is an integer of 0 to 11.
(In equation (2),
Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
m is an integer of 2 to 4, and b is an integer of 1 to 10. )]
Ｘ１は、同一または異なって、水素、炭素数１～１２のアルキル基または下記式（２）で示されるポリオキシアルキル基であり、
Ｙは、炭素数２～１２のアルキレン基であり、
Ｚ１は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
ｐは０～１３の整数、ｑおよびｒはそれぞれ０～１６の整数、ｎは２～４の整数、ａは０～１１の整数である。
Ｚ２は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
Ｘ２は、水素もしくは炭素数１～１２のアルキル基であり、
ｍは２～４の整数、ｂは１～１０の整数である。）］ [In equation (1),
X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
Y is an alkylene group having 2 to 12 carbon atoms.
Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
p is an integer of 0 to 13, q and r are integers of 0 to 16, respectively, n is an integer of 2 to 4, and a is an integer of 0 to 11.
Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
m is an integer of 2 to 4, and b is an integer of 1 to 10. )]
このような構成により、非常に優れた潤滑性を有し、かつ、低残渣性を有する、シロキサン化合物を提供することができる。
With such a configuration, it is possible to provide a siloxane compound having very excellent lubricity and low residue property.
また、前記シロキサン化合物は、その粘度指数が２００以上であり、かつ、１４０℃で１００時間加熱後、２５０℃で７００時間加熱した後の残渣量が２０％以下であることが好ましい。それにより、上述した効果をより確実に得ることができると考えられる。
Further, it is preferable that the siloxane compound has a viscosity index of 200 or more, and the amount of residue after heating at 140 ° C. for 100 hours and then at 250 ° C. for 700 hours is 20% or less. Thereby, it is considered that the above-mentioned effect can be obtained more reliably.
さらに、本発明の他の局面に係る潤滑油組成物は、（Ａ）請求項１または２に記載のシロキサン化合物と、（Ｂ）炭化水素系潤滑油と、（Ｃ）極圧剤および（Ｄ）酸化防止剤のうち少なくとも一つと、を少なくとも含むことを特徴とする。このような構成により、非常に優れた潤滑性を有し、かつ、低残渣性を有する、潤滑油組成物を提供することができる。
Further, the lubricating oil composition according to another aspect of the present invention includes (A) the siloxane compound according to claim 1 or 2, (B) a hydrocarbon-based lubricating oil, (C) an extreme pressure agent, and (D). ) It is characterized by containing at least one of the antioxidants. With such a configuration, it is possible to provide a lubricating oil composition having very excellent lubricity and low residue property.
本発明のさらに他の局面に関する潤滑剤は、上述のシロキサン化合物または潤滑油組成物を用いることを特徴とする。また、本発明には、上記シロキサン化合物、それを用いた潤滑組成物や潤滑剤、それらを用いたグリース及びエマルション、並びに、それらを使用した潤滑方法が包含される。
The lubricant according to still another aspect of the present invention is characterized by using the above-mentioned siloxane compound or lubricating oil composition. Further, the present invention includes the above-mentioned siloxane compound, a lubricating composition or lubricant using the same, greases and emulsions using them, and a lubrication method using them.
以下、本発明の実施例について説明するが、本発明はこれらに限定されるものではない。
まず、本実施例で使用した各原料を以下に示す。 Examples of the present invention will be described below, but the present invention is not limited thereto.
First, each raw material used in this example is shown below.
まず、本実施例で使用した各原料を以下に示す。 Examples of the present invention will be described below, but the present invention is not limited thereto.
First, each raw material used in this example is shown below.
〔（Ａ）シロキサン化合物（シリコーン油）の合成〕
・シリコーンＡ-１
シリコーンＡ－１は、東京化成工業（株）製の１，１，３，３－テトラメチルジシロキサン（平均分子量１３４、ジメチルユニット（上記式（１）におけるｐ）の平均個数０個）である。 [(A) Synthesis of siloxane compound (silicone oil)]
・ Silicone A-1
Silicone A-1 is 1,1,3,3-tetramethyldisiloxane manufactured by Tokyo Chemical Industry Co., Ltd. (average molecular weight 134, average number of dimethyl units (p in the above formula (1) is 0)). ..
・シリコーンＡ-１
シリコーンＡ－１は、東京化成工業（株）製の１，１，３，３－テトラメチルジシロキサン（平均分子量１３４、ジメチルユニット（上記式（１）におけるｐ）の平均個数０個）である。 [(A) Synthesis of siloxane compound (silicone oil)]
・ Silicone A-1
Silicone A-1 is 1,1,3,3-tetramethyldisiloxane manufactured by Tokyo Chemical Industry Co., Ltd. (average molecular weight 134, average number of dimethyl units (p in the above formula (1) is 0)). ..
（合成例１：シリコーンＡ－２とＡ－３）
５００ｍＬセパラブルフラスコに、前記シリコーンＡ－１を１５０ｇ（１．１ｍｏｌ）と、信越化学工業（株）製のデカメチルシクロペンタシロキサン（商品名：ＫＦ－９９５）４１６ｇ（０．９ｍｏｌ）と、活性白土３ｇとを入れ、６５℃で７時間撹拌した。室温に冷却した後、ろ過によって活性白土を取り除いた。続いて、ろ液を５００ｍＬのセパラブルフラスコに入れ、加熱・減圧し、留出物として、低分子量の分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（シリコーンＡ－２）１９１ｇと釜に残った高分子量の分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（シリコーンＡ－３）３４３ｇを得た。 (Synthesis Example 1: Silicone A-2 and A-3)
150 g (1.1 mol) of the silicone A-1 and 416 g (0.9 mol) of decamethylcyclopentasiloxane (trade name: KF-995) manufactured by Shin-Etsu Chemical Co., Ltd. in a 500 mL separable flask. 3 g of white clay was added, and the mixture was stirred at 65 ° C. for 7 hours. After cooling to room temperature, the activated clay was removed by filtration. Subsequently, the filtrate was placed in a 500 mL separable flask, heated and depressurized, and remained in a kettle with 191 g of low molecular weight molecular chain both-terminal hydrodimethylsiloxy group-sealed dimethylsiloxane (silicone A-2) as a distillate. 343 g of high molecular weight molecular chain biterminal hydrodimethylsiloxy group-blocking dimethylsiloxane (silicone A-3) was obtained.
５００ｍＬセパラブルフラスコに、前記シリコーンＡ－１を１５０ｇ（１．１ｍｏｌ）と、信越化学工業（株）製のデカメチルシクロペンタシロキサン（商品名：ＫＦ－９９５）４１６ｇ（０．９ｍｏｌ）と、活性白土３ｇとを入れ、６５℃で７時間撹拌した。室温に冷却した後、ろ過によって活性白土を取り除いた。続いて、ろ液を５００ｍＬのセパラブルフラスコに入れ、加熱・減圧し、留出物として、低分子量の分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（シリコーンＡ－２）１９１ｇと釜に残った高分子量の分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（シリコーンＡ－３）３４３ｇを得た。 (Synthesis Example 1: Silicone A-2 and A-3)
150 g (1.1 mol) of the silicone A-1 and 416 g (0.9 mol) of decamethylcyclopentasiloxane (trade name: KF-995) manufactured by Shin-Etsu Chemical Co., Ltd. in a 500 mL separable flask. 3 g of white clay was added, and the mixture was stirred at 65 ° C. for 7 hours. After cooling to room temperature, the activated clay was removed by filtration. Subsequently, the filtrate was placed in a 500 mL separable flask, heated and depressurized, and remained in a kettle with 191 g of low molecular weight molecular chain both-terminal hydrodimethylsiloxy group-sealed dimethylsiloxane (silicone A-2) as a distillate. 343 g of high molecular weight molecular chain biterminal hydrodimethylsiloxy group-blocking dimethylsiloxane (silicone A-3) was obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－２とシリコーンＡ－３を解析した結果、シリコーンＡ－２は、平均分子量５２９、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．３個であり、シリコーンＡ－３は、平均分子量１１５４、ジメチルユニット（上記式（１）におけるｐ）の平均個数１３．８個であることがわかった。
1 As a result of analyzing silicone A-2 and silicone A-3 obtained by using H-NMR, the silicone A-2 has an average molecular weight of 529 and an average number of dimethyl units (p in the above formula (1)) of 5. It was found that the number of silicones A-3 was 1154, and the average number of dimethyl units (p in the above formula (1)) was 13.8.
図１に、シリコーンＡ－２のＮＭＲデータを示す。
FIG. 1 shows the NMR data of silicone A-2.
なお、シリコーンＡ－２～Ａ－３に示す分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンの１Ｈ－ＮＭＲ解析方法は以下の通りである。
ａ（ケミカルシフト０．０５～０．１０ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．１７～０．２２ｐｐｍ）は分子鎖両末端のハイドロジメチルシロキシ基のメチル基由来の水素のピークを示す。 The 1 H-NMR analysis method for the hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain shown in Silicones A-2 to A-3 is as follows.
a (chemical shift 0.05 to 0.10 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane.
b (chemical shift 0.17 to 0.22 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
ａ（ケミカルシフト０．０５～０．１０ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．１７～０．２２ｐｐｍ）は分子鎖両末端のハイドロジメチルシロキシ基のメチル基由来の水素のピークを示す。 The 1 H-NMR analysis method for the hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain shown in Silicones A-2 to A-3 is as follows.
a (chemical shift 0.05 to 0.10 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane.
b (chemical shift 0.17 to 0.22 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
そして、平均分子量、並びに、ジメチルユニット（上記式（１）におけるｐ）の平均個数は上記ａ、ｂのピークの積分値（比）をもとに、次の計算式よりそれぞれ算出した。
ジメチルユニットの平均個数＝２ａ÷ｂ
平均分子量＝ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のハイドロジメチルシロキシ基の分子量 Then, the average molecular weight and the average number of dimethyl units (p in the above formula (1)) were calculated from the following formulas based on the integrated values (ratio) of the peaks of the above a and b, respectively.
Average number of dimethyl units = 2a ÷ b
Average molecular weight = average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrodimethylsiloxy groups at both ends of the molecular chain
ジメチルユニットの平均個数＝２ａ÷ｂ
平均分子量＝ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のハイドロジメチルシロキシ基の分子量 Then, the average molecular weight and the average number of dimethyl units (p in the above formula (1)) were calculated from the following formulas based on the integrated values (ratio) of the peaks of the above a and b, respectively.
Average number of dimethyl units = 2a ÷ b
Average molecular weight = average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrodimethylsiloxy groups at both ends of the molecular chain
シリコーンＡ－２のＮＭＲデータは以下の通りであった。
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０５～０．１０ｐｐｍの積分値を１０．０とすると、
δ＝０．１７～０．２２ｐｐｍの積分値は３．８。 The NMR data of Silicone A-2 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.05 to 0.10 ppm is 10.0,
The integral value of δ = 0.17 to 0.22 ppm is 3.8.
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０５～０．１０ｐｐｍの積分値を１０．０とすると、
δ＝０．１７～０．２２ｐｐｍの積分値は３．８。 The NMR data of Silicone A-2 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.05 to 0.10 ppm is 10.0,
The integral value of δ = 0.17 to 0.22 ppm is 3.8.
（合成例２：シリコーンＡ－４）
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５２２、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．２個）４０ｇ（７７ｍｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末２５ｍｇ（Ｐｔ換算：２１ｐｐｍ）を入れ、滴下ロートに日油（株）製のポリエチレングリコールジアリルエーテル（商品名：ユニオックス ＡＡ－４８０Ｒ）１９ｇ（３８ｍｍｏｌ）を入れ、窒素置換を行った。分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンと白金触媒の混合液を加熱し、液温が８５℃に到達した後、ポリエチレングリコールジアリルエーテルの滴下を開始した。ポリエチレングリコールジアリルエーテルをすべて滴下した後、１２５℃で６時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。室温に冷却した後、ろ過によって白金触媒を取り除いた。続いて、ろ液を２００ｍＬのセパラブルフラスコに入れ、加熱・減圧し、反応物から残存する分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンを除去し、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－４）５１ｇを得た。 (Synthesis Example 2: Silicone A-4)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 522, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .2 pieces) 40 g (77 mmol) and 25 mg (Pt equivalent: 21 ppm) of Pt alumina powder, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added, and polyethylene glycol diallyl ether manufactured by Nichiyu Co., Ltd. was added to the dropping funnel. (Product name: Uniox AA-480R) 19 g (38 mmol) was added, and nitrogen substitution was performed. A mixed solution of hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and a platinum catalyst was heated, and after the solution temperature reached 85 ° C., polyethylene glycol diallyl ether was started to be added dropwise. After all the polyethylene glycol diallyl ether was added dropwise, the mixture was aged at 125 ° C. for 6 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. After cooling to room temperature, the platinum catalyst was removed by filtration. Subsequently, the filtrate was placed in a 200 mL separable flask, heated and depressurized to remove the residual hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain from the reaction product, and the hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecule. 51 g of a polyether copolymer (silicone A-4) was obtained.
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５２２、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．２個）４０ｇ（７７ｍｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末２５ｍｇ（Ｐｔ換算：２１ｐｐｍ）を入れ、滴下ロートに日油（株）製のポリエチレングリコールジアリルエーテル（商品名：ユニオックス ＡＡ－４８０Ｒ）１９ｇ（３８ｍｍｏｌ）を入れ、窒素置換を行った。分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンと白金触媒の混合液を加熱し、液温が８５℃に到達した後、ポリエチレングリコールジアリルエーテルの滴下を開始した。ポリエチレングリコールジアリルエーテルをすべて滴下した後、１２５℃で６時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。室温に冷却した後、ろ過によって白金触媒を取り除いた。続いて、ろ液を２００ｍＬのセパラブルフラスコに入れ、加熱・減圧し、反応物から残存する分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンを除去し、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－４）５１ｇを得た。 (Synthesis Example 2: Silicone A-4)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 522, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .2 pieces) 40 g (77 mmol) and 25 mg (Pt equivalent: 21 ppm) of Pt alumina powder, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added, and polyethylene glycol diallyl ether manufactured by Nichiyu Co., Ltd. was added to the dropping funnel. (Product name: Uniox AA-480R) 19 g (38 mmol) was added, and nitrogen substitution was performed. A mixed solution of hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and a platinum catalyst was heated, and after the solution temperature reached 85 ° C., polyethylene glycol diallyl ether was started to be added dropwise. After all the polyethylene glycol diallyl ether was added dropwise, the mixture was aged at 125 ° C. for 6 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. After cooling to room temperature, the platinum catalyst was removed by filtration. Subsequently, the filtrate was placed in a 200 mL separable flask, heated and depressurized to remove the residual hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain from the reaction product, and the hydrodimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecule. 51 g of a polyether copolymer (silicone A-4) was obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－４を解析した結果、シリコーンＡ－４は、平均分子量３５４６、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．６個、ジメチルシロキサン・ポリエーテルの繰り返しユニット（上記式（１）におけるｒ）が３．１個、オキシエチレンの繰り返し数（上記式（１）におけるａ）が１０．１個であることがわかった。
1 As a result of analyzing the silicone A-4 obtained using 1 H-NMR, the silicone A-4 has an average molecular weight of 3546, an average number of dimethyl units (p in the above formula (1)) of 4.6, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.1, and the number of repeating units of oxyethylene (a in the above formula (1)) was 10.1.
