CN110272447A - A method of preparing organosilicon Biolubrication oil base oil - Google Patents
A method of preparing organosilicon Biolubrication oil base oil Download PDFInfo
- Publication number
- CN110272447A CN110272447A CN201810221650.7A CN201810221650A CN110272447A CN 110272447 A CN110272447 A CN 110272447A CN 201810221650 A CN201810221650 A CN 201810221650A CN 110272447 A CN110272447 A CN 110272447A
- Authority
- CN
- China
- Prior art keywords
- oil
- organosilicon
- reaction
- aliphatic ester
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003921 oil Substances 0.000 title claims abstract description 49
- 239000002199 base oil Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 aliphatic ester Chemical class 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 235000019198 oils Nutrition 0.000 claims abstract description 48
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 23
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 150000007530 organic bases Chemical class 0.000 claims abstract description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 11
- 239000008158 vegetable oil Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 238000013517 stratification Methods 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007142 ring opening reaction Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 claims description 6
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 claims description 6
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 4
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 4
- 229940073769 methyl oleate Drugs 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011973 solid acid Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- WFZQLUSOXHIVKL-QXMHVHEDSA-N ethyl (13Z)-docosenoate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OCC WFZQLUSOXHIVKL-QXMHVHEDSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- JYYFMIOPGOFNPK-AGRJPVHOSA-N ethyl linolenate Chemical compound CCOC(=O)CCCCCCC\C=C/C\C=C/C\C=C/CC JYYFMIOPGOFNPK-AGRJPVHOSA-N 0.000 claims description 2
- 229940090028 ethyl linolenate Drugs 0.000 claims description 2
- JYYFMIOPGOFNPK-UHFFFAOYSA-N ethyl linolenate Natural products CCOC(=O)CCCCCCCC=CCC=CCC=CCC JYYFMIOPGOFNPK-UHFFFAOYSA-N 0.000 claims description 2
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 claims description 2
- 229940093471 ethyl oleate Drugs 0.000 claims description 2
- ZYNDJIBBPLNPOW-UHFFFAOYSA-N eurucic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-UHFFFAOYSA-N 0.000 claims description 2
- ZYNDJIBBPLNPOW-KHPPLWFESA-N methyl erucate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-KHPPLWFESA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 claims 1
- 229940031016 ethyl linoleate Drugs 0.000 claims 1
- 235000019197 fats Nutrition 0.000 claims 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 claims 1
- 229960004488 linolenic acid Drugs 0.000 claims 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- YEYZNBKNDWPFSQ-UHFFFAOYSA-N methanol;urea Chemical compound OC.NC(N)=O YEYZNBKNDWPFSQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012047 saturated solution Substances 0.000 abstract 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 239000004359 castor oil Substances 0.000 description 8
- 235000019438 castor oil Nutrition 0.000 description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019483 Peanut oil Nutrition 0.000 description 7
- 235000012343 cottonseed oil Nutrition 0.000 description 7
- 239000002385 cottonseed oil Substances 0.000 description 7
- 239000000312 peanut oil Substances 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 235000020238 sunflower seed Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 235000019486 Sunflower oil Nutrition 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000002600 sunflower oil Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002924 oxiranes Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- DVWSXZIHSUZZKJ-UHFFFAOYSA-N 18:3n-3 Natural products CCC=CCC=CCC=CCCCCCCCC(=O)OC DVWSXZIHSUZZKJ-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001299699 Idesia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DVWSXZIHSUZZKJ-YSTUJMKBSA-N methyl linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OC DVWSXZIHSUZZKJ-YSTUJMKBSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- 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
-
- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
- C10M2227/045—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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Abstract
The present invention relates to one kind using vegetable oil as raw material, by aliphatic ester epoxidation and the modified method for preparing organosilicon Biolubrication oil base oil of the direct open loop of organosilicon, includes the following steps: that vegetable oil and alcohol carry out ester exchange reaction and obtain aliphatic ester；Aliphatic ester is added in urea-methanol saturated solution to be separated using urea adduct method, obtains unsaturated fatty acid ester；Unsaturated fatty acid ester reacts to obtain epoxy aliphatic ester with organic acid, acidic catalyst；Epoxy aliphatic ester obtains organo-silicic oil base oil by the direct open loop of organosilicon under the action of organic base.The method mild condition, reaction efficiency is high, by-product in reaction process is few, and production process does not generate harmful substance, and the organosilicon Biolubrication oil base oil pour point being prepared is low, viscosity-temperature characteristics energy is good, Viscosity Index is big, oxidation stability is good, abrasion resistance is preferable.
