AU1035601A - A process for producing bismuth dithiocarbamates and dithiophosphorates - Google Patents
A process for producing bismuth dithiocarbamates and dithiophosphorates Download PDFInfo
- Publication number
- AU1035601A AU1035601A AU10356/01A AU1035601A AU1035601A AU 1035601 A AU1035601 A AU 1035601A AU 10356/01 A AU10356/01 A AU 10356/01A AU 1035601 A AU1035601 A AU 1035601A AU 1035601 A AU1035601 A AU 1035601A
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- Australia
- Prior art keywords
- bismuth
- represented
- dithiocarbamate
- dithiophosphorate
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims description 29
- CXZIVLHEAFSOQK-UHFFFAOYSA-K bismuth;tricarbamodithioate Chemical class [Bi+3].NC([S-])=S.NC([S-])=S.NC([S-])=S CXZIVLHEAFSOQK-UHFFFAOYSA-K 0.000 title claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 27
- 229910052797 bismuth Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 10
- 239000012990 dithiocarbamate Substances 0.000 claims description 9
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- KSQXYSITBYUVGV-UHFFFAOYSA-K bismuth;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Bi+3].[O-]P([O-])([S-])=S KSQXYSITBYUVGV-UHFFFAOYSA-K 0.000 claims description 6
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 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
- 239000003570 air Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 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
- 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
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 12
- 239000000725 suspension Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000005069 Extreme pressure additive Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- -1 BISMUTH DITHIOCARBAMATES Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- JWHFYIKVRLMUCH-UHFFFAOYSA-N dipentylcarbamodithioic acid Chemical compound CCCCCN(C(S)=S)CCCCC JWHFYIKVRLMUCH-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- YGMLOGWOEDZXIJ-UHFFFAOYSA-N 2-ethylhexylsulfanyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCC(CC)CSP(O)(O)=S YGMLOGWOEDZXIJ-UHFFFAOYSA-N 0.000 description 2
- 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- FPLIHVCWSXLMPX-UHFFFAOYSA-M lithium 12-hydroxystearate Chemical compound [Li+].CCCCCCC(O)CCCCCCCCCCC([O-])=O FPLIHVCWSXLMPX-UHFFFAOYSA-M 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- MGJYZNJAQSLHOL-UHFFFAOYSA-M n,n-dioctylcarbamodithioate Chemical compound CCCCCCCCN(C([S-])=S)CCCCCCCC MGJYZNJAQSLHOL-UHFFFAOYSA-M 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
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Description
WO 01/32612 PCT/GBOO/03909 1 A PROCESS FOR PRODUCING BISMUTH DITHIOCARBAMATES AND DITHIOPHOSPHORATES The present invention concerns a process for producing oil-soluble bismuth dithiocarbamates and dithiophosphorates. In the past, bismuth dithiocarbamates have been prepared by reacting bismuth halide such as bismuth trichloride with a dithiocarbamate. The reaction is a displacement reaction which produces hydrogen chloride as a by-product. One drawback of this reaction is that undesirable residues of chloride can remain in the product. These residues can be from partially reacted by-products, unreacted bismuth trihalide or metal halides generated in situ. Even small amounts of these residues are considered to be undesirable. US-A-5,631,214 discloses a process for producing bismuth dithiocarbamates using an exchange reaction between a bismuth carboxylate and a metal dithiocarbamate. Although the product produced in this reaction is not contaminated with a residue of chloride, it is contaminated with metal carboxylate (see lines 62-64 in column 2) An aim of this invention is to provide an improved method for producing oil-soluble bismuth dithiocarbamates and dithiophosphorates. A further aim of this invention is to provide a method for producing bismuth dithiocarbamates and dithiophosphorates in which the product is not contaminated with residues of chloride or metal carboxylate. In accordance with the present invention there is provided a process for producing a bismuth dithiocarbamate or dithiophosphorate by the reaction of a bismuth hydroxide, bismuth oxide or bismuth oxynitrate with either a dithiocarbamate or dithiophosphoric acid.
