CN117917417A - Boron-containing organic matter and preparation method and application thereof - Google Patents
Boron-containing organic matter and preparation method and application thereof Download PDFInfo
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 45
- 239000005416 organic matter Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 150000001875 compounds Chemical class 0.000 claims description 50
- 125000002947 alkylene group Chemical group 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 21
- 239000004327 boric acid Substances 0.000 claims description 21
- -1 ethylene, propylene Chemical group 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000010687 lubricating oil Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- MWEZYKWGRQWLKM-UHFFFAOYSA-N n,n-dihydroxyicosan-3-amine Chemical compound CCCCCCCCCCCCCCCCCC(CC)N(O)O MWEZYKWGRQWLKM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000004593 Epoxy Substances 0.000 description 27
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 23
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 21
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 21
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 21
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 239000002199 base oil Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229960000541 cetyl alcohol Drugs 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VLKQQIZFPCDLRZ-UHFFFAOYSA-N OO[S](=O)=O Chemical compound OO[S](=O)=O VLKQQIZFPCDLRZ-UHFFFAOYSA-N 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003831 antifriction material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- FFKSQDWRKALCJY-UHFFFAOYSA-N 2-(hexadecylamino)ethane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCNCC(O)O FFKSQDWRKALCJY-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 101100407037 Oryza sativa subsp. japonica PAO6 gene Proteins 0.000 description 1
- 101150092791 PAO4 gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004237 preparative chromatography Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a boron-containing organic matter, a preparation method and application thereof, wherein the structure of the boron-containing organic matter is shown as a formula (I):
Description
Technical Field
The invention relates to a boron-containing organic matter, in particular to a sulfur-free and phosphorus-free boron-containing organic matter, a preparation method and application thereof.
Background
With the development of mechanical equipment towards the directions of reducing volume, reducing mass, increasing power, improving efficiency, increasing reliability and being environment-friendly, more severe requirements are also put on the performance of the lubricating oil used by the mechanical equipment, and besides good tribological performance, the mechanical equipment also has excellent thermal oxidation stability so as to meet the requirements of energy conservation, environmental protection and long service life, thereby prolonging the service cycle of the oil product and reducing the maintenance cost of the mechanical equipment.
The organic borate has the characteristics of good bearing capacity and lubricating property, no toxicity, no odor, good environmental adaptability and the like, but has the defects of easy hydrolysis and poor antioxidant property. CN101735255A discloses a boron-containing nitride prepared by the reaction of oleic acid, triethanolamine, tributyl borate, butanol or ethanolamine, which has better antiwear and antifriction effects when added into base oil such as liquid paraffin. CN102936527a discloses an organoboron antifriction agent prepared by reacting boric acid, natural grease and organic alcohol amine, which has better antifriction property and oil solubility. CN106366106a discloses a nitrogen-containing borate lubricating oil additive prepared by reacting boric acid, fatty alcohol and ethanolamine, which has better antiwear and antifriction properties and hydrolytic resistance. CN112410096a discloses a nitrogen-containing borate lubricant additive prepared by reacting boric acid, thiol and aromatic diethanolamide, which can protect equipment machinery, increase antifriction performance of lubricant and reduce energy consumption.
The prior art well meets the performance requirements of lubricating oil on wear resistance and antifriction, but does not help to improve the antioxidant performance of the lubricating oil. The sulfur-free phosphorus and metal-free additive capable of simultaneously meeting the performances of oxidation resistance, wear resistance and antifriction conforms to the development trend of multifunction and environmental protection of the additive, can reduce the variety and the dosage of the additive in a formula system, avoid the countermeasure effect among different additives, effectively improve the formula applicability and is favorable for meeting the requirements of energy conservation and environmental protection.
Disclosure of Invention
The invention provides a boron-containing organic matter, a preparation method and application thereof, wherein the boron-containing organic matter has excellent oxidation resistance, wear resistance and antifriction performance. The present invention includes the following.
In a first aspect, the present invention provides a boron-containing organic compound.
The structure of the boron-containing organic matter is shown as a formula (I):
In formula (I), y R groups are bonded to the benzene ring; y is selected from integers between 0 and 4; each R group is independently selected from H and C 1-4 straight or branched alkyl; n is an integer between 1 and 5; each R 1 is independently selected from C 1-10 straight or branched alkylene; r 2 in the n repeating units are the same or different from each other and are each independently selected from a single bond and a C 1-10 straight or branched alkylene group; r 3 is selected from H and C 1-10 straight or branched alkyl; the A groups in the n repeating units are the same or different from each other and are each independently selected from the group represented by formula (II),
In the formula (II), each G group is independently selected from a group shown in the formula (III), a group shown in the formula (IV) and H, and one or two G groups in the formula (II) are selected from a group shown in the formula (III) and a group shown in the formula (IV);
In formula (III), each R 4 group is independently selected from the group consisting of a linear or branched alkyl group of C 5～C25, a group of formula (V),
The R 7 groups in formula (V) are selected from the group consisting of linear or branched alkylene groups of C 2～C5, the R 8 groups are each independently selected from the group consisting of linear or branched alkylene groups of C 2～C20, and m is an integer between 0 and 5;
The R 5 group in the formula (IV) is selected from C 2～C5 straight-chain or branched-chain alkylene, and the R 6 group is selected from H, a group shown in the formula (V) and C 5～C25 straight-chain or branched-chain alkyl.
