CN107986954A - 一种烷基水杨酸盐及其制备方法 - Google Patents
一种烷基水杨酸盐及其制备方法 Download PDFInfo
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- CN107986954A CN107986954A CN201610942331.6A CN201610942331A CN107986954A CN 107986954 A CN107986954 A CN 107986954A CN 201610942331 A CN201610942331 A CN 201610942331A CN 107986954 A CN107986954 A CN 107986954A
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- Prior art keywords
- alkylsalicylate
- alkyl
- accordance
- acid
- salicylate
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 Alkyl salicylate Chemical compound 0.000 claims abstract description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229960001860 salicylate Drugs 0.000 claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000002608 ionic liquid Substances 0.000 claims description 15
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 15
- 229960004889 salicylic acid Drugs 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 15
- 229920000193 polymethacrylate Polymers 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000003921 oil Substances 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000002585 base Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000009423 ventilation Methods 0.000 description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 229960004424 carbon dioxide Drugs 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229960004025 sodium salicylate Drugs 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 241000238370 Sepia Species 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000002199 base oil Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000007701 flash-distillation Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 108010002352 Interleukin-1 Proteins 0.000 description 3
- 108010002350 Interleukin-2 Proteins 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical class [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000000203 Salix gracilistyla Species 0.000 description 2
- GOMPLJOPYGQBPL-UHFFFAOYSA-K [F-].[F-].[F-].F.[B+3] Chemical compound [F-].[F-].[F-].F.[B+3] GOMPLJOPYGQBPL-UHFFFAOYSA-K 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- LYJZNXAVZMEXDH-UHFFFAOYSA-N octadecan-8-yl 2-methylprop-2-enoate Chemical class CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCC LYJZNXAVZMEXDH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- FIWQZURFGYXCEO-UHFFFAOYSA-M sodium;decanoate Chemical compound [Na+].CCCCCCCCCC([O-])=O FIWQZURFGYXCEO-UHFFFAOYSA-M 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- HTPLIUHHIVJPGO-UHFFFAOYSA-K CCCCN1C=CN(C)C1.[B+3].[F-].[F-].[F-].F Chemical class CCCCN1C=CN(C)C1.[B+3].[F-].[F-].[F-].F HTPLIUHHIVJPGO-UHFFFAOYSA-K 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003870 salicylic acids Chemical class 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
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
本发明提出了一种烷基水杨酸盐及其制备方法。本发明的烷基水杨酸盐,其制备方法包括:将烷基水杨酸、溶剂、促进剂、中性油、碱金属和/或碱土金属的氧化物、水、助促进剂A进行中和反应,然后加入助促进剂B、通入二氧化碳进行碳酸化反应,收集产物。本发明的烷基水杨酸盐与磺酸盐的相容性好,除具有较好的清净性、抗氧化性、酸中和性外,还具有优异的分散性能、抗磨性、低温性能,是一种性能全面的清净剂。
Description
技术领域
本发明涉及烷基水杨酸盐,特别涉及烷基水杨酸盐的制备方法。
背景技术
烷基水杨酸钙是20世纪40年代初出现的润滑油清净剂之一,具有良好的高温清净性、酸中和能力、较高的热稳定性以及一定的低温分散能力和抗氧化抗腐蚀性能,不含硫、磷等元素,特别适合作为内燃机油的清净剂使用,目前关于烷基水杨酸钙合成的专利报道较多。
CN 1504451公开了一种烷基水杨酸钙制备的方法,该方法是以有机羧酸为原料,加入一定量的碱土金属氧化物或氢氧化物进行中和反应,待反应完后,再加入烷基水杨酸及氢氧化钙进行碳酸化反应。合成的产品粘度小、浊度小,与烷基苯磺酸盐相容性好。CN1199086、CN 1114348公开了一种相容性能改善及抗氧能力提高了的烷基水杨酸盐润滑油添加剂及制备方法,该方法使用烯基丁二酸酯可以解决水杨酸盐与磺酸盐复合沉淀的问题。
US 6599867公开了一种碱值大于200MgKOH/g、活性组分大于70%,金属比大于13、运动黏度小于1000mm2/s的烷基水杨酸盐的制备方法,该清净剂主要用于船用油中。EP0248465公开了制备烷基水杨酸盐的方法,其中包括两步碳酸化反应,得到的产品黏度较小。
但是,以上烷基水杨酸盐采用的烷基水杨酸均是通过柯尔贝-施密特(Kolbe-Schmidt)反应得到,以烷基酚为初始原料来制备烷基水杨酸钙共有五、六步反应,十余道工序,工艺十分复杂,生产成本过高、环保问题严重。
因此,现有的烷基水杨酸制备工艺也在不断改善。