Description
Technical field
The invention belongs to biological lubricant preparation field more particularly to aliphatic ester epoxidations and the direct open loop of organosilicon to change
Property prepares the process of organosilicon Biolubrication oil base oil.
Technical background
Lubricating oil is mainly made of base oil and additive, and base oil usually accounts for 80%~95% in lubricating oil, master
It is divided into 3 seed type of mineral oil, synthetic oil and vegetable and animals oils.Mineral oil derives from petroleum, is a kind of non-renewable rare money
Source.The biological degradability of mineral oil and most of synthetic oil is all poor, often will appear leakage in use and pollutes
Environment.Vegetable oil based lubricating oil is nontoxic, and degradation rate is up to 95% or more under natural conditions, be increasingly becoming it is a kind of effectively and can be again
Raw, relatively inexpensive lube base oil source.Natural non-modified vegetable oil greasy property is good, and viscosity-temperature characteristic is good, dodges
Point is high.But containing a large amount of C=C key in natural plants oil molecule, unsaturated double-bond property is active, containing unstable β-H,
Oxidation reaction easily occurs, stability is poor.
It is at present epoxy-ring-opening reaction or hydrosilylation, both methods to the most effective method of modifying of vegetable oil
It can effectively improve the oxidation stability and flash-point of vegetable oil.But ring opening process be unable to do without the use of formic acid, so that long flow path, and
By-product is more；Catalyst for addition reaction of hydrogen and silicon is expensive, severe reaction conditions.
CN104962341A is using castor oil as raw material in the prior art, through esterification, epoxy, the modified obtained lubricating oil of open loop
Basic oil flash point is high, oxidation stability is good, wearability is good.CN107011963A is also reported using idesia polycarpa oil as raw material,
The product chemical stability obtained by esterification, epoxy, transesterification is strong, viscosity is high.Although epoxy-ring-opening reaction can improve rouge
Fat acid esters oxidation stability and low temperature flow, however its product acidity is high, ingredient mixes, and friction, lubrication performance need to be mentioned
It is high.
CN104877731A and CN103789062A is obtained using borine, metal platinum as catalyst by hydrosilylation respectively
The silicon substrate lube base oil flash point arrived is high, oxidation stability is good, viscosity-temperature characteristics energy is good.Shorter with reaction process, catalyst is living
Property it is higher the advantages that, but used catalyst is expensive and toxicity is big, cost of material is higher, severe reaction conditions, production cost
Height is not suitable for large-scale industrial production.Therefore biomass lube base can be improved comprehensively by needing to develop a kind of new process
The greasy property of oil, and it is able to achieve industrialized production.
Summary of the invention
The purpose of the present invention is to provide a kind of methods, and organo-silicic oil base oil is prepared, and this method is in organic base
Effect is lower to carry out Silanization reaction using the direct open loop of organosilicon, in addition to organic base and without using other high in the reaction step
Expensive catalyst also avoids the use of formic acid during conventional open loop.
Another object of the present invention is to carry out chemical modification as starting material using cheap vegetable oil, to reduce life
Produce cost of material.
To achieve the above object, the invention adopts the following technical scheme:
A method of organosilicon Biolubrication oil base oil is prepared, it is modified using aliphatic ester epoxy and the direct open loop of organosilicon
Method, comprising the following steps:
A: potassium hydroxide or 5~30g of sodium hydroxide are added in 100~300g of methanol or ethyl alcohol, then with commercially available conventional plant
150~500g of oil is placed in together in the flask with condensing reflux system, the heating stirring in thermostat water bath, reaction temperature 30
~60 DEG C, 1~6h of reaction time.To after reaction, stratification, upper layer is aliphatic ester, lower layer is then crude glycerine.Upper layer
Aliphatic ester distillation removing light component, obtained residue is aliphatic ester.
B: 50~300g of urea is added in 200~1000ml of methanol, and after urea is completely dissolved, above-mentioned aliphatic ester 50 is added
~200g stirs 30min at 60 DEG C, then will liquid be placed in it is cooling in -4~4 DEG C of low temperature crystallization is precipitated, obtain mother after filtering
Liquid, the residue that evaporated mother liquor obtains are unsaturated fatty acid ester.
