CN106565568B - A kind of method of selectivity synthesis di-t-butyl trithioether - Google Patents
A kind of method of selectivity synthesis di-t-butyl trithioether Download PDFInfo
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- CN106565568B CN106565568B CN201610977907.2A CN201610977907A CN106565568B CN 106565568 B CN106565568 B CN 106565568B CN 201610977907 A CN201610977907 A CN 201610977907A CN 106565568 B CN106565568 B CN 106565568B
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- butyl
- polythiaether
- trithioether
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- aqueous solutions
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 150000003568 thioethers Chemical class 0.000 claims abstract description 25
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 17
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- BRHMIYSGEOXTJV-UHFFFAOYSA-N [Cl-].C(CCCCCCC)C([NH2+]C)(CCCCCCCC)CCCCCCCC Chemical compound [Cl-].C(CCCCCCC)C([NH2+]C)(CCCCCCCC)CCCCCCCC BRHMIYSGEOXTJV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- -1 dodecyl dimethyl benzyl Chemical group 0.000 claims description 3
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000005864 Sulphur Substances 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 abstract description 8
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NWBUZSZSVCYEMR-UHFFFAOYSA-N [S].C(CCC)S Chemical compound [S].C(CCC)S NWBUZSZSVCYEMR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical class [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000008116 organic polysulfides Chemical class 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing 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
- 239000002904 solvent Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method of selectivity synthesis di-t-butyl trithioether, isobutene, sulphur and hydrogen sulfide are used as raw material one-step synthesis method di-t-butyl polythiaether under high pressure, although belong to atomic economy reaction, conversion ratio is close to 100%, but until six thioether of di-t-butyl is in almost normal distribution, the mole percent of wherein di-tert-butyl disulfide only accounts for 30% ~ 40% for tert-butyl mercaptan, di-t-butyl list thioether in product form.The present invention that is, in the presence of a phase transfer catalyst, di-t-butyl polythiaether mixture is handled with sodium sulfide solution, low-sulfur ether therein and high thioether are subjected to disproportionated reaction, so as to selectively obtain di-t-butyl trithioether, the molar content of the di-t-butyl trithioether in product is improved to more than 90%.Traditional rectification under vacuum can be avoided to detach the process of trithioether in this way, reduce energy expenditure and raw materials consumption.
Description
Technical field
The invention belongs to the preparation method of organic polysulfide, specifically, the present invention is a kind of two uncle of selectivity synthesis
The method of butyl trithioether.
Background technology
Sulfide isobutene, i.e. di-t-butyl polysulfide, the extreme pressure anti-wear additives as lubricating oil have been widely recognized,
Wherein di-t-butyl trithioether corrosivity is minimum, and four thioether of di-t-butyl and other high-sulfur ethers are to corrosion of metal
Property it is maximum.Due to during sulfide isobutene is synthesized generate the high thioether by-product of di-t-butyl, how selectivity synthesis
Di-t-butyl trithioether just becomes the problem of particularly important.
U.S. US 5442123, US 5457234, US 530163, US 5786511, US 5146000, US
6051739th, technical solution disclosed in US 6399832, US 6242652 etc. uses tert-butyl mercaptan and sulfur reaction, selection system
Standby di-t-butyl trithioether, but the raw material tert-butyl mercaptan cost of material that the circuit uses is prohibitively expensive, and byproduct of reaction
For hydrogen sulfide, production procedure is excessively complicated.
Using isobutene, sulphur and hydrogen sulfide, one-step method can synthesize di-t-butyl polythiaether under high pressure for raw material,
Reaction equation is as follows：
Although the reaction meets atomic economy reaction principle, conversion ratio is close to 100 %, reaction product be single thioether extremely
The selectivity of the mixture of six thioethers, wherein trithioether is only the % (US 4119550, US 4191659, US of 30 %~40
4344854, US 41195492, US 6472354).