CN 103508881公开了一种合成烷基水杨酸的方法,该方法包括把碳数为4-50的烯烃与水杨酸混合,在芳基磺酸催化作用下于50℃-160℃下进行烷基化反应。该方法采用芳基磺酸为催化剂,转化率可达到60%-95%,催化剂对设备无腐蚀作用,而且可以循环使用。CN 103508882公开了一种制备烷基水杨酸的方法,该方法包括把碳数为6~50的烯烃与水杨酸混合,在甲基磺酸和98%浓硫酸的混合酸催化作用下于80℃-150℃下进行烷基化反应,转化率可达到60%~80%。CN 1708470公开了一种制备烷基水杨酸的方法,该方法包括在作为催化剂的全氟烷基磺酸、烷基磺酸或酸性粘土的存在下于高温下使水杨酸与具有至少四个碳原子的烯烃反应。US 7045654公开了一种烷基水杨酸的制备工艺,采用至少4个碳原子的烯烃和水杨酸在高温下反应,采用的催化剂是全氟磺酸反应,或者是酸性白土为催化剂。EP 0771782公开了一种烷基水杨酸的制备方法,该方法采用硫酸为催化剂、至少6个碳原子烯烃为原料来制备烷基水杨酸。US 5434293公开了一种烷基水杨酸的制备方法,该方法采用固体酸为催化剂,同时采用等摩尔的水杨酸甲酯和烯烃进行烷基化。
发明内容
本发明提出了一种烷基水杨酸盐及其制备方法。
本发明的烷基水杨酸盐,其制备方法包括:将烷基水杨酸、溶剂、促进剂、中性油、碱金属和/或碱土金属的氧化物、水、助促进剂A进行中和反应,然后加入助促进剂B、通入二氧化碳进行碳酸化反应,收集产物。
所述烷基水杨酸的制备方法是:将α-烯烃、水杨酸和/或水杨酸酯在催化剂作用下进行烷基化反应,收集产物;所述催化剂是将离子液体、多聚磷酸和有机酸盐在30~100℃混合1~12h而得。
所述的α-烯烃为C10-C30的α-烯烃,优选C12-C24的α-烯烃,最优选C14-C20的α-烯烃。
所述的水杨酸酯是C1-C4的水杨酸酯,优选C1-C2的水杨酸酯,最优选水杨酸甲酯。
所述的水杨酸和/或水杨酸酯与α-烯烃的摩尔比为1~2:1,优选1~1.6:1,最优选1.1~1.3:1。
所述离子液体的阳离子为烷基咪唑或烷基吡啶,所述离子液体的阴离子为四氟硼酸根、三氟甲基磺酸根、六氟磷酸根、对甲苯磺酸根、硝酸根、高氯酸根、甲磺酸根、草酸根和硫氢酸根中的一种。
所述烷基咪唑的结构为:
其中的R1、R2分别独立地选自C1-C6的烷基,优选C1-C4的烷基。
所述烷基吡啶的结构为:
其中的R为C1-C6的烷基,优选C1-C4的烷基。
所述四氟硼酸根、三氟甲基磺酸根、六氟磷酸根、对甲苯磺酸根、硝酸根、高氯酸根、甲磺酸根、草酸根和硫氢酸根的结构依次为:
所述离子液体可以选用烷基咪唑四氟硼酸盐、烷基咪唑三氟甲基磺酸盐、烷基咪唑六氟磷酸、烷基咪唑硫氢酸盐、烷基吡啶四氟硼酸盐、烷基吡啶三氟甲基磺酸盐、烷基吡啶六氟磷酸和烷基吡啶六氢酸盐中的一种或多种。
所述多聚磷酸的结构为:Hn+2PnO3n+1,其中n为大于等于1的正整数,优选1-3的正整数。
所述多聚磷酸可以选用磷酸(H3PO4)、焦磷酸(H4P2O7)和三聚磷酸(H5P3O10)中的一种或多种。
所述有机酸盐优选有机羧酸的金属盐和/或有机磺酸的金属盐。所述的有机羧酸优选C2-C18的脂肪酸,最优选C3-C15的脂肪酸。所述的有机磺酸优选C6-C18的磺酸或带有C6-C18烷基的苯磺酸,最优选带有C8-C15烷基的苯磺酸。所述的金属是碱金属和/或碱土金属,例如锂、钠、钾、钙、镁和钡中的一种或多种,优选钠和/或钙。
所述催化剂是将离子液体、多聚磷酸和有机酸盐在30-100℃混合1-12h而得,其中所述离子液体、多聚磷酸和有机酸盐之间的质量比为100:5~30:5~20,优选100:10~25:5~15。
所述催化剂的加入量是α-烯烃、水杨酸和/或水杨酸酯的总质量的1%-100%,优选2%-50%,最优选3%-10%。
所述烷基化反应的温度为50~250℃,优选80~200℃,最优选100~160℃。
所述烷基化反应的时间为1~16小时,优选2~12小时,最优选3~8小时。
本发明所述碱金属和/或碱土金属的氧化物可以选用氧化钠、氧化锂、氧化钙、氧化镁和氧化钡中的一种或多种,优选氧化钠、氧化锂、氧化钙和氧化镁中的一种或多种,最优选氧化钙。
本发明所述溶剂可以是烷烃,也可以是芳香烃,优选馏程在60~180℃的直馏汽油、正辛烷、苯、甲苯和二甲苯中的一种或多种。
本发明所述中性油优选100℃运动黏度为2~6mm2/S的润滑基础油,例如可以选用100SN、150SN润滑油老三套工艺处理油和100N、150N加氢精制油中的一种或多种。
