Classifications

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  • 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
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/02—Well-defined hydrocarbons
  • C10M105/04—Well-defined hydrocarbons aliphatic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2282—Unsaturated compounds used as ligands
  • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
  • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
  • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
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  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
  • C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
  • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C323/45—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms doubly-bound to the carbon skeleton
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  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/04—Nickel compounds
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  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/04—Nickel compounds
  • C07F15/045—Nickel compounds without a metal-carbon linkage
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
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  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/08—Butenes
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
  • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
  • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
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  • 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
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
  • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/824—Palladium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/847—Nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
  • B01J2540/20—Non-coordinating groups comprising halogens
  • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
  • B01J2540/225—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate comprising perfluoroalkyl groups or moieties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
  • B01J2540/30—Non-coordinating groups comprising sulfur
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
  • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
  • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
  • C07C2603/20—Acenaphthenes; Hydrogenated acenaphthenes
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  • C07C2603/00—Systems containing at least three condensed rings
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  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
  • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
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  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/302—Viscosity
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  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/304—Pour point, cloud point, cold flow properties
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  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/10—Lubricating oil
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  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
  • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

• the invention relates to the field of base oils in the field of catalysis and lubricating oils, in particular to a class of X-diimine nickel, palladium catalysts and preparation techniques thereof, and under the action of such catalysts, direct realization of olefins such as ethylene, propylene and butene Process for the preparation of oily hyperbranched alkanes and use of oily hyperbranched alkanes.
• Industrial base oils for lubricating oils are mixtures of various branched alkanes obtained by petroleum cracking or alpha-olefin oligomerization. Among them, hydrazine is a very important and excellent lubricating base oil obtained by oligomerization of ⁇ -olefins.
• the main raw materials are ⁇ -octene, ⁇ -pinene, ⁇ -dodecene and other expensive high-grade ⁇ . - olefins.
• the premise of obtaining high-quality base oils is that it is necessary to first catalyze the oligomerization of ethylene to obtain ⁇ -olefins, especially ⁇ -pinene. It is technically difficult to selectively produce ⁇ -olefins of C6 or higher.
• the preparation of high-performance base oils directly from inexpensive olefins such as ethylene, propylene, and butene is economical and efficient.
• inexpensive olefins such as ethylene, propylene, and butene
• Nickel complexes were considered to be only catalysts for olefin oligomerization before 1995.
• the well-known SHOP catalyst can catalyze the oligomerization of ethylene to obtain a series of ⁇ -olefins in accordance with the Flory distribution.
• Braokhart et al. J. Am. Chem. Soc. 1995, 117, 6414.
• Polymerization obtained branched high molecular weight polyethylene, the melting point (Tm) of the polymer is between 39-132 ° C, lower than ordinary polyethylene resin.
• Du Pont has applied for a number of patents in this regard (WO 96/23010, WO 98/03521, WO 98/40374, WO 99/05189, WO 99/62968, WO 00 /06620, US 6, 103,658, US 6,660,677) This type of polymeric product is protected.
• An oily polyethylene can be obtained from the corresponding cationic palladium system.
• the polyolefin has a high degree of branching, but its catalytic activity is very low, and the catalyst is known to have a very serious ⁇ - ⁇ elimination phenomenon. Under the action of the catalyst, ⁇ - The elimination of carbon-carbon double bonds and Pd-H species is the most important route for this type of catalytic cycle, so the polymer has high unsaturation (high bromine number).
• the morphology and properties of polyethylene are closely related to its degree of branching, and the catalyst structure is the core of the control of polyethylene structure.
• the polyethylene obtained by the nickel-based catalyst of Braokhart et al. already has a certain degree of branching, but still cannot meet the requirements of applications such as lubricating base oils, and the product is in a solid state.
• Industrial synthetic lubricants are required to maintain viscosity over a wide temperature range, that is, to have a high viscosity index, while having a lower pour point, comparable to a third type of oil (class III base oil) or The pour point is lower.
• the degree of branching BI of the polymer can be better correlated with these properties of the lubricating oil.
• the characterization of the NMR of the H NMR is 0. 5_2. 1 section.
• the pour point of the lubricating oil will decrease, that is, the lubricating oil will change from liquid to solid. The temperature will decrease and the pour point will help to expand the application of the lubricant.
• the goal of synthetic lubricants is to ensure that the lubricants remain liquid at reduced temperatures, while having a high viscosity index and maintaining a high viscosity at high temperatures such as 100 °C.
• the catalyst system can directly produce a highly branched oily polymer from an inexpensive olefin such as ethylene, propylene or butene.