Preferably, in formula (I), y is selected from integers between 1 and 3, the R group is selected from tert-butyl, the R group is located in the ortho or para position to the hydroxyl group on the benzene ring; n is an integer between 1 and 3; each R 1 is independently selected from C 1-8 straight or branched alkylene; r 2 in the n repeating units are each independently selected from a single bond and a C 1-4 straight or branched alkylene group; r 3 is selected from H and C 1-4 straight or branched alkyl; in formula (III), each R 4 group is independently selected from the group consisting of a linear or branched alkyl group of C 10～C20, a group of formula (V); the R 5 group in the formula (IV) is selected from ethylene and propylene, and the R 6 group is selected from H, a group shown in the formula (V) and a linear or branched alkyl of C 10～C20; the R 7 groups in formula (V) are selected from ethylene, propylene, and the R 8 groups are each independently selected from C 2～C18 linear or branched alkylene, m being 0, 1,2, 3 or 4.
More preferably, in formula (I) according to the invention, y is selected from 1, the R group is selected from tert-butyl, the R group is located in the ortho position to the hydroxyl group on the benzene ring, the R 1 group is para to the hydroxyl group.
Examples of the boron-containing organic substance that may be cited according to the present invention include one or more of the following structural compounds:
The boron-containing organic matter of the invention has excellent oxidation resistance and wear resistance and antifriction performance.
In a second aspect, the present invention provides a method for preparing a boron-containing organic compound.
The preparation method of the boron-containing organic matter comprises the following steps:
(1) Reacting a compound represented by formula (X) with a peroxide;
In formula (X), y R groups are bonded to the benzene ring; y is selected from integers between 0 and 4; each R group is independently selected from H and C 1-4 straight or branched alkyl; n is an integer between 1 and 5; each R 1 is independently selected from C 1-10 straight or branched alkylene; r 2 in the n repeating units are the same or different from each other and are each independently selected from a single bond and a C 1-10 straight or branched alkylene group; r 3 is selected from H and C 1-10 straight or branched alkyl;
(2) Subjecting the reaction product of step (1) to hydrolysis;
(3) Esterifying a compound shown in a formula (Y) and/or a compound shown in a formula (Z) with a hydrolysis reaction product of the step (2), and collecting the product;
In the formula (Y), each R 4 group is independently selected from a linear or branched alkyl group of C 5～C25, a group represented by the formula (V),
The R 7 groups in formula (V) are selected from the group consisting of linear or branched alkylene groups of C 2～C5, the R 8 groups are each independently selected from the group consisting of linear or branched alkylene groups of C 2～C20, and m is an integer between 0 and 5;
The R 5 group in the formula (Z) is selected from the group consisting of C 2～C5 straight-chain or branched-chain alkylene, and the R 6 group is selected from the group consisting of H, a group represented by the formula (V), and C 5～C25 straight-chain or branched-chain alkyl.
According to the present invention, in step (1), the molar ratio between the compound represented by formula (X) and the peroxide is preferably 1:0.5 to 10, more preferably 1:2 to 3; in step (3), the molar ratio between the hydrolysis reaction product of step (2) and the compound represented by formula (Y) and/or the compound represented by formula (Z) is preferably 1:0.5 to 15, more preferably 1:2 to 8.
According to the present invention, the reaction temperature in step (1) is preferably 40 to 100 ℃, more preferably 60 to 80 ℃; the reaction temperature in the step (2) is preferably 50 to 150 ℃, more preferably 70 to 100 ℃; the reaction temperature in the step (3) is preferably 80 to 200℃and more preferably 110 to 160 ℃.
According to the present invention, the longer the reaction time of step (1), step (2) and step (3), the better, the reaction time of step (1) is preferably 1 to 10 hours, more preferably 3 to 5 hours; the reaction time in the step (2) is preferably 0.5 to 10 hours, more preferably 1 to 3 hours; the reaction time in the step (3) is preferably 1 to 10 hours, more preferably 3 to 6 hours.
According to the invention, in the step (1), a catalyst, preferably an acidic catalyst, for example, one or more of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid and titanium silicalite molecular sieve can be added, and the addition amount of the catalyst is preferably 0.01% -3% of the mass of the compound shown in the formula (X). After the end of the reaction in step (1), the catalyst may be removed by alkali washing and/or water washing.