US 4937385 synthesizes di-t-butyl trithioether with high selectivity using two sections of continuity methods, and the first segment process first will
Tert-butyl mercaptan is obtained by the reaction in isobutene and hydrogen sulfide, by tert-butyl mercaptan and sulfur reaction in second segment flow, using NaY
Molecular sieve or ZnO/Al2O3Catalyst can reach 94 %~95 in normal pressure, 60 DEG C of reactions, the selectivity of di-t-butyl trithioether
%.Since this method is related to recycling by-product H repeatedly2The tert-butyl mercaptan raw material of S and excess, thus production technology is excessively
It is complicated.
Invention content
The purpose of the present invention is：Isobutene, sulphur and hydrogen sulfide is used to be closed in next step in high pressure, 140 DEG C of conditions for raw material
Into sulfide isobutene product, this product is the mixture of di-t-butyl polythiaether, including tert-butyl mercaptan and di-t-butyl list
Thioether to di-t-butyl polythiaether, although based on di-t-butyl trithioether, low-sulfur ether and high thioether and tert-butyl mercaptan
Still account for 60% ~ 70%, it is impossible to use as extreme pressure antiwear agent for lubricant oil.Therefore, seek by simply chemically reacting low-sulfur ether
Di-t-butyl trithioether is generated by disproportionated reaction with high thioether, target product di-t-butyl trithio ether content is made to improve to 90%
More than, finally obtain the extreme pressure anti-wear additives of function admirable.
Technical solution provided by the invention：
It is polythiaether mixture Na of the raw material in high pressure one-step synthesis by isobutene, sulphur and hydrogen sulfide2S aqueous solutions with
And a small amount of quaternary ammonium salt consisting of phase-transferring agent processing, low-sulfur ether and high thioether are subjected to disproportionated reaction, so as to realize highly selective conjunction
Into the purpose of di-t-butyl trithioether.
Sulphur is added in autoclave, adds in n-butylamine catalyst, the mass percent based on sulphur is 0.068
Then % is sealed, with the air 3 times of 2.0 Mpa high pure nitrogen replacement reaction kettles Inner, H is passed through into reaction kettle2S, stirring, 320
140 DEG C of rpm, heating heating and temperature control, then inject isobutene by metering pump, and pressure is down to 0.4 MPa after reacting 6 h, drops
Temperature is to 100 DEG C and discharges kettle Inner gases to normal pressure, and the mixture of kettle Inner products, that is, di-t-butyl polythiaether, crude product yield can
Up to 97 wt %.
Above-mentioned polythiaether is determined by high resolution nuclear magnetic resonance hydrogen spectrum (III 500 MHz of Bruker AVANCE)
Property and quantitative analysis, the chemical shift of each component and typical product composition see attached drawing 1,.Wherein sulphur butanethiol abbreviation TBS0,
Di-t-butyl list thioether abbreviation TBS1, di-tert-butyl disulfide abbreviation TBS2, di-t-butyl trithioether abbreviation TBS3, di-t-butyl
Four thioether abbreviation TBS4, five thioether abbreviation TBS of di-t-butyl5, six thioether abbreviation TBS of di-t-butyl6.It can from 1 data of attached drawing
Go out, normal distribution is almost presented in product composition, although based on trithioether, low-sulfur ether and high thioether still account for about 60 %~70
%。
In order to obtain di-t-butyl trithio ether product as much as possible, the technical solution adopted by the present invention is：By season
Ammonium salt phase transfer catalyst (PTC) is dissolved in Na2In S aqueous solutions, di-t-butyl polythiaether mixture is used at a certain temperature
Na containing PTC2S aqueous solutions are stirred to react certain time, and disproportionated reaction occurs, i.e., low-sulfur ether and high thioether S atom occur
Transfer reaction, reaction equation are as follows：
Polythiaether mixture and Na2The temperature that is stirred to react of S/PTC aqueous solutions is 60 DEG C~100 DEG C, preferably reaction temperature
Spend 70 DEG C~80 DEG C
Polythiaether mixture and Na2S/PTC aqueous solutions are stirred to react the time as 6~14 h, and preferably reaction is 8~12
h。
Polythiaether mixture and Na2Na in S/PTC reactant aqueous solutions2The mass percent concentration of S is the % of 20 %~60, excellent
Select Na2The % of a concentration of 30 % of S aqueous solutions~50.
