CN1387510A - Process for producing bismuth dithiocarbamates and dithiophosphorates - Google Patents
Process for producing bismuth dithiocarbamates and dithiophosphorates Download PDFInfo
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- CN1387510A CN1387510A CN 00815376 CN00815376A CN1387510A CN 1387510 A CN1387510 A CN 1387510A CN 00815376 CN00815376 CN 00815376 CN 00815376 A CN00815376 A CN 00815376A CN 1387510 A CN1387510 A CN 1387510A
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- China
- Prior art keywords
- bismuth
- phosphorodithioic acid
- acid bismuth
- aforementioned
- phosphorodithioic
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- 238000000034 method Methods 0.000 title claims abstract description 30
- CXZIVLHEAFSOQK-UHFFFAOYSA-K bismuth;tricarbamodithioate Chemical class [Bi+3].NC([S-])=S.NC([S-])=S.NC([S-])=S CXZIVLHEAFSOQK-UHFFFAOYSA-K 0.000 title abstract 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 13
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 13
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims abstract description 12
- 229940049676 bismuth hydroxide Drugs 0.000 claims abstract description 11
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 10
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 3
- -1 phosphorodithioic acid bismuth Chemical compound 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- KVRDBCPHNXJTCC-UHFFFAOYSA-M [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].O[Bi+3] Chemical compound [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].O[Bi+3] KVRDBCPHNXJTCC-UHFFFAOYSA-M 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000005069 Extreme pressure additive Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- 230000001050 lubricating effect Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002199 base oil Substances 0.000 claims description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000003449 preventive effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000009472 formulation Methods 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- 235000003140 Panax quinquefolius Nutrition 0.000 description 3
- 240000005373 Panax quinquefolius Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WCCZUQJPUQBMRD-UHFFFAOYSA-N 2-ethylhexoxy-hydroxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCC(CC)COP(O)(S)=S WCCZUQJPUQBMRD-UHFFFAOYSA-N 0.000 description 1
- KHFRJOPGKUBZLL-UHFFFAOYSA-N 7-methyl-n-(7-methyloctyl)octan-1-amine Chemical compound CC(C)CCCCCCNCCCCCCC(C)C KHFRJOPGKUBZLL-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- JZGCHBKDZSRVPQ-UHFFFAOYSA-K antimony(3+);tricarbamodithioate Chemical compound [Sb+3].NC([S-])=S.NC([S-])=S.NC([S-])=S JZGCHBKDZSRVPQ-UHFFFAOYSA-K 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- ZLWLTDZLUVBSRJ-UHFFFAOYSA-K chembl2360149 Chemical compound [Na+].[Na+].[Na+].O=C1C(N=NC=2C=CC(=CC=2)S([O-])(=O)=O)=C(C(=O)[O-])NN1C1=CC=C(S([O-])(=O)=O)C=C1 ZLWLTDZLUVBSRJ-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for producing a bismuth dithiocarbamate or dithiophosphorate by the reaction of a bismuth hydroxide, bismuth oxide or bismuth oxynitrate with a dithiocarbamate or a dithiophosphoric acid. The bismuth dithiocarbamates and dithiophosphorates exhibit very good EP and antiwear properties and are useful in lubricant formulations.
Description
The present invention relates to a kind of method of produce oil dissolubility dithiocarbamic acid bismuth and phosphorodithioic acid bismuth.
In the past, by halogenation bismuth and dithiocarbamic acid prepared in reaction dithiocarbamic acid bismuth such as Trichlorobismuthine.This reaction is a replacement(metathesis)reaction, generates hydrogen chloride by-product.A shortcoming of this reaction is can retain undesirable chloride residue in product.These residues can be from the by product of partial reaction, unreacted three halogenation bismuths or the metal halide that generates on the spot.Even a spot of these residues also are considered to bad.