According to the present invention, a catalyst may be added in the step (2), and the catalyst may be an acidic catalyst or a basic catalyst, for example, one of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, sodium hydroxide, and potassium hydroxide, preferably concentrated sulfuric acid, and the addition amount of the catalyst is preferably 0.5% to 10% of the sum of the mass of the compound represented by the formula (X) and the mass of the peroxide in the step (1). After the reaction of step (2), the catalyst may be removed by alkali washing (acid catalyst), acid washing (alkaline catalyst), and water washing.
According to the present invention, a catalyst may be added in the step (3), preferably an acidic catalyst, for example, one or more of concentrated sulfuric acid, zinc chloride, aluminum trichloride, benzenesulfonic acid and titanate esters may be selected, and the amount of the catalyst added is preferably 0.01% to 2% of the sum of the mass of the compound represented by the formula (Y) and/or the compound represented by the formula (Z) and the hydrolysis reaction product of the step (2). After the end of the reaction in step (3), the catalyst may be removed by alkali washing and/or water washing.
According to the invention, preferably, in formula (X), y is selected from integers ranging from 1 to 3, the R group is selected from tertiary butyl, the R group is located in the ortho or para position to the hydroxyl group on the benzene ring; n is an integer between 1 and 3; each R 1 is independently selected from C 1-8 straight or branched alkylene; r 2 in the n repeating units are each independently selected from a single bond and a C 1-4 straight or branched alkylene group; r 3 is selected from H and C 1-4 straight or branched alkyl; in formula (Y), each R 4 group is independently selected from the group consisting of a linear or branched alkyl group of C 10～C20, a group represented by formula (V); the R 5 group in the formula (Z) is selected from ethylene and propylene, and the R 6 group is selected from H, a group shown in the formula (V) and a linear or branched alkyl of C 10～C20; the R 7 groups in formula (V) are selected from ethylene, propylene, and the R 8 groups are each independently selected from C 2～C18 linear or branched alkylene, m being 0, 1,2, 3 or 4.
More preferably, in formula (X), y is selected from the group consisting of 1, R is selected from the group consisting of tert-butyl, R is located in the ortho position to the hydroxyl group on the benzene ring and in the para position to the R 1 group.
According to the present invention, in step (1), the compound represented by formula (X) may be selected from cardanol, alkylated cardanol, which may be obtained by reacting cardanol with an alkylating agent, for example, tert-butylated cardanol may be obtained by reacting cardanol with tert-butylchloride.
According to the present invention, in the step (1), the peroxide is preferably one or more of hydrogen peroxide, peroxyformic acid, peroxyacetic acid, peroxysulfonic acid, m-chloroperoxybenzoic acid, t-butyl hydroperoxide, t-butyl peroxyacetate, methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide, more preferably one or more of hydrogen peroxide, peroxyformic acid, peroxyacetic acid and peroxysulfonic acid.
According to the present invention, in the step (3), the compound represented by the formula (Y) and/or the compound represented by the formula (Z) is produced by: reacting one or more of R 4 OH, a compound represented by formula (alpha) and a compound represented by formula (beta) with boric acid, and collecting a product;
The R 4 group is selected from the group consisting of linear or branched alkyl of C 5～C25; the R 7 groups in formula (alpha) are selected from the group consisting of linear or branched alkylene groups of C 2～C5, the R 8 groups are each independently selected from the group consisting of linear or branched alkylene groups of C 2～C20, and m is an integer between 0 and 5; the R 5 group in the formula (. Beta.) is selected from the group consisting of C 2～C5 straight-chain or branched alkylene groups, and the R 6 group is selected from the group consisting of H, a group represented by the formula (V) (as described above), and C 5～C25 straight-chain or branched alkyl groups.
According to the invention, preferably, the R 4 groups are each independently selected from the group consisting of linear or branched alkyl groups of C 10～C20; the R 5 group is selected from ethylene and propylene, and the R 6 group is selected from H, a group shown in a formula (V) (as described above) and a linear or branched alkyl group of C 10～C20; the R 7 groups are selected from ethylene, propylene, and the R 8 groups are each independently selected from C 2～C18 linear or branched alkylene, m is 0, 1, 2,3 or 4.
According to the invention, R 4 OH can be one or more of dodecanol, tetradecanol, hexadecanol and octadecanol.
According to the invention, the compounds of formula (α) may be selected from ethanolamine and/or N- (2-hydroxyethyl) ethylenediamine.
According to the present invention, the compound represented by the formula (β) may be one or more selected from diethanolamine, N-dihydroxyethyldodecamine, N-dihydroxyethylhexadecylamine and N, N-dihydroxyethyloctadecylamine.
According to the present invention, the molar ratio between one or more of R 4 OH, the compound represented by the formula (α) and the compound represented by the formula (β) as a whole and boric acid is preferably 0.5 to 5:1, more preferably 1.5 to 3:1, for example, may be 2:1.