図２に、シリコーンＡ－４のＮＭＲデータを示す。
FIG. 2 shows the NMR data of silicone A-4.
なお、シリコーンＡ－４、及び後述するシリコーンＡ－７、Ａ－８、Ａ－１２に示す分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・ポリエーテル共重合体の１Ｈ－ＮＭＲ解析方法は以下の通りである。
ａ（ケミカルシフト０．０１～０．１０ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．１６～０．２１ｐｐｍ）は分子鎖両末端のハイドロジメチルシロキシ基のメチル基由来の水素のピークを示す。
ｃ（ケミカルシフト０．４０～１．１０ｐｐｍ）はケイ素に結合したポリエーテル部のケイ素の隣のＣＨ２由来の水素のピークを示す。
ｄ（ケミカルシフト３．３０～３．７０ｐｐｍ）はポリエーテル部のオキシエチレンの繰り返し部分とオキシエチレンの繰り返し部とケイ素を繋ぐ炭化水素部の酸素と結合するＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method for silicone A-4 and the hydrodimethylsiloxy group-blocking dimethylsiloxane / polyether copolymer at both ends of the molecule shown in silicones A-7, A-8, and A-12, which will be described later, is as follows. It's a street.
a (chemical shift 0.01 to 0.10 ppm) indicates a peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether.
b (chemical shift 0.16 to 0.21 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
c (chemical shift 0.40 to 1.10 ppm) indicates the peak of hydrogen derived from CH 2 next to silicon in the polyether portion bonded to silicon.
d (chemical shift 3.30 to 3.70 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
ａ（ケミカルシフト０．０１～０．１０ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．１６～０．２１ｐｐｍ）は分子鎖両末端のハイドロジメチルシロキシ基のメチル基由来の水素のピークを示す。
ｃ（ケミカルシフト０．４０～１．１０ｐｐｍ）はケイ素に結合したポリエーテル部のケイ素の隣のＣＨ２由来の水素のピークを示す。
ｄ（ケミカルシフト３．３０～３．７０ｐｐｍ）はポリエーテル部のオキシエチレンの繰り返し部分とオキシエチレンの繰り返し部とケイ素を繋ぐ炭化水素部の酸素と結合するＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method for silicone A-4 and the hydrodimethylsiloxy group-blocking dimethylsiloxane / polyether copolymer at both ends of the molecule shown in silicones A-7, A-8, and A-12, which will be described later, is as follows. It's a street.
a (chemical shift 0.01 to 0.10 ppm) indicates a peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether.
b (chemical shift 0.16 to 0.21 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
c (chemical shift 0.40 to 1.10 ppm) indicates the peak of hydrogen derived from CH 2 next to silicon in the polyether portion bonded to silicon.
d (chemical shift 3.30 to 3.70 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
平均分子量、ジメチルユニットの平均個数、並びに、ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数、オキシエチレンの繰り返しの平均個数は上記ａ、ｂ、ｃ、ｄのピークの積分値（比）をもとに、次の計算式よりそれぞれ算出した。
ジメチルユニットの平均個数＝（２ａ－６ｂ－ｃ）÷３ｂ
ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＝
３ｂ÷ｃ
オキシエチレンの繰り返し数＝ｄ÷ｂ－１
平均分子量＝（オキシエチレンの繰り返し数×オキシエチレンの分子量＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋ポリエーテル部とケイ素を繋ぐ炭化水素部の分子量＋ポリエーテル部と炭化水素部を介して繋がったケイ素部の分子量）×ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のハイドロジメチルシロキシ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are based on the integrated values (ratio) of the peaks of a, b, c, and d. In addition, it was calculated from the following formulas.
Average number of dimethyl units = (2a-6bc) ÷ 3b
Average number of repeating units of dimethylsiloxane / polyether =
3b ÷ c
Number of repetitions of oxyethylene = d ÷ b-1
Average molecular weight = (repeated number of oxyethylene x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon part connecting polyether part and silicon + connecting via polyether part and hydrocarbon part (Molecular weight of silicon part) x average number of repeating units of dimethylsiloxane / polyether + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon siloxy groups at both ends of the molecular chain
ジメチルユニットの平均個数＝（２ａ－６ｂ－ｃ）÷３ｂ
ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＝
３ｂ÷ｃ
オキシエチレンの繰り返し数＝ｄ÷ｂ－１
平均分子量＝（オキシエチレンの繰り返し数×オキシエチレンの分子量＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋ポリエーテル部とケイ素を繋ぐ炭化水素部の分子量＋ポリエーテル部と炭化水素部を介して繋がったケイ素部の分子量）×ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のハイドロジメチルシロキシ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are based on the integrated values (ratio) of the peaks of a, b, c, and d. In addition, it was calculated from the following formulas.
Average number of dimethyl units = (2a-6bc) ÷ 3b
Average number of repeating units of dimethylsiloxane / polyether =
3b ÷ c
Number of repetitions of oxyethylene = d ÷ b-1
Average molecular weight = (repeated number of oxyethylene x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon part connecting polyether part and silicon + connecting via polyether part and hydrocarbon part (Molecular weight of silicon part) x average number of repeating units of dimethylsiloxane / polyether + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon siloxy groups at both ends of the molecular chain
シリコーンＡ－４のＮＭＲデータは以下の通りであった。
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０１～０．１０ｐｐｍの積分値を１０．０とすると、
δ＝０．１６～０．２１ｐｐｍの積分値は１．０
δ＝０．４０～１．１０ｐｐｍの積分値は０．９
δ＝３．３０～３．７０ｐｐｍの積分値は１０．６。 The NMR data of Silicone A-4 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.01 to 0.10 ppm is 10.0,
The integral value of δ = 0.16 to 0.21 ppm is 1.0
The integral value of δ = 0.40 to 1.10 ppm is 0.9
The integral value of δ = 3.30 to 3.70 ppm is 10.6.
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０１～０．１０ｐｐｍの積分値を１０．０とすると、
δ＝０．１６～０．２１ｐｐｍの積分値は１．０
δ＝０．４０～１．１０ｐｐｍの積分値は０．９
δ＝３．３０～３．７０ｐｐｍの積分値は１０．６。 The NMR data of Silicone A-4 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.01 to 0.10 ppm is 10.0,
The integral value of δ = 0.16 to 0.21 ppm is 1.0
The integral value of δ = 0.40 to 1.10 ppm is 0.9
The integral value of δ = 3.30 to 3.70 ppm is 10.6.
（合成例３：シリコーンＡ－５）
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５５８、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．７個）２０ｇ（３６ｍｍｏｌ）とトルエン７０ｇを入れ、滴下ロートに出光興産（株）製のジイソブチレン２４ｇ（２１４ｍｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液３μＬ（Ｐｔ換算：２ｐｐｍ）を入れ、窒素置換を行った。分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンとトルエンの混合溶液を加熱し、液温が６０℃に到達した後、ジイソブチレンと白金触媒の混合液の滴下を開始した。ジイソブチレンと白金触媒の混合液をすべて滴下した後、９５℃で４．５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存するジイソブチレンと溶剤として使用したトルエンを除去し、分子両末端イソオクチルジメチルシロキ基封鎖ジメチルシロキサン（シリコーンＡ－５）２８ｇを得た。 (Synthesis Example 3: Silicone A-5)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 558, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .7 pieces) 20 g (36 mmol) and 70 g of toluene were added, and 24 g (214 mmol) of diisobutylene manufactured by Idemitsu Kosan Co., Ltd. and Pt-CTS-toluene, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added to the dropping funnel. 3 μL of the solution (Pt equivalent: 2 ppm) was added, and nitrogen substitution was performed. The mixed solution of hydrodimethylsiloxy group-blocking dimethylsiloxane and toluene at both ends of the molecular chain was heated, and after the liquid temperature reached 60 ° C., the mixed solution of diisobutylene and a platinum catalyst was started to be added dropwise. After dropping all the mixed solution of diisobutylene and platinum catalyst, it was aged at 95 ° C. for 4.5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual diisobutylene and toluene used as a solvent from the reaction product to obtain 28 g of isooctyldimethylsiloki group-blocking dimethylsiloxane (silicone A-5) at both ends of the molecule.
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５５８、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．７個）２０ｇ（３６ｍｍｏｌ）とトルエン７０ｇを入れ、滴下ロートに出光興産（株）製のジイソブチレン２４ｇ（２１４ｍｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液３μＬ（Ｐｔ換算：２ｐｐｍ）を入れ、窒素置換を行った。分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンとトルエンの混合溶液を加熱し、液温が６０℃に到達した後、ジイソブチレンと白金触媒の混合液の滴下を開始した。ジイソブチレンと白金触媒の混合液をすべて滴下した後、９５℃で４．５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存するジイソブチレンと溶剤として使用したトルエンを除去し、分子両末端イソオクチルジメチルシロキ基封鎖ジメチルシロキサン（シリコーンＡ－５）２８ｇを得た。 (Synthesis Example 3: Silicone A-5)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 558, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .7 pieces) 20 g (36 mmol) and 70 g of toluene were added, and 24 g (214 mmol) of diisobutylene manufactured by Idemitsu Kosan Co., Ltd. and Pt-CTS-toluene, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added to the dropping funnel. 3 μL of the solution (Pt equivalent: 2 ppm) was added, and nitrogen substitution was performed. The mixed solution of hydrodimethylsiloxy group-blocking dimethylsiloxane and toluene at both ends of the molecular chain was heated, and after the liquid temperature reached 60 ° C., the mixed solution of diisobutylene and a platinum catalyst was started to be added dropwise. After dropping all the mixed solution of diisobutylene and platinum catalyst, it was aged at 95 ° C. for 4.5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual diisobutylene and toluene used as a solvent from the reaction product to obtain 28 g of isooctyldimethylsiloki group-blocking dimethylsiloxane (silicone A-5) at both ends of the molecule.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－５を解析した結果、シリコーンＡ－５は、平均分子量７３９、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．１個であることがわかった。
1 As a result of analyzing the silicone A-5 obtained by using 1 H-NMR, the silicone A-5 has an average molecular weight of 739 and an average number of dimethyl units (p in the above formula (1)) of 5.1. I understood it.
図３に、シリコーンＡ－５のＮＭＲデータを示す。
FIG. 3 shows the NMR data of Silicone A-5.
なお、シリコーンＡ－５、並びに後述するシリコーンＡ－６に示す分子両末端アルキルジメチルシロキ基封鎖ジメチルシロキサンの１Ｈ－ＮＭＲ解析方法は以下の通りである。
ａ（ケミカルシフト０．０６～０．１２ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．４５～０．７２ｐｐｍ）はケイ素に結合したアルキル基のケイ素の隣のＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method for silicone A-5 and the molecular double-ended alkyldimethylsiloki group-blocking dimethylsiloxane shown in silicone A-6 described later is as follows.
a (chemical shift 0.06 to 0.12 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane.
b (chemical shift 0.45 to 0.72 ppm) indicates the peak of hydrogen derived from CH 2 next to the silicon of the alkyl group bonded to silicon.
ａ（ケミカルシフト０．０６～０．１２ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．４５～０．７２ｐｐｍ）はケイ素に結合したアルキル基のケイ素の隣のＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method for silicone A-5 and the molecular double-ended alkyldimethylsiloki group-blocking dimethylsiloxane shown in silicone A-6 described later is as follows.
a (chemical shift 0.06 to 0.12 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane.
b (chemical shift 0.45 to 0.72 ppm) indicates the peak of hydrogen derived from CH 2 next to the silicon of the alkyl group bonded to silicon.
そして、平均分子量、並びに、ジメチルユニットの平均個数は上記ａ、ｂのピークの積分値（比）をもとに、次の計算式よりそれぞれ算出した。
ジメチルユニットの平均個数＝２ａ÷３ｂ
平均分子量＝ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のアルキルジメチルシロキシ基の分子量 Then, the average molecular weight and the average number of dimethyl units were calculated from the following formulas based on the integrated values (ratio) of the peaks a and b.
Average number of dimethyl units = 2a ÷ 3b
Average molecular weight = average number of dimethyl units x molecular weight of dimethyl units + molecular weight of alkyldimethylsiloxy groups at both ends of the molecular chain
ジメチルユニットの平均個数＝２ａ÷３ｂ
平均分子量＝ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のアルキルジメチルシロキシ基の分子量 Then, the average molecular weight and the average number of dimethyl units were calculated from the following formulas based on the integrated values (ratio) of the peaks a and b.
Average number of dimethyl units = 2a ÷ 3b
Average molecular weight = average number of dimethyl units x molecular weight of dimethyl units + molecular weight of alkyldimethylsiloxy groups at both ends of the molecular chain
シリコーンＡ－５のＮＭＲデータは以下の通りであった。
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０６～０．１２ｐｐｍの積分値を１０．０とすると、
δ＝０．４５～０．７２ｐｐｍの積分値は１．３。 The NMR data of Silicone A-5 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.06 to 0.12 ppm is 10.0,
The integral value of δ = 0.45 to 0.72 ppm is 1.3.
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０６～０．１２ｐｐｍの積分値を１０．０とすると、
δ＝０．４５～０．７２ｐｐｍの積分値は１．３。 The NMR data of Silicone A-5 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.06 to 0.12 ppm is 10.0,
The integral value of δ = 0.45 to 0.72 ppm is 1.3.
（合成例４：シリコーンＡ－６）
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５５８、ジメチルユニット（ｐ）の平均個数５．７個）２３ｇ（４１ｍｍｏｌ）とトルエン７１ｇを入れ、滴下ロートに出光興産（株）製の１－ヘキセン（商品名：リニアレン６）１８ｇ（２１４ｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液３μＬ（Ｐｔ換算：２ｐｐｍ）を入れ、窒素置換を行った。分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンとトルエンの混合溶液を加熱し、液温が６０℃に到達した後、１－ヘキセンと白金触媒の混合液の滴下を開始した。１－ヘキセンと白金触媒の混合液をすべて滴下した後、８０℃で６時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存する１－ヘキセンと溶剤として使用したトルエンを除去し、分子両末端ヘキシルジメチルシロキ基封鎖ジメチルシロキサン（シリコーンＡ－６）３０ｇを得た。 (Synthesis Example 4: Silicone A-6)
In a 200 mL separable flask, 23 g (average molecular weight 558, average number of dimethyl units (p) 5.7) obtained by the same method as in Synthesis Example 1 and hydrodimethylsiloxy group-sealed dimethylsiloxane (average molecular weight 558) 41 mmol) and 71 g of toluene were added, and 18 g (214 mol) of 1-hexene (trade name: Linearene 6) manufactured by Idemitsu Kosan Co., Ltd. and Pt-CTS, a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added to the dropping funnel. -Toluene solution 3 μL (Pt equivalent: 2 ppm) was added and nitrogen substitution was performed. The mixed solution of hydrodimethylsiloxy group-blocking dimethylsiloxane and toluene at both ends of the molecular chain was heated, and after the liquid temperature reached 60 ° C., the mixed solution of 1-hexene and a platinum catalyst was started to be added dropwise. After dropping all the mixed solution of 1-hexene and platinum catalyst, it was aged at 80 ° C. for 6 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual 1-hexene and toluene used as a solvent from the reaction product to obtain 30 g of hexyldimethylsiloki group-blocking dimethylsiloxane (silicone A-6) at both ends of the molecule.
