CN104761579A - Borate derivative containing xanthic acid, preparation method and application thereof - Google Patents
Borate derivative containing xanthic acid, preparation method and application thereof Download PDFInfo
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- CN104761579A CN104761579A CN201510106632.0A CN201510106632A CN104761579A CN 104761579 A CN104761579 A CN 104761579A CN 201510106632 A CN201510106632 A CN 201510106632A CN 104761579 A CN104761579 A CN 104761579A
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- acid group
- carbon atom
- ester derivative
- xanthogenic acid
- derivative containing
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- 239000002253 acid Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 12
- 150000001642 boronic acid derivatives Chemical class 0.000 title abstract 3
- 239000000654 additive Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical group CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 25
- 150000002148 esters Chemical class 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- -1 monoethanolamine fatty acid Chemical class 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 239000010687 lubricating oil Substances 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 239000002199 base oil Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OMKVZYFAGQKILB-UHFFFAOYSA-M potassium;butoxymethanedithioate Chemical compound [K+].CCCCOC([S-])=S OMKVZYFAGQKILB-UHFFFAOYSA-M 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000019484 Rapeseed oil Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- WLTVMXLKVVOCGZ-UHFFFAOYSA-N CCCCCCCC[K] Chemical compound CCCCCCCC[K] WLTVMXLKVVOCGZ-UHFFFAOYSA-N 0.000 description 3
- 239000005069 Extreme pressure additive Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 150000002169 ethanolamines Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000863032 Trieres Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical compound CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
A borate derivative containing xanthic acid has a structural formula being represented as follows, wherein the R1 is a straight-chain or branched-chain alkane being 4-16 in carbon atom number or is an aromatic ring group in which a benzene ring has a branched chain having not less than four carbon atoms; the R2 is a straight-chain or branched-chain alkane being 4-16 in carbon atom number or is an aromatic ring group in which a benzene ring has a branched chain having not less than four carbon atoms; the m and n is 1 or 2 and m+n=3. The borate derivative containing the xanthic acid group can be used as a substitute of a conventional sulfur-series load additive.
Description
Technical field
The invention belongs to lubricating oil additive organic compound technical field, particularly relate to a kind of boric ester derivative containing xanthogenic acid group and its production and use.
Background technology
Sulphur system additive be apply the earliest, be also the best lubricating oil extreme-pressure additive of effect, there is good extreme-pressure anti-wear effect, and kind is more, mainly comprise: sulfuration grease, monothioester, xanthate, olefine sulfide class, dithiocar-bamate, sulfonate etc.Sulfur-containing extreme-pressure additive most widely used is at present olefine sulfide (wherein sulfide isobutene output is maximum, and trade names are T321, and it has become topmost product in current all sulphur systems extreme pressure anti-wear additives).It is very extensive that the above-mentioned various advantages of sulfide isobutene causes it to apply in lubricating oil.But still there is the problem of the following aspects in it:
(1) raw materials for production have severe corrosive, serious to equipment corrosion, and also can produce a large amount of " three wastes " in producing (a large amount of HCl, H are released in reaction simultaneously
2the corrosive gasess such as S, and produce the waste residues such as a large amount of NaCl, sulfide), serious environment pollution.
(2) irritating smell specific to olefine sulfide becomes its maximum denouncing, and this often allows operator stand in actual use, all the more so for industry open gear oil, and this also just greatly limit its commercial applications.
(3) because the sulphur content in olefine sulfide is high, activity large, it has strong corrosive nature to the metal parts containing Copper and its alloy in wheel shaft and wheel box.
(4) day by day harsh along with power operation operating mode condition, the poor thermostability of olefine sulfide also causes people more to worry gradually.
For the various shortcoming that olefine sulfide is above-mentioned, people have made extensive work in exploitation olefine sulfide surrogate, such as use sulfuration over base sulfosalt instead as gear oil host, improve etc. olefine sulfide production technique, but do not obtain perfect solution up to now.Therefore, under the prerequisite guaranteeing to provide excellent supporting capacity, the potential surrogate seeking olefine sulfide is still a long-term goal in research.