Polythiaether mixture and Na2Na in S/PTC reactant aqueous solutions2The dosage of S aqueous solutions is the % of 40 %~80, based on more
The mass percent of mixture of sulfides, preferably Na2S amount of aqueous solution used is the % of 50 %~70.
By having lipophilic group and hydrophilic group in phase transfer catalyst PTC molecular structures, therefore PTC can be effectively by S2-It carries
Into the organic phase of more sulphur mixtures, so as to efficiently be catalyzed the disproportionated reaction of low-sulfur ether and high thioether.PTC phase transfer catalysts
Including：Tetrabutylammonium chloride, tetrabutylammonium bromide, tri-n-octyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, the tetradecane
Base trimethyl ammonium chloride, octadecyltrimethylammonium chloride, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, ten
Dialkyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride.
The positive effect of the present invention：
Using isobutene, sulphur, hydrogen sulfide, as raw material, single step reaction synthesizes di-t-butyl polythiaether under high pressure, although this is anti-
Atomic economy reaction should be belonged to, product yield is up to 97 more than %, but the selectivity of trithioether is relatively low.It is deposited in phase transfer catalyst
Under, with Na2S aqueous solutions handle the mixture of di-t-butyl polythiaether, low-sulfur ether therein and high thioether be disproportionated anti-
Should, di-t-butyl trithioether is highly selectively generated, selectivity can avoid traditional rectification under vacuum point in this way up to 90 more than %
Process from trithioether reduces energy expenditure and raw materials consumption.
Description of the drawings
Fig. 1 is the product distribution schematic diagram of high pressure one-step synthesis method polythiaether.
Specific embodiment
The synthesis of di-t-butyl polythiaether is in 2.5 liters of autoclaves（The sensible reaction kettle factory in Dalian, temperature-controlled precision ± 0.5
℃）Middle completion.Isobutene（99.5%, 4L steel cylinder, Dalian Guangming Special Gas Products Co., Ltd.）.Hydrogen sulfide（99.5%, 4L steel cylinder,
Dalian Guangming Special Gas Products Co., Ltd.）.The addition of isobutene and hydrogen sulfide is measured using electronic platform scale.The more sulphur of di-t-butyl
The disproportionated reaction of ether uses 250 mL normal-pressure reaction kettles.
In the present invention, synthetic product1H NRM wave spectrums are completed on 500 nuclear magnetic resonance chemical analysers of Bruker AV, solvent
For CDCl3, using tetramethylsilane TMS as internal standard, resonant frequency is 500 MHz.Sulphur butanethiol（Abbreviation TBS0）, two uncles
Butyl list thioether（Abbreviation TBS1）, di-tert-butyl disulfide（Abbreviation TBS2）, di-t-butyl trithioether（Abbreviation TBS3）, two tertiary fourths
Four thioether of base（Abbreviation TBS4）, five thioether of di-t-butyl（Abbreviation TBS5）With six thioether of di-t-butyl（Abbreviation TBS6）Chemical potential
It is respectively 1.438,1.427,1.312,1.376,1.405,1.413 and 1.421 to move, and the peak area of each component is integrated,
The molar content of each component is calculated by normalization method.
Embodiment 1
By 320 g（10.0 mol）Sulphur is added in 2.5 L reaction kettles, adds in 2.28 g n-butylamine catalyst（3 mL,
Mole percent based on sulphur is 0.25%）, then reinforce sealing.With 2.0 MPa high pure nitrogens purge 3 times, finally discharge to
Normal pressure.Isobutene is passed through into aforesaid reaction vessel（561g, 10.0 mol）, then H2S (170g, 5 mol) is passed through, start to stir
（Rotating speed 231pm）, 140 oC of set temperature controller temperature, reactor pressure is down to 0.5 after 10 h are reacted at 140 DEG C
MPa discharges pressure in kettle, collects product in kettle, obtains di-t-butyl polythiaether crude product 1006.5g, liquid yield 95.6%,
The molar content of each component is shown in Table 1 in crude product.