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５５８、ジメチルユニット（ｐ）の平均個数５．７個）２３ｇ（４１ｍｍｏｌ）とトルエン７１ｇを入れ、滴下ロートに出光興産（株）製の１－ヘキセン（商品名：リニアレン６）１８ｇ（２１４ｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液３μＬ（Ｐｔ換算：２ｐｐｍ）を入れ、窒素置換を行った。分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンとトルエンの混合溶液を加熱し、液温が６０℃に到達した後、１－ヘキセンと白金触媒の混合液の滴下を開始した。１－ヘキセンと白金触媒の混合液をすべて滴下した後、８０℃で６時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存する１－ヘキセンと溶剤として使用したトルエンを除去し、分子両末端ヘキシルジメチルシロキ基封鎖ジメチルシロキサン（シリコーンＡ－６）３０ｇを得た。 (Synthesis Example 4: Silicone A-6)
In a 200 mL separable flask, 23 g (average molecular weight 558, average number of dimethyl units (p) 5.7) obtained by the same method as in Synthesis Example 1 and hydrodimethylsiloxy group-sealed dimethylsiloxane (average molecular weight 558) 41 mmol) and 71 g of toluene were added, and 18 g (214 mol) of 1-hexene (trade name: Linearene 6) manufactured by Idemitsu Kosan Co., Ltd. and Pt-CTS, a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added to the dropping funnel. -
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－６を解析した結果、シリコーンＡ－６は、平均分子量６７７、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．１個であることがわかった。
1 As a result of analyzing the silicone A-6 obtained by using 1 H-NMR, the silicone A-6 has an average molecular weight of 677 and an average number of dimethyl units (p in the above formula (1)) of 5.1. I understood it.
（合成例５：シリコーンＡ－７）
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５２２、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．２個）２５ｇ（４８ｍｍｏｌ）とトルエン３１ｇ、東京化成工業（株）製のトリエチレングリコールジビニルエーテル５ｇ（２５ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末１２ｍｇ（Ｐｔ換算：２０ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、６０℃で５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 5: Silicone A-7)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 522, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .2) 25 g (48 mmol) and 31 g of toluene, 5 g (25 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., and 12 mg (Pt) of Pt alumina powder, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd. Conversion: 20 ppm) was added, and nitrogen substitution was performed. The mixed solution was heated and aged at 60 ° C. for 5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５２２、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．２個）２５ｇ（４８ｍｍｏｌ）とトルエン３１ｇ、東京化成工業（株）製のトリエチレングリコールジビニルエーテル５ｇ（２５ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末１２ｍｇ（Ｐｔ換算：２０ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、６０℃で５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 5: Silicone A-7)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 522, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .2) 25 g (48 mmol) and 31 g of toluene, 5 g (25 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., and 12 mg (Pt) of Pt alumina powder, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd. Conversion: 20 ppm) was added, and nitrogen substitution was performed. The mixed solution was heated and aged at 60 ° C. for 5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
続いて、ろ液を２００ｍＬのナスフラスコに入れ、加熱・減圧し、反応物から残存する分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンと溶剤として使用したトルエンを除去し、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－７）２０ｇを得た。
Subsequently, the filtrate was placed in a 200 mL eggplant flask, heated and depressurized to remove the residual hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and toluene used as a solvent, and the hydrodimethylsiloxy at both ends of the molecule. 20 g of a base-sealed dimethylsiloxane / polyether copolymer (silicone A-7) was obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－７を解析した結果、シリコーンＡ－７は、平均分子量１４７０、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．９個、ジメチルシロキサン・ポリエーテルの繰り返しユニット（上記式（１）におけるｒ）が１．４個、オキシエチレンの繰り返し数（上記式（１）におけるａ）が３．１個であることがわかった。
1 As a result of analyzing the silicone A-7 obtained using 1 H-NMR, the silicone A-7 has an average molecular weight of 1470, an average number of dimethyl units (p in the above formula (1)) of 4.9, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 1.4, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.1.
（合成例６：シリコーンＡ－８）
５００ｍＬのセパラブルフラスコに、前記合成例１で得られたシリコーンＡ－２を１５０ｇ（２８７ｍｍｏｌ）とトルエン１５０ｇ、東京化成工業（株）製のトリエチレングリコールジビニルエーテル４５ｇ（２２ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末８１ｍｇ（Ｐｔ換算：２０ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、７５℃で４．５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 6: Silicone A-8)
In a 500 mL separable flask, 150 g (287 mmol) and 150 g of toluene of the silicone A-2 obtained in Synthesis Example 1, 45 g (22 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., NE.E. 81 mg (Pt equivalent: 20 ppm) of Pt alumina powder, which is a platinum catalyst manufactured by Chemcat Co., Ltd., was added and nitrogen substitution was performed. The mixed solution was heated and aged at 75 ° C. for 4.5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
５００ｍＬのセパラブルフラスコに、前記合成例１で得られたシリコーンＡ－２を１５０ｇ（２８７ｍｍｏｌ）とトルエン１５０ｇ、東京化成工業（株）製のトリエチレングリコールジビニルエーテル４５ｇ（２２ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末８１ｍｇ（Ｐｔ換算：２０ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、７５℃で４．５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 6: Silicone A-8)
In a 500 mL separable flask, 150 g (287 mmol) and 150 g of toluene of the silicone A-2 obtained in Synthesis Example 1, 45 g (22 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., NE.E. 81 mg (Pt equivalent: 20 ppm) of Pt alumina powder, which is a platinum catalyst manufactured by Chemcat Co., Ltd., was added and nitrogen substitution was performed. The mixed solution was heated and aged at 75 ° C. for 4.5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
続いて、ろ液を５００ｍＬのナスフラスコに入れ、加熱・減圧し、反応物から残存する分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンと溶剤として使用したトルエンを除去し、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－８）１６０ｇを得た。
Subsequently, the filtrate was placed in a 500 mL eggplant flask, heated and depressurized to remove the residual hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and toluene used as a solvent, and the hydrodimethylsiloxy at both ends of the molecule. 160 g of a base-sealed dimethylsiloxane / polyether copolymer (silicone A-8) was obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－８を解析した結果、シリコーンＡ－８は、平均分子量２７６０、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．６個、ジメチルシロキサン・ポリエーテルの繰り返しユニット（上記式（１）におけるｒ）が３．５個、オキシエチレンの繰り返し数（上記式（１）におけるａ）が３．０個であることがわかった。
1 As a result of analyzing the silicone A-8 obtained using H-NMR, the silicone A-8 has an average molecular weight of 2760, an average number of dimethyl units (p in the above formula (1)) of 4.6, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.5, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.0.
（合成例７：シリコーンＡ－９）
２００ｍＬのセパラブルフラスコに、前記合成例７で得られたシリコーンＡ－８を５０ｇ（１８ｍｍｏｌ）を入れ、滴下ロートに出光興産（株）製の１－ヘキセン（商品名：リニアレン６）３２ｇ（０．４ｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液１０μＬ（Ｐｔ換算：３ｐｐｍ）を入れ、窒素置換を行った。シリコーンＡ－８を加熱し、液温が３０℃に到達した後、１－ヘキセンと白金触媒の混合液の滴下を開始した。この時、液温を６５～７５℃に保つよう滴下の速度を調節した。１－ヘキセンと白金触媒の混合液をすべて滴下した後、６５℃で５．５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存する１－ヘキセンとトルエンを除去し、分子両末端ヘキシルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－９）５２ｇを得た。 (Synthesis Example 7: Silicone A-9)
50 g (18 mmol) of the silicone A-8 obtained in Synthesis Example 7 was placed in a 200 mL separable flask, and 1-hexene (trade name: Linearene 6) manufactured by Idemitsu Kosan Co., Ltd., 32 g (0) was placed in the dropping funnel. .4 mol) and 10 μL of Pt-CTS-toluene solution (Pt equivalent: 3 ppm), which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added and nitrogen substitution was performed. Silicone A-8 was heated, and after the liquid temperature reached 30 ° C., dropping of a mixed liquid of 1-hexene and a platinum catalyst was started. At this time, the dropping speed was adjusted so as to keep the liquid temperature at 65 to 75 ° C. After dropping all the mixed solution of 1-hexene and platinum catalyst, it was aged at 65 ° C. for 5.5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual 1-hexene and toluene from the reaction product to obtain 52 g of a dimethylsiloxane-polyether copolymer (silicone A-9) having both ends of the molecule sealed with a hexyldimethylsiloki group.
２００ｍＬのセパラブルフラスコに、前記合成例７で得られたシリコーンＡ－８を５０ｇ（１８ｍｍｏｌ）を入れ、滴下ロートに出光興産（株）製の１－ヘキセン（商品名：リニアレン６）３２ｇ（０．４ｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液１０μＬ（Ｐｔ換算：３ｐｐｍ）を入れ、窒素置換を行った。シリコーンＡ－８を加熱し、液温が３０℃に到達した後、１－ヘキセンと白金触媒の混合液の滴下を開始した。この時、液温を６５～７５℃に保つよう滴下の速度を調節した。１－ヘキセンと白金触媒の混合液をすべて滴下した後、６５℃で５．５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存する１－ヘキセンとトルエンを除去し、分子両末端ヘキシルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－９）５２ｇを得た。 (Synthesis Example 7: Silicone A-9)
50 g (18 mmol) of the silicone A-8 obtained in Synthesis Example 7 was placed in a 200 mL separable flask, and 1-hexene (trade name: Linearene 6) manufactured by Idemitsu Kosan Co., Ltd., 32 g (0) was placed in the dropping funnel. .4 mol) and 10 μL of Pt-CTS-toluene solution (Pt equivalent: 3 ppm), which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added and nitrogen substitution was performed. Silicone A-8 was heated, and after the liquid temperature reached 30 ° C., dropping of a mixed liquid of 1-hexene and a platinum catalyst was started. At this time, the dropping speed was adjusted so as to keep the liquid temperature at 65 to 75 ° C. After dropping all the mixed solution of 1-hexene and platinum catalyst, it was aged at 65 ° C. for 5.5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual 1-hexene and toluene from the reaction product to obtain 52 g of a dimethylsiloxane-polyether copolymer (silicone A-9) having both ends of the molecule sealed with a hexyldimethylsiloki group.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－９を解析した結果、シリコーンＡ－９は、平均分子量２７７２、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．４個、ジメチルシロキサン・ポリエーテルの繰り返しユニット（上記式（１）におけるｒ）が３．３個、オキシエチレンの繰り返し数（上記式（１）におけるａ）が３．１個であることがわかった。
1 As a result of analyzing the silicone A-9 obtained using 1 H-NMR, the silicone A-9 has an average molecular weight of 2772, an average number of dimethyl units (p in the above formula (1)) of 4.4, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.3, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.1.
図４に、シリコーンＡ－９のＮＭＲデータを示す。
FIG. 4 shows the NMR data of Silicone A-9.
なお、シリコーンＡ－９、並びに後述するシリコーンＡ－１１に示す分子両末端アルキルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体の１Ｈ－ＮＭＲ解析方法は以下の通りである。
ａ（ケミカルシフト０．０１～０．１５ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基とアルキル基と結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．８０～０．９５ｐｐｍ）はケイ素に結合したアルキル基の末端のＣＨ３由来の水素のピークを示す。
ｃ（ケミカルシフト０．９５～１．１０ｐｐｍ）はケイ素に結合したポリエーテル部のケイ素の隣のＣＨ２の隣のＣＨ２由来の水素のピークを示す。
ｄ（ケミカルシフト３．３０～３．７５ｐｐｍ）はポリエーテル部のオキシエチレンの繰り返し部分とオキシエチレンの繰り返し部とケイ素を繋ぐ炭化水素部の酸素と結合するＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method for silicone A-9 and the molecular double-ended alkyldimethylsiloki group-blocking dimethylsiloxane / polyether copolymer shown in silicone A-11, which will be described later, is as follows.
a (chemical shift 0.01 to 0.15 ppm) is a peak of hydrogen derived from the methyl group of the dimethylsiloxane repeating unit, the methyl group of the dimethylsiloxane unit bonded to the polyether, and the methyl group of the dimethylsiloxane unit bonded to the alkyl group. Is shown.
b (chemical shift 0.80 to 0.95 ppm) indicates the peak of hydrogen derived from CH 3 at the terminal of the alkyl group bonded to silicon.
c (chemical shift 0.95 ~ 1.10 ppm) shows a peak of hydrogen from CH 2 next to the CH 2 next to the silicon polyether portion bonded to silicon.
d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
ａ（ケミカルシフト０．０１～０．１５ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基とアルキル基と結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．８０～０．９５ｐｐｍ）はケイ素に結合したアルキル基の末端のＣＨ３由来の水素のピークを示す。
ｃ（ケミカルシフト０．９５～１．１０ｐｐｍ）はケイ素に結合したポリエーテル部のケイ素の隣のＣＨ２の隣のＣＨ２由来の水素のピークを示す。
ｄ（ケミカルシフト３．３０～３．７５ｐｐｍ）はポリエーテル部のオキシエチレンの繰り返し部分とオキシエチレンの繰り返し部とケイ素を繋ぐ炭化水素部の酸素と結合するＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method for silicone A-9 and the molecular double-ended alkyldimethylsiloki group-blocking dimethylsiloxane / polyether copolymer shown in silicone A-11, which will be described later, is as follows.
a (chemical shift 0.01 to 0.15 ppm) is a peak of hydrogen derived from the methyl group of the dimethylsiloxane repeating unit, the methyl group of the dimethylsiloxane unit bonded to the polyether, and the methyl group of the dimethylsiloxane unit bonded to the alkyl group. Is shown.
b (chemical shift 0.80 to 0.95 ppm) indicates the peak of hydrogen derived from CH 3 at the terminal of the alkyl group bonded to silicon.
c (chemical shift 0.95 ~ 1.10 ppm) shows a peak of hydrogen from CH 2 next to the CH 2 next to the silicon polyether portion bonded to silicon.
d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
そして、平均分子量、ジメチルユニットの平均個数、ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数、並びにオキシエチレンの繰り返しの平均個数は上記ａ、ｂ、ｃ、ｄのピークの積分値（比）をもとに、次の計算式よりそれぞれ算出した。
ジメチルユニットの平均個数＝（２ａ－８ｂ－６ｃ）÷３ｃ
ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数
＝３ｃ÷２ｂ
オキシエチレンの繰り返し数＝ｄ÷ｃ－１
平均分子量＝（オキシエチレンの繰り返し数×オキシエチレンの分子量＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋ポリエーテル部とケイ素を繋ぐ炭化水素部の分子量＋ポリエーテル部と炭化水素部を介して繋がったケイ素部の分子量）×ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のアルキルジメチルシロキシ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are also the integrated values (ratio) of the peaks of a, b, c, and d. And, each was calculated from the following formulas.