US-A-5631214 has described a kind of method of producing the dithiocarbamic acid bismuth, uses bismuth carboxylate and metal dithionite for the permutoid reaction between the carbamate.Do not pollute although the product that this reaction generates is chlorinated the thing residue, it is by the carboxylate metal salt pollution.(seeing that the 2nd hurdle 62-64 is capable)
The method that the purpose of this invention is to provide a kind of improved be used to produce oil dissolubility dithiocarbamic acid bismuth and phosphorodithioic acid bismuth.
Another object of the present invention provides a kind of method of producing dithiocarbamic acid bismuth and phosphorodithioic acid bismuth, and wherein product is not chlorinated the residue pollution of thing or metal carboxylate.
According to the present invention, provide a kind of method of producing dithiocarbamic acid bismuth or phosphorodithioic acid bismuth by bismuth hydroxide, bismuth oxide or hydroxyl Bismuth trinitrate (bismuth oxynitrate) and dithiocarbamate or phosphorodithioic acid reaction.
In reaction, water generates as by product, and it can easily be removed from reaction.
Dithiocarbamic acid bismuth of Sheng Chenging or phosphorodithioic acid bismuth do not contain with contained pollutent in the organo-metallic dithio compound of method production formerly in the method.Dithiocarbamic acid bismuth that this method is produced or phosphorodithioic acid bismuth are also structurally different with the organo-metallic dithio compound of the above-mentioned production of method formerly.
Dithiocarbamic acid bismuth of Sheng Chaning or phosphorodithioic acid bismuth are extraordinary extreme pressure additive (extreme pressure agent) in the method.It also shows extraordinary resistance to abrasion.These performances make this product useful and unique in lubricant formulation.
Bismuth oxide, bismuth hydroxide or hydroxyl Bismuth trinitrate can be represented with following formula respectively: Bi
2O
3, Bi (OH)
3Or BiO (OH)
9(NO
3)
4
Dithiocarbamate or dithiophosphates as starting raw material preferably prepares before use, newly distills or generate on the spot in the method for the invention.
In reaction, can use solvent, but dispensable.The solvent that is fit to is for example dimethyl sulfoxide (DMSO), N, and dinethylformamide, tetrahydrofuran (THF), acetonitrile, benzene nitrile or polarity or aprotic solvent commonly used comprise the paraffinic hydrocarbons and the naphthalane basic raw material (basestocks) of any viscosity grade.
Preferred solvent is acetonitrile or 100SUS base oil.
Reaction is preferably carried out at 50-200 ℃.Reaction is more preferably carried out at 60-130 ℃.
Reaction is preferably carried out under 10-1000psi nitrogen, air or hydrogen sulfide pressure.Most preferred pressure is 60-250psi nitrogen.
Dithiocarbamate is preferably represented with following formula:
R wherein
3And R
4Can be identical or different, or they one of be H.R
3And R
4Be preferably selected from following radicals: alkyl, thiazolinyl, cycloalkyl, cycloalkenyl group, aryl, aralkyl or alkyl, choose wantonly and contain heteroatoms, such as nitrogen, oxygen or sulphur atom.
R
3And R
4Preferably represent with following formula:
CH
3(CH
2)
m-X-(CH
2)
n-wherein: m is 1-30, preferred 1-20, n is 1-10, preferred 1-5.X can be oxygen, nitrogen or sulphur.
When bismuth oxide, bismuth hydroxide or hydroxyl Bismuth trinitrate and dithiocarbamate (being commonly referred to " DTC ") reacted according to the present invention, product can be represented by the formula:
Bi (OH)
x(DTC)
y(NO
3)
zX+y+z=3 wherein, when with bismuth oxide or bismuth hydroxide during as one of starting raw material, z is 0.
Phosphorodithioic acid is preferably represented with following formula:
R wherein
5Be alkyl with 1-20 carbon chain lengths, preferred 1-10.Phosphorodithioic acid can be by having R
5The alcohol of group and thiophosphoric anhydride prepared in reaction, this is well known to a person skilled in the art.The temperature of reaction of bismuth oxide, bismuth hydroxide or hydroxyl Bismuth trinitrate and phosphorodithioic acid reaction and time are identical with description during above bismuth hydroxide or bismuth oxide react with dithiocarbamate.