100g di-t-butyl polythiaethers crude product is taken to add in autoclave, adds in 55 g Na2S aqueous solutions（30
wt%）, 1.5 g tetrabutylammonium bromide are added, are then replaced 3 times using nitrogen high pressure, empty residual air in kettle, setting is anti-
80 DEG C of temperature is answered to react 8 hours.Material is taken out after cooling, separates the as clear as crystal organic phase in upper strata with separatory funnel, product is each
A component molar percentage composition is shown in Table 1.
Each component molar percentage composition before and after 1 disproportionated reaction of table
| Component | TBS0 | TBS1 | TBS2 | TBS3 | TBS4 | TBS5 | TBS6 |
| Before reaction | 4.9 | 1.2 | 22.4 | 40.3 | 23.4 | 6.0 | 1.7 |
| After reaction | 0 | 0 | 2.5 | 93.6 | 3.9 | 0 | 0 |
Embodiment 2
The di-t-butyl polythiaether crude product in 100g embodiments 1 is taken to add in autoclave, adds in 70 g Na2S
Aqueous solution（30 wt%）, 2.5 g benzyltriethylammoinium chlorides are added, is then replaced 3 times, emptied residual in kettle using nitrogen high pressure
It leaves blank gas, 90 DEG C of setting reaction temperature is reacted 8 hours.Material is taken out after cooling, it is as clear as crystal to separate upper strata with separatory funnel
Organic phase, each component molar percentage composition of product are shown in Table 2.
Each component molar percentage composition before and after 2 disproportionated reaction of table
| Component | TBS0 | TBS1 | TBS2 | TBS3 | TBS4 | TBS5 | TBS6 |
| Before reaction | 4.9 | 1.2 | 22.4 | 40.3 | 23.4 | 6.0 | 1.7 |
| After reaction | 0 | 0 | 1.7 | 95.4 | 2.9 | 0 | 0 |
Embodiment 3
The di-t-butyl polythiaether crude product in 100g embodiments 1 is taken to add in autoclave, adds in 60 g Na2S
Aqueous solution（45 wt%）, 4.0 g tri-n-octyl dimethyl ammonium chlorides are added, is then replaced 3 times, is emptied in kettle using nitrogen high pressure
Residual air, 70 DEG C of setting reaction temperature are reacted 12 hours.Material is taken out after cooling, it is as clear as crystal to separate upper strata with separatory funnel
Organic phase, each component molar percentage composition of product is shown in Table 3.
Each component molar percentage composition before and after 3 disproportionated reaction of table
| Component | TBS0 | TBS1 | TBS2 | TBS3 | TBS4 | TBS5 | TBS6 |
| Before reaction | 4.9 | 1.2 | 22.4 | 40.3 | 23.4 | 6.0 | 1.7 |
| After reaction | 0 | 0 | 3.2 | 92.8 | 4.0 | 0 | 0 |
Embodiment 4
The di-t-butyl polythiaether crude product in 100g embodiments 1 is taken to add in autoclave, adds in 70 g Na2S
Aqueous solution（30 wt%）, add 5.0 g stearyl dimethyl benzyl ammonium chlorides, then using nitrogen high pressure replace 3 times, clearly
Residual air in empty kettle, 70 DEG C of setting reaction temperature are reacted 12 hours.Material is taken out after cooling, it is clear to separate upper strata with separatory funnel
Clear transparent organic phase, each component molar percentage composition of product are shown in Table 4.
Each component molar percentage composition before and after 4 disproportionated reaction of table
| Component | TBS0 | TBS1 | TBS2 | TBS3 | TBS4 | TBS5 | TBS6 |
| Before reaction | 4.9 | 1.2 | 22.4 | 40.3 | 23.4 | 6.0 | 1.7 |
| After reaction | 0 | 0 | 1.6 | 96.7 | 1.7 | 0 | 0 |
Embodiment 5
The di-t-butyl polythiaether crude product in 100g embodiments 1 is taken to add in autoclave, adds in 60 g Na2S
Aqueous solution（40 wt%）, add 4.0 g dodecyl benzyl dimethyl ammonium chlorides, then using nitrogen high pressure replace 3 times, clearly
Residual air in empty kettle, 80 DEG C of setting reaction temperature are reacted 10 hours.Material is taken out after cooling, it is clear to separate upper strata with separatory funnel
Clear transparent organic phase, each component molar percentage composition of product are shown in Table 5.