Average number of dimethyl units = (2a-8b-6c) ÷ 3c
Average number of repeating units of dimethylsiloxane / polyether = 3c ÷ 2b
Number of repetitions of oxyethylene = d ÷ c-1
Average molecular weight = (repeated number of oxyethylene x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon part connecting polyether part and silicon + connecting via polyether part and hydrocarbon part (Molecular weight of silicon part) x average number of repeating units of dimethylsiloxane / polyether + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of alkyldimethylsiloxy groups at both ends of the molecular chain
ジメチルユニットの平均個数＝（２ａ－８ｂ－６ｃ）÷３ｃ
ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数
＝３ｃ÷２ｂ
オキシエチレンの繰り返し数＝ｄ÷ｃ－１
平均分子量＝（オキシエチレンの繰り返し数×オキシエチレンの分子量＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋ポリエーテル部とケイ素を繋ぐ炭化水素部の分子量＋ポリエーテル部と炭化水素部を介して繋がったケイ素部の分子量）×ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のアルキルジメチルシロキシ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are also the integrated values (ratio) of the peaks of a, b, c, and d. And, each was calculated from the following formulas.
Average number of dimethyl units = (2a-8b-6c) ÷ 3c
Average number of repeating units of dimethylsiloxane / polyether = 3c ÷ 2b
Number of repetitions of oxyethylene = d ÷ c-1
Average molecular weight = (repeated number of oxyethylene x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon part connecting polyether part and silicon + connecting via polyether part and hydrocarbon part (Molecular weight of silicon part) x average number of repeating units of dimethylsiloxane / polyether + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of alkyldimethylsiloxy groups at both ends of the molecular chain
シリコーンＡ－９のＮＭＲデータは以下の通りであった。
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０５～０．１５ｐｐｍの積分値を１０．０とすると、
δ＝０．８０～０．９５ｐｐｍの積分値は０．４
δ＝０．９５～１．１０ｐｐｍの積分値は０．９
δ＝３．５０～３．７５ｐｐｍの積分値は３．６。 The NMR data of Silicone A-9 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.05 to 0.15 ppm is 10.0,
The integral value of δ = 0.80 to 0.95 ppm is 0.4
The integral value of δ = 0.95 to 1.10 ppm is 0.9
The integral value of δ = 3.50 to 3.75 ppm is 3.6.
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０５～０．１５ｐｐｍの積分値を１０．０とすると、
δ＝０．８０～０．９５ｐｐｍの積分値は０．４
δ＝０．９５～１．１０ｐｐｍの積分値は０．９
δ＝３．５０～３．７５ｐｐｍの積分値は３．６。 The NMR data of Silicone A-9 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.05 to 0.15 ppm is 10.0,
The integral value of δ = 0.80 to 0.95 ppm is 0.4
The integral value of δ = 0.95 to 1.10 ppm is 0.9
The integral value of δ = 3.50 to 3.75 ppm is 3.6.
（合成例８：シリコーンＡ－１０）
２００ｍＬのセパラブルフラスコに、前記合成例７で得られたシリコーンＡ－８を２５ｇ（９ｍｍｏｌ）とトルエン５３ｇを入れ、滴下ロートに三井化学（株）製のアルファメチルスチレン（ＡＭＳ）５ｇ（４２ｍｍｏｌ）とトルエン１１ｇとエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液５５μＬ（Ｐｔ換算：４７ｐｐｍ）を入れ、窒素置換を行った。シリコーンＡ－８を加熱し、液温が３０℃に到達した後、滴下ロートの混合溶液の滴下を開始した。滴下ロートの混合溶液をすべて滴下した後、８０℃で２２時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存するアルファメチルスチレン（ＡＭＳ）と溶媒として使用したトルエンを除去し、分子両末端２－フェニルプロピルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－１０）２４ｇを得た。 (Synthesis Example 8: Silicone A-10)
25 g (9 mmol) of the silicone A-8 obtained in Synthesis Example 7 and 53 g of toluene were placed in a 200 mL separable flask, and 5 g (42 mmol) of alpha-methylstyrene (AMS) manufactured by Mitsui Kagaku Co., Ltd. was added to the dropping funnel. Toluene (11 g) and 55 μL (Pt equivalent: 47 ppm) of Pt-CTS-toluene solution, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added and nitrogen substitution was performed. Silicone A-8 was heated, and after the liquid temperature reached 30 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 80 ° C. for 22 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual alphamethylstyrene (AMS) and toluene used as a solvent from the reaction product, and a 2-phenylpropyldimethylsiloki group-blocking dimethylsiloxane-polyether copolymer (silicone) at both ends of the molecule. A-10) 24 g was obtained.
２００ｍＬのセパラブルフラスコに、前記合成例７で得られたシリコーンＡ－８を２５ｇ（９ｍｍｏｌ）とトルエン５３ｇを入れ、滴下ロートに三井化学（株）製のアルファメチルスチレン（ＡＭＳ）５ｇ（４２ｍｍｏｌ）とトルエン１１ｇとエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液５５μＬ（Ｐｔ換算：４７ｐｐｍ）を入れ、窒素置換を行った。シリコーンＡ－８を加熱し、液温が３０℃に到達した後、滴下ロートの混合溶液の滴下を開始した。滴下ロートの混合溶液をすべて滴下した後、８０℃で２２時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存するアルファメチルスチレン（ＡＭＳ）と溶媒として使用したトルエンを除去し、分子両末端２－フェニルプロピルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－１０）２４ｇを得た。 (Synthesis Example 8: Silicone A-10)
25 g (9 mmol) of the silicone A-8 obtained in Synthesis Example 7 and 53 g of toluene were placed in a 200 mL separable flask, and 5 g (42 mmol) of alpha-methylstyrene (AMS) manufactured by Mitsui Kagaku Co., Ltd. was added to the dropping funnel. Toluene (11 g) and 55 μL (Pt equivalent: 47 ppm) of Pt-CTS-toluene solution, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added and nitrogen substitution was performed. Silicone A-8 was heated, and after the liquid temperature reached 30 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 80 ° C. for 22 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual alphamethylstyrene (AMS) and toluene used as a solvent from the reaction product, and a 2-phenylpropyldimethylsiloki group-blocking dimethylsiloxane-polyether copolymer (silicone) at both ends of the molecule. A-10) 24 g was obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－１０を解析した結果、シリコーンＡ－１０は、平均分子量３９３３、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．７個、ジメチルシロキサン・ポリエーテルの繰り返しユニット（上記式（１）におけるｒ）が４．８個、オキシエチレンの繰り返し数（上記式（１）におけるａ）が２．９個であることがわかった。
1 As a result of analyzing the silicone A-10 obtained using 1 H-NMR, the silicone A-10 has an average molecular weight of 3933, an average number of dimethyl units (p in the above formula (1)) of 4.7, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 4.8, and the number of repeating units of oxyethylene (a in the above formula (1)) was 2.9.
図５に、シリコーンＡ－１０のＮＭＲデータを示す。
FIG. 5 shows the NMR data of Silicone A-10.
なお、シリコーンＡ－１０に示す分子両末端２－フェニルプロピルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体の１Ｈ－ＮＭＲ解析方法は以下の通りである。
ａ（ケミカルシフト０．０１～０．１５ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．９９～１．０５ｐｐｍ）はケイ素に結合したポリエーテル部のケイ素の隣のＣＨ２由来の水素のピークを示す。
ｃ（ケミカルシフト２．８５～３．００ｐｐｍ）はケイ素に結合したアラルキル基のＣＨ由来の水素のピークを示す。
ｄ（ケミカルシフト３．３０～３．７５ｐｐｍ）はポリエーテル部のオキシエチレンの繰り返し部分とオキシエチレンの繰り返し部とケイ素を繋ぐ炭化水素部の酸素と結合するＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method of the 2-phenylpropyldimethylsiloki group-blocking dimethylsiloxane / polyether copolymer shown at both ends of the molecule shown in Silicone A-10 is as follows.
a (chemical shift 0.01 to 0.15 ppm) indicates a peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether.
b (chemical shift 0.99 to 1.05 ppm) shows the peak of hydrogen derived from CH 2 next to silicon in the polyether portion bonded to silicon.
c (chemical shift 2.85 to 3.00 ppm) indicates the peak of hydrogen derived from CH of the aralkyl group bonded to silicon.
d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
ａ（ケミカルシフト０．０１～０．１５ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．９９～１．０５ｐｐｍ）はケイ素に結合したポリエーテル部のケイ素の隣のＣＨ２由来の水素のピークを示す。
ｃ（ケミカルシフト２．８５～３．００ｐｐｍ）はケイ素に結合したアラルキル基のＣＨ由来の水素のピークを示す。
ｄ（ケミカルシフト３．３０～３．７５ｐｐｍ）はポリエーテル部のオキシエチレンの繰り返し部分とオキシエチレンの繰り返し部とケイ素を繋ぐ炭化水素部の酸素と結合するＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method of the 2-phenylpropyldimethylsiloki group-blocking dimethylsiloxane / polyether copolymer shown at both ends of the molecule shown in Silicone A-10 is as follows.
a (chemical shift 0.01 to 0.15 ppm) indicates a peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether.
b (chemical shift 0.99 to 1.05 ppm) shows the peak of hydrogen derived from CH 2 next to silicon in the polyether portion bonded to silicon.
c (chemical shift 2.85 to 3.00 ppm) indicates the peak of hydrogen derived from CH of the aralkyl group bonded to silicon.
d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from CH 2 that binds to oxygen in the repeating portion of oxyethylene in the polyether portion, the repeating portion of oxyethylene, and the hydrocarbon portion connecting silicon.
そして、平均分子量、ジメチルユニットの平均個数、ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数、並びに、オキシエチレンの繰り返しの平均個数は上記ａ、ｂ、ｃ、ｄのピークの積分値（比）をもとに、次の計算式よりそれぞれ算出した。
ジメチルユニットの平均個数＝（２ａ－６ｂ）÷３ｂ
ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数
＝ｂ÷２ｃ
オキシエチレンの繰り返し数＝ｄ÷ｂ－１
平均分子量＝（オキシエチレンの繰り返し数×オキシエチレンの分子量＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋ポリエーテル部とケイ素を繋ぐ炭化水素部の分子量＋ポリエーテル部と炭化水素部を介して繋がったケイ素部の分子量）×ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子両末端２－フェニルプロピルジメチルシロキ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are the integrated values (ratio) of the peaks of a, b, c, and d. Based on this, each was calculated from the following formulas.
Average number of dimethyl units = (2a-6b) ÷ 3b
Average number of repeating units of dimethylsiloxane / polyether = b / 2c
Number of repetitions of oxyethylene = d ÷ b-1
Average molecular weight = (repeated number of oxyethylene x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon part connecting polyether part and silicon + connecting via polyether part and hydrocarbon part (Molecular weight of silicon part) x average number of repeating units of dimethylsiloxane / polyether + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of 2-phenylpropyldimethylshiroki groups at both ends
ジメチルユニットの平均個数＝（２ａ－６ｂ）÷３ｂ
ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数
＝ｂ÷２ｃ
オキシエチレンの繰り返し数＝ｄ÷ｂ－１
平均分子量＝（オキシエチレンの繰り返し数×オキシエチレンの分子量＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋ポリエーテル部とケイ素を繋ぐ炭化水素部の分子量＋ポリエーテル部と炭化水素部を介して繋がったケイ素部の分子量）×ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子両末端２－フェニルプロピルジメチルシロキ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are the integrated values (ratio) of the peaks of a, b, c, and d. Based on this, each was calculated from the following formulas.
Average number of dimethyl units = (2a-6b) ÷ 3b
Average number of repeating units of dimethylsiloxane / polyether = b / 2c
Number of repetitions of oxyethylene = d ÷ b-1
Average molecular weight = (repeated number of oxyethylene x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon part connecting polyether part and silicon + connecting via polyether part and hydrocarbon part (Molecular weight of silicon part) x average number of repeating units of dimethylsiloxane / polyether + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of 2-phenylpropyldimethylshiroki groups at both ends
シリコーンＡ－１０のＮＭＲデータは以下の通りであった。
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０１～０．１５ｐｐｍの積分値を１０．０とすると、
δ＝０．９９～１．０５ｐｐｍの積分値は０．１
δ＝２．８５～３．００ｐｐｍの積分値は１．０
δ＝３．３０～３．７５ｐｐｍの積分値は３．８。 The NMR data of Silicone A-10 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.01 to 0.15 ppm is 10.0,
The integral value of δ = 0.99 to 1.05 ppm is 0.1
The integral value of δ = 2.85 to 3.00 ppm is 1.0
The integral value of δ = 3.30 to 3.75 ppm is 3.8.
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０１～０．１５ｐｐｍの積分値を１０．０とすると、
δ＝０．９９～１．０５ｐｐｍの積分値は０．１
δ＝２．８５～３．００ｐｐｍの積分値は１．０
δ＝３．３０～３．７５ｐｐｍの積分値は３．８。 The NMR data of Silicone A-10 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.01 to 0.15 ppm is 10.0,
The integral value of δ = 0.99 to 1.05 ppm is 0.1
The integral value of δ = 2.85 to 3.00 ppm is 1.0
The integral value of δ = 3.30 to 3.75 ppm is 3.8.
（合成例９：シリコーンＡ－１１）
２００ｍＬのセパラブルフラスコに、前記合成例７で得られたシリコーンＡ－８を２５ｇ（９ｍｍｏｌ）とトルエン５０ｇを入れ、滴下ロートに出光興産（株）製の１－ドデセン（商品名：リニアレン１２）６ｇ（３６ｍｍｏｌ）とトルエン１０ｇ、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液５９μＬ（Ｐｔ換算：４９ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、液温が３０℃に到達した後、滴下ロートの混合溶液の滴下を開始した。滴下ロートの混合溶液をすべて滴下した後、８５℃で１６時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存する１－ドデセンと溶媒として使用したトルエンを除去し、分子両末端ドデシルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－１１）２７ｇを得た。 (Synthetic Example 9: Silicone A-11)
25 g (9 mmol) of the silicone A-8 obtained in Synthesis Example 7 and 50 g of toluene were placed in a 200 mL separable flask, and 1-Dodecene manufactured by Idemitsu Kosan Co., Ltd. (trade name: Linearene 12) was placed in a dropping funnel. 6 g (36 mmol), 10 g of toluene, and 59 μL of a Pt-CTS-toluene solution (Pt equivalent: 49 ppm), which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added to carry out nitrogen substitution. The mixed solution was heated, and after the liquid temperature reached 30 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 85 ° C. for 16 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual 1-dodecene and toluene used as a solvent from the reaction product, and 27 g of a dimethylsiloxane-polyether copolymer (silicone A-11) with both ends of the molecule dodecene dimethylshiroki group-blocked Obtained.