The most promising in boron system additive is organic boric acid ester class, and large quantity research finds, nearly all organic boric acid ester all has antifriction quality, and some also has anti-wear effect.In addition, its thermostability is very good, and at high temperature corrosion-free to copper; to iron and steel, there is good rustless property, also there is good seal compatibility simultaneously, nontoxic odorless; be conducive to environment protection, these advantages be all those traditional phosphorous, sulphur load carrying additive is incomparable.
Organic boric acid ester is as multifunction additive, himself nontoxic odorless, there is good antifriction antiwear, anti-oxidative stability and high thermostability, in addition, corrodibility and selectivity is there is not in borate ester additive to friction pair material, be the study hotspot of additive R&D workers for a long time always, there is good application prospect.
Although boron system additive all has good antifriction performance, can be used for the research of the boric ester derivative of olefine sulfide surrogate always there are no bibliographical information.
Summary of the invention
In view of above-mentioned, the object of the invention is openly a kind of boric ester derivative containing xanthogenic acid group, this product is used as lubricating oil additive, there is the tribological property compared favourably with most popular olefine sulfide class additive T321 on market, and T321 can be overcome well have corrosive nature and the bad shortcoming of thermostability to friction pair material, can be used as the surrogate of traditional sulphur system load carrying additive.
In order to realize described goal of the invention, the present invention adopts following technical scheme: a kind of boric ester derivative containing xanthogenic acid group, and the structural formula of the described boric ester derivative containing xanthogenic acid group is
Wherein R
1be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring; R
2be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring; Wherein m, n are 1 or 2, and m+n=3.
The preparation method of the boric ester derivative containing xanthogenic acid group of the present invention, its preparation process is:
(1) potassium hydroxide and alcoholic solution are reacted 1 ~ 3h at 20 ~ 120 DEG C to dissolve to potassium hydroxide, then add dithiocarbonic anhydride, at 20 ~ 100 DEG C, react 1 ~ 4h, prepare potassium xanthonate derivative, its structural formula is general formula 1:
r
1be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring;
(2) using the derivative of the potassium xanthonate of synthesis in step (1) and 2-ethylene halohydrin as reactant, under tetrahydrofuran (THF) reaction medium exists, add catalyzer, under normal temperature ~ reflux temperature, react 2 ~ 8h, generation contains the hydroxy derivatives of xanthogenic acid group as general formula 2:
r
1be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring;
(3) using the hydroxy derivatives containing xanthogenic acid group of synthesis in step (2) with boric acid, monoethanolamine fatty acid as reactant, back flow reaction 2 ~ 8h in a solvent, generates the boric ester derivative containing xanthogenic acid group:
wherein R
1, R
2be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring; Wherein m, n are 1 or 2, and m+n=3;
In step of the present invention (1), the mol ratio of potassium hydroxide and alcoholic solution is 1:(2.3 ~ 2.8).
Alcoholic solution in step of the present invention (1) is propyl carbinol or n-Octanol solution.
2-ethylene halohydrin in step of the present invention (2) is 2-chloroethanol, 2-bromoethanol or 2-ethylene iodohydrin.
Catalyzer in step of the present invention (2) is KI.
The derivative of the potassium xanthonate in step of the present invention (2) and the mol ratio of 2-ethylene halohydrin are 1:(1 ~ 1.5).
Solvent in step of the present invention (3) is benzene,toluene,xylene or BTX aromatics.
The mol ratio containing the hydroxy derivatives of xanthogenic acid group and boric acid, monoethanolamine fatty acid in step of the present invention (3) is (1 ~ 2): 1:(1 ~ 2).
Boric ester derivative containing xanthogenic acid group of the present invention joins in base oil, as the application of lubricating oil extreme-pressure additive.
Owing to have employed technique scheme, the present invention has following beneficial effect: the boric ester derivative containing xanthogenic acid group provided by the invention can be used as the surrogate of traditional sulphur system load carrying additive, joined in base oil, there is obvious extreme pressure property and antiwear and friction reduction property, and this compound does not have obvious smell, thermostability is high, not obvious to copper corrosion effect, to the corrosion-free effect of friction pair material and selective action, it is a kind of lubricating oil low friction compound of environmental protection of excellent performance.
Accompanying drawing explanation
Fig. 1 is product and the T321 TGA figure in a nitrogen atmosphere of the embodiment of the present invention two.