According to the present invention, the temperature at which one or more of R 4 OH, the compound represented by the formula (α) and the compound represented by the formula (β) reacts with boric acid is preferably 80 to 200 ℃, more preferably 120 to 200 ℃; the reaction time is preferably 1 to 10 hours, more preferably 3 to 5 hours.
According to the present invention, a catalyst may be added to the reaction of boric acid with one or more of R 4 OH, the compound represented by formula (α) and the compound represented by formula (β), preferably an acidic catalyst, for example, one or more of concentrated sulfuric acid, zinc chloride, aluminum trichloride, benzenesulfonic acid and titanate may be selected, and the addition amount of the catalyst is preferably 0.5% to 10% of the sum of the mass of boric acid with one or more of R 4 OH, the compound represented by formula (α) and the compound represented by formula (β). After the end of the reaction, the catalyst may be removed by alkali washing and/or water washing.
According to the present invention, a solvent may be added to the reaction of boric acid with one or more of R 4 OH, the compound represented by formula (α) and the compound represented by formula (β). The solvent can be one or more of C 6-20 aromatic hydrocarbons (such as benzene, toluene, xylene and isopropylbenzene), C 6-10 alkane (such as normal hexane, cyclohexane and petroleum ether) and solvent gasoline. The solvent may be removed after the reaction is completed using a method well known to those skilled in the art, for example, the solvent is distilled off under normal pressure or reduced pressure.
According to the present invention, the reaction of one or more of R 4 OH, the compound represented by the formula (. Alpha.) and the compound represented by the formula (. Beta.) with boric acid may be carried out under the protection of an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include nitrogen and argon.
According to the invention, the steps (1), (2) and (3) may be carried out in the presence of a diluent and/or a solvent. According to the invention, the diluent can be one or more of API I, II, III, IV and V base oils, and common commercial products or marks comprise 150SN、200SN、350SN、500SN、650SN、150BS、HVI-100、HVI-150、HVI-200、HVI-350、HVI-400、HVI-500、HVI-150BS、PAO4、PAO6、PAO8、PAO10、 alkylbenzene, alkyl naphthalene and the like. The solvent can be one or more of C 6-20 aromatic hydrocarbons (such as benzene, toluene, xylene and isopropylbenzene), C 6-10 alkane (such as normal hexane, cyclohexane and petroleum ether) and solvent gasoline. The solvent may be removed after the reaction is completed using a method well known to those skilled in the art, for example, the solvent is distilled off under normal pressure or reduced pressure. The diluent and/or solvent may be added at any stage of the reaction step in an amount conventional in the art, and is not particularly limited.
According to the invention, it is evident that the steps (1), (2) and (3) can be performed under the protection of an inert gas atmosphere. Examples of the inert gas include nitrogen and argon, but are not particularly limited.
According to the present invention, by the aforementioned method for producing a boron-containing organic material, as a reaction product, a single boron-containing organic material can be produced, or a mixture of a plurality of boron-containing organic materials, or a mixture of one or more of the boron-containing organic materials and the aforementioned diluent (if used) can be produced. These reaction products are all contemplated by the present invention and the differences in their form of presence do not affect the achievement of the effects of the present invention. Accordingly, these reaction products are collectively referred to herein without distinction as boron-containing organics. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product or to further separate a boron-containing organic substance of a specific structure from the reaction product. Of course, this purification or isolation is preferred for further enhancement of the intended effect of the invention, but is not required for the invention. The purification or separation method may be, for example, a method of purifying or separating the reaction product by column chromatography or preparative chromatography.
The preparation method of the boron-containing organic matter has simple steps and high conversion rate in the reaction process.
In a third aspect, the present invention provides the use of a boron-containing organic compound according to the first aspect or a boron-containing organic compound prepared according to the preparation method of the second aspect.
The boron-containing organic matter of the first aspect or the boron-containing organic matter produced by the production method of the second aspect can be used as an antioxidant, antiwear agent, antifriction agent for lubricating oil.
Drawings
FIG. 1 is an infrared spectrum of the product of example 4, and FIG. 2 is a nuclear magnetism 1 H spectrum of the product of example 4.