２００ｍＬのセパラブルフラスコに、前記合成例７で得られたシリコーンＡ－８を２５ｇ（９ｍｍｏｌ）とトルエン５０ｇを入れ、滴下ロートに出光興産（株）製の１－ドデセン（商品名：リニアレン１２）６ｇ（３６ｍｍｏｌ）とトルエン１０ｇ、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液５９μＬ（Ｐｔ換算：４９ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、液温が３０℃に到達した後、滴下ロートの混合溶液の滴下を開始した。滴下ロートの混合溶液をすべて滴下した後、８５℃で１６時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、加熱・減圧し、反応物から残存する１－ドデセンと溶媒として使用したトルエンを除去し、分子両末端ドデシルジメチルシロキ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－１１）２７ｇを得た。 (Synthetic Example 9: Silicone A-11)
25 g (9 mmol) of the silicone A-8 obtained in Synthesis Example 7 and 50 g of toluene were placed in a 200 mL separable flask, and 1-Dodecene manufactured by Idemitsu Kosan Co., Ltd. (trade name: Linearene 12) was placed in a dropping funnel. 6 g (36 mmol), 10 g of toluene, and 59 μL of a Pt-CTS-toluene solution (Pt equivalent: 49 ppm), which is a platinum catalyst manufactured by NE Chemcat Co., Ltd., were added to carry out nitrogen substitution. The mixed solution was heated, and after the liquid temperature reached 30 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 85 ° C. for 16 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, the mixture was heated and depressurized to remove residual 1-dodecene and toluene used as a solvent from the reaction product, and 27 g of a dimethylsiloxane-polyether copolymer (silicone A-11) with both ends of the molecule dodecene dimethylshiroki group-blocked Obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－１１を解析した結果、シリコーンＡ－１１は、平均分子量２８６５、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．４個、ジメチルシロキサン・ポリエーテルの繰り返しユニット（上記式（１）におけるｒ）が３．２個、オキシエチレンの繰り返し数（上記式（１）におけるａ）が３．０個であることがわかった。
1 As a result of analyzing the silicone A-11 obtained using H-NMR, the silicone A-11 has an average molecular weight of 2865, an average number of dimethyl units (p in the above formula (1)) of 4.4, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 3.2, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.0.
（合成例１０：シリコーンＡ－１２）
２００ｍＬのセパラブルフラスコに、前記合成例１で得られたシリコーンＡ－２を３５ｇ（６６ｍｍｏｌ）と東京化成工業（株）製のトリエチレングリコールジビニルエーテル１３ｇ（６４ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末２２ｍｇ（Ｐｔ換算：２３ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、７５℃で３時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 10: Silicone A-12)
In a 200 mL separable flask, 35 g (66 mmol) of the silicone A-2 obtained in Synthesis Example 1 and 13 g (64 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., NE Chemcat Co., Ltd. ), Which is a platinum catalyst, was added with 22 mg of Pt alumina powder (Pt equivalent: 23 ppm), and nitrogen substitution was performed. The mixed solution was heated and aged at 75 ° C. for 3 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
２００ｍＬのセパラブルフラスコに、前記合成例１で得られたシリコーンＡ－２を３５ｇ（６６ｍｍｏｌ）と東京化成工業（株）製のトリエチレングリコールジビニルエーテル１３ｇ（６４ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末２２ｍｇ（Ｐｔ換算：２３ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、７５℃で３時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合のピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 10: Silicone A-12)
In a 200 mL separable flask, 35 g (66 mmol) of the silicone A-2 obtained in Synthesis Example 1 and 13 g (64 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., NE Chemcat Co., Ltd. ), Which is a platinum catalyst, was added with 22 mg of Pt alumina powder (Pt equivalent: 23 ppm), and nitrogen substitution was performed. The mixed solution was heated and aged at 75 ° C. for 3 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
続いて、ろ液を１００ｍＬのナスフラスコに入れ、加熱・減圧し、反応物から残存するシリコーンＡ－２を除去し、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・ポリエーテル共重合体（シリコーンＡ－１２）３２ｇを得た。
Subsequently, the filtrate was placed in a 100 mL eggplant flask, heated and depressurized to remove residual silicone A-2 from the reaction product, and a hydrodimethylsiloxy group-blocked dimethylsiloxane-polyether copolymer (silicone A) at both ends of the molecule was removed. -12) 32 g was obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－１２を解析した結果、シリコーンＡ－１２は、平均分子量１０５７２、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．１個、ジメチルシロキサン・ポリエーテルの繰り返しユニット（上記式（１）におけるｒ）が１６．２個、オキシエチレンの繰り返し数（上記式（１）におけるａ）が３．０個であることがわかった。
1 As a result of analyzing the silicone A-12 obtained using H-NMR, the silicone A-12 has an average molecular weight of 10572, an average number of dimethyl units (p in the above formula (1)) of 4.1, and dimethyl. It was found that the number of repeating units of siloxane / polyether (r in the above formula (1)) was 16.2, and the number of repeating units of oxyethylene (a in the above formula (1)) was 3.0.
（合成例１１：シリコーンＡ－１３）
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５２２、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．２個）２５ｇ（４８ｍｍｏｌ）とトルエン５８ｇ、東京化成工業（株）製の１，５－ヘキサジエン２ｇ（２４ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末１０ｍｇ（Ｐｔ換算：１９ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、８０℃で５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合ピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 11: Silicone A-13)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 522, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .2) 25 g (48 mmol) and 58 g of toluene, 2 g (24 mmol) of 1,5-hexadien manufactured by Tokyo Chemical Industry Co., Ltd., and 10 mg (Pt) of Pt alumina powder, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd. Conversion: 19 ppm) was added, and nitrogen substitution was performed. The mixed solution was heated and aged at 80 ° C. for 5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
２００ｍＬのセパラブルフラスコに、前記合成例１と同様の方法で得られた分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン（平均分子量５２２、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．２個）２５ｇ（４８ｍｍｏｌ）とトルエン５８ｇ、東京化成工業（株）製の１，５－ヘキサジエン２ｇ（２４ｍｍｏｌ）、エヌ・イー・ケムキャット（株）製の白金触媒であるＰｔアルミナ粉末１０ｍｇ（Ｐｔ換算：１９ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、８０℃で５時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用して不飽和二重結合ピークの消失を確認した。続いて、室温に冷却した後、ろ過によって白金触媒を取り除いた。 (Synthesis Example 11: Silicone A-13)
In a 200 mL separable flask, the average number of hydrodimethylsiloxy group-sealed dimethylsiloxanes (average molecular weight 522, dimethyl units (p in the above formula (1)) obtained by the same method as in Synthesis Example 1 is 5 .2) 25 g (48 mmol) and 58 g of toluene, 2 g (24 mmol) of 1,5-hexadien manufactured by Tokyo Chemical Industry Co., Ltd., and 10 mg (Pt) of Pt alumina powder, which is a platinum catalyst manufactured by NE Chemcat Co., Ltd. Conversion: 19 ppm) was added, and nitrogen substitution was performed. The mixed solution was heated and aged at 80 ° C. for 5 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the unsaturated double bond peak. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.
続いて、ろ液を１００ｍＬのナスフラスコに入れ、加熱・減圧し、反応物から残存する分子鎖両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサンと溶剤として使用したトルエンを除去し、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・へキシレン共重合体１４ｇを得た。１Ｈ－ＮＭＲを使用して得られた共重合体を解析した結果、共重合体は、平均分子量１２０１、ジメチルユニット（上記式（１）におけるｐ）の平均個数５．３個、ジメチルシロキサン・へキシレンの繰り返しユニット（上記式（１）におけるｑ）が１．１個であることがわかった。
Subsequently, the filtrate was placed in a 100 mL eggplant flask, heated and depressurized to remove the residual hydrodimethylsiloxy group-blocking dimethylsiloxane at both ends of the molecular chain and toluene used as a solvent, and the hydrodimethylsiloxy at both ends of the molecule. 14 g of a base-sealed dimethylsiloxane / hexylene copolymer was obtained. 1 As a result of analyzing the copolymer obtained by using H-NMR, the copolymer had an average molecular weight of 1201, an average number of dimethyl units (p in the above formula (1)) of 5.3, and dimethylsiloxane. It was found that the number of repeating units of hexylene (q in the above formula (1)) was 1.1.
図６に、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・へキシレン共重合体のＮＭＲデータを示す。
FIG. 6 shows NMR data of the hydrodimethylsiloxy group-blocking dimethylsiloxane / hexylene copolymer at both ends of the molecule.
なお、分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・へキシレン共重合体の１Ｈ－ＮＭＲ解析方法は以下の通りである。
ａ（ケミカルシフト０．０１～０．１１ｐｐｍ）はヘキシレン基と結合したジメチルシロキサンユニットのメチル基とジメチルシロキサンの繰り返しユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．１７～０．２１ｐｐｍ）は分子鎖両末端のハイドロジメチルシロキシ基のメチル基由来の水素のピークを示す。
ｃ（ケミカルシフト０．４５～０．６０ｐｐｍ）はケイ素に結合したヘキシレン基のケイ素の隣のＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method of the hydrodimethylsiloxy group-blocked dimethylsiloxane / hexylene copolymer at both ends of the molecule is as follows.
a (chemical shift 0.01 to 0.11 ppm) indicates the peak of hydrogen derived from the methyl group of the dimethylsiloxane unit bonded to the hexylene group and the methyl group of the repeating unit of dimethylsiloxane.
b (chemical shift 0.17 to 0.21 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
c (chemical shift 0.45 to 0.60 ppm) indicates the peak of hydrogen derived from CH 2 next to the silicon of the hexylene group bonded to silicon.
ａ（ケミカルシフト０．０１～０．１１ｐｐｍ）はヘキシレン基と結合したジメチルシロキサンユニットのメチル基とジメチルシロキサンの繰り返しユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト０．１７～０．２１ｐｐｍ）は分子鎖両末端のハイドロジメチルシロキシ基のメチル基由来の水素のピークを示す。
ｃ（ケミカルシフト０．４５～０．６０ｐｐｍ）はケイ素に結合したヘキシレン基のケイ素の隣のＣＨ２由来の水素のピークを示す。 The 1 H-NMR analysis method of the hydrodimethylsiloxy group-blocked dimethylsiloxane / hexylene copolymer at both ends of the molecule is as follows.
a (chemical shift 0.01 to 0.11 ppm) indicates the peak of hydrogen derived from the methyl group of the dimethylsiloxane unit bonded to the hexylene group and the methyl group of the repeating unit of dimethylsiloxane.
b (chemical shift 0.17 to 0.21 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrodimethylsiloxy group at both ends of the molecular chain.
c (chemical shift 0.45 to 0.60 ppm) indicates the peak of hydrogen derived from CH 2 next to the silicon of the hexylene group bonded to silicon.
そして、平均分子量、ジメチルユニットの平均個数、並びにジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数は上記ａ、ｂ、ｃのピークの積分値（比）をもとに、次の計算式によりそれぞれ算出した。
ジメチルユニットの平均個数＝（２ａ－ｂ－６ｃ）÷３ｃ
ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＝３ｃ÷ｂ
平均分子量＝（ジメチルユニットの平均個数×ジメチルユニットの分子量＋ヘキシレンの分子量＋ヘキシレン部と繋がったケイ素部の分子量）×ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のハイドロジメチルシロキシ基の分子量 Then, the average molecular weight, the average number of dimethyl units, and the average number of repeating units of dimethylsiloxane / hexylene were calculated by the following formulas based on the integrated values (ratio) of the peaks a, b, and c above. ..
Average number of dimethyl units = (2ab-6c) ÷ 3c
Average number of repeating units of dimethylsiloxane / hexylene = 3c ÷ b
Average molecular weight = (average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hexylene + molecular weight of silicon part connected to hexylene part) x average number of repeating units of dimethylsiloxane / hexylene + average number of dimethyl units x dimethyl units Molecular weight + molecular weight of hydrodimethylsiloxy groups at both ends of the molecular chain
ジメチルユニットの平均個数＝（２ａ－ｂ－６ｃ）÷３ｃ
ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＝３ｃ÷ｂ
平均分子量＝（ジメチルユニットの平均個数×ジメチルユニットの分子量＋ヘキシレンの分子量＋ヘキシレン部と繋がったケイ素部の分子量）×ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のハイドロジメチルシロキシ基の分子量 Then, the average molecular weight, the average number of dimethyl units, and the average number of repeating units of dimethylsiloxane / hexylene were calculated by the following formulas based on the integrated values (ratio) of the peaks a, b, and c above. ..
Average number of dimethyl units = (2ab-6c) ÷ 3c
Average number of repeating units of dimethylsiloxane / hexylene = 3c ÷ b
Average molecular weight = (average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hexylene + molecular weight of silicon part connected to hexylene part) x average number of repeating units of dimethylsiloxane / hexylene + average number of dimethyl units x dimethyl units Molecular weight + molecular weight of hydrodimethylsiloxy groups at both ends of the molecular chain
分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・へキシレン共重合体のＮＭＲデータは以下の通りであった。
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０１～０．１１ｐｐｍの積分値を１０．０とすると、
δ＝０．１７～０．２１ｐｐｍの積分値は２．２
δ＝０．４５～０．６０ｐｐｍの積分値は０．８。 The NMR data of the hydrodimethylsiloxy group-blocking dimethylsiloxane / hexylene copolymer at both ends of the molecule was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.01 to 0.11 ppm is 10.0,
The integral value of δ = 0.17 to 0.21 ppm is 2.2
The integral value of δ = 0.45 to 0.60 ppm is 0.8.
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０１～０．１１ｐｐｍの積分値を１０．０とすると、
δ＝０．１７～０．２１ｐｐｍの積分値は２．２
δ＝０．４５～０．６０ｐｐｍの積分値は０．８。 The NMR data of the hydrodimethylsiloxy group-blocking dimethylsiloxane / hexylene copolymer at both ends of the molecule was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.01 to 0.11 ppm is 10.0,
The integral value of δ = 0.17 to 0.21 ppm is 2.2
The integral value of δ = 0.45 to 0.60 ppm is 0.8.