In figure: 1, the product of the embodiment of the present invention two TGA curve in a nitrogen atmosphere; 2, T321 TGA curve in a nitrogen atmosphere.
Embodiment
By explanation the present invention that the following examples can be detailed, disclose object of the present invention and be intended to protect all technological improvements in the scope of the invention.
Embodiment one
In 500ml there-necked flask, add 0.50molKOH and 1.15mol propyl carbinol, be warming up to about 105 DEG C back flow reaction under nitrogen protection, insulation 1h almost dissolves completely to potassium hydroxide, naturally cools to room temperature; Then within half an hour, slowly 0.55mol CS is dripped under stirring
2, dripping process system temperature more than 40 DEG C, must not be warming up to about 60 DEG C and continues reaction 2h, react complete steaming except excessive propyl carbinol, obtained pale yellow powder shape potassium n butylxanthate crude product thereafter; Recrystallization in dehydrated alcohol again, can obtain large needle-like pale yellow crystals potassium n butylxanthate crude product after vacuum-drying.
The potassium n butylxanthate 0.50mol synthesized in upper step is added in 250ml there-necked flask, adds 150ml tetrahydrofuran (THF) and make solvent, be heated to backflow, make it to dissolve; Add after a small amount of KI makes catalyzer, slowly drip the ClCH of 0.50mol
2cH
2oH, under nitrogen protection, back flow reaction 4 ~ 8h, filters out solid, steams after desolventizing and adds anhydrous diethyl ether dissolving, wash three times, anhydrous MgSO
4dried overnight, steams and namely obtains the xanthic hydroxy derivatives of glassy yellow transparent liquid normal-butyl except after ether.
Being joined with the mol ratio of 2:1:1 by the monoethanolamine salt of xanthic for normal-butyl hydroxy derivatives and boric acid, butanic acid is furnished with in the reaction flask of water trap; a point aqua is made with appropriate benzene; and add a small amount of acidic resins and make catalyzer; under nitrogen protection; vigorous reflux reaction 4 ~ 6h; after separating the water close to theoretical amount, reaction terminates, and steams solvent and obtain the boric acid ester that glassy yellow clear viscous liquids is target product normal-butyl xanthogenic acid hydroxy derivatives after filtration.
Embodiment two
Add 0.50molKOH and 1.30mol n-Octanol in 500ml there-necked flask, be warming up to about 105 DEG C backflows under nitrogen protection, insulation 1h, until KOH almost dissolves completely, naturally cools to room temperature; Within half an hour, slowly 0.55mol CS is dripped under stirring
2, dripping process system temperature more than 40 DEG C, must not be warming up to about 60 DEG C and continues reaction 2h, react complete steaming except excessive n-Octanol, obtain pale yellow powder shape n-octyl potassium xanthonate crude product thereafter; Recrystallization in dehydrated alcohol again, can obtain large needle-like pale yellow crystals n-octyl potassium xanthonate after vacuum-drying.
Get step n-octyl potassium xanthonate 0.50mol to add in 250ml there-necked flask, add 150ml tetrahydrofuran (THF) and make solvent, be heated to backflow, make it to dissolve; Add after a small amount of KI makes catalyzer, slowly drip the ClCH of 0.63mol
2cH
2oH, under nitrogen protection, back flow reaction 4 ~ 8h, filters out solid, steams after desolventizing and adds anhydrous diethyl ether dissolving, wash three times, anhydrous MgSO
4dried overnight, steams and namely obtains the xanthic hydroxy derivatives of n-octyl (glassy yellow transparent liquid) except after ether.
Being joined with the mol ratio of 1:1:2 by the monoethanolamine salt of xanthic for n-octyl hydroxy derivatives and boric acid, butanic acid is furnished with in the reaction flask of water trap; a point aqua is made with appropriate benzene; and add a small amount of acidic resins and make catalyzer; under nitrogen protection; vigorous reflux reaction 4 ~ 6h; after separating the water close to theoretical amount, reaction terminates, and steams solvent and obtain the boric acid ester that glassy yellow clear viscous liquids is target product n-octyl xanthogenic acid hydroxy derivatives after filtration.