Each component molar percentage composition before and after 5 disproportionated reaction of table
| Component | TBS0 | TBS1 | TBS2 | TBS3 | TBS4 | TBS5 | TBS6 |
| Before reaction | 4.9 | 1.2 | 22.4 | 40.3 | 23.4 | 6.0 | 1.7 |
| After reaction | 0 | 0 | 2.6 | 94.9 | 2.5 | 0 | 0 |
It can be seen that from the experimental data in embodiment 1 ~ 5, pass through Na2S/PTC disproportionated reactions, can be effectively by di-t-butyl
The molar content of trithioether in polythiaether mixture is improved to more than 90%.
Claims (7)
- A kind of 1. method of selectivity synthesis di-t-butyl trithioether, it is characterised in that：In quaternary ammonium salt phase transfer catalyst PTC Under the conditions of existing, di-t-butyl polythiaether mixture is reacted with sodium sulfide solution, reaction temperature is 60 DEG C~100 DEG C, the time is stirred to react as 6~14 h, single thioether, disulfide and four thioethers, five thioethers in mixture be disproportionated anti- Should, oil phase is detached after reaction obtains the lubricating oil extreme-pressure anti-wear that di-t-butyl trithioether molar content is 92% ~ 97% Agent product.
- 2. preparation method described in accordance with the claim 1, it is characterised in that：Polythiaether mixture and Na2S/PTC reactant aqueous solutions Middle Na2The mass percent concentration of S aqueous solutions is the % of 20 %~60.
- 3. preparation method described in accordance with the claim 2, it is characterised in that：Na2The mass percent concentration of S aqueous solutions is 30 % ~50 %.
- 4. preparation method described in accordance with the claim 1, it is characterised in that：Polythiaether mixture and Na2S/PTC reactant aqueous solutions Middle Na2The dosage of S aqueous solutions is the % of 40 % based on polythiaether mixture quality percentage~80.
- 5. according to the preparation method described in claim 4, it is characterised in that：Na2The dosage of S aqueous solutions is to be mixed based on polythiaether The % of 50 % of amount of substance percentage~70.
- 6. preparation method described in accordance with the claim 1, it is characterised in that：Quaternary ammonium salt phase transfer catalyst is tetrabutyl chlorination Ammonium, tetrabutylammonium bromide, tri-n-octyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, Octadecyltrimethylammonium chloride, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, dodecyl dimethyl benzyl Any one of ammonium chloride, stearyl dimethyl benzyl ammonium chloride.
- 7. preparation method described in accordance with the claim 1, it is characterised in that：The dosage of quaternary ammonium salt phase transfer catalyst is based on more The % of 1 % of mixture of sulfides mass percent~5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4119550A (en) * | 1975-03-21 | 1978-10-10 | The Lubrizol Corporation | Sulfurized compositions |
| US4191659A (en) * | 1975-03-21 | 1980-03-04 | The Lubrizol Corporation | Sulfurized compositions |
| CN103864650A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Method for continuously producing dimethyl disulfide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4119550A (en) * | 1975-03-21 | 1978-10-10 | The Lubrizol Corporation | Sulfurized compositions |
| US4191659A (en) * | 1975-03-21 | 1980-03-04 | The Lubrizol Corporation | Sulfurized compositions |
| CN103864650A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Method for continuously producing dimethyl disulfide |
Non-Patent Citations (1)
| Title |
|---|
| Rhodium-Catalyzed Synthesis of Diaryl Sulfides Using Aryl Fluorides and Sulfur/Organopolysulfides;Mieko Arisawa et al.;《Org. Lett.》;20121005;第14卷(第20期);5318–5321 * |
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