Detailed Description
In this specification, the term "single bond" is sometimes used in the definition of a group. By "single bond" is meant that the group is absent. For example, assume the structural formula-CH 2-A-CH3, wherein the group a is defined as selected from single bonds and methyl. In view of this, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly reduced to-CH 2-CH3.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
The main raw materials used are as follows:
Cardanol, shanghai Material competition technology Co., ltd, industrial products
Zinc chloride, national medicine group chemical reagent Co., ltd., analytical grade
Concentrated sulfuric acid, national pharmaceutical group chemical reagent Co., ltd., analytical grade
Hydrogen peroxide (30%), national medicine group chemical reagent Co., ltd., analytical grade
Formic acid, national medicine group chemical reagent Co., ltd., analytical grade
Boric acid, national pharmaceutical group chemical reagent Co., ltd., chemical purity
Diethanolamine, national medicine group chemical reagent Co., ltd., chemical purity
Ethanolamine, a chemical reagent of national medicine group Co., ltd., chemical purity
N- (2-hydroxyethyl) ethylenediamine, national medicine group chemical reagent Co., ltd., chemical purity
Tert-butyl chloride, national medicine group chemical reagent Co., ltd., analytically pure
Antioxidant T501, xingpu, institute of petrochemistry and technology, industrial products
Antioxidant T512, xingpu, institute of petrochemistry and technology, industrial products
Cetyl alcohol, national medicine group chemical reagent Co., ltd., chemical purity
Tricresyl phosphate (TCP), national medicine group chemical reagent Co., ltd., chemical purity
Hydrogenated 150N base oil, china petrochemical lubricating oil Shanghai division, and industrial products
Polyol ester (trade name 5101), china petrochemical lubricating oil Chongqing division, industrial example 1 preparation of tert-butyl epoxy Cardanol
100G of cardanol, 8g of formic acid, 0.3g of sulfuric acid and 200g of hydrogen peroxide are taken and added into a three-neck flask with a mechanical stirring and reflux condenser and temperature control, and stirring and heating are started. The reaction temperature was maintained at 70℃and the reaction was carried out for 3 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. Filtering the reaction product, performing alkali washing with 5% KOH solution, washing with distilled water to neutrality, and distilling the organic phase under reduced pressure at 100Pa and 150 ℃ for 1h to remove water and unreacted raw materials to obtain the orange-red transparent liquid epoxidized cardanol.
35G of epoxidized cardanol is dissolved in 100ml of acetone, and the mixture is put into a 250ml three-neck reaction flask after dissolution, 0.9g of zinc chloride catalyst is added, and stirring and heating are started. The reaction temperature was maintained at 60℃and 9.5g of t-butyl chloride was slowly added dropwise to the reaction flask, followed by further reaction for 3 hours after completion of the dropwise addition. And cooling after the reaction is finished to obtain brownish red transparent liquid. Filtering the reaction product, performing alkali washing with 5% KOH solution, washing with distilled water to neutrality, and performing reduced pressure distillation at 1000Pa and 120 ℃ for 1h to remove solvent, water and unreacted raw materials to obtain brownish red viscous liquid tert-butyl epoxy cardanol.
An example reaction scheme of the above reaction is shown below.
EXAMPLE 2 hydrolysis of tert-butylated epoxy Cardanol
10G of tert-butyl epoxy cardanol, 1g of concentrated sulfuric acid, 20g of water and 100g of dimethylbenzene are taken and added into a three-neck flask with a mechanical stirring and reflux condenser, and the mixture is stirred, heated and reacted for 1h at 90 ℃. Cooling after the reaction is finished to obtain a brownish red transparent liquid, filtering the brownish red transparent liquid, performing alkali washing with a 5% KOH solution, then performing water washing with distilled water to neutrality, performing reduced pressure distillation on an organic phase for 1h at 100Pa and 150 ℃, and removing water and dimethylbenzene to obtain a hydrolysate of the tert-butyl epoxy cardanol.
Since tert-butylated epoxy cardanol is a mixture of tert-butylated epoxy cardanol such as mono-epoxy, di-epoxy and tri-epoxy, and the like, and a large number of reaction products are produced after hydrolysis reaction, the main reaction formulas of hydrolysis reaction using mono-epoxy tert-butylated epoxy cardanol as a raw material are typically exemplified as follows.
EXAMPLE 3 preparation of the Compound (boric acid half ester) of formula (Y)
14G of boric acid and 40g of cetyl alcohol are put into a flask with a water diversion reflux device and a thermometer, stirred and heated, and reacted for 4 hours at 180 ℃, and water generated in the reaction is removed in the reaction process. Cooling after the reaction is finished to obtain yellowish transparent liquid, washing with distilled water to be neutral, decompressing and distilling an organic phase for 1h at the temperature of 100Pa and 150 ℃ to remove water and unreacted raw materials to obtain boric acid half-ester. An example reaction scheme is shown below.
Example 4
11G of the product of example 2, 32g of the product of example 3 and 50g of xylene are taken and placed in a flask with a water diversion reflux device and a thermometer, and the mixture is heated and stirred, and the reflux reaction is carried out for 5 hours at 140 ℃, and water generated in the reaction is removed during the reaction. Cooling after the reaction is finished to obtain brownish red transparent liquid, washing the brownish red transparent liquid with distilled water to be neutral, decompressing and distilling an organic phase for 1h at the temperature of 100Pa and 150 ℃ to remove water and dimethylbenzene, thereby obtaining the boron-containing organic substance W-01 with the reaction conversion rate of 90.2 percent.
Since the reaction raw materials contain a mixture of hydrolysis products of tert-butyl epoxy cardanol such as mono-epoxy, di-epoxy and tri-epoxy, and the like, the reaction products are more, the main reaction formulas in which the hydrolysis products of mono-epoxy tert-butyl epoxy cardanol are used as raw materials are typically exemplified as follows.