本发明所述的促进剂为C1~C4醇,优选为甲醇、乙醇、丙醇、丁醇和乙二醇中的一种或多种。所述促进剂可以作为无机相和有机相的载体,使得反应混合物中气、液、固三相之间的传质速率更快,油相和水相混合均匀,使反应易于进行。
本发明所述的助促进剂A为C4-C10的脂肪族伯胺、氨水和氯化钙中的一种或多种。
本发明所述的助促进剂B为聚甲基丙烯酸酯和/或聚丙烯酸酯,优选甲基丙烯酸C1~C25烷基酯的共聚物和/或丙烯酸C1~C25烷基酯的共聚物。
在本发明的烷基水杨酸盐的制备方法中,烷基水杨酸的用量为100份;促进剂的用量为20~200份,优选为40~100份;溶剂的用量为200~800份,优选为100~300份;中性油的用量为50~300份,优选为80~150份;碱金属和/或碱土金属的氧化物的用量为15~150份,优选为15~100份;水的用量为10~50份,优选为20~40份;助促进剂A的用量为2~50份,优选为5~50份;助促进剂B的用量为1~50份,优选为1~30份。
在本发明的烷基水杨酸盐的制备方法中,所述中和反应的温度为40~60℃,优选为45~55℃,反应时间优选20~60min。
在本发明的烷基水杨酸盐的制备方法中,所述二氧化碳的通入量为理论值的60%~140%,所述二氧化碳通入量的理论值是:与烷基水杨酸反应后剩余的碱金属和/或碱土金属的氧化物再与二氧化碳完全发生反应的量;所述碳酸化反应的温度是40~60℃,优选为45~55℃,反应时间优选30~100min。
本发明的烷基水杨酸盐与磺酸盐的相容性好,除具有较好的清净性、抗氧化性、酸中和性外,还具有优异的分散性能、抗磨性、低温性能,是一种性能全面的清净剂。
具体实施方式
以下通过实施例进一步说明本发明,而不是对本发明进行限制。
除非特别说明,以下提到的百分比均为质量百分比。
原料来源:
N-甲基咪唑,1-溴代正丁烷,均为分析纯,购自Acros公司;
乙酸乙酯,NaBF4,二氯甲烷,焦磷酸,偏磷酸,三聚磷酸,NaHSO4,吡啶,三氟甲基磺酸,石油醚,十二烷基苯磺酸钠,癸酸钠,水杨酸,水杨酸甲酯,C16α-烯烃,氨水,甲醇,乙二胺,氯化钙均为分析纯,购自国药集团北京化学试剂公司;
十二烷基苯磺酸钙,采用十二烷基苯磺酸钠通过复分解反应得到;
120号溶剂汽油,150SN基础油,购自中国石化燕山石化公司;氧化钙,纯度≥99.5%,江苏常熟氧化钙厂。
催化剂制备实施例1
1-甲基-3-丁基咪唑四氟化硼盐-偏磷酸-十二烷基苯磺酸钠催化剂IL-1的合成
在三口烧瓶中加入1mol N-甲基咪唑、1.05mol 1-溴代正丁烷,通入N2吹扫20mim后,开启搅拌并加热至85℃维持30~36h。反应结束后静置冷却至室温,溶液下层为淡黄色,上层为未反应的原料。倾去上层液体,将3倍体积的乙酸乙酯加入到下层液体中清洗,然后分离出乙酸乙酯,以除去未反应的原料。洗完后,在70℃干燥24h,得到淡黄色粘稠的1-甲基-3-丁基咪唑溴盐。
将得到的1-甲基-3-丁基咪唑溴盐溶解于二氯甲烷中,在其中加入NaBF4含量为1mol的水溶液,常温下搅拌反应24h。反应完毕,将二氯甲烷相用水少量多次洗涤,然后利用旋转蒸发仪除去二氯甲烷,真空干燥,得到离子液体1-甲基-3-丁基咪唑四氟化硼盐。
取上述合成的1-甲基-3-丁基咪唑四氟化硼盐100克,加入到三口烧瓶中,加入10克偏磷酸,7克十二烷基苯磺酸钠,升温到75℃,搅拌3小时,形成黄色粘稠液体,即为1-甲基-3-丁基咪唑四氟化硼盐-偏磷酸-十二烷基苯磺酸钠催化剂,记为IL-1。
催化剂制备实施例2
1-甲基-3-丁基咪唑硫氢酸盐-三聚磷酸-癸酸钠催化剂IL-2的合成
在三口烧瓶中加入1mol N-甲基咪唑、1.05mol 1-溴代正丁烷,通入N2吹扫20mim后,开启搅拌并加热至85℃维持30~36h。反应结束后静置冷却至室温,溶液下层为淡黄色,上层为未反应的原料。倾去上层液体,将3倍体积的乙酸乙酯加入到下层液体中清洗,然后分离出乙酸乙酯,以除去未反应的原料。洗完后,在70℃干燥24h,得到淡黄色粘稠的1-甲基-3-丁基咪唑溴盐。
将得到的1-甲基-3-丁基咪唑溴盐溶解于甲醇中,在其中加入1mol NaHSO4,常温下搅拌反应24h。然后抽滤,过滤后的清液转去甲醇,真空干燥,得到离子液体1-甲基-3-丁基咪唑硫氢酸盐。
取上述合成的1-甲基-3-丁基咪唑硫氢酸盐100克,加入到三口烧瓶中,加入12克三聚磷酸,8克癸酸钠升温到80℃,搅拌3小时,此时形成了黄色的粘稠液体,即1-甲基-3-丁基咪唑硫氢酸盐-三聚磷酸-癸钨酸催化剂,记为IL-2。
制备烷基水杨酸的实施例3