Phosphorodithioic acid bismuth produced according to the invention is preferably represented with following general formula:
Bi (OH)
m(DTP)
n(NO
3)
oM+n+o=3 wherein is when use Bi in reaction
2O
3Or Bi (OH)
3The time, o is 0.
Product can show as red-brown oil or yellow solid, and it is very easily molten in the non-polar solvent of for example pentane or hexane.This product shows fabulous solvability in paraffinic hydrocarbons or naphthalane basic raw material.
Dithiocarbamic acid bismuth and the phosphorodithioic acid bismuth produced in the inventive method show anti-load and abrasion resistance.Dithiocarbamic acid bismuth and phosphorodithioic acid bismuth can for example mix in the standard lubricating grease preparation.
Now, with reference to following embodiment, the present invention only is described by way of example.
Embodiment 1 usefulness bismuth oxide prepares diamyl dithiocarbamate bismuth (III)
(9.2g is 0.0198mol) with diamyl dithiocarbamate ester (27.9g, suspension 0.119mol) for bismuth oxide (III) in acetonitrile (200ml).With suspension returning, remained on this temperature then 5 hours.Generate brown suspension.Filter brown suspension, solvent evaporated under reduced pressure generates sticking brown liquid (13.0g).
Embodiment 2 usefulness bismuth oxides prepare dioctyl dithiocarbamic acid bismuth (III)
(34.3g is 0.0736mol) with di-n-octyl amine (106g, suspension 0.4416mol) for preparation bismuth oxide (III) in acetonitrile (200ml).Suspension is cooled to 15 ℃, then with slowly added in 30 minutes dithiocarbonic anhydride (27ml, 0.4416mol).Then mixture was refluxed 5 hours, the color of mixture is become brown by yellow during this period.Filter the mixture that generates, solvent evaporated under reduced pressure generates sticking brown oil (120g).
Embodiment 3 usefulness hydroxyl Bismuth trinitrates prepare diamyl dithiocarbamate bismuth (III)
(20.5g is 0.0789mol) with diamyl amine (37.2g, suspension 0.2367mol) for preparation hydroxyl Bismuth trinitrate (III) in acetonitrile (200ml).Envrionment temperature slowly add dithiocarbonic anhydride (15ml, 0.2367mol).Slight heat release takes place, and makes temperature of reaction rise 10 ℃.Generate yellow mixture, it was refluxed 5 hours, generate brown liquid.Filter this brown liquid, evaporating solvent generates brown liquid (40g).
Embodiment 4 usefulness hydroxyl Bismuth trinitrates prepare diisononyl dithiocarbamic acid bismuth (III)
(24.4g is 0.0936mol) with diisononyl amine (75.5g, suspension 0.2808mol) for preparation hydroxyl Bismuth trinitrate (III) in acetonitrile (200ml).Envrionment temperature slowly add dithiocarbonic anhydride (17ml, 0.2367mol).The adding of dithiocarbonic anhydride causes slight heat release, makes temperature rise 10 ℃.Generate yellow mixture, it was refluxed 5 hours.Filter and remove desolvate after, the product of generation is brown mashed prod (47g).Further purifying is that brown mashed prod is dissolved in the hexane (300ml), then 40 cool overnight with recrystallization effectively, generate the glassy yellow solid.
Embodiment 5 usefulness bismuth hydroxides prepare 2-ethylhexyl phosphorodithioic acid bismuth (III)
Preparation bismuth hydroxide (III) in acetonitrile (200ml) (27.0g, 0.1036mol) and 2,6 di tert butyl 4 methyl phenol (BHT, suspension 500mg).With added in 15 minutes 2-ethylhexyl phosphorodithioic acid (109g, 0.3108mol).The suspension returning heating that obtains 8 hours generates yellow liquid.Filter yellow liquid, solvent evaporated under reduced pressure generates blush oil (131g).