次に、２００ｍＬのセパラブルフラスコに、上記で得られた分子両末端ハイドロジメチルシロキシ基封鎖ジメチルシロキサン・へキシレン共重合体を９ｇ（７ｍｍｏｌ）とトルエン７２ｇを入れ、滴下ロートに日油（株）製のメトキシポリエチレングリコールアリルエーテル（商品名：ユニオックス ＰＫＡ－５００７）２４ｇ（６０ｍｍｏｌ）とエヌ・イー・ケムキャット（株）製の白金触媒であるＰｔ－ＣＴＳ－トルエン溶液６３μＬ（Ｐｔ換算：４９ｐｐｍ）を入れ、窒素置換を行った。混合溶液を加熱し、液温が３５℃に到達した後、滴下ロートの混合溶液の滴下を開始した。滴下ロートの混合溶液をすべて滴下した後、７５℃で２３時間熟成した。熟成終了後、１Ｈ－ＮＭＲを使用してＳｉＨ基のピークの消失を確認した。続いて、得られた反応液に蒸留水とヘキサンを加え、ヘキサン層を回収し、溶媒として使用したヘキサンとトルエンを除去し、分子両末端ポリオキシアルキルジメチルシロキ基封鎖ジメチルシロキサン・へキシレン共重合体（シリコーンＡ－１３）４ｇを得た。
Next, 9 g (7 mmol) of the hydrodimethylsiloxy group-sealed dimethylsiloxane / hexylene copolymer obtained above at both ends of the molecule and 72 g of toluene were placed in a 200 mL separable flask, and Nichiyu Co., Ltd. was added to the dropping funnel. 24 g (60 mmol) of methoxypolyethylene glycol allyl ether (trade name: Uniox PKA-5007) and 63 μL of Pt-CTS-toluene solution (Pt conversion: 49 ppm), which is a platinum catalyst manufactured by NE Chemcat Co., Ltd. And nitrogen substitution was performed. The mixed solution was heated, and after the liquid temperature reached 35 ° C., dropping of the mixed solution of the dropping funnel was started. After dropping all the mixed solution of the dropping funnel, it was aged at 75 ° C. for 23 hours. After completion of aging, 1 H-NMR was used to confirm the disappearance of the SiH group peak. Subsequently, distilled water and hexane were added to the obtained reaction solution, the hexane layer was recovered, hexane and toluene used as solvents were removed, and both ends of the molecule were polyoxyalkyldimethylsiloki group-blocked dimethylsiloxane / hexylene co-weight. 4 g of coalesced (silicone A-13) was obtained.
１Ｈ－ＮＭＲを使用して得られたシリコーンＡ－１３を解析した結果、シリコーンＡ－１３は、平均分子量１８９７、ジメチルユニット（上記式（１）におけるｐ）の平均個数４．６個、ジメチルシロキサン・へキシレンの繰り返しユニット（上記式（１）におけるｑ）が１．４個、分子末端のオキシエチレンの繰り返し数（上記式（２）におけるｂ）が６．０個であることがわかった。
1 As a result of analyzing the silicone A-13 obtained by using 1 H-NMR, the silicone A-13 has an average molecular weight of 1897, an average number of dimethyl units (p in the above formula (1)) of 4.6, and dimethyl. It was found that the number of repeating units of siloxane / hexylene (q in the above formula (1)) was 1.4, and the number of repeating units of oxyethylene at the molecular terminal (b in the above formula (2)) was 6.0. ..
図７に、シリコーンＡ－１３のＮＭＲデータを示す。
FIG. 7 shows the NMR data of Silicone A-13.
なお、シリコーンＡ－１３に示す分子両末端ポリオキシアルキルジメチルシロキシ基封鎖ジメチルシロキサン・アルキレン共重合体の１Ｈ－ＮＭＲ解析方法は以下の通りである。
ａ（ケミカルシフト０．０１～０．１５ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基とヘキシレン基と結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト１．２０～１．４０ｐｐｍ）はケイ素に結合していないヘキシレン基のＣＨ２由来の水素のピークを示す。
ｃ（ケミカルシフト１．５０～１．７０ｐｐｍ）はケイ素に結合したポリオキシアルキル基のケイ素の隣のＣＨ２の隣のＣＨ２由来の水素のピークを示す。
ｄ（ケミカルシフト３．５０～３．７０ｐｐｍ）はポリオキシアルキル部のエチレンの繰り返し部分由来の水素のピークを示す。 The 1 H-NMR analysis method of the molecular double-ended polyoxyalkyldimethylsiloxy group-blocking dimethylsiloxane / alkylene copolymer shown in Silicone A-13 is as follows.
a (chemical shift 0.01 to 0.15 ppm) is the peak of hydrogen derived from the methyl group of the dimethylsiloxane unit bonded to the methyl group of the dimethylsiloxane repeating unit and the methyl group of the dimethylsiloxane unit bonded to the polyether group. Is shown.
b (chemical shift 1.20 to 1.40 ppm) shows the peak of hydrogen derived from CH 2 of the hexylene group not bonded to silicon.
c (chemical shift 1.50 ~ 1.70ppm) shows a peak of hydrogen from CH 2 next to the CH 2 next to the silicon polyoxyethylene alkyl group attached to silicon.
d (chemical shift 3.50 to 3.70 ppm) indicates the peak of hydrogen derived from the repeating portion of ethylene in the polyoxyalkyl moiety.
ａ（ケミカルシフト０．０１～０．１５ｐｐｍ）はジメチルシロキサンの繰り返しユニットのメチル基とポリエーテルと結合したジメチルシロキサンユニットのメチル基とヘキシレン基と結合したジメチルシロキサンユニットのメチル基由来の水素のピークを示す。
ｂ（ケミカルシフト１．２０～１．４０ｐｐｍ）はケイ素に結合していないヘキシレン基のＣＨ２由来の水素のピークを示す。
ｃ（ケミカルシフト１．５０～１．７０ｐｐｍ）はケイ素に結合したポリオキシアルキル基のケイ素の隣のＣＨ２の隣のＣＨ２由来の水素のピークを示す。
ｄ（ケミカルシフト３．５０～３．７０ｐｐｍ）はポリオキシアルキル部のエチレンの繰り返し部分由来の水素のピークを示す。 The 1 H-NMR analysis method of the molecular double-ended polyoxyalkyldimethylsiloxy group-blocking dimethylsiloxane / alkylene copolymer shown in Silicone A-13 is as follows.
a (chemical shift 0.01 to 0.15 ppm) is the peak of hydrogen derived from the methyl group of the dimethylsiloxane unit bonded to the methyl group of the dimethylsiloxane repeating unit and the methyl group of the dimethylsiloxane unit bonded to the polyether group. Is shown.
b (chemical shift 1.20 to 1.40 ppm) shows the peak of hydrogen derived from CH 2 of the hexylene group not bonded to silicon.
c (chemical shift 1.50 ~ 1.70ppm) shows a peak of hydrogen from CH 2 next to the CH 2 next to the silicon polyoxyethylene alkyl group attached to silicon.
d (chemical shift 3.50 to 3.70 ppm) indicates the peak of hydrogen derived from the repeating portion of ethylene in the polyoxyalkyl moiety.
そして、平均分子量、ジメチルユニットの平均個数、ジメチルシロキサン・ポリエーテルの繰り返しユニットの平均個数、並びに、オキシエチレンの繰り返しの平均個数は上記ａ、ｂ、ｃ、ｄのピークの積分値（比）をもとに、次の計算式よりそれぞれ算出した。
ジメチルユニットの平均個数＝（４ａ－６ｂ－１８ｃ）÷３ｂ
ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＝ｂ÷２ｃ
オキシエチレンの繰り返し数＝ｄ÷２ｃ
平均分子量＝（ジメチルユニットの平均個数×ジメチルユニットの分子量＋ヘキシレンの分子量＋ヘキシレン部と繋がったケイ素部の分子量）×ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のポリオキシアルキルジメチルシロキシ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are the integrated values (ratio) of the peaks of a, b, c, and d. Based on this, each was calculated from the following formulas.
Average number of dimethyl units = (4a-6b-18c) ÷ 3b
Average number of repeating units of dimethylsiloxane / hexylene = b / 2c
Number of repetitions of oxyethylene = d ÷ 2c
Average molecular weight = (average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hexylene + molecular weight of silicon part connected to hexylene part) x average number of repeating units of dimethylsiloxane / hexylene + average number of dimethyl units x dimethyl units Molecular weight + molecular weight of polyoxyalkyldimethylsiloxy groups at both ends of the molecular chain
ジメチルユニットの平均個数＝（４ａ－６ｂ－１８ｃ）÷３ｂ
ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＝ｂ÷２ｃ
オキシエチレンの繰り返し数＝ｄ÷２ｃ
平均分子量＝（ジメチルユニットの平均個数×ジメチルユニットの分子量＋ヘキシレンの分子量＋ヘキシレン部と繋がったケイ素部の分子量）×ジメチルシロキサン・ヘキシレンの繰り返しユニットの平均個数＋ジメチルユニットの平均個数×ジメチルユニットの分子量＋分子鎖両末端のポリオキシアルキルジメチルシロキシ基の分子量 The average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane / polyether, and the average number of repeating units of oxyethylene are the integrated values (ratio) of the peaks of a, b, c, and d. Based on this, each was calculated from the following formulas.
Average number of dimethyl units = (4a-6b-18c) ÷ 3b
Average number of repeating units of dimethylsiloxane / hexylene = b / 2c
Number of repetitions of oxyethylene = d ÷ 2c
Average molecular weight = (average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hexylene + molecular weight of silicon part connected to hexylene part) x average number of repeating units of dimethylsiloxane / hexylene + average number of dimethyl units x dimethyl units Molecular weight + molecular weight of polyoxyalkyldimethylsiloxy groups at both ends of the molecular chain
シリコーンＡ－１３のＮＭＲデータは以下の通りであった。
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０５～０．１５ｐｐｍの積分値を１０．０とすると、
δ＝１．２０～１．４０ｐｐｍの積分値は１．５
δ＝１．５０～１．７０ｐｐｍの積分値は０．６
δ＝３．５０～３．７０ｐｐｍの積分値は６．７。 The NMR data of Silicone A-13 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.05 to 0.15 ppm is 10.0,
The integral value of δ = 1.20 to 1.40 ppm is 1.5
The integral value of δ = 1.50 to 1.70 ppm is 0.6
The integral value of δ = 3.50 to 3.70 ppm is 6.7.
１Ｈ－ＮＭＲ（溶媒：重クロロホルム、基準物質：ＴＭＳ）
δ＝０．０５～０．１５ｐｐｍの積分値を１０．０とすると、
δ＝１．２０～１．４０ｐｐｍの積分値は１．５
δ＝１．５０～１．７０ｐｐｍの積分値は０．６
δ＝３．５０～３．７０ｐｐｍの積分値は６．７。 The NMR data of Silicone A-13 was as follows.
1 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS)
Assuming that the integral value of δ = 0.05 to 0.15 ppm is 10.0,
The integral value of δ = 1.20 to 1.40 ppm is 1.5
The integral value of δ = 1.50 to 1.70 ppm is 0.6
The integral value of δ = 3.50 to 3.70 ppm is 6.7.
以上の（Ａ）シロキサン化合物（シリコーン油）のデータを表１にまとめる。表１における、Ｘは上述の式（１）および式（２）におけるＸ１およびＸ２を示し、並びに、Ｙ、Ｚ１、ｐ、ｑ、ｒ、ａ、ｎ、Ｚ２、ｂおよびｍは、それぞれ、上述の式（１）および式（２）におけるものと同じ意味である。
The data of the above (A) siloxane compound (silicone oil) are summarized in Table 1. In Table 1, X represents X 1 and X 2 in the above equations (1) and (2), and Y, Z 1 , p, q, r, a, n, Z 2 , b and m , They have the same meanings as those in the above equations (1) and (2), respectively.
また、表中の残渣量（重量％）は、後述する方法によって測定した。なお、表１に示すシリコーン油のうち、シリコーンＡ－３については、式（１）におけるｐの値が１３を超えているため、残渣量が増えてしまったと考えられる。
The amount of residue (% by weight) in the table was measured by the method described later. Of the silicone oils shown in Table 1, for silicone A-3, the value of p in the formula (1) exceeds 13, so it is considered that the amount of residue has increased.