C: by unsaturated fatty acid ester and organic acid (formic acid or acetic acid), the conventional acid catalyst (liquid such as phosphoric acid, sulfuric acid, nitric acid
One of solid acids such as body acid or acid cation exchange resin) it is mixed to join in flask, oxidant H is slowly added dropwise2O2,
The mass ratio of oxidant and unsaturated fatty acid ester is 0.60~0.90, the mass ratio of organic acid and aliphatic ester be 0.1~
0.3, the mass ratio of acidic catalyst and aliphatic ester be 0.01~0.1, reaction temperature be 35~75 DEG C, the reaction time be 1~
6h, stratification, takes supernatant liquid to be washed to neutrality after reaction, and distillation, dry removal light component and moisture obtain epoxy
Aliphatic ester.
D: epoxy aliphatic ester is stirred and heated to reaction temperature (30~70 DEG C), organic base is first added, has been slow added into
Machine silicon carries out organosilicon ring-opening reaction, isolates solid while hot after reaction, and liquid distillation removal light component obtains organosilicon
Biolubrication oil base oil.
Further, unsaturated fatty acid ester described in step c is methyl oleate, ethyl oleate, methyl linoleate, sub- oil
One of vegetable oil unsaturated fatty acid ester such as acetoacetic ester, methyl linolenate, ethyl linolenate, methyl erucate, ethyl erucate
Or several mixture.
Organosilicon described in step d has following molecular formula: R3SiX, R be methyl, ethyl, in phenyl any one or
Several combinations, one of X Cl, Br, I.
Further, organic base described in step d is sodium acetate, pyridine, triethylamine, diethylamine, N, N- diisopropyl second
The combination of one or more of base amine, dimethylformamide, 4-dimethylaminopyridine or other organic bases.
The molar ratio of epoxy group and organosilicon in epoxy aliphatic ester described in step c be 1:0.1~2, preferably 1:
1.25~1.5.
The molar ratio of epoxy group and organic base in epoxy aliphatic ester described in step c be 1:0.1~2, preferably 1:
1.25~1.5.
Further, reaction temperature described in step c is 35~75 DEG C, preferably 45~55 DEG C.
Further, the reaction time described in step c is 1~6h, preferably 2~3h.
The direct open loop method of urea clathrate partition method and epoxy-organic silicon that the present invention uses uses vegetable oil as starting
Raw material does not use formic acid in ring opening process, without using expensive catalyst yet, reduces costs, improves the purity of reactant,
Each unrelated component separation is easy after the reaction was completed, small to the corrosivity of equipment.Raw material is cheap and easily-available, and process equipment is of less demanding,
It is easy to operate, solve in conventional epoxy-ring-opening reaction that reaction step is more, byproduct of reaction is miscellaneous, product acidity height and unstable
The problem of.
The present invention by carrying out transesterification, urea clathrate separation, the direct open loop modification of epoxy, organosilicon to vegetable oil, gram
The disadvantages such as aliphatic ester pour point is high, oxidation stability is poor, flash-point is low have been taken, have obtained that a kind of pour point is low, flash-point is high, viscosity index (VI)
The environmental type lube base oil high, oxidation stability is good, wear resistence is good.
Detailed description of the invention
Fig. 1: step c~d flow diagram of the present invention.As an example, using methyl oleate and methyl linoleate as step c
Raw material, the organosilicon in step d selects trim,ethylchlorosilane, and organic base selects sodium acetate.
Fig. 2: the infrared spectrogram for the organosilicon Biolubrication oil base oil that embodiment 1 is prepared.
Fig. 3: the trim,ethylchlorosilane that embodiment 1 uses29Si- nuclear magnetic resonance map, and the organosilicon being prepared
Biolubrication oil base oil29Si- nuclear magnetic resonance map.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
Step 1, potassium hydroxide 25g is added in methanol 300g, is then placed in together with soybean oil 500g with condensing reflux system
In the flask of system, the heating stirring in thermostat water bath, 60 DEG C of reaction temperature, reaction time 2h.To after reaction, pour into point
Cooling layering in liquid funnel, upper layer is aliphatic ester, and lower layer is then crude glycerine.Upper-layer fat acid esters distillation removing light component, obtains
The residue arrived is soya fatty acid ester.