• Another object of the invention is to provide a use of a novel class of catalytic systems for the synthesis of highly branched alkanes.
• Another object of the present invention is to provide a class of highly branched alkanes useful in advanced lubricating base oils.
• Z and Y are each hydrogen, dC 4 alkyl or dC 4 haloalkyl, unsubstituted or substituted phenyl, or Z and Y together with an adjacent carbon atom constitute an unsubstituted or substituted group selected from the group consisting of: An anthracenyl, phenanthryl and C5-C8 cycloalkyl group, wherein the substituted phenyl, indenyl, phenanthryl or cycloalkyl has from 1 to 5 substituents selected from the group consisting of halogen, dC 4 alkane And dC 4 haloalkyl;
• RR 2 , R 3 and R 4 are each H, halogen, dC 8 alkyl, dC 8 haloalkyl, unsubstituted or substituted phenyl, -0-R a , -CH 2 -0-R a , -SR b Or -CH 2 -SR b , wherein ⁇ and R b are respectively dC 8 alkyl, unsubstituted or substituted phenyl, and RR 2 , R 3 and R 4 satisfy the condition: R ⁇ R 3 and/or R 2 ⁇ R 4 ; the substituted phenyl group has 1 to 5 substituents selected from the group consisting of halogen, dC 4 alkyl and dC 4 haloalkyl;
• R 5 , R 6 and R 7 are each independently halogen, nitro, hydrogen, dC 8 alkyl, Ci-C 8 haloalkyl, -0-R a , -CH 2 -0-R a , or -N (FQ 2 , wherein ⁇ 8 is an alkyl group, an unsubstituted or substituted phenyl, and ⁇ 4 is alkyl or haloalkyl; said substituted phenyl substituted with 1-5 substituents selected from the group group: halo, dC 4 Alkyl and dC 4 haloalkyl.
• 1-3 substituents of RR 2 , R 3 and R 4 are dC 8 alkyl, dC 8 haloalkyl or unsubstituted or substituted phenyl, and 1-3 substituents are H Or halogen.
• the substituted phenyl group has 1-3 substituents.
• Z and Y together with adjacent carbon atoms constitute an unsubstituted or substituted fluorenyl group.
• R 1 and R 2 are selected from the group consisting of H, methyl, halogen or -CH 2 -0-R a .
• R 1 and R 2 are selected from the group consisting of phenyl, benzyl, halogen or -CH 2 -0-R a .
• R 1 and R 2 are selected from the group consisting of: -SR b or -CH2-SR, and in a second aspect of the invention, a complex is provided, the complex being the present invention A complex formed on the one hand with a divalent metal salt selected from the group consisting of nickel, palladium or a combination thereof.
• Z, Y, RR 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined above;
• X is halogen, dC 4 alkyl, C 2 -C 6 alkenyl, allyl or benzyl.
• X is chlorine, bromine, iodine, methyl, allyl or benzyl.
• X is chlorine, bromine or iodine.
• the compound of the first aspect is reacted with a divalent metal salt in an inert solvent to form a complex described in the second aspect, wherein the metal precursor is a divalent nickel compound or a divalent palladium compound.
• the metal precursor comprises: NiCl 2 , NiBr 2 , Nil 2 , (DME)NiBr 2 , PdCl 2 , PdBr 2 , Pd(OTf) 2 , Pd(OAc) 2 or a combination thereof .
• reaction is carried out under almost anhydrous conditions (e.g., water content ⁇ 0.1%).
• reaction is carried out under an inert atmosphere such as nitrogen.
• step (a) or the step (b) is heated in an inert solvent for 1-96 hours (preferably, 2-72 hours).
• 0.001 to 100% of a corresponding catalyst for promoting the condensation reaction is added to the step or step (b), wherein acetic acid, p-toluenesulfonic acid, TiCl 4 , orthosilicate are preferred.
• the ratio of the compound A to the B in the step (a) is (0.7 - 1.2): 1.
• the ratio of the compound C to D in the step (b) is (0.7 - 1.2): 1.
• the inert solvent in the step (a) or the step (b) comprises: an alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, a halogenated hydrocarbon, an ether, an ester solvent.
• the inert solvent in the step (a) or the step (b) is methanol, ethanol, toluene, xylene or trimethylbenzene.
• the olefin comprises an unsubstituted C 2 -C 1Q olefin, substituted. Olefins or combinations thereof.
• the olefin is ethylene, propylene, butylene or any combination thereof.
• the olefin is any combination of ethylene, propylene and/or butene with other c 5 -c 12 olefins. In another preferred embodiment, the olefin is ethylene.