（（Ｂ）炭化水素系潤滑油）
・エステル油：日油（株）製のペンタエリスリトール脂肪酸エステル、製品名：ユニスター ＨＲ－３２（４０℃動粘度：３３．５：ｍｍ２／ｓ、１００℃動粘度：５．８ｍｍ２／ｓ、ＶＩ：１１５、引火点：２７４℃、流動点：－５０℃）
・エステル油：日油（株）製のトリメチロールプロパン脂肪酸エステル（Ｃ６－Ｃ１２）、製品名：ユニスター Ｈ－３３４Ｒ（４０℃動粘度：１９．６ｍｍ２／ｓ、１００℃動粘度：４．４ｍｍ２／ｓ、ＶＩ：１３８、流動点－４０℃）
・ＰＡＧ（ポリブチレングリコール）：ＤＯＷ株式会社製「ＵＣＯＮ ＯＳＰ－３２」（４０℃動粘度：３２．０ｍｍ２／ｓ、１００℃動粘度：６．５ｍｍ２／ｓ、ＶＩ：１４６）
・ＰＡＯ油：Ｃｈｅｖｒｏｎ Ｐｈｉｌｌｉｐｓ製のポリαオレフィン、製品名：Ｓｙｎｆｌｕｉｄ ＰＡＯ ６ ｃＳｔ（４０℃動粘度：３０．５ｍｍ２／ｓ、１００℃動粘度：５．９ｍｍ２／ｓ、ＶＩ：１３７）
・エーテル油：（株）ＭＯＲＥＳＣＯ製のアルキルジフェニルエーテル「モレスコハイルーブ ＬＢ－１００」（４０℃動粘度：１０２．６ｍｍ２／ｓ、１００℃動粘度：１２．６ｍｍ２／ｓ、ＶＩ：１１７）
・鉱油：コスモ石油ルブリカンツ（株）製の鉱油、製品名：コスモピュアスピンＴＫ（４０℃動粘度：９．３ｍｍ２／ｓ、１００℃動粘度：２．５ｍｍ２／ｓ、ＶＩ：９４）
・流動パラフィン：（株）ＭＯＲＥＳＣＯ製の「モレスコホワイト Ｐ－７０」（４０℃動粘度：１２．６ｍｍ２／ｓ、１００℃動粘度：２．９ｍｍ２／ｓ、ＶＩ：５６）
・ＰＡＧ（ポリアルキレングリコール）：三洋化成株式会社製「ニューポール ＨＢ５０－６６０」（４０℃動粘度：１３０．１ｍｍ２／ｓ、１００℃動粘度：２０．１ｍｍ２／ｓ、ＶＩ：１７８） ((B) Hydrocarbon-based lubricating oil)
-Ester oil: Pentaerythritol fatty acid ester manufactured by Nichiyu Co., Ltd., Product name: Unistar HR-32 (40 ° C kinematic viscosity: 33.5: mm 2 / s, 100 ° C kinematic viscosity: 5.8 mm 2 / s, VI: 115, flash point: 274 ° C, pour point: -50 ° C)
-Ester oil: Trimethylolpropane fatty acid ester (C6-C12) manufactured by Nichiyu Co., Ltd., Product name: Unistar H-334R (40 ° C kinematic viscosity: 19.6 mm 2 / s, 100 ° C kinematic viscosity: 4.4 mm 2 / s, VI: 138, pour point -40 ° C)
-PAG (polybutylene glycol): "UCON OSP-32" manufactured by DOWN Co., Ltd. (40 ° C. kinematic viscosity: 32.0 mm 2 / s, 100 ° C. kinematic viscosity: 6.5 mm 2 / s, VI: 146)
-PAO oil: poly-α-olefin manufactured by Chevron Phillips, product name:Synfluid PAO 6 cSt (40 ° C. kinematic viscosity: 30.5 mm 2 / s, 100 ° C. kinematic viscosity: 5.9 mm 2 / s, VI: 137)
-Ether oil: Alkyl diphenyl ether "Moresco High Lube LB-100" manufactured by MORESCO Co., Ltd. (40 ° C kinematic viscosity: 102.6 mm 2 / s, 100 ° C kinematic viscosity: 12.6 mm 2 / s, VI: 117)
-Mineral oil: Mineral oil manufactured by Cosmo Oil Lubricants Co., Ltd., Product name: Cosmo Pure Spin TK (40 ° C kinematic viscosity: 9.3 mm 2 / s, 100 ° C kinematic viscosity: 2.5 mm 2 / s, VI: 94)
- Liquid paraffin: manufactured) MORESCO manufactured "Moresco White P-70" (40 ° C. kinematic viscosity: 12.6mm 2 / s, 100 ℃ kinematic viscosity: 2.9mm 2 / s, VI: 56)
-PAG (Polyalkylene Glycol): "New Pole HB50-660" manufactured by Sanyo Chemical Industries, Ltd. (40 ° C. kinematic viscosity: 130.1 mm 2 / s, 100 ° C. kinematic viscosity: 20.1 mm 2 / s, VI: 178)
・エステル油：日油（株）製のペンタエリスリトール脂肪酸エステル、製品名：ユニスター ＨＲ－３２（４０℃動粘度：３３．５：ｍｍ２／ｓ、１００℃動粘度：５．８ｍｍ２／ｓ、ＶＩ：１１５、引火点：２７４℃、流動点：－５０℃）
・エステル油：日油（株）製のトリメチロールプロパン脂肪酸エステル（Ｃ６－Ｃ１２）、製品名：ユニスター Ｈ－３３４Ｒ（４０℃動粘度：１９．６ｍｍ２／ｓ、１００℃動粘度：４．４ｍｍ２／ｓ、ＶＩ：１３８、流動点－４０℃）
・ＰＡＧ（ポリブチレングリコール）：ＤＯＷ株式会社製「ＵＣＯＮ ＯＳＰ－３２」（４０℃動粘度：３２．０ｍｍ２／ｓ、１００℃動粘度：６．５ｍｍ２／ｓ、ＶＩ：１４６）
・ＰＡＯ油：Ｃｈｅｖｒｏｎ Ｐｈｉｌｌｉｐｓ製のポリαオレフィン、製品名：Ｓｙｎｆｌｕｉｄ ＰＡＯ ６ ｃＳｔ（４０℃動粘度：３０．５ｍｍ２／ｓ、１００℃動粘度：５．９ｍｍ２／ｓ、ＶＩ：１３７）
・エーテル油：（株）ＭＯＲＥＳＣＯ製のアルキルジフェニルエーテル「モレスコハイルーブ ＬＢ－１００」（４０℃動粘度：１０２．６ｍｍ２／ｓ、１００℃動粘度：１２．６ｍｍ２／ｓ、ＶＩ：１１７）
・鉱油：コスモ石油ルブリカンツ（株）製の鉱油、製品名：コスモピュアスピンＴＫ（４０℃動粘度：９．３ｍｍ２／ｓ、１００℃動粘度：２．５ｍｍ２／ｓ、ＶＩ：９４）
・流動パラフィン：（株）ＭＯＲＥＳＣＯ製の「モレスコホワイト Ｐ－７０」（４０℃動粘度：１２．６ｍｍ２／ｓ、１００℃動粘度：２．９ｍｍ２／ｓ、ＶＩ：５６）
・ＰＡＧ（ポリアルキレングリコール）：三洋化成株式会社製「ニューポール ＨＢ５０－６６０」（４０℃動粘度：１３０．１ｍｍ２／ｓ、１００℃動粘度：２０．１ｍｍ２／ｓ、ＶＩ：１７８） ((B) Hydrocarbon-based lubricating oil)
-Ester oil: Pentaerythritol fatty acid ester manufactured by Nichiyu Co., Ltd., Product name: Unistar HR-32 (40 ° C kinematic viscosity: 33.5: mm 2 / s, 100 ° C kinematic viscosity: 5.8 mm 2 / s, VI: 115, flash point: 274 ° C, pour point: -50 ° C)
-Ester oil: Trimethylolpropane fatty acid ester (C6-C12) manufactured by Nichiyu Co., Ltd., Product name: Unistar H-334R (40 ° C kinematic viscosity: 19.6 mm 2 / s, 100 ° C kinematic viscosity: 4.4 mm 2 / s, VI: 138, pour point -40 ° C)
-PAG (polybutylene glycol): "UCON OSP-32" manufactured by DOWN Co., Ltd. (40 ° C. kinematic viscosity: 32.0 mm 2 / s, 100 ° C. kinematic viscosity: 6.5 mm 2 / s, VI: 146)
-PAO oil: poly-α-olefin manufactured by Chevron Phillips, product name:
-Ether oil: Alkyl diphenyl ether "Moresco High Lube LB-100" manufactured by MORESCO Co., Ltd. (40 ° C kinematic viscosity: 102.6 mm 2 / s, 100 ° C kinematic viscosity: 12.6 mm 2 / s, VI: 117)
-Mineral oil: Mineral oil manufactured by Cosmo Oil Lubricants Co., Ltd., Product name: Cosmo Pure Spin TK (40 ° C kinematic viscosity: 9.3 mm 2 / s, 100 ° C kinematic viscosity: 2.5 mm 2 / s, VI: 94)
- Liquid paraffin: manufactured) MORESCO manufactured "Moresco White P-70" (40 ° C. kinematic viscosity: 12.6mm 2 / s, 100 ℃ kinematic viscosity: 2.9mm 2 / s, VI: 56)
-PAG (Polyalkylene Glycol): "New Pole HB50-660" manufactured by Sanyo Chemical Industries, Ltd. (40 ° C. kinematic viscosity: 130.1 mm 2 / s, 100 ° C. kinematic viscosity: 20.1 mm 2 / s, VI: 178)
（（Ｃ）極圧剤）
・硫黄系極圧剤：イソブテン硫化物、ＲｈｅｉｎＣｈｅｍｉｅ製、「ＲＣ ２５４５」
・硫黄－リン系極圧剤：チオリン酸エステル、ＬＵＢＲＩＺＯＬ製「ＬＵＢＲＩＺＯＬ ＩＣ９ＡＷ３１」
・リン系極圧剤：脂肪酸リン酸エステルのアミン塩、Ｋｉｎｇｉｎｄｕｓｔｒｉｅｓ製「ＮＡ－ＬＵＢＥ ＡＷ－６４００ＦＧ」 ((C) Extreme pressure agent)
-Sulfur-based extreme pressure agent: isobutylene sulfide, manufactured by Rhein Chemie, "RC 2545"
-Sulfur-phosphorus extreme pressure agent: Thiophosphate ester, made by LUBRIZOL "LUBRIZOL IC9AW31"
-Phosphorus-based extreme pressure agent: Amin salt of fatty acid phosphate, "NA-LUBE AW-6400FG" manufactured by Kingindustries
・硫黄系極圧剤：イソブテン硫化物、ＲｈｅｉｎＣｈｅｍｉｅ製、「ＲＣ ２５４５」
・硫黄－リン系極圧剤：チオリン酸エステル、ＬＵＢＲＩＺＯＬ製「ＬＵＢＲＩＺＯＬ ＩＣ９ＡＷ３１」
・リン系極圧剤：脂肪酸リン酸エステルのアミン塩、Ｋｉｎｇｉｎｄｕｓｔｒｉｅｓ製「ＮＡ－ＬＵＢＥ ＡＷ－６４００ＦＧ」 ((C) Extreme pressure agent)
-Sulfur-based extreme pressure agent: isobutylene sulfide, manufactured by Rhein Chemie, "RC 2545"
-Sulfur-phosphorus extreme pressure agent: Thiophosphate ester, made by LUBRIZOL "LUBRIZOL IC9AW31"
-Phosphorus-based extreme pressure agent: Amin salt of fatty acid phosphate, "NA-LUBE AW-6400FG" manufactured by Kingindustries
（（Ｄ）酸化防止剤）
・一次酸化防止剤：ＢＡＳＦ製の芳香族アミン系化合物、「ＩＲＧＡＮＯＸ Ｌ－５７」・一次酸化防止剤：ＢＡＳＦ製のフェノール系化合物、「ＩＲＧＡＮＯＸ Ｌ－１３５」・二次酸化防止剤：城北化学工業(株)製の亜リン酸エステル系化合物、「ＪＰ－３１０」 ((D) Antioxidant)
-Primary antioxidant: BASF's aromatic amine compound, "IRGANOX L-57" -Primary antioxidant: BASF's phenolic compound, "IRGANOX L-135" -Secondary antioxidant: Johoku Chemical Industry "JP-310", a phosphite ester compound manufactured by Co., Ltd.
・一次酸化防止剤：ＢＡＳＦ製の芳香族アミン系化合物、「ＩＲＧＡＮＯＸ Ｌ－５７」・一次酸化防止剤：ＢＡＳＦ製のフェノール系化合物、「ＩＲＧＡＮＯＸ Ｌ－１３５」・二次酸化防止剤：城北化学工業(株)製の亜リン酸エステル系化合物、「ＪＰ－３１０」 ((D) Antioxidant)
-Primary antioxidant: BASF's aromatic amine compound, "IRGANOX L-57" -Primary antioxidant: BASF's phenolic compound, "IRGANOX L-135" -Secondary antioxidant: Johoku Chemical Industry "JP-310", a phosphite ester compound manufactured by Co., Ltd.
（その他）
・金属不活性剤：ＶＡＮＤＥＲＢＩＬＴ製のベンゾトリアゾール化合物「ＣＵＶＡＮ３０３」
・比較試験で使用したシリコーン１：メチルフェニルシリコーン、東レ・ダウコーニング（株）製「ＳＨ－５５０」（４０℃動粘度：７５．３ｍｍ２／ｓ、１００℃動粘度：２０．１ｍｍ２／ｓ、ＶＩ：２９１）
・比較試験で使用したシリコーン２：アルキルシリコーン、信越化学工業（株）製「ＫＦ－４９１７」（４０℃動粘度：１３．８ｍｍ２／ｓ、１００℃動粘度：４．６ｍｍ２／ｓ、ＶＩ：２９２） (Other)
-Metal inactivating agent: Vanderbilt's benzotriazole compound "CUVAN303"
-Silicone used in the comparative test 1: Methylphenyl silicone, "SH-550" manufactured by Toray Dow Corning Co., Ltd. (40 ° C kinematic viscosity: 75.3 mm 2 / s, 100 ° C kinematic viscosity: 20.1 mm 2 / s , VI: 291)
-Silicone used in the comparative test: Alkylic silicone, "KF-4917" manufactured by Shin-Etsu Chemical Co., Ltd. (40 ° C kinematic viscosity: 13.8 mm 2 / s, 100 ° C kinematic viscosity: 4.6 mm 2 / s, VI : 292)
・金属不活性剤：ＶＡＮＤＥＲＢＩＬＴ製のベンゾトリアゾール化合物「ＣＵＶＡＮ３０３」
・比較試験で使用したシリコーン１：メチルフェニルシリコーン、東レ・ダウコーニング（株）製「ＳＨ－５５０」（４０℃動粘度：７５．３ｍｍ２／ｓ、１００℃動粘度：２０．１ｍｍ２／ｓ、ＶＩ：２９１）
・比較試験で使用したシリコーン２：アルキルシリコーン、信越化学工業（株）製「ＫＦ－４９１７」（４０℃動粘度：１３．８ｍｍ２／ｓ、１００℃動粘度：４．６ｍｍ２／ｓ、ＶＩ：２９２） (Other)
-Metal inactivating agent: Vanderbilt's benzotriazole compound "CUVAN303"
-Silicone used in the comparative test 1: Methylphenyl silicone, "SH-550" manufactured by Toray Dow Corning Co., Ltd. (40 ° C kinematic viscosity: 75.3 mm 2 / s, 100 ° C kinematic viscosity: 20.1 mm 2 / s , VI: 291)
-Silicone used in the comparative test: Alkylic silicone, "KF-4917" manufactured by Shin-Etsu Chemical Co., Ltd. (40 ° C kinematic viscosity: 13.8 mm 2 / s, 100 ° C kinematic viscosity: 4.6 mm 2 / s, VI : 292)
〔実施例１～２２および比較例１～６〕
実施例１～１０については、表２に示す、上記合成例で得られた各種シロキサン化合物（シリコーン油）をそのまま使用した。実施例１１～２２及び比較例１～６については、それぞれの成分を、下記表２および３に示す割合（質量％）となるように配合して、（Ａ）シリコーン油と（Ｂ）炭化水素系油、（Ｃ）極圧剤、及び（Ｄ）酸化防止剤、その他添加剤を１００℃に加熱して混合することによってそれぞれの潤滑油組成物を調製した。 [Examples 1 to 22 and Comparative Examples 1 to 6]
For Examples 1 to 10, various siloxane compounds (silicone oils) obtained in the above synthesis examples shown in Table 2 were used as they were. In Examples 11 to 22 and Comparative Examples 1 to 6, the respective components were blended in proportions (% by mass) shown in Tables 2 and 3 below, and (A) silicone oil and (B) hydrocarbons were blended. Each lubricating oil composition was prepared by heating the system oil, (C) extreme pressure agent, (D) antioxidant, and other additives to 100 ° C. and mixing them.
実施例１～１０については、表２に示す、上記合成例で得られた各種シロキサン化合物（シリコーン油）をそのまま使用した。実施例１１～２２及び比較例１～６については、それぞれの成分を、下記表２および３に示す割合（質量％）となるように配合して、（Ａ）シリコーン油と（Ｂ）炭化水素系油、（Ｃ）極圧剤、及び（Ｄ）酸化防止剤、その他添加剤を１００℃に加熱して混合することによってそれぞれの潤滑油組成物を調製した。 [Examples 1 to 22 and Comparative Examples 1 to 6]
For Examples 1 to 10, various siloxane compounds (silicone oils) obtained in the above synthesis examples shown in Table 2 were used as they were. In Examples 11 to 22 and Comparative Examples 1 to 6, the respective components were blended in proportions (% by mass) shown in Tables 2 and 3 below, and (A) silicone oil and (B) hydrocarbons were blended. Each lubricating oil composition was prepared by heating the system oil, (C) extreme pressure agent, (D) antioxidant, and other additives to 100 ° C. and mixing them.
［評価方法］
得られた各実施例および各比較例のシロキサン化合物及び潤滑油組成物について、潤滑性を以下の試験方法で評価した。 [Evaluation method]
The lubricity of each of the obtained siloxane compounds and lubricating oil compositions of Examples and Comparative Examples was evaluated by the following test method.
得られた各実施例および各比較例のシロキサン化合物及び潤滑油組成物について、潤滑性を以下の試験方法で評価した。 [Evaluation method]
The lubricity of each of the obtained siloxane compounds and lubricating oil compositions of Examples and Comparative Examples was evaluated by the following test method.