Step 2, urea 200g is added in 1000ml methanol, after urea is completely dissolved, 200g soybean oil fat is added
Acid esters stirs 30min at 60 DEG C, then will liquid be placed in it is cooling in -4~4 DEG C of low temperature crystallization is precipitated, obtain mother liquor after filtering,
Evaporated mother liquor removes light component, and obtained residue is soybean oil unsaturated fatty acid ester.
Step 3, the resulting soybean oil unsaturated fatty acid ester of 100g step 2 is mixed to join with 23g formic acid, 5g phosphoric acid
In three-necked flask, 80g hydrogen peroxide is slowly added dropwise, 2h is reacted at 60 DEG C, after reaction stratification, takes supernatant liquid water
It is washed till neutrality, distillation, dry removal light component and moisture obtain soybean oil epoxy aliphatic ester.
Step 4, it takes the resulting 20g soybean oil epoxy aliphatic ester of step 3 to be put into three-necked flask, is heated with stirring to 40
DEG C, sodium acetate 8.2g is added, 8.4g trim,ethylchlorosilane is added dropwise in reaction system, time for adding 0.5h, heats up
To 55 DEG C, reaction time 2h, solid is directly isolated while hot after reaction, liquid distillation removal light component obtains organic
Silicon Biolubrication oil base oil.
Structural characterization is carried out to 1 gained organo-silicic oil base oil of example using Fourier infrared spectrograph (FT-IR),
As a result see Fig. 2, spectrogram 1,2,3 is unsaturated fatty acid ester, epoxy aliphatic ester, organosilicon Biolubrication oil base respectively in Fig. 2
The infrared spectrogram of plinth oil.846.37cm-1It is the stretching vibration peak of epoxide ring, 1658.12cm-1It is the flexible vibration of carbon-carbon double bond
Dynamic peak, 3007.64cm-1It is=the stretching vibration peak of C-H that is connected with C=C, the comparison of spectrogram 1 and 2 can be obtained, epoxidation reaction
Afterwards, 1658.12cm-1、3007.64cm-1Peak disappear, and increase 846.37cm-1Peak, illustrate the C=in aliphatic ester
C has been at least partially epoxidized；2 and 3 spectrogram is compared into discovery, 846.37cm after ring-opening reaction-1The peak at place disappears, illustrate epoxide ring by
Organosilicon open loop；There is 1085.34cm in spectrogram 3-1The stretching vibration peak for locating Si-O-C, illustrates epoxy group by organosilicon open loop
Success synthesizing organo-silicon Biolubrication oil base oil.
Fig. 3 is trim,ethylchlorosilane (lower half portion in figure) and the organosilicon Biolubrication oil base oil that embodiment 1 obtains
(top half in figure)29Si- nuclear magnetic resonance silicon spectrogram.There are two peak on the silicon spectrogram of trimethylchloro-silicane, wherein θ 30-31ppm
Place is the chemical shift peak of element silicon in trim,ethylchlorosilane, and trim,ethylchlorosilane will lead to element silicon after reacting with epoxy group
Locating chemical environment variation, therefore the element silicon chemical shift peak in organosilicon Biolubrication oil base oil is in θ 15-18ppm
Place.There is element silicon in Si-OH at the θ 7ppm on trim,ethylchlorosilane and the silicon spectrogram of organosilicon Biolubrication oil base oil
Chemical shift peak, this is because minimal amount of Si- in minimal amount of Si-Cl and organosilicon open-loop products in trim,ethylchlorosilane
Caused by O-C resolves into Si-OH.
Embodiment 2
Step 1, by 100g methyl linoleate and 18g formic acid, 7g solid acid Nb2O5It is mixed to join in three-necked flask, slowly drips
Add 90g hydrogen peroxide, 6h is reacted at 50 DEG C, after reaction stratification, supernatant liquid is taken to be washed to neutrality, distillation is done
Dry removal light component and moisture, obtain epoxy methyl linoleate.
Step 2, it takes 30g epoxy methyl linoleate to be put into the three-necked flask with thermometer, is heated with stirring to 45 DEG C,
10.2g N, N- diisopropyl ethyl amine is added, 11.88g bromotrimethylsilane is added dropwise in reaction system, time for adding
For 0.5h, reaction time 3h, solid is isolated while hot after reaction, liquid distills to obtain organosilicon biological lubricant basis
Oil.