• the oily polyethylene is highly branched; more preferably, the high branching refers to polyethylene.
• the number of methyl groups corresponding to 1000 methylene groups (CH 2 ) is 100-500.
• a cocatalyst is also present in step (a).
• the cocatalyst is selected from the group consisting of alkylaluminum reagents (e.g., alkyl aluminoxanes, diethylaluminum chloride and ethylaluminum dichloride).
• alkylaluminum reagents e.g., alkyl aluminoxanes, diethylaluminum chloride and ethylaluminum dichloride.
• reaction temperature of the step (a) is from 0 to 100 °C.
• reaction conditions of the step (a) are: pressure (gauge pressure) 0.1-3 MPa, the cocatalyst is an alkyl aluminoxane or diethyl aluminum chloride, wherein the promoter aluminum and the nickel in the catalyst The molar ratio is 10-5000.
• step (a) is carried out under a polymerization solvent selected from the group consisting of toluene, n-hexane, dichloromethane, 1,2-dichloroethane, chlorobenzene, tetrahydrofuran or a combination thereof.
• a polymerization solvent selected from the group consisting of toluene, n-hexane, dichloromethane, 1,2-dichloroethane, chlorobenzene, tetrahydrofuran or a combination thereof.
• step (a) can be carried out in an oily polyethylene or oily alkane mixture.
• the method further includes the steps of:
• the oily alkane mixture has the following characteristics:
• step of step (a) and step (b) further comprises the step of: separating the oily polyolefin.
• step (b) can be carried out in an inert solvent or directly with an oily polyolefin as a solvent.
• an oily olefin polymer having the following characteristics: 1000 methylene corresponding to a methyl group of 100 to 500 and a molecular weight of 300 to 500,000 g/ Mol.
• the oily polymer is prepared by the method of the fifth aspect of the invention.
• the oily olefin polymer is an oily polyethylene.
• an oily alkane mixture characterized in that the oily alkane mixture has the following characteristics: 1000 methylene corresponding to a methyl group of 100 to 500 and a bromine number of less than 0.5 g/100 g.
• the oily alkane mixture is a hydrogenated product of the oily polyolefin described in the sixth aspect. In another preferred embodiment, the oily alkane mixture is a hydrogenated product of an oily polyethylene.
• oily alkane mixture is prepared by the following method:
• the oily alkane mixture has the following characteristics:
• step of step (a) and step (b) further comprises the step of: separating the oily polyethylene.
• the hydrogenation reaction is simultaneously carried out in the step (a).
• step (b) may be carried out in an inert solvent or directly with an oily polyolefin as a solvent.
• oily alkane mixture of the seventh aspect of the invention which is used as a base oil for lubricating oils, an additive for lubricating oils, a plasticizer or a processing aid for resins.
• a lubricating oil comprising the oily alkane mixture of the seventh aspect.
• the lubricating oil contains from 0.1 to 100% by weight, preferably from 1 to 90% by weight, of the oily alkane mixture.
• the complex of the second aspect of the invention which is used as a catalyst for the polymerization of olefins.
• the olefin polymerization is carried out under homogeneous conditions.
• the catalyst is supported on an inorganic or organic support.
• an oily alkane mixture having the following characteristics: (a) a viscosity index of from 100 to 300; (b) a pour point of from -50 ° C to -10 ° C (c) a molecular weight of 300 to 500,000 g/mol; and (d) a number of methyl groups corresponding to 100 to 500 per 1000 methylene groups.
• the oily alkane mixture further has the following characteristics:
• the oily alkane mixture has a viscosity index of from 150 to 300, more preferably from 180 to 300, most preferably from 200 to 290.
• the degree of branching is 0.20 to 0.50, preferably 0.22 to 0.45, more preferably 0.24 to 0.40.
• the oily alkane mixture has a molecular weight of from 500 to 500,000 g/mol, more preferably from 800 to 200,000 g/mol, from 1000 to 100,000 g/mol.
• a process for the preparation of the oily alkane mixture according to the eleventh aspect comprising the step of obtaining an oily alkane mixture by hydrogenation reaction of an oily olefin polymer, wherein the oily olefin polymer has the following Features: 1000 methylene corresponding to 100-500 methyl groups and molecular weight 300-500,000 g/moL
• the oily olefin polymer (i.e., oily polyolefin) contains from about 100 to about 500 alkyl branches per 1000 methylene groups and contains 20 per 100 methyl branches. - 100 ethyl branches, 2-50 propyl branches, 20-100 butyl branches, 2-50 pentyl branches and 20-200 hexyl or longer branches.