WO 01/32612 PCT/GBOO/03909 2 In the reaction, water is produced as a by-product, which can be easily removed from the reaction. The bismuth dithiocarbamate or dithiophosphorate produced in this process is free from the contaminants contained in the organometallic dithio-compounds produced by the prior art methods. The bismuth dithiocarbamate or dithiophosphorate produced by this process is also structurally different from the organometallic dithio-compounds produced in the above mentioned prior art methods. The bismuth dithiocarbamate or dithiophosphorate produced in this process is a very good extreme pressure agent. It also exhibits very good anti-wear properties. These properties make the product useful and unique in lubricant formulations. The bismuth oxide, bismuth hydroxide or bismuth oxynitrate may be represented by the following formulas: Bi 2
O
3 , Bi(OH) 3 , or BiO(OH) 9
(NO
3
)
4 respectively. The dithiocarbamate or dithiophosphorate used as the starting material in the process of the present invention is preferably prepared prior to use, freshly distilled or generated in situ. A solvent can be used in the reaction, but is not essential. Suitable solvents are, for example, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, benzonitrile, or commonly used polar or aprotic solvents, including any viscosity grade of paraffinic and naphthanic basestocks. The preferred solvent is acetonitrile or a 100 SUS base oil. The reaction is preferably conducted at a temperature between 50 to 200 "C. The reaction is more preferably conducted at a temperature between 60 and 130 OC. The reaction is preferably conducted under pressure of 10-1000 psi of nitrogen, air or hydrogen sulfide. The most preferred pressure is between 60-250 psi of nitrogen.
WO 01/32612 PCT/GBOO/03909 3 The dithiocarbamate is preferably represented by the following formula:
R
3 S C -SH R 4 wherein R 3 and R 4 may be the same or different, or one of them is a H. R 3 and R 4 are preferably selected from the following groups: alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl or hydrocarbyl groups, optionally incorporated with hetero atoms such as nitrogen, oxygen or sulfur atoms.
R
3 and R 4 are preferably represented by the following formula:
CH
3
(CH
2 )m-X-(CH 2 )n wherein: m is 1-30, preferably 1-20, and n ranges from 1-10, preferably from 1-5. X can be oxygen, nitrogen or sulfur. When bismuth oxide, hydroxide or oxynitrate is reacted with dithiocarbamate (commonly referred to as 'DTC') in accordance with the present invention, the product can be represented by the following formula: Bi(OH),(DTC)y(NO 3 ), wherein x+y+z=3, and z is zero when the bismuth oxide or hydroxide is used as one of the starting materials. The dithiophosphoric acid is preferably represented by the following formula
R
5 0 S P- SH
R
5 0 wherein R 5 is a hydrocarbyl group having a carbon chain length of 1-20, preferably of 1-10. The dithiophosphoric acid can be prepared by reaction of the an alcohol having the R 5 group with a phosphorous pentasulfide, which is well-known to persons skilled in the art. The reaction temperature and time for the reaction of the WO 01/32612 PCT/GBOO/03909 4 bismuth oxide, hydroxide or oxynitrate with the dithiophosphoric acid are the same as mentioned above for the reaction of the bismuth hydroxide or oxide with the dithiocarbamate. The bismuth dithiophosphorate produced in accordance with the present invention is preferably represented by the following general formula: Bi(OH)m(DTP)n(NO 3 )o wherein m+n+o=3, and o is zero when Bi 2 0 3 or Bi(OH) 3 is used in the process. The product may appear as a brown-red oil or a yellow solid which is very soluble in non-polar solvents such as pentane or hexane. The product exhibits excellent solubility in paraffinic or naphthanic base stocks. The bismuth dithiocarbamates and dithiophosphorates produced in the process of the present invention exhibit load-carrying and antiwear characteristics. The bismuth dithiocarbamates and dithiophosphorates may, for example, be incorporated into a standard grease formulation. The present invention will now be described, by way of example only, with reference to the following examples: Example 1 Preparation of Bismuth (1ll) diamyldithiocarbamate using Bismuth Oxide A suspension of bismuth (Ill) oxide (9.2g, 0.0198 mol) and diamyldithiocarbamate (27.9g, 0.119 mol) was prepared in acetonitrile (200 ml). The suspension was brought to reflux and then maintained at that temperature for 5 hours. A brown suspension was produced. The brown suspension was filtered, and the solvent was evaporated under reduced pressure to produce a viscous brown liquid (13.0g).