Embodiment 3
Step 1, potassium hydroxide 20g is added in methanol 280g, is then placed in together with castor oil 400g with condensing reflux system
In the flask of system, the heating stirring in thermostat water bath, 60 DEG C of reaction temperature, reaction time 3h.To after reaction, pour into point
Cooling layering in liquid funnel, upper layer is aliphatic ester, and lower layer is then crude glycerine.The residue that upper-layer fat acid esters distills is
Castor Oil Fatty Acid ester.
Step 2, urea 300g is added in 900ml methanol, after urea is completely dissolved, 200g Castor Oil Fatty Acid is added
Ester stirs 30min at 60 DEG C, then by liquid be placed in it is cooling in -4~4 DEG C of low temperature crystallization is precipitated, decompression obtains mother after filtering
Liquid, the residue that evaporated mother liquor obtains are castor oil unsaturated fatty acid ester.
Step 3, step 2 gained 100g castor oil unsaturated fatty acid ester and 25g formic acid, 14g NKC-9 cation are handed over
It changes resin to be mixed to join in three-necked flask, 75g hydrogen peroxide is slowly added dropwise, 5h is reacted at 55 DEG C, is stood after reaction
Layering, takes supernatant liquid to be washed to neutrality, and distillation, dry removal light component and moisture obtain epoxy castor oil aliphatic ester.
Step 4, it takes 25g step 3 gained epoxy castor oil aliphatic ester to be put into three-necked flask, is heated with stirring to 50
DEG C, 8.2g pyridine is added, 13.4g Iodotrimethylsilane is added dropwise in reaction system, time for adding 0.5h, the reaction time
For 2.5h, solid is isolated while hot after reaction, liquid distills to obtain organosilicon Biolubrication oil base oil.
Embodiment 4
Step 1, potassium hydroxide 15g is added in methanol 200g, is then placed in together with cottonseed oil 300g with condensing reflux system
In the flask of system, the heating stirring in thermostat water bath, 60 DEG C of reaction temperature, reaction time 2h.To after reaction, pour into point
Cooling layering in liquid funnel, upper layer is aliphatic ester, and lower layer is then crude glycerine.The residue that upper-layer fat acid esters distills is
Cottonseed oil fatty acid ester.
Step 2, urea 200g is added in 800ml methanol, after urea is completely dissolved, 200g cottonseed oil fatty acid is added
Ester stirs 30min at 60 DEG C, then by liquid be placed in it is cooling in -4~4 DEG C of low temperature crystallization is precipitated, decompression obtains mother after filtering
Liquid, the residue that evaporated mother liquor obtains are cottonseed oil unsaturated fatty acid ester.
Step 3, step 2 gained 100g cottonseed oil unsaturated fatty acid ester is mixed into addition with 40g acetic acid, 1.5g concentrated nitric acid
Into three-necked flask, 80g hydrogen peroxide is slowly added dropwise, 5h is reacted at 45 DEG C, after reaction stratification, takes supernatant liquid
It is washed to neutrality, distillation, dry removal light component and moisture obtain epoxy cottonseed oil aliphatic ester.
Step 4, it takes 30g step 3 gained epoxy cottonseed oil aliphatic ester to be put into three-necked flask, is heated with stirring to 45
DEG C, 8.8g diethylamine is added, 12.6g chlorotriethyl silane is added dropwise in reaction system, time for adding 0.5h, when reaction
Between be 3h, isolate solid while hot after reaction, liquid distills to obtain organosilicon Biolubrication oil base oil.
Embodiment 5
Step 1, potassium hydroxide 20g is added in methanol 200g, is then placed in together with peanut oil 200g with condensing reflux system
In the flask of system, the heating stirring in thermostat water bath, 60 DEG C of reaction temperature, reaction time 3h.To after reaction, pour into point
Cooling layering in liquid funnel, upper layer is aliphatic ester, and lower layer is then crude glycerine.The residue that upper-layer fat acid esters distills is
Peanut oil fatty acid ester.
Step 2, urea 200g is added in 900ml methanol, after urea is completely dissolved, 150g peanut oil fatty acid is added
Ester stirs 30min at 60 DEG C, then by liquid be placed in it is cooling in -4~4 DEG C of low temperature crystallization is precipitated, decompression obtains mother after filtering
Liquid, the residue that evaporated mother liquor obtains are peanut oil unsaturated fatty acid ester.