The product prepared in example 4 was subjected to infrared spectrum and nuclear magnetism 1 H spectrum analysis, the infrared spectrum is shown in FIG. 1, the analysis result is shown in Table 1, the nuclear magnetism 1 H spectrum is shown in FIG. 2, and the analysis result is shown in Table 2.
TABLE 1 Infrared analysis results of the products
As shown in the analysis results of Table 1, characteristic peaks such as C-OH stretching vibration peak, benzene ring skeleton stretching vibration peak and B-O stretching vibration peak exist in the product, and it can be shown that the synthesized product is the target compound.
TABLE 2 Nuclear magnetic 1 H Spectrum analysis results of the products
As shown by the analysis results in Table 2, the characteristic peaks such as proton peak on B-O-CH 2, phenolic hydroxyl proton peak and proton peak on benzene ring exist in the product, which can indicate that the synthesized product is the target compound.
Example 5
6G of boric acid, 10.5g of diethanolamine and 100g of dimethylbenzene are taken and put into a flask with a water diversion reflux device and a thermometer, and the mixture is stirred, heated and reacted for 3 hours at 120 ℃, and water generated in the reaction is removed in the reaction process. After the reaction, cooling to obtain yellowish transparent liquid, continuously adding 8g of the product of the example 2 into a reaction bottle, starting heating and stirring, and refluxing at 140 ℃ for 6 hours, wherein water generated in the reaction is removed in the reaction process. Cooling after the reaction is finished to obtain brownish red transparent liquid, washing the brownish red transparent liquid with distilled water to be neutral, decompressing and distilling an organic phase for 1h at the temperature of 100Pa and 150 ℃ to remove water and dimethylbenzene, thereby obtaining the boron-containing organic substance W-02 with the reaction conversion rate of 91.3 percent.
Since the reaction raw materials contain a mixture of hydrolysis products of tert-butyl epoxy cardanol such as mono-epoxy, di-epoxy and tri-epoxy, and the like, the reaction products are more, the main reaction formulas in which the hydrolysis products of mono-epoxy tert-butyl epoxy cardanol are used as raw materials are typically exemplified as follows.
Example 6
6G of boric acid, 24.5g of cetyl alcohol, 10.5g N- (2-hydroxyethyl) ethylenediamine and 100g of dimethylbenzene are put into a flask with a water diversion reflux device and a thermometer, stirred, heated and reacted for 5 hours at 160 ℃, and water generated in the reaction is removed in the reaction process. After the reaction is finished, cooling to obtain yellowish transparent liquid, continuously adding 12g of the product of the example 2 into a reaction bottle, starting heating and stirring, and carrying out reflux reaction for 5 hours at 140 ℃, wherein water generated in the reaction is removed in the reaction process. Cooling after the reaction is finished to obtain brownish red transparent liquid, washing the brownish red transparent liquid with distilled water to be neutral, decompressing and distilling an organic phase for 1h at the temperature of 100Pa and 150 ℃ to remove water and dimethylbenzene, thereby obtaining the boron-containing organic substance W-03 with the reaction conversion rate of 91.1%.
Since the reaction raw materials contain a mixture of hydrolysis products of tert-butyl epoxy cardanol such as mono-epoxy, di-epoxy and tri-epoxy, and the like, the reaction products are more, the main reaction formulas in which the hydrolysis products of mono-epoxy tert-butyl epoxy cardanol are used as raw materials are typically exemplified as follows.
Comparative example 1
36.3G of cetyl alcohol, 18.3g of ethanolamine, 6.2g of boric acid and 90g of toluene solvent are added into a reaction vessel, stirred and heated, reacted for 6 hours at 145 ℃, and finally filtered, distilled to remove the solvent and unreacted ethanolamine, thus obtaining the comparative boron-containing organic substance V-01.
Comparative example 2
6G of boric acid, 6g of butanol, 10.5g N- (2-hydroxyethyl) ethylenediamine and 100g of dimethylbenzene are put into a flask with a water diversion reflux device and a thermometer, stirred, heated and reacted for 5 hours at 160 ℃, and water generated in the reaction is removed in the reaction process. After the reaction is finished, cooling to obtain yellowish transparent liquid, continuously adding 12g of the product of the example 2 into a reaction bottle, starting heating and stirring, and carrying out reflux reaction for 5 hours at 140 ℃, wherein water generated in the reaction is removed in the reaction process. Cooling after the reaction is finished to obtain brownish red transparent liquid, washing with distilled water to be neutral, decompressing and distilling an organic phase for 1h at the temperature of 100Pa and 150 ℃ to remove water and dimethylbenzene, and obtaining the boron-containing organic substance V-02.