• a lubricating oil comprising a base oil and an additive, the base oil being the oily alkane mixture of the eleventh aspect.
• the additive is selected from the group consisting of a viscosity index improver, a pour point depressant, an antioxidant, a detergent dispersant, a friction moderator, an oil agent, an extreme pressure agent, an anti-foaming agent, and a metal passivation.
• the additive is selected from the group consisting of a viscosity index improver, a pour point depressant, an antioxidant, a detergent dispersant, a friction moderator, an oil agent, an extreme pressure agent, an anti-foaming agent, and a metal passivation.
• Figure 1 shows a polymer nuclear magnetic carbon spectrum prepared in an example of the present invention.
• Figure 2 shows the structure of the complex in one example of the present invention. detailed description
• the inventors have conducted extensive and intensive research to prepare novel ligand compounds, complexes and catalytic systems by changing the structure of the catalyst, thereby catalyzing the direct polymerization of ethylene for the first time to obtain a highly branched oily polymer.
• the catalytic system can also directly catalyze the direct polymerization of olefins such as propylene and butene to obtain a highly branched oily polymer.
• the oily polymer of the present invention can be used to prepare highly branched alkanes with excellent properties, which greatly reduces the cost of high-grade lubricating oils.
• the present invention has been completed on this basis. the term
• Class I base oil means that the production process is based primarily on physical processes and does not alter the base oil produced by the hydrocarbon structure. The quality of Group I base oils is greatly affected by the raw materials and is limited in performance.
• Group II base oil refers to a base oil produced by a combination process (a combination of a solvent process and a hydrogenation process). Although the properties such as thermal stability have been improved, the properties such as viscosity index and pour point are not satisfactory.
• Class II I base oil refers to a base oil produced by a full hydrogenation process. Although Class II I base oils have the advantage of low volatility, some properties such as viscosity index and pour point are still not sufficient for certain applications.
• Representative olefins include substituted or unsubstituted C2-C10 olefins, preferably C2-C6 olefins such as ethylene, propylene, butylene, and the like.
• the kind and amount of the substituent are not particularly limited, and usually one monomer may have 1 to 5 substituents, and representative substituents include, but are not limited to, a hydroxyl group, an ester group, a silyl group, a silyl group, an amine group ( Substituted amine), cyano, halogen, ketone carbonyl, heterocyclic substituent, carboxy, trifluoromethyl.
• Representative substituted olefins are various functionalized polar monomers that are still capable of undergoing polymerization.
• each group is as defined above.
• Functional groups which may be present in the Z, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 substituted hydrocarbyl groups include hydroxy, ether, ester, dialkylamino, carboxy, oxo (aldehyde) Ketone), nitro, amide, thioether.
• Preferred groups are hydroxy, ether, dialkylamino groups.
• Z and Y are each independently methyl, phenyl, or phenyl substituted by alkyl, halogen, alkoxy; said halogen includes fluorine, chlorine, bromine or iodine; said alkoxy
• the group is preferably a methoxy group, an ethoxy group or an isopropoxy group; the alkyl group-substituted phenyl group is preferably a phenyl group substituted by a 6 alkyl group, more preferably a dC 4 alkyl group, most preferably a methyl group, an ethyl group, Isopropyl and butyl groups, the substituent group may be in any position of the phenyl ring which may be substituted
• Z and Y together with adjacent carbon atoms form a mercapto group .
• Z and Y together with adjacent carbon atoms form a cyclohexyl group.
• R 1 2 is ⁇ 8 ⁇ 8 alkyl group or a substituted alkyl group, and R 3, R 4 is hydrogen, halogen or CF 3; with the proviso that I 1, R 2 and R 3, R 4 are not identical;
• R 11 2 is 8 hydrocarbyl or 8- substituted alkyl
• R 3 is hydrogen, halogen or CF 3
• 11 4 is an 8- substituted alkyl group.
• RR 2 is dC 4 alkyl or ⁇ 4 substituted alkyl
• R 3 is halogen or CF 3 and R 4 is halogen.
• R 1 and 11 2 are 11, methyl, halogen, -CH 2 -0-Ra or -0-Ra.
• R 1 and R 2 are phenyl, benzyl, halogen, -CH 2 -0-Ra or -0-Ra.
• R1 and R2 are selected from the group consisting of: -SR b or -CH 2 -SR b .
• R 5 , R 6 , R 7 are hydrogen, dC 8 alkyl, dC 8 substituted alkyl, halogen, nitro, methoxy, dimethylamino, trifluoromethyl;
• the substituted alkyl group is preferably an alkyl group substituted by a halogen, an alkoxy group or a phenoxy group;
• the halogen includes fluorine, chlorine, bromine or iodine;
• the alkoxy group is preferably a methoxy group or an ethoxy group. Isopropoxy group, more preferably methoxy.