IL-1催化的水杨酸烷基化反应
在500mL三口烧瓶中加入20克催化剂IL-1、100克C16α-烯烃(Mn=224.4,0.446摩尔)、70.78克水杨酸(Mn=138.12,0.512摩尔),通入氮气,开启搅拌,加热,控制温度在140℃-142℃之间,反应5小时。
反应结束后,将三口烧瓶降温,当物料降温至40℃以下时,停止搅拌,加入150克120号溶剂汽油。将三口烧瓶中的物料取出,置于分液漏斗中分层,收集上层的油相,下层的离子液体可以重复使用。在油相中加入300克蒸馏水洗涤三次,脱除油相中未反应的水杨酸,并用无水硫酸镁干燥油相,最后得到深褐色的烷基水杨酸A。
用气相色谱外标法分析油相中的剩余α-烯烃的含量,计算后发现,烷基水杨酸A的转化率为90.2%,产物烷基水杨酸A的酸值为63.2mgKOH/g(SH/T0092石油酸检验法)。
制备烷基水杨酸酯的实施例4
IL-2催化的水杨酸酯烷基化反应
在具有温控、加热、搅拌的500mL三口烧瓶中加入26克催化剂IL-2、100克C14-C18α-烯烃(平均Mn=224.4,0.446摩尔)、65.61克水杨酸甲酯(Mn=154.12,0.535摩尔),通入氮气,开启搅拌,加热,控制温度在145℃-147℃之间,反应6小时。
反应结束后,将三口烧瓶降温,当物料降温至40℃以下时,停止搅拌,加入140克90-120℃石油醚。将三口烧瓶中的物料取出,置于分液漏斗中分层,收集上层的油相,下层的离子液体可以重复使用。在油相中加入300克蒸馏水洗涤三次,脱除油相中未反应的水杨酸,并用无水硫酸镁干燥油相,最后得到深褐色的烷基水杨酸酯B。
用气相色谱外标法分析油相中的剩余α-烯烃的含量,计算后发现,烷基水杨酸酯B的转化率为93.1%,产物烷基水杨酸B的羟值为65.1mgKOH/g(GB/T 7383方法)。
实施5聚甲基丙烯酸酯PMA1的合成
在三口烧瓶中,加入40克基础油150SN(中国石化燕山石化生产,100℃运动粘度为5.7mm2/s),15克甲基丙烯酸癸酯,5克甲基丙烯酸甲酯,30克甲基丙烯酸十四醇酯,10克甲基丙烯酸十二醇酯,加入0.08克偶氮二异丁腈,引入氮气保护反应物,打开搅拌并升温至75℃,此时观察反应物有明显的放热,控制反应温度为90℃,预聚反应2小时,物料明显变粘稠,再加入0.05克偶氮二异丁腈,逐渐升温至105℃进行共聚反应5小时,得到浅黄色的粘稠液体。在氮气保护下,将反应后物料降至25℃,得到甲基丙烯酸甲酯、甲基丙烯酸癸酯、甲基丙烯酸十二醇酯、甲基丙烯酸十四醇酯的四元共聚物,为本发明所述的润滑油粘度指数改进剂PMA1。在所得的共聚物中,各聚合单体含量分别为:甲基丙烯酸甲酯8.3质量%、甲基丙烯酸癸酯25质量%、甲基丙烯酸十二醇酯16.7质量%、甲基丙烯酸十四醇酯50质量%,其Mn为25280。
实施例6高碱值烷基水杨酸钙Ca-1的合成
在带有电动机搅拌器及冷凝管的500毫升三口烧瓶中加入烷基水杨酸A100克,120号溶剂汽油250毫升,甲醇25克,蒸馏水6克,150SN中性油50克(中国石化燕山石化公司生产),氢氧化铵6克,氧化钙30克,聚甲基丙烯酸酯(PMA1)5克,控制反应温度在45~50℃,中和反应30min后,通入二氧化碳,通气速率在0.062L/min之间,通入量达到理论值(10.74L)的90%时,停止通气,然后升温到120℃脱醇、水。得到的物料中加入100毫升汽油,然后放入医用离心机中,以转速4000rpm离心,将离心后的闪蒸物放入带有减压设施的蒸馏瓶中,首先升温到120℃常压蒸馏,然后给系统进行减压蒸馏,最后得到棕褐色的粘稠的151克添加剂。产品的碱值为298mgKOH/g,浊度为72JTU,产品运动黏度为62.3mm2/s。
实施例7中碱值烷基水杨酸钙Ca-2的合成
在带有电动机搅拌器及冷凝管的500毫升三口烧瓶中加入烷基水杨酸A100克,120号溶剂汽油200毫升,甲醇25克,蒸馏水5克,150SN中性油75克(中国石化燕山石化公司生产),20%氯化钙5克,氧化钙21克,聚甲基丙烯酸酯(PMA1)4克,控制反应温度在45~50℃,中和反应30min后,通入二氧化碳,通气速率在0.062L/min之间,通入量达到理论值(7.12L)的90%时,停止通气,然后升温到120℃脱醇、水。得到的物料中加入100毫升汽油,然后放入医用离心机中,以转速4000rpm离心,将离心后的闪蒸物放入带有减压设施的蒸馏瓶中,首先升温到120℃常压蒸馏,然后给系统进行减压蒸馏,最后得到棕褐色的粘稠的156克添加剂。产品的碱值为172mgKOH/g,浊度为52JTU,产品运动黏度为46.2mm2/s。