Example 7
The wear resistance and antifriction performance of the hydrogenated mineral base oil 150N and the polyol ester (the boron-containing organic matters account for 0.5% of the total mass of the oil product) are measured by adding the W-01, the W-02, the W-03, the V-01 and the V-02 into the hydrogenated mineral base oil 150N and the polyol ester respectively according to the dosage of 0.5%. The SRV tester is used for evaluating the wear resistance and antifriction performance by adopting a national energy agency standard NB/SH/T0847-2010 method, and the testing conditions are as follows: the temperature is 30 ℃, the load is 100N, the stroke is 1mm, the test time is 1 hour, and the frequency is 50Hz. The test results are shown in Table 3.
TABLE 3SRV test results
As can be seen from Table 3, the boron-containing organic matter of the present invention has better antiwear and antifriction properties.
Example 8
Adding W-01, W-02, W-03, V-01, V-02 and hindered phenol antioxidants T501 and T512 into hydrogenated mineral base oil 150N and polyol ester (boron-containing organic matters or comparative antioxidants account for 0.5% of the total mass of the oil) according to the dosage of 0.5%, and testing the oxidation resistance, wherein a testing instrument is a TA5000 DSC instrument of the American TA company, and the testing conditions are that: 190 ℃, oxygen pressure is 0.5MPa, and heating speed is 10 ℃/min. The test results are shown in Table 4.
Table 4 antioxidant test results
Compared with the boron-containing organic matter and the comparative antioxidant, the boron-containing organic matter and the antioxidant provided by the invention obviously improve the oxidation induction period, and particularly have extremely excellent oxidation resistance in the polyol ester base oil, thus being an antioxidant with excellent performance.
Claims (13)
1. The structure of the boron-containing organic matter is shown as a formula (I):
In formula (I), y R groups are bonded to the benzene ring; y is selected from integers between 0 and 4; each R group is independently selected from H and C 1-4 straight or branched alkyl; n is an integer between 1 and 5; each R 1 is independently selected from C 1-10 straight or branched alkylene; r 2 in the n repeating units are the same or different from each other and are each independently selected from a single bond and a C 1-10 straight or branched alkylene group; r 3 is selected from H and C 1-10 straight or branched alkyl; the A groups in the n repeating units are the same or different from each other and are each independently selected from the group represented by formula (II),
In the formula (II), each G group is independently selected from a group shown in the formula (III), a group shown in the formula (IV) and H, and one or two G groups in the formula (II) are selected from a group shown in the formula (III) and a group shown in the formula (IV);
In formula (III), each R 4 group is independently selected from the group consisting of a linear or branched alkyl group of C 5～C25, a group of formula (V),
The R 7 groups in formula (V) are selected from the group consisting of linear or branched alkylene groups of C 2～C5, the R 8 groups are each independently selected from the group consisting of linear or branched alkylene groups of C 2～C20, and m is an integer between 0 and 5;
The R 5 group in the formula (IV) is selected from C 2～C5 straight-chain or branched-chain alkylene, and the R 6 group is selected from H, a group shown in the formula (V) and C 5～C25 straight-chain or branched-chain alkyl.
2. The boron-containing organic compound according to claim 1, wherein in the formula (I), y is selected from integers of 1 to 3, R is selected from t-butyl, and R is located at the ortho-or para-position to the hydroxyl group on the benzene ring; n is an integer between 1 and 3; each R 1 is independently selected from C 1-8 straight or branched alkylene; r 2 in the n repeating units are each independently selected from a single bond and a C 1-4 straight or branched alkylene group; r 3 is selected from H and C 1-4 straight or branched alkyl; in formula (III), each R 4 group is independently selected from the group consisting of a linear or branched alkyl group of C 10～C20, a group of formula (V); the R 5 group in the formula (IV) is selected from ethylene and propylene, and the R 6 group is selected from H, a group shown in the formula (V) and a linear or branched alkyl of C 10～C20; the R 7 groups in formula (V) are selected from ethylene, propylene, and the R 8 groups are each independently selected from C 2～C18 linear or branched alkylene, m being 0, 1,2, 3 or 4.
3. The boron-containing organic compound according to claim 2, wherein in the formula (I), y is selected from 1, R is selected from t-butyl, R is located in the ortho position to the hydroxyl group on the benzene ring and is para to the R 1 group.