The dithiocarbamic acid bismuth that the foregoing description 3 and 5 prepares respectively and the performance of phosphorodithioic acid bismuth and commodity EP additive are relatively.The result is as described below:
| Test | The ASTM method | The lubricating grease of commodity in use EP additive | Use the lubricating grease of the BiDADTC of embodiment 3 preparations | Use the lubricating grease of the BiDIODTP of embodiment 5 preparations |
| Four ball EP welding carrying (Weld Load) Kg | D-2596 | 400 | ?500 | 400 |
| Four ball wear mm scars | D2265 | 0.54 | ?0.83 | 0.51 |
The lubricating grease that uses in above-mentioned test is the 12-hydroxy lithium stearate.Commodity EP additive is an antimony dithiocarbamate.
As implied above, the oil soluble dithiocarbamic acid bismuth of embodiment 3 preparations shows than the better EP result of commodity EP additive.
As implied above, the phosphorodithioic acid bismuth of embodiment 5 preparations shows than the better wear results of commodity EP additive.
In the above-described embodiments the oil soluble phosphorodithioic acid bismuth of Sheng Chaning also show improved on frictional coefficient reduction and the heat-oxidative stability of raising.
Claims (15)
1. one kind is passed through the method that bismuth hydroxide, bismuth oxide or hydroxyl Bismuth trinitrate and dithiocarbamate or phosphorodithioic acid reaction are produced dithiocarbamic acid bismuth or phosphorodithioic acid bismuth.
2. the process of claim 1 wherein that bismuth oxide, bismuth hydroxide or hydroxyl Bismuth trinitrate represent with following formula respectively: Bi
2O
3, Bi (OH)
3Or BiO (OH)
9(NO
3)
4
3. claim 1 or 2 method are not wherein used solvent in the method.
4. the method for claim 3, wherein solvent is selected from dimethyl sulfoxide (DMSO), N, and dinethylformamide, tetrahydrofuran (THF), acetonitrile, benzene nitrile or polarity or aprotic solvent commonly used comprise paraffinic hydrocarbons and naphthalane basic raw material.
5. claim 3 or 4 method, wherein solvent is acetonitrile or 100 SUS base oils.
6. each method in the aforementioned claim wherein is reflected at 50-200 ℃ and carries out, and preferably carries out at 60-130 ℃.
7. each method in the aforementioned claim wherein is reflected under 10-1000psi nitrogen, air or the hydrogen sulfide pressure and carries out; Preferably under the 6-250psi nitrogen pressure, carry out.
8. each method in the aforementioned claim, wherein phosphorodithioic acid is represented with following formula:
R wherein
3And R
4Can be identical or different, and they one of be H; R
3And R
4Be selected from following radicals: alkyl, thiazolinyl, cycloalkyl, cycloalkenyl group, aryl, aralkyl or alkyl, optional heteroatoms, for example nitrogen or the Sauerstoffatom of containing; And R
3And R
4Preferably represent with following formula:
CH
3(CH
2)
m-X-(CH
2)
n-wherein: m is 1-30, preferred 1-20, n is 1-10, preferred 1-5.X can be oxygen or nitrogen.
9. each method in the aforementioned claim, wherein the dithiocarbamic acid bismuth shown in the following formula is produced in reaction:
Bi (OH)
x(DTC)
y(NO
3)
zX+y+z=3 wherein, and when bismuth oxide or bismuth hydroxide with Bi
2O
3Or Bi (OH)
3During expression, z is 0.
10. each method in the aforementioned claim, wherein phosphorodithioic acid is represented with following formula:
R wherein
5Be to have 1-20, the alkyl of preferred 1-10 carbon chain lengths.
11. the method for claim 10, the phosphorodithioic acid bismuth shown in the general formula below wherein this method is produced:
Bi (OH)
m(DTP)
n(NO
3)
oM+n+o=3 wherein is when using Bi
2O
3Or Bi (OH)
3The time, o is 0.