实施例8高碱值烷基水杨酸钙Ca-3的合成
在带有电动机搅拌器及冷凝管的500毫升三口烧瓶中加入烷基水杨酸酯B100克,120号溶剂汽油260毫升,甲醇30克,蒸馏水3克,150SN中性油80克(中国石化燕山石化公司生产),乙二胺6克,氢氧化钙45克,聚甲基丙烯酸酯(PMA1)6克,控制反应温度在45~50℃,中和反应30min后,通入二氧化碳,通气速率在0.062L/min之间,通入量达到理论值的90%时,停止通气,然后升温到120℃脱醇、水。得到的物料中加入100毫升汽油,然后放入医用离心机中,以转速4000rpm离心,将离心后的闪蒸物放入带有减压设施的蒸馏瓶中,首先升温到120℃常压蒸馏,然后给系统进行减压蒸馏,最后得到棕褐色的粘稠的185克添加剂。产品的碱值为296mgKOH/g,浊度为63JTU,产品运动黏度为77.1mm2/s。
对比例1用传统烷基水杨酸合成烷基水杨酸钙Ca-4
在带有电动机搅拌器及冷凝管的500毫升三口烧瓶中加入传统的烷基水杨酸100克(采用K-B工艺合成,购自兰州路博润添加剂厂,酸值65.3mgKOH/g),120号溶剂汽油250毫升,甲醇25克,蒸馏水6克,150SN中性油50克(中国石化燕山石化公司生产),氢氧化铵6克,氧化钙30克,聚甲基丙烯酸酯PMA15克,控制反应温度在45~50℃,中和反应30min后,通入二氧化碳,通气速率在0.062L/min之间,通入量达到理论值的90%时,停止通气,然后升温到120℃脱醇、水。得到的物料中加入100毫升汽油,然后放入医用离心机中,以转速4000rpm离心,将离心后的闪蒸物放入带有减压设施的蒸馏瓶中,首先升温到120℃常压蒸馏,然后给系统进行减压蒸馏,最后得到棕褐色的粘稠的143克添加剂。产品的碱值为277mgKOH/g,浊度为83JTU,产品运动黏度为92.3mm2/s。
对比例2不采用助促进剂B合成烷基水杨酸钙Ca-5
在带有电动机搅拌器及冷凝管的500毫升三口烧瓶中加入传统的烷基水杨酸100克(采用K-B工艺合成,酸值65.3mgKOH/g),120号溶剂汽油250毫升,甲醇25克,蒸馏水6克,150SN中性油55克(中国石化燕山石化公司生产),氢氧化铵6克,氧化钙30克,控制反应温度在45~50℃,中和反应30min后,通入二氧化碳,通气速率在0.062L/min之间,通入量达到理论值的90%时,停止通气,然后升温到120℃脱醇、水。得到的物料中加入100毫升汽油,然后放入医用离心机中,以转速4000rpm离心,将离心后的闪蒸物放入带有减压设施的蒸馏瓶中,首先升温到120℃常压蒸馏,然后给系统进行减压蒸馏,最后得到棕褐色的粘稠的148克添加剂。产品的碱值=296mgKOH/g,浊度=53JTU,产品运动黏度为56.1mm2/s。
合成的烷基水杨酸盐的性能评价
分别将实施例6-8、对比例1-2的烷基水杨酸钙以5%的剂量调制于500SN基础油中,分别评定清净性、抗氧化性、与磺酸盐的相容性、分散性、低温性能、酸中和作用、抗磨性,测试结果见表1。
具体评定方法如下:
清净性试验:成焦试验,板温为320℃,油温为100℃,试验1h;成漆试验,板温为300℃,油温为150℃,试验4h。
PDSC氧化试验:升温速度为100℃/min,恒温60min,氧压3.5MPa。
酸中和速度试验:在10g碱值为5mgKOH/g的150SN润滑油溶液中,注入0.2mL 25%的硫酸溶液,通过秒表和U型管高度计算酸中和速度。
分散性试验:20mL试油加热恒温至120℃,滴加10μL试油到250℃已经磨制好的铁板上,测量试油在60s内扩散的直径。
SH/T0189润滑油抗磨损性能测定法(四球机法)。
GB/T 3535石油倾点测定法。
与磺酸盐的相容性/%:分别将上面制备的一种实施例或对比例的烷基水杨酸钙与市售的磺酸钙T106各以5%的加入量加入到150SN基础油中,调制成测试油样,将这些测试油样放入锥型管中,在100℃烘箱中贮存7天,记录生成沉淀的体积百分数。
表1烷基水杨酸盐的性能评价
由表1可以看出,采用本发明方法制备的烷基水杨酸盐具有较好的清净性、抗氧化性、酸中和性、分散性、低温性能,与磺酸盐相容性好,是一种性能全面的清净剂。
Claims (20)