Embodiment three
Add 0.50molKOH and 1.40mol propyl carbinol in 500ml there-necked flask, be warming up to about 105 DEG C backflows under nitrogen protection, insulation 1h, until KOH almost dissolves completely, naturally cools to room temperature; Within half an hour, slowly 0.55mol CS is dripped under stirring
2, dripping process system temperature more than 40 DEG C, must not be warming up to about 60 DEG C and continues reaction 2h, react complete steaming except excessive propyl carbinol, obtain pale yellow powder shape potassium n butylxanthate crude product thereafter; Recrystallization in dehydrated alcohol again, can obtain large needle-like pale yellow crystals potassium n butylxanthate after vacuum-drying.
Get step potassium n butylxanthate 0.50mol to add in 250ml there-necked flask, add 150ml tetrahydrofuran (THF) and make solvent, be heated to backflow, make it to dissolve; Add after a small amount of KI makes catalyzer, slowly drip the ClCH of 0.75mol
2cH
2oH, under nitrogen protection, back flow reaction 4 ~ 8h, filters out solid, steams after desolventizing and adds anhydrous diethyl ether dissolving, wash three times, anhydrous MgSO
4dried overnight, steams and namely obtains the xanthic hydroxy derivatives of normal-butyl (glassy yellow transparent liquid) except after ether.
Being joined with the mol ratio of 1.5:1:1.5 by the monoethanolamine salt of xanthic for normal-butyl hydroxy derivatives and boric acid, n-caprylic acid is furnished with in the reaction flask of water trap; a point aqua is made with appropriate benzene; and add a small amount of acidic resins and make catalyzer; under nitrogen protection; vigorous reflux reaction 4 ~ 6h; after separating the water close to theoretical amount, reaction terminates, and steams solvent and obtain the boric acid ester that glassy yellow clear viscous liquids is target product normal-butyl xanthogenic acid hydroxy derivatives after filtration.
Respectively to the product of embodiment three, application examples experiment is done to embodiment one, its experimentation and result as follows.
Oil soluble is tested:
The rapeseed oil that biological degradability is good, eco-toxicity is low selected by base oil.To make an addition in the rapeseed oil of commercially available high-quality with massfraction 1.0%, 2.0%, 2.5% respectively by the product obtained in embodiment 1 and 2, stir and make it dissolve, ambient temperatare puts observation oil product, and experimental result is as shown in table 1.
The oil soluble experimental result of the additive of table 1 three kinds of embodiments
In figure: 1, "-" oil product clear; 2, there is precipitation or layering in " * " oil product.
Can be found out by the experimental result of table 1, the oil soluble of embodiment 1 product is suitable, and when lower concentration, (1.0%) can stable existence 4 months, and during higher concentration, (2.5%) can only stable existence 1 month; The oil soluble of the product of embodiment 2 and example 3 is good, and each concentration formation testing is at room temperature placed after 6 months and still kept clear, occurs, maintain good solubility and stability without precipitation, demixing phenomenon.Therefore, the carbon atom number of the alcohol used during optimum synthesis or lipid acid is greater than 8.
Tribological property is tested:
The product of three embodiments is made an addition in rapeseed oil with massfraction 1.0% and 2.0% respectively, load-carrying properties four ball frictional testing machiness (the MQ-12-EP type that Jinan trier factory produces) test, frictional wear experiment when mechanical type is long, wearing resistance test machine (the MRS-1J type that Jinan trier factory produces) carries out.Comparative additive selects a kind of sulfide isobutene of business level (provided by Lanzhou LubrizolLanlian Additive Co.Ltd, trade names are T321).Test-results is in table 2.
The tribological property experimental result of table 2 four kinds of additives in rapeseed oil
As can be seen from Table 2, the product in three embodiments and comparative additive T321 all significantly can improve the seizure-resistant load P of base oil
bvalue and anti-sintering load P
dvalue, proves that the additive provided in the present invention has the load-carrying properties similar with T321.
Wear scar diameter and the frictional coefficient of three embodiment products and comparative additive T321 are tested under the load of 392N.Experimental result as can be seen from table 2, three embodiment products obviously can reduce wear scar diameter WSD value and the frictional coefficient of rapeseed oil, prove that three can improve abrasion resistance and the antifriction performance of formation testing.In addition, the lower-magnitude of three embodiment products to wear scar diameter and frictional coefficient is similar to T321, proves that the abrasion resistance of the additive provided in the present invention and antifriction performance can match in excellence or beauty with T321.