12. dithiocarbamic acid bismuth that each method of claim 1-11 is produced or phosphorodithioic acid bismuth are as the purposes of extreme pressure additive and/or wear preventive additive.
13. lubricant or lubricating grease contain the dithiocarbamic acid bismuth or the phosphorodithioic acid bismuth of each production of claim 1-11.
14. the dithiocarbamic acid bismuth shown in the following general formula:
Bi (OH)
x(DTC)
y(NO
3)
zX+y+z=3 wherein.
15. the phosphorodithioic acid bismuth shown in the following general formula:
Bi (OH)
m(DTP)
n(NO
3)
oM+n+o=3 wherein.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16356999P | 1999-11-05 | 1999-11-05 | |
| US60/163,569 | 1999-11-05 | ||
| GB0002524.7 | 2000-02-04 | ||
| GBGB0002524.7A GB0002524D0 (en) | 2000-02-04 | 2000-02-04 | A process for producing organometallic dithio-compounds and the orgenometallic dithio-compounds produced therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1387510A true CN1387510A (en) | 2002-12-25 |
Family
ID=26243562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00815376 Pending CN1387510A (en) | 1999-11-05 | 2000-10-12 | Process for producing bismuth dithiocarbamates and dithiophosphorates |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1226117A1 (en) |
| JP (1) | JP2003513067A (en) |
| CN (1) | CN1387510A (en) |
| AU (1) | AU1035601A (en) |
| BR (1) | BR0015134A (en) |
| CA (1) | CA2389296A1 (en) |
| WO (1) | WO2001032612A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104395264A (en) * | 2012-07-13 | 2015-03-04 | Oxea有限责任公司 | Isononylamine from 2-ethylhexanol, preparation processe thereof and uses therof |
| CN105056986A (en) * | 2015-08-10 | 2015-11-18 | 南京信息工程大学 | Method for preparing flake shaped bismuth oxide nitrate hydroxide photocatalyst and catalyst application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2801603A1 (en) * | 2003-07-04 | 2014-11-12 | Jtekt Corporation | Grease composition for rolling bearing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4632950A (en) * | 1985-09-09 | 1986-12-30 | Pennwalt Corporation | Scorch resistant, crosslinkable composition containing mixture of copper and metal dithiocarbamates |
| US5631214A (en) * | 1995-07-31 | 1997-05-20 | R.T. Vanderbilt Company, Inc. | Preparation of bismuth dithiocarbamates |
-
2000
- 2000-10-12 BR BR0015134-3A patent/BR0015134A/en not_active IP Right Cessation
- 2000-10-12 WO PCT/GB2000/003909 patent/WO2001032612A1/en not_active Application Discontinuation
- 2000-10-12 AU AU10356/01A patent/AU1035601A/en not_active Abandoned
- 2000-10-12 CA CA002389296A patent/CA2389296A1/en not_active Abandoned
- 2000-10-12 JP JP2001534765A patent/JP2003513067A/en active Pending
- 2000-10-12 EP EP00971516A patent/EP1226117A1/en not_active Withdrawn
- 2000-10-12 CN CN 00815376 patent/CN1387510A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104395264A (en) * | 2012-07-13 | 2015-03-04 | Oxea有限责任公司 | Isononylamine from 2-ethylhexanol, preparation processe thereof and uses therof |
| CN104395264B (en) * | 2012-07-13 | 2016-05-25 | Oxea有限责任公司 | Different nonyl amine, the Its Preparation Method And Use prepared by 2-Ethylhexyl Alcohol |
| CN105056986A (en) * | 2015-08-10 | 2015-11-18 | 南京信息工程大学 | Method for preparing flake shaped bismuth oxide nitrate hydroxide photocatalyst and catalyst application |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1035601A (en) | 2001-05-14 |
| CA2389296A1 (en) | 2001-05-10 |
| EP1226117A1 (en) | 2002-07-31 |
| JP2003513067A (en) | 2003-04-08 |
| WO2001032612A1 (en) | 2001-05-10 |
| BR0015134A (en) | 2002-06-25 |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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