WO 01/32612 PCT/GBOO/03909 5 Example 2 Preparation of Bismuth (111) Dioctyldithiocarbamate using Bismuth Oxide A suspension of bismuth (111) oxide (34.3g, 0.0736 mol) and di-n-octylamine (106g, 0.4416 mol) was prepared in acetonitrile (200 ml). The suspension was cooled to 15 'C, followed by a slow addition of carbon disulfide (27 ml, 0.4416 mol) over a 30 minute period. The mixture was then refluxed for 5 hours during which the colour of the mixture changed from yellow to a brownish colour. The resultant mixture was filtered and the solvent was evaporated under reduced pressure to produce a viscous brown oil (120g). Example 3 Preparation of Bismuth (111) Diamyldithiocarbamate Using Bismuth Oxynitrate A suspension of bismuth (Ill) oxynitrate (20.5g, 0.0789 mol) and diamylamine (37.2g, 0.2367 mol) was prepared in acetonitrile (200 ml). Carbon disulfide (15mI, 0.2367 mol) was slowly added at ambient temperature. A slight exotherm occurred which took the reaction temperature up by 10 0 C. A yellow mixture was produced which was refluxed for 5 hours to produce a brown liquid. The brown liquid was filtered and the solvent was evaporated to produce a brown liquid (40g). Example 4 Preparation of Bismuth (Ill) Diisononyldithiocarbamate Using Bismuth Oxynitrate A suspension of bismuth (111) oxynitrate (24.4g, 0.0936 mol) and diisononylamine (75.5g, 0.2808 mol) was prepared in acetonitrile (200 ml). Carbon disulfide (17ml, 0.2367 mol) was added slowly at ambient temperature. A slight exotherm took place on addition of the carbon disulfide which brought the temperature up by 10 *C. A yellow mixture was produced which was refluxed for 5 hours. After filtration and WO 01/32612 PCT/GBOO/03909 6 solvent removal, the product produced was a brown paste (47g). Further purification was conducted by dissolving the brown paste in hexane (300 ml), followed by cooling at 40 OF overnight to effect recrystallization and produce a bright yellow solid. Example 5 Preparation of Bismuth (Ill) 2-Ethylhexyldithiophosphorate Using Bismuth Hydroxide A suspension of bismuth (ll) hydroxide (27.0g, 0.1036 mol) and 2,6-di-t-butyl-4-methyl phenol (BHT, 500mg) was prepared in acetonitrile (200ml). 2-ethylhexyldithiophosphoric acid (109g, 0.3108 mol) was added over a 15 minute period. The resultant suspension was heated under reflux for 8 hours to produce a yellow liquid. The yellow liquid was filtered and the solvent was evaporated under reduced pressure to produce a reddish oil (131g). The performance of the bismuth dithiocarbamate and bismuth dithiophosphorate prepared above in Examples 3 and 5 respectively were compared to a commercial EP additive. The results are given below: TEST ASTM Grease with Grease with Grease with METHOD Commercial BiDADTC BiDIODTP EP Additive prepared in prepared in Example 3 Example 5 Four-ball EP D-2596 400 500 400 Weld Load, Kg Four-ball D2265 0.54 0.83 0.51 Wear mm Scar The grease used in the above test was lithium 12-hydroxystearate. The commercial EP additive was antimony dithiocarbamate. As shown above, the oil-soluble bismuth dithiocarbamate prepared in Example 3 exhibited better EP results than the commercial EP additive.
WO 01/32612 PCT/GBOO/03909 7 As also shown above, the bismuth dithiophosphorate prepared in Example 5 exhibited better wear results than the commercial EP additive. The oil-soluble bismuth dithiophosphorates produced in the above Examples also exhibited an improved reduction in the coefficient of friction and enhanced thermo-oxidative stability.
Claims (15)
1. A process for producing a bismuth dithiocarbamate or dithiphosphorate by the reaction of bismuth hydroxide, bismuth oxide or bismuth oxynitrate with a dithiocarbamate or dithiophosphoric acid.
2. The process claimed in claim 1, wherein the bismuth oxide, bismuth hydroxide or bismuth oxynitrate is represented by the following formulas: Bi 2 0 3 , Bi(OH) 3 , or BiO(OH) 9 (NO 3 ) 4 respectively.
3. The process claimed in claims 1 or 2, wherein a solvent is not used in the process.
4. The process claimed in claim 3, wherein the solvent is selected from: dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, benzonitrile, or commonly used polar or aprotic solvents including paraffinic and naphthanic basestocks.
5. The process claimed in claims 3 or 4, wherein the solvent is acetonitrile or a 100 SUS base oil.
6. The process claimed in any one of the preceding claims, wherein the reaction is conducted at a temperature between 50 to 200 "C, preferably at a temperature between 60 and 130 "C.