1.一种烷基水杨酸盐,其制备方法包括:将烷基水杨酸、溶剂、促进剂、中性油、碱金属和/或碱土金属的氧化物、水、助促进剂A进行中和反应,然后加入助促进剂B、通入二氧化碳进行碳酸化反应,收集产物。
2.按照权利要求1所述的烷基水杨酸盐,其特征在于,所述烷基水杨酸的制备方法是:将α-烯烃、水杨酸和/或水杨酸酯在催化剂作用下进行烷基化反应,收集产物;所述催化剂是将离子液体、多聚磷酸和有机酸盐在30~100℃混合1~12h而得。
3.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述的α-烯烃为C10-C30的α-烯烃,所述的水杨酸酯是C1-C4的水杨酸酯。
4.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述的水杨酸和/或水杨酸酯与α-烯烃的摩尔比为1~2:1。
5.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述离子液体的阳离子为烷基咪唑或烷基吡啶,所述离子液体的阴离子为四氟硼酸根、三氟甲基磺酸根、六氟磷酸根、对甲苯磺酸根、硝酸根、高氯酸根、甲磺酸根、草酸根和硫氢酸根中的一种。
6.按照权利要求5所述的烷基水杨酸盐,其特征在于,所述烷基咪唑的结构为:
其中的R1、R2分别独立地选自C1-C6的烷基;
所述烷基吡啶的结构为:
其中的R为C1-C6的烷基。
7.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述离子液体选自烷基咪唑四氟硼酸盐、烷基咪唑三氟甲基磺酸盐、烷基咪唑六氟磷酸、烷基咪唑硫氢酸盐、烷基吡啶四氟硼酸盐、烷基吡啶三氟甲基磺酸盐、烷基吡啶六氟磷酸和烷基吡啶六氢酸盐中的一种或多种。
8.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述多聚磷酸的结构为:Hn+ 2PnO3n+1,其中n为大于等于1的正整数。
9.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述多聚磷酸选自磷酸、焦磷酸和三聚磷酸中的一种或多种。
10.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述有机酸盐选自有机羧酸的金属盐和/或有机磺酸的金属盐。
11.按照权利要求10所述的烷基水杨酸盐,其特征在于,所述的有机羧酸为C2-C18的脂肪酸,所述的有机磺酸为C6-C18的磺酸或带有C6-C18烷基的苯磺酸,所述的金属是碱金属和/或碱土金属。
12.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述离子液体、多聚磷酸和有机酸盐之间的质量比为100:5~30:5~20。
13.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述催化剂的加入量是α-烯烃、水杨酸和/或水杨酸酯的总质量的1%~100%。
14.按照权利要求2所述的烷基水杨酸盐,其特征在于,所述烷基化反应的温度为50~250℃,所述烷基化反应的时间为1~16小时。
15.按照权利要求1所述的烷基水杨酸盐,其特征在于,所述的促进剂为C1~C4醇,所述的助促进剂A为C4-C10的脂肪族伯胺、氨水和氯化钙中的一种或多种,所述的助促进剂B为聚甲基丙烯酸酯和/或聚丙烯酸酯。
16.按照权利要求1所述的烷基水杨酸盐,其特征在于,所述烷基水杨酸的用量为100份;所述促进剂的用量为20~200份;所述溶剂的用量为200~800份;所述中性油的用量为50~300份;所述碱金属和/或碱土金属的氧化物的用量为15~150份;所述水的用量为10~50份;所述助促进剂A的用量为2~50份;所述助促进剂B的用量为1~50份。
17.按照权利要求1所述的烷基水杨酸盐,其特征在于,所述中和反应的温度为40~60℃。
18.按照权利要求1所述的烷基水杨酸盐,其特征在于,所述二氧化碳的通入量为理论值的60%~140%。
19.按照权利要求1所述的烷基水杨酸盐,其特征在于,所述碳酸化反应的温度是40~60℃。
20.一种烷基水杨酸盐的制备方法,包括:将烷基水杨酸、溶剂、促进剂、中性油、碱金属和/或碱土金属的氧化物、水、助促进剂A进行中和反应,然后加入助促进剂B、通入二氧化碳进行碳酸化反应,收集产物。
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