Copper corrosion performance test:
Copper corrosion experiment is carried out: the copper sheet glass hook of one piece of polishing is immersed well in sample oil (mass concentration is 2.0%), and experimental temperature is 121 DEG C, and experimental period is 3h by ASTM D130 standard method.After experiment terminates, take out copper sheet, dry after solvent (ethanol-benzene, 1:4) cleaning, observe copper sheet color, and compare with ASTM Corrosion standards colour table, to determine copper corrosion rank.Experimental result is as shown in table 3.
The copper corrosion performance test result of table 3 five kinds of formation testings
As can be seen from Table 3, comparative additive T321 has obvious corrosive nature to copper sheet, and its corrosion level is 3b grade; And the corrosion class of three embodiment products formation testing is 1b, very weak to copper corrosion effect, can think that its corrosive nature on oil product is without impact.
Thermostability is tested:
Use thermogravimetric analysis (TGA) to investigate the thermostability of additive, Fig. 1 is product and the T321 thermogravimetric analysis spectrogram in a nitrogen atmosphere of embodiment 2.As can be seen from Figure 1, T321 just starts to decompose at about 130 DEG C, and the speed of decomposing is very fast, to about 301 DEG C just almost all cracking; And embodiment two product not only temperature of initial decomposition (231.06 DEG C) will far above T321, and until 348.97 DEG C of complete cracking of ability, this has higher thermostability with regard to demonstrating the additive provided in the present invention.
From the experimental result of application examples, the additive provided in the present invention not only has the tribological property compared favourably with most popular T321 on market, and not there is corrosive nature to friction pair material, there is high thermostability, overcome the shortcoming of T321 well, therefore the additive provided in the present invention can as the surrogate of olefine sulfide class additive.
From the application examples experimental result of embodiment one to embodiment three, boric ester derivative containing xanthogenic acid group provided by the invention joins in base oil, there is obvious extreme pressure property and antiwear and friction reduction property, and this compound does not have obvious smell, thermostability is high, not obvious to copper corrosion effect, to the corrosion-free effect of friction pair material and selective action, be a kind of lubricating oil low friction compound of environmental protection of excellent performance.Can be used as the surrogate of traditional sulphur system load carrying additive.
Part not in the detailed description of the invention is prior art.
Claims (10)
1. containing a boric ester derivative for xanthogenic acid group, it is characterized in that: the structural formula of the described boric ester derivative containing xanthogenic acid group is
Wherein R
1be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring; R
2be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring; Wherein m, n are 1 or 2, and m+n=3.
2. a preparation method for the boric ester derivative containing xanthogenic acid group as claimed in claim 1, is characterized in that: its preparation process is:
(1) back flow reaction at 20 ~ 120 DEG C by potassium hydroxide and alcoholic solution, insulation 1 ~ 3h dissolves to potassium hydroxide, then adds dithiocarbonic anhydride, and at 20 ~ 100 DEG C, react 1 ~ 4h, prepare potassium xanthonate derivative, its structural formula is general formula 1:
r
1be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring;
(2) using the derivative of the potassium xanthonate of synthesis in step (1) and 2-ethylene halohydrin as reactant, under tetrahydrofuran (THF) reaction medium exists, add catalyzer, under normal temperature ~ reflux temperature, react 2 ~ 8h, generation contains the hydroxy derivatives of xanthogenic acid group as general formula 2:
r
1be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring;
(3) using the hydroxy derivatives containing xanthogenic acid group of synthesis in step (2) with boric acid, monoethanolamine fatty acid as reactant, back flow reaction 2 ~ 8h in a solvent, generates the boric ester derivative containing xanthogenic acid group:
wherein R
1be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring; R
2be the alkane of the straight or branched of 4 ~ 16 for carbon atom number, or be with the aromatic ring group being no less than four carbon atom side chain on phenyl ring; Wherein m, n are 1 or 2, and m+n=3.
3. the preparation method of the boric ester derivative containing xanthogenic acid group as claimed in claim 2, is characterized in that: in step (1), the mol ratio of potassium hydroxide and alcoholic solution is 1:(2.3 ~ 2.8).