4. The boron-containing organic compound according to claim 1, wherein the boron-containing organic compound is one or more of the following structural compounds:
5. The preparation method of the boron-containing organic matter comprises the following steps:
(1) Reacting a compound represented by formula (X) with a peroxide;
In formula (X), y R groups are bonded to the benzene ring; y is selected from integers between 0 and 4; each R group is independently selected from H and C 1-4 straight or branched alkyl; n is an integer between 1 and 5; each R 1 is independently selected from C 1-10 straight or branched alkylene; r 2 in the n repeating units are the same or different from each other and are each independently selected from a single bond and a C 1-10 straight or branched alkylene group; r 3 is selected from H and C 1-10 straight or branched alkyl;
(2) Subjecting the reaction product of step (1) to hydrolysis;
(3) Esterifying a compound shown in a formula (Y) and/or a compound shown in a formula (Z) with a hydrolysis reaction product of the step (2), and collecting the product;
In the formula (Y), each R 4 group is independently selected from a linear or branched alkyl group of C 5～C25, a group represented by the formula (V),
The R 7 groups in formula (V) are selected from the group consisting of linear or branched alkylene groups of C 2～C5, the R 8 groups are each independently selected from the group consisting of linear or branched alkylene groups of C 2～C20, and m is an integer between 0 and 5;
The R 5 group in the formula (Z) is selected from the group consisting of C 2～C5 straight-chain or branched-chain alkylene, and the R 6 group is selected from the group consisting of H, a group represented by the formula (V), and C 5～C25 straight-chain or branched-chain alkyl.
6. The method according to claim 5, wherein in the step (1), the molar ratio between the compound represented by the formula (X) and the peroxide is 1:0.5 to 10; in the step (3), the molar ratio between the hydrolysis reaction product of the step (2) and the compound represented by the formula (Y) and/or the compound represented by the formula (Z) is 1:0.5 to 15; the reaction temperature of the step (1) is 40-100 ℃; the reaction temperature of the step (2) is 50-150 ℃; the reaction temperature of the step (3) is 80-200 ℃.
7. The process according to claim 5, wherein in formula (X), y is selected from integers ranging from 1 to 3, the R group is selected from tert-butyl, and the R group is located in the ortho-or para-position to the hydroxyl group on the benzene ring; n is an integer between 1 and 3; each R 1 is independently selected from C 1-8 straight or branched alkylene; r 2 in the n repeating units are each independently selected from a single bond and a C 1-4 straight or branched alkylene group; r 3 is selected from H and C 1-4 straight or branched alkyl; in formula (Y), each R 4 group is independently selected from the group consisting of a linear or branched alkyl group of C 10～C20, a group represented by formula (V); the R 5 group in the formula (Z) is selected from ethylene and propylene, and the R 6 group is selected from H, a group shown in the formula (V) and a linear or branched alkyl of C 10～C20; the R 7 groups in formula (V) are selected from ethylene, propylene, and the R 8 groups are each independently selected from C 2～C18 linear or branched alkylene, m being 0, 1,2, 3 or 4.
8. The process according to claim 7, wherein in formula (X), y is selected from 1, the R group is selected from t-butyl, the R group is located in the ortho position to the hydroxyl group on the benzene ring and in the para position to the R 1 group.
9. The process according to claim 5, wherein in the step (3), the compound represented by the formula (Y) and/or the compound represented by the formula (Z) is produced by: reacting one or more of R 4 OH, a compound represented by formula (alpha) and a compound represented by formula (beta) with boric acid, and collecting a product;
The R 4 group is selected from the group consisting of linear or branched alkyl of C 5～C25; the R 7 groups in formula (alpha) are selected from the group consisting of linear or branched alkylene groups of C 2～C5, the R 8 groups are each independently selected from the group consisting of linear or branched alkylene groups of C 2～C20, and m is an integer between 0 and 5; the R 5 group in the formula (beta) is selected from the group consisting of C 2～C5 straight-chain or branched-chain alkylene, and the R 6 group is selected from the group consisting of H, a group shown in the formula (V), and C 5～C25 straight-chain or branched-chain alkyl.
10. The method of claim 9, wherein each R 4 group is independently selected from the group consisting of linear and branched alkyl groups of C 10～C20; the R 5 group is selected from ethylene and propylene, and the R 6 group is selected from H, a group shown in a formula (V) and a linear or branched alkyl of C 10～C20; the R 7 groups are selected from ethylene, propylene, and the R 8 groups are each independently selected from C 2～C18 linear or branched alkylene, m is 0, 1, 2, 3 or 4.
11. The method of claim 9, wherein R 4 OH is selected from one or more of dodecanol, tetradecanol, hexadecanol, and octadecanol; the compound shown in the formula (alpha) is selected from ethanolamine and/or N- (2-hydroxyethyl) ethylenediamine; the compound shown in the formula (beta) is selected from one or more of diethanolamine, N-dihydroxyethyl dodecyl amine, N-dihydroxyethyl hexadecamine and N, N-dihydroxyethyl octadecylamine.
12. The method according to claim 9, wherein the molar ratio of one or more of R 4 OH, the compound represented by formula (α) and the compound represented by formula (β) as a whole to boric acid is 0.5 to 5:1, a step of; the temperature at which one or more of R 4 OH, the compound shown in the formula (alpha) and the compound shown in the formula (beta) reacts with boric acid is 80-200 ℃.
13. Use of a boron-containing organic compound according to any one of claims 1 to 4 or a boron-containing organic compound prepared according to any one of claims 5 to 12 as an antioxidant, antiwear agent, friction reducer for lubricating oils.
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