7. The process claimed in any one of the preceding claims, wherein the reaction is conducted under pressure between 10-1000 psi of nitrogen, air or hydrogen sulfide; preferably 6-250 psi of nitrogen.
8. The process claimed in any one of the preceding claims, wherein the dithiophosphoric acid is represented by the following formula: WO 01/32612 PCT/GBOO/03909 9 R 3 S C -SH R 4 wherein R 3 and R 4 may be the same or different, and only one of them is a H; R 3 and R 4 are selected from the following groups: alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl or hydrocarbyl groups, optionally with hetero atoms such as nitrogen or oxygen atoms; and R 3 and R 4 are preferably represented by the following formula: CH 3 (CH 2 )m-X-(CH 2 )n wherein: m is 1-30, preferably 1-20, and n ranges from 1-10, preferably from 1-5. X can be oxygen or nitrogen.
9. The process claimed in any one of the preceding claims, wherein the process produces a bismuth dithiocarbamate represented by the following formula: Bi(OH),((DTC)y(NO3), wherein x+y+z=3, and z is zero when the bismuth oxide or hydroxide is represented by Bi 2 0 3 or Bi(OH) 3 .
10. The process claimed in any one of the preceding claims, wherein the dithiophosphoric acid is represented by the following formula: R 5 0 S \| P- SH R 5 0 wherein R 5 is a hydrocarbyl group having a carbon chain length of 1-20, preferably of 1-10.
11. The process claimed in claim 10, wherein the process produces a bismuth dithiophosphorate represented by the following general formula: Bi(OH)m(DTP)n(NO 3 )o wherein m+n+o=3, and o is zero when Bi 2 0 3 or Bi(OH) 3 is used. WO 01/32612 PCT/GBOO/03909 10
12. Use of the bismuth dithiocarbamate or dithiophosphorate produced by any one of the processes claimed in claims 1-11, as an extreme pressure agent and/or an antiwear agent.
13. A lubricant or a grease comprising the bismuth dithiocarbamate or dithiophosphorate produced in any one of claims 1-11.
14. A bismuth dithiocarbamate represented by the following general formula: Bi(OH),(DTC)y(NO3), wherein x+y+z=3.
15. A bismuth dithiophosphorate represented by the following general formula: Bi(OH).(DTP)n(NO 3 )o wherein m+n+o=3.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16356999P | 1999-11-05 | 1999-11-05 | |
| US60163569 | 1999-11-05 | ||
| GB0002524 | 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 |
| PCT/GB2000/003909 WO2001032612A1 (en) | 1999-11-05 | 2000-10-12 | A process for producing bismuth dithiocarbamates and dithiophosphorates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU1035601A true AU1035601A (en) | 2001-05-14 |
Family
ID=26243562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU10356/01A Abandoned AU1035601A (en) | 1999-11-05 | 2000-10-12 | A 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1498472B1 (en) | 2003-07-04 | 2016-11-16 | JTEKT Corporation | Use of a Grease Composition in a Rolling Bearing |
| DE102012014395B3 (en) * | 2012-07-13 | 2013-08-22 | Oxea Gmbh | Isononylamines starting from 2-ethylhexanol, process for their preparation and their use |
| CN105056986B (en) * | 2015-08-10 | 2017-04-05 | 南京信息工程大学 | A kind of method and catalyst applications for preparing lamellar hydroxyl bismuth subnitrate photocatalyst |
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 EP EP00971516A patent/EP1226117A1/en not_active Withdrawn
- 2000-10-12 CN CN 00815376 patent/CN1387510A/en active Pending
- 2000-10-12 BR BR0015134-3A patent/BR0015134A/en not_active IP Right Cessation
- 2000-10-12 CA CA002389296A patent/CA2389296A1/en not_active Abandoned
- 2000-10-12 JP JP2001534765A patent/JP2003513067A/en active Pending
- 2000-10-12 WO PCT/GB2000/003909 patent/WO2001032612A1/en not_active Ceased
- 2000-10-12 AU AU10356/01A patent/AU1035601A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| BR0015134A (en) | 2002-06-25 |
| EP1226117A1 (en) | 2002-07-31 |
| CA2389296A1 (en) | 2001-05-10 |
| CN1387510A (en) | 2002-12-25 |
| JP2003513067A (en) | 2003-04-08 |
| WO2001032612A1 (en) | 2001-05-10 |
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