4. the preparation method of the boric ester derivative containing xanthogenic acid group as claimed in claim 2, is characterized in that: the alcoholic solution in step (1) is propyl carbinol or n-Octanol solution.
5. the preparation method of the boric ester derivative containing xanthogenic acid group as claimed in claim 2, is characterized in that: the 2-ethylene halohydrin in step (2) is 2-chloroethanol, 2-bromoethanol or 2-ethylene iodohydrin.
6. the preparation method of the boric ester derivative containing xanthogenic acid group as claimed in claim 2, is characterized in that: the catalyzer in step (2) is KI.
7. the preparation method of the boric ester derivative containing xanthogenic acid group as claimed in claim 2, is characterized in that: the derivative of the potassium xanthonate in step (2) and the mol ratio of 2-ethylene halohydrin are 1:(1 ~ 1.5).
8. the preparation method of the boric ester derivative containing xanthogenic acid group as claimed in claim 2, is characterized in that: the solvent in step (3) is benzene,toluene,xylene or BTX aromatics.
9. the preparation method of the boric ester derivative containing xanthogenic acid group as claimed in claim 2, is characterized in that: in step (3) is (1 ~ 2) containing the hydroxy derivatives of xanthogenic acid group and the mol ratio of boric acid, monoethanolamine fatty acid: 1:(1 ~ 2).
10. the boric ester derivative containing xanthogenic acid group as claimed in claim 1, is characterized in that: join the application as lubricating oil additive in base oil.
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| CN105384669A (en) * | 2015-12-09 | 2016-03-09 | 中南大学 | Preparation method of xanthate |
| CN108569989A (en) * | 2018-05-25 | 2018-09-25 | 中南大学 | A method of preparing thiourethane co-production 2 mercapto ethanol or O- alkylthio group ethyl xanthates |
| CN108722677A (en) * | 2018-05-25 | 2018-11-02 | 中南大学 | A kind of O- alkyl-S- hydroxyalkyl xanthate collecting agents and its preparation and application |
| CN115261105A (en) * | 2022-09-15 | 2022-11-01 | 汉能（青岛）润滑科技有限公司 | Preparation method of anti-wear energy-saving lubricating oil |
| CN117586294A (en) * | 2024-01-18 | 2024-02-23 | 山东海化集团有限公司 | Preparation method of sodium tetra (hexafluoroisopropoxy) borate and application of sodium tetra (hexafluoroisopropoxy) borate in sodium electricity |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384669A (en) * | 2015-12-09 | 2016-03-09 | 中南大学 | Preparation method of xanthate |
| WO2017097156A1 (en) * | 2015-12-09 | 2017-06-15 | 中南大学 | Preparation method of xanthate |
| CN105384669B (en) * | 2015-12-09 | 2018-02-27 | 中南大学 | The preparation method of xanthates |
| CN108569989A (en) * | 2018-05-25 | 2018-09-25 | 中南大学 | A method of preparing thiourethane co-production 2 mercapto ethanol or O- alkylthio group ethyl xanthates |
| CN108722677A (en) * | 2018-05-25 | 2018-11-02 | 中南大学 | A kind of O- alkyl-S- hydroxyalkyl xanthate collecting agents and its preparation and application |
| US11970441B2 (en) | 2018-05-25 | 2024-04-30 | Central South University | Method for preparing thionocarbamate and co-producing 2-mercaptoethanol or O-alkylthioethyl xanthate |
| CN115261105A (en) * | 2022-09-15 | 2022-11-01 | 汉能（青岛）润滑科技有限公司 | Preparation method of anti-wear energy-saving lubricating oil |
| CN117586294A (en) * | 2024-01-18 | 2024-02-23 | 山东海化集团有限公司 | Preparation method of sodium tetra (hexafluoroisopropoxy) borate and application of sodium tetra (hexafluoroisopropoxy) borate in sodium electricity |
| CN117586294B (en) * | 2024-01-18 | 2024-05-28 | 山东海化集团有限公司 | Preparation method of sodium tetra (hexafluoroisopropoxy) borate and application of sodium tetra (hexafluoroisopropoxy) borate in sodium electricity |
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Application publication date: 20150708 |