Step 3, step 2 gained 100g peanut oil unsaturated fatty acid ester and 30g acetic acid, the 2g concentrated sulfuric acid are mixed to join
In three-necked flask, 95g hydrogen peroxide is slowly added dropwise, 6h is reacted at 50 DEG C, after reaction stratification, takes supernatant liquid water
It is washed till neutrality, distillation, dry removal light component and moisture obtain epoxy peanut oil fatty acid ester.
Step 4, it takes 25g step 3 gained epoxy peanut oil fatty acid ester to be put into three-necked flask, is heated with stirring to 50
DEG C, 10.2g triethylamine is added, 12.6g triethyl group bromo-silicane is added dropwise in reaction system, time for adding 0.5h, reaction
Time is 4h, isolates solid while hot after reaction, and liquid distills to obtain organosilicon Biolubrication oil base oil.
Embodiment 6
Step 1,100g methyl oleate and 18g formic acid, 6g phosphoric acid are mixed to join in three-necked flask, 70g peroxide is slowly added dropwise
Change hydrogen, 2h is reacted at 55 DEG C, after reaction stratification, supernatant liquid is taken to be washed to neutrality, distillation, dry light group of removal
Point and moisture, obtain epoxyoleic acid methyl esters.
Step 2, it takes the resulting 30g epoxyoleic acid methyl esters of step 1 to be put into three-necked flask, is heated with stirring to 45 DEG C, adds
Enter 11.4g dimethylformamide, 13.6g Iodotrimethylsilane is added dropwise in reaction system, time for adding 0.5h, reaction
Time is 2h, isolates solid while hot after reaction, and liquid distills to obtain organosilicon Biolubrication oil base oil.
Embodiment 7
Step 1, potassium hydroxide 30g is added in methanol 350g, is then placed in together with sunflower oil 450g with condensing reflux
In the flask of system, the heating stirring in thermostat water bath, 60 DEG C of reaction temperature, reaction time 3.5h.To after reaction,
Enter cooling layering in separatory funnel, upper layer is aliphatic ester, and lower layer is then crude glycerine.The residual that upper-layer fat acid esters distills
Object is sunflower seed oil fatty acids ester.
Step 2, urea 250g is added in 1000ml methanol, after urea is completely dissolved, 200g sunflower seeds grease is added
Fat acid esters stirs 30min at 60 DEG C, then by liquid be placed in it is cooling in -4~4 DEG C of low temperature crystallization is precipitated, decompression obtains after filtering
Mother liquor, the residue that evaporated mother liquor obtains are sunflower oil unsaturated fatty acid ester.
Step 3, step 2 gained 100g sunflower oil unsaturated fatty acid ester is mixed with 30g acetic acid, 12g sodium bisulfate
It is added in three-necked flask, 85g hydrogen peroxide is slowly added dropwise, 6h is reacted at 50 DEG C, after reaction stratification, take upper layer
Liquid is washed to neutrality, and distillation, dry removal light component and moisture obtain epoxy sunflower seed oil fatty acids ester.
Step 4, it takes 25g step 3 gained epoxy sunflower seed oil fatty acids ester to be put into three-necked flask, is heated with stirring to 45
DEG C, 12.4g 4-dimethylaminopyridine is added, 9.6g trim,ethylchlorosilane is added dropwise in reaction system, and time for adding is
0.5h, reaction time 4h, isolate solid while hot after reaction, and liquid distills to obtain organosilicon biological lubricant basis
Oil.
In order to prove beneficial effects of the present invention, the profit for the organo-silicic oil base oil that inventor prepares embodiment 1
Slip can be carried out test, and the specific test method is as follows:
The viscosity and viscosity index (VI) of base oil are surveyed according to GB/T265-88 " oil product kinematic viscosity method of testing "；According to
GB/T261-2008 " Flash Point for Petroleum Products method of testing (silent agar diffusion method) " measures close flash point value；According to SH/T0193-2008 " profit
Lubricating oil oxidation stability method of testing (rotary bomb oxidation test) " survey oxidation stability；According to GB/3142-82 " load carrying capacity of lubricant
Method of testing (four ball method) " survey base oil wear-resisting property.Test result is shown in Table 1.
1 test result of table
Note: 150SN is document (Enzhu H.The role of soot particles in the tribological
Behavior of engine lubricating oils, 2013,5 (2): 152-161.) and document (Ren Q
G.Preparation of lubricant base stock through chemical modification of
Biodiesel.Journal of Fuel Chemistry&Technology, 2015,43 (01): 54-58.) data.