（粘度指数）
粘度指数（ＶＩ）は、ＪＩＳ Ｋ ２２８３（２０００年）に従って測定、算出した。評価基準は以下の通りとした。 (Viscosity index)
The viscosity index (VI) was measured and calculated according to JIS K 2283 (2000). The evaluation criteria are as follows.
粘度指数（ＶＩ）は、ＪＩＳ Ｋ ２２８３（２０００年）に従って測定、算出した。評価基準は以下の通りとした。 (Viscosity index)
The viscosity index (VI) was measured and calculated according to JIS K 2283 (2000). The evaluation criteria are as follows.
粘度指数（ＶＩ）２５０以上 ◎
粘度指数（ＶＩ）１８０～２５０ ○
粘度指数（ＶＩ）１８０未満 × Viscosity index (VI) 250 or more ◎
Viscosity index (VI) 180-250 ○
Viscosity index (VI) less than 180 ×
粘度指数（ＶＩ）１８０～２５０ ○
粘度指数（ＶＩ）１８０未満 × Viscosity index (VI) 250 or more ◎
Viscosity index (VI) 180-250 ○
Viscosity index (VI) less than 180 ×
（残渣量の測定）
内径３ｃｍのガラス製のシャーレに、各試料を０．２ｇ秤量し、１４０℃の恒温槽で１００時間加熱後、２５０℃の恒温槽で７００時間加熱した。その後に、それぞれの残渣量を測定した。評価基準は以下の通りとした。 (Measurement of residue amount)
0.2 g of each sample was weighed in a glass petri dish having an inner diameter of 3 cm, heated in a constant temperature bath at 140 ° C. for 100 hours, and then heated in a constant temperature bath at 250 ° C. for 700 hours. After that, the amount of each residue was measured. The evaluation criteria are as follows.
内径３ｃｍのガラス製のシャーレに、各試料を０．２ｇ秤量し、１４０℃の恒温槽で１００時間加熱後、２５０℃の恒温槽で７００時間加熱した。その後に、それぞれの残渣量を測定した。評価基準は以下の通りとした。 (Measurement of residue amount)
0.2 g of each sample was weighed in a glass petri dish having an inner diameter of 3 cm, heated in a constant temperature bath at 140 ° C. for 100 hours, and then heated in a constant temperature bath at 250 ° C. for 700 hours. After that, the amount of each residue was measured. The evaluation criteria are as follows.
残渣の割合（重量％）が１０％以下 ◎
残渣の割合（重量％）が１０％超～２０％以下 ○
残渣の割合（重量％）が２０％超 ×
以上の結果を表２および３に示す。 Residue ratio (% by weight) is 10% or less ◎
Residue ratio (% by weight) is more than 10% to 20% or less ○
Residue ratio (% by weight) exceeds 20% ×
The above results are shown in Tables 2 and 3.
残渣の割合（重量％）が１０％超～２０％以下 ○
残渣の割合（重量％）が２０％超 ×
以上の結果を表２および３に示す。 Residue ratio (% by weight) is 10% or less ◎
Residue ratio (% by weight) is more than 10% to 20% or less ○
Residue ratio (% by weight) exceeds 20% ×
The above results are shown in Tables 2 and 3.
（考察）
実施例１～１０の結果より、本発明のシロキサン化合物は、単独で使用しても高い粘度指数と低残渣性を両立できることが示された。 (Discussion)
From the results of Examples 1 to 10, it was shown that the siloxane compound of the present invention can achieve both a high viscosity index and low residue property even when used alone.
実施例１～１０の結果より、本発明のシロキサン化合物は、単独で使用しても高い粘度指数と低残渣性を両立できることが示された。 (Discussion)
From the results of Examples 1 to 10, it was shown that the siloxane compound of the present invention can achieve both a high viscosity index and low residue property even when used alone.
また、実施例１１～２２では、本発明のシロキサン化合物を他の成分と共に組成物として使用しても、同じく、高い粘度指数と低残渣性を両立できることが示された。特に、実施例２～３及び１１～１５の結果により、シロキサン化合物の配合量が多い方が、加熱後の残渣が非常に少ないことが示された。さらに、実施例１６～１７の結果により、シロキサン化合物の配合量が多い方が粘度指数においても優れていることがわかった。
Further, in Examples 11 to 22, it was shown that even if the siloxane compound of the present invention is used as a composition together with other components, a high viscosity index and a low residual property can be achieved at the same time. In particular, from the results of Examples 2 to 3 and 11 to 15, it was shown that the larger the amount of the siloxane compound blended, the smaller the residue after heating. Furthermore, from the results of Examples 16 to 17, it was found that the larger the amount of the siloxane compound blended, the better the viscosity index.
一方、本発明のシロキサン化合物を使用していない比較例１～６では、粘度指数および低残渣性の少なくとも一方において実施例の結果より劣っていた。
On the other hand, in Comparative Examples 1 to 6 in which the siloxane compound of the present invention was not used, at least one of the viscosity index and the low residual property was inferior to the result of the example.
特に、比較例１～２の結果から、従来から使用されている一般的なシリコーン油では粘度指数は高いものの、残渣量が多いことがわかった。また、比較例３～５で使用した合成油である、エステル油、ＰＡＧ油については、残渣量は少なかったが、十分な粘度指数を示さなかった。比較的粘度指数が高い合成油として知られるＰＡＧ油であっても、粘度指数は１８０未満であった。比較例６では、従来のシリコーン油と残渣量が少ないエステル油を組み合わせてみたが、残渣量を抑えることができたものの粘度指数まで下がってしまうという結果になった。
In particular, from the results of Comparative Examples 1 and 2, it was found that the general silicone oil used conventionally has a high viscosity index but a large amount of residue. The synthetic oils used in Comparative Examples 3 to 5 such as ester oil and PAG oil did not show a sufficient viscosity index, although the amount of residue was small. Even PAG oil, known as a synthetic oil with a relatively high viscosity index, had a viscosity index of less than 180. In Comparative Example 6, a combination of a conventional silicone oil and an ester oil having a small amount of residue was tried, but the result was that the viscosity index was lowered even though the amount of residue could be suppressed.
この出願は、２０１９年１２月２０日に出願された日本国特許出願特願２０１９－２２９８３３を基礎とするものであり、その内容は、本願に含まれるものである。
This application is based on Japanese Patent Application No. 2019-229833 filed on December 20, 2019, the contents of which are included in the present application.
本発明を表現するために、前述において具体例等を参照しながら実施形態を通して本発明を適切かつ十分に説明したが、当業者であれば前述の実施形態を変更及び／又は改良することは容易になし得ることであると認識すべきである。したがって、当業者が実施する変更形態又は改良形態が、請求の範囲に記載された請求項の権利範囲を離脱するレベルのものでない限り、当該変更形態又は当該改良形態は、当該請求項の権利範囲に包括されると解釈される。
In order to express the present invention, the present invention has been appropriately and sufficiently described through the embodiments with reference to specific examples and the like, but those skilled in the art can easily change and / or improve the above-described embodiments. It should be recognized that it can be done. Therefore, unless the modified or improved form implemented by a person skilled in the art is at a level that deviates from the scope of rights of the claims stated in the claims, the modified form or the improved form is the scope of rights of the claims. It is interpreted as being comprehensively included in.
本発明のシロキサン化合物及び潤滑油組成物は、優れた潤滑性を有する潤滑油として使用できるため、各種用途の潤滑剤、例えば、ターボ機械用潤滑剤、圧縮機用の潤滑剤、油圧機器用の潤滑剤、工作機械用の潤滑剤、グリース基油、冷凍機油、可塑剤等として好適に用いることができる。特に高荷重の用途に好適である。
Since the siloxane compound and the lubricating oil composition of the present invention can be used as a lubricating oil having excellent lubricity, they can be used as lubricants for various purposes, for example, lubricants for turbo machinery, lubricants for compressors, and hydraulic equipment. It can be suitably used as a lubricant, a lubricant for machine tools, a grease base oil, a refrigerating machine oil, a plasticizer and the like. Especially suitable for high load applications.
Claims (7)
- 下記式（１）で示される、シロキサン化合物。
Ｘ１は、同一または異なって、水素、炭素数１～１２のアルキル基または下記式（２）で示されるポリオキシアルキル基であり、
Ｙは、炭素数２～１２のアルキレン基であり、
Ｚ１は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
ｐは０～１３の整数、ｑおよびｒはそれぞれ０～１６の整数、ｎは２～４の整数、ａは０～１１の整数である。
Ｚ２は、炭素－ケイ素結合によって隣接ケイ素原子に、かつ、酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、
Ｘ２は、水素もしくは炭素数１～１２のアルキル基であり、
ｍは２～４の整数、ｂは１～１０の整数である。）］ A siloxane compound represented by the following formula (1).
X 1 is the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
Y is an alkylene group having 2 to 12 carbon atoms.
Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
p is an integer of 0 to 13, q and r are integers of 0 to 16, respectively, n is an integer of 2 to 4, and a is an integer of 0 to 11.
Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom.
X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
m is an integer of 2 to 4, and b is an integer of 1 to 10. )] - 粘度指数が２００以上であり、かつ、１４０℃で１００時間加熱後、２５０℃で７００時間加熱した後の残渣量が２０％以下である、請求項１に記載のシロキサン化合物。 The siloxane compound according to claim 1, wherein the viscosity index is 200 or more, and the amount of residue after heating at 140 ° C. for 100 hours and then at 250 ° C. for 700 hours is 20% or less.
- （Ａ）請求項１または２に記載のシロキサン化合物と、
（Ｂ）炭化水素系潤滑油と、
（Ｃ）極圧剤および（Ｄ）酸化防止剤のうち少なくとも一つと、
を少なくとも含む、潤滑油組成物。 (A) The siloxane compound according to claim 1 or 2,
(B) Hydrocarbon-based lubricating oil and
With at least one of (C) extreme pressure agent and (D) antioxidant,
Lubricating oil composition containing at least. - 請求項１もしくは２に記載のシロキサン化合物、または請求項３に記載の潤滑油組成物を用いる、潤滑剤。 A lubricant using the siloxane compound according to claim 1 or 2 or the lubricating oil composition according to claim 3.
- 請求項１もしくは２に記載のシロキサン化合物、請求項３に記載の潤滑油組成物又は請求項４に記載の潤滑剤を用いる、グリース。 A grease using the siloxane compound according to claim 1 or 2, the lubricating oil composition according to claim 3, or the lubricant according to claim 4.
- 請求項１もしくは２に記載のシロキサン化合物、請求項３に記載の潤滑油組成物又は請求項４に記載の潤滑剤を用いる、エマルション。 An emulsion using the siloxane compound according to claim 1 or 2, the lubricating oil composition according to claim 3, or the lubricant according to claim 4.
- 請求項１もしくは２に記載のシロキサン化合物、請求項３に記載の潤滑油組成物又は請求項４に記載の潤滑剤を使用する、潤滑方法。 A lubrication method using the siloxane compound according to claim 1 or 2, the lubricating oil composition according to claim 3, or the lubricant according to claim 4.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5534228A (en) * | 1978-09-01 | 1980-03-10 | Toray Silicone Co Ltd | Polysiloxane composition |
| JPH0762102A (en) * | 1993-08-25 | 1995-03-07 | Kao Corp | Organo(poly)siloxane modified with sulfuric acid ester and preparation thereof |
| JPH11217390A (en) * | 1998-01-30 | 1999-08-10 | Dow Corning Toray Silicone Co Ltd | Production of organic functional organopentasiloxane, organic resin-modifying agent and organic resin |
| JP2004217866A (en) * | 2003-01-17 | 2004-08-05 | Daisan Kogyo Kk | Undiluted lubricant solution for container carrying conveyer belt and lubricant |
| JP2006286509A (en) * | 2005-04-04 | 2006-10-19 | Shin Etsu Chem Co Ltd | Nonaqueous electrolytic solution and secondary battery using the same |
| JP2011116701A (en) * | 2009-12-03 | 2011-06-16 | Dow Corning Toray Co Ltd | Novel organopolysiloxane and cosmetic |
| JP2012207082A (en) * | 2011-03-29 | 2012-10-25 | Jx Nippon Oil & Energy Corp | Lubricant oil composition |
| JP2017061613A (en) * | 2015-09-25 | 2017-03-30 | 信越化学工業株式会社 | Thermosoftening heat-conductive silicone grease composition, method for forming heat-conductive coating film, heat radiation structure and power module device |
| JP2018090732A (en) * | 2016-12-06 | 2018-06-14 | 株式会社ニッペコ | Grease composition and movable coupling |
-
2020
- 2020-11-24 WO PCT/JP2020/043615 patent/WO2021124807A1/en active Application Filing
- 2020-11-24 JP JP2021565405A patent/JPWO2021124807A1/ja active Pending
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Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5534228A (en) * | 1978-09-01 | 1980-03-10 | Toray Silicone Co Ltd | Polysiloxane composition |
| JPH0762102A (en) * | 1993-08-25 | 1995-03-07 | Kao Corp | Organo(poly)siloxane modified with sulfuric acid ester and preparation thereof |
| JPH11217390A (en) * | 1998-01-30 | 1999-08-10 | Dow Corning Toray Silicone Co Ltd | Production of organic functional organopentasiloxane, organic resin-modifying agent and organic resin |
| JP2004217866A (en) * | 2003-01-17 | 2004-08-05 | Daisan Kogyo Kk | Undiluted lubricant solution for container carrying conveyer belt and lubricant |
| JP2006286509A (en) * | 2005-04-04 | 2006-10-19 | Shin Etsu Chem Co Ltd | Nonaqueous electrolytic solution and secondary battery using the same |
| JP2011116701A (en) * | 2009-12-03 | 2011-06-16 | Dow Corning Toray Co Ltd | Novel organopolysiloxane and cosmetic |
| JP2012207082A (en) * | 2011-03-29 | 2012-10-25 | Jx Nippon Oil & Energy Corp | Lubricant oil composition |
| JP2017061613A (en) * | 2015-09-25 | 2017-03-30 | 信越化学工業株式会社 | Thermosoftening heat-conductive silicone grease composition, method for forming heat-conductive coating film, heat radiation structure and power module device |
| JP2018090732A (en) * | 2016-12-06 | 2018-06-14 | 株式会社ニッペコ | Grease composition and movable coupling |
Non-Patent Citations (1)
| Title |
|---|
| URYU, TOSHIZO ET AL.: "Molecular Weight of Silicones and its Measurements", KOBUNSHI KAGAKU, vol. 15, no. 153, 1958, pages 55 - 59, ISSN: 0023-2556 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850706A (en) * | 2022-12-12 | 2023-03-28 | 上海东大化学有限公司 | Silane modified polymer, synthesis method thereof and method for preparing waterproof coating by using silane modified polymer |
Also Published As
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|---|---|
| JPWO2021124807A1 (en) | 2021-06-24 |
| TW202136385A (en) | 2021-10-01 |
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