Statistics indicate that, organosilicon Biolubrication oil base oil pour point prepared by the present invention is low in table 1, viscosity index (VI) it is high it is good,
Flash-point is high, oxidation stability is outstanding, frictional behaviour is excellent.
Claims (8)
1. a kind of method for preparing organosilicon Biolubrication oil base oil, which is characterized in that using aliphatic ester epoxy and organic
The modified method of the direct open loop of silicon, includes the following steps:
A: potassium hydroxide or 5~30g of sodium hydroxide are added in 100~300g of methanol or ethyl alcohol, then with commercially available conventional plant
150~500g of oil is placed in reactor together, the heating stirring in constant temperature bath, and 30~60 DEG C of reaction temperature, the reaction time 1~
6h.To after reaction, stratification, upper layer is aliphatic ester, lower layer is then crude glycerine.The distillation removing of upper-layer fat acid esters is light
Component, obtained residue are aliphatic ester.
B: 50~300g of urea is added in 200~1000ml of methanol, and after urea is completely dissolved, above-mentioned aliphatic ester 50 is added
~200g stirs 30min at 60 DEG C, then will liquid be placed in it is cooling in -4~4 DEG C of low temperature crystallization is precipitated, obtain mother after filtering
Liquid, evaporated mother liquor remove light component, and obtained residue is unsaturated fatty acid ester.
C: by unsaturated fatty acid ester and organic acid (formic acid or acetic acid), the conventional acid catalyst (liquid such as phosphoric acid, sulfuric acid, nitric acid
Body acid, one of solid acids such as acid cation exchange resin) it is mixed to join in reactor, it is slowly added oxidant H2O2,
The mass ratio of oxidant and unsaturated fatty acid ester is 0.60~0.90, the mass ratio of organic acid and aliphatic ester be 0.1~
0.3, the mass ratio of acidic catalyst and aliphatic ester be 0.01~0.1, reaction temperature be 35~75 DEG C, the reaction time be 1~
6h, stratification, takes supernatant liquid after reaction, is washed to neutrality, and distillation, dry removal light component and moisture obtain ring
Oxygen aliphatic ester.
D: epoxy aliphatic ester is stirred and heated to reaction temperature (30~70 DEG C), organic base is first added, has been slow added into
Machine silicon carries out organosilicon ring-opening reaction, isolates solid after reaction, and liquid distillation removal light component obtains organosilicon biology
Lube base oil.
2. a kind of method for preparing organosilicon Biolubrication oil base oil as described in claim 1, it is characterised in that: step c
Described in unsaturated fatty acid ester main component be methyl oleate, ethyl oleate, methyl linoleate, ethyl linoleate, linolenic acid
The mixing of one or more of the vegetable oil unsaturated fatty acid ester such as methyl esters, ethyl linolenate, methyl erucate, ethyl erucate
Object.
3. a kind of method for preparing organosilicon Biolubrication oil base oil as described in claim 1, it is characterised in that: step d
Described in organosilicon have following molecular formula: R3SiX, R are methyl, ethyl, any one or the combination of several of them in phenyl, X
For one of Cl, Br, I.
4. a kind of method for preparing organosilicon Biolubrication oil base oil as described in claim 1, it is characterised in that: step d
Described in organic base be sodium acetate, pyridine, triethylamine, diethylamine, N, N- diisopropyl ethyl amine, dimethylformamide, 4- bis-
The combination of one or more of dimethylaminopyridine or other organic bases.
5. a kind of method for preparing organosilicon Biolubrication oil base oil as described in claim 1, it is characterised in that: step d
Described in the molar ratio of epoxy group and organosilicon in epoxy aliphatic ester be 1:0.1~2, preferably 1:1.25~1.5.
6. a kind of method for preparing organosilicon Biolubrication oil base oil as described in claim 1, it is characterised in that: step d
Described in the molar ratio of epoxy group and organic base in epoxy aliphatic ester be 1:0.1~2, preferably 1:1.25~1.5.
7. a kind of method for preparing organosilicon Biolubrication oil base oil as described in claim 1, it is characterised in that: step d
Described in reaction temperature be 35~75 DEG C, preferably 45~55 DEG C.
8. a kind of method for preparing organosilicon Biolubrication oil base oil as described in claim 1, it is characterised in that: step d
Described in the reaction time be 1~6h, preferably 2~3h.
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