• the compound of formula I can be reacted with a divalent nickel or a divalent palladium metal salt to form the corresponding nickel or palladium complex.
• X may be halogen, dC 4 alkyl, C 2 -C 6 alkenyl, allyl, benzyl; the CC 4 alkyl group is preferably a methyl group; the halogen is preferably bromine, chlorine or iodine.
• X is chlorine, bromine, iodine, methyl, allyl or benzyl.
• X is chlorine, bromine or iodine.
• the ligand compound I of the present invention can be reacted with a corresponding divalent metal precursor in an inert solvent to form a complex.
• the divalent nickel or divalent palladium metal salt as the metal precursor of the reaction comprises: NiCl 2 , NiBr 2 , Nil 2 , (DME) NiBr 2 (DME) NiCl 2 , (DME) NiI 2 PdCl 2 , PdBr 2 , Pd(OTf) 2 and Pd(OAc) 2 .
• the metal complex of the present invention can catalyze the polymerization of ethylene under the action of a cocatalyst to give an oily polymer. Preparation of ligand compounds and complexes
• the invention also provides a synthesis of a compound of the formula S, comprising the steps of:
• a corresponding catalyst for promoting the condensation reaction such as acetic acid, p-toluenesulfonic acid, TiCl 4 , orthosilicate.
• a corresponding catalyst for promoting the condensation reaction such as acetic acid, p-toluenesulfonic acid, TiCl 4 , orthosilicate.
• the diketone A and the amine B are mixed in an inert solvent, and activated under the activation of 0.001-100% acetic acid or the like to form a monoimine C, and C continues to react with the amine D to obtain a product represented by the formula (I).
• the inert solvent may be all solvents commonly used in condensation reactions, including alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ethers, ester solvents, preferably alcohol solvents such as methanol, ethanol; aromatic hydrocarbon solvents may also be given Excellent results, such as toluene, xylene, toluene, etc.
• different substituent groups should be selected for the two amines B and D, especially RR 2 and R 3 , R 4 , but the substituent groups at the 2 and 6 positions in the same amine compound may be the same. Or different.
• the step (a) or the step (b) is preferably heated separately in an inert solvent for 1-96 hours.
• step (a) or the step (b) it is preferred in the step (a) or the step (b) to add 0.001 to 100% of a corresponding catalyst for promoting the condensation reaction, of which acetic acid, p-toluenesulfonic acid, TiCl 4 and orthosilicate are preferred.
• the ratio of the preferred compounds A to B in the step (a) is (0.7 - 1.2): 1.
• the ratio of the preferred compounds C to D in the step (b) is (0.7 - 1.2): 1.
• the preferred inert solvents in step (a) or step (b) are alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ethers, ester solvents.
• step (a) or step (b) is methanol, ethanol, toluene, xylene or trimethylbenzene.
• Step (a) The separated C is separated and purified or directly subjected to the step (b) without separation and purification.
• the invention also provides a method of preparing a complex.
• compound I and a metal precursor including NiCl 2 , NiBr 2 Nil 2 or (DME)NiBr 2 , (DME)NiCl 2 , (DME)NiI
• inertia The effect in the solvent is obtained.
• the inert solvent may be any solvent which is conventionally used and does not affect the progress of the reaction, and includes alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ethers, esters, nitrile solvents, preferably halogenated hydrocarbon solvents.
• halogenated hydrocarbon and a lipid solvent and preferred examples are dichloromethane, 1,2-dichloroethane, ethyl acetate, and tetrahydrofuran.
• Ri-R 7 X is as described above.
• DME means ethylene glycol dimethyl ether; when X is a hydrocarbon group, such as a methyl group or a benzyl group, it is often possible to use a corresponding chloride or bromide oxime with a methyl Grignard reagent or a benzyl Grignard reagent.
• X in the complex is a halogen or a hydrocarbon group or any other group which can coordinate with the nickel metal, such as a nitrogen-containing compound or an oxygen-containing compound, as long as the complex is in the alkyl group.
• This catalysis can be achieved by the formation of Ni-C bonds or Ni-H bonds by the action of aluminum.
• the present invention provides a catalytic system capable of catalyzing the polymerization of olefins such as ethylene to obtain a mixture of high-branched alkane, the catalytic system comprising 1) a complex of a nickel, palladium metal precursor and a ligand of formula I; 2) Hydrogenation system.
• each group is as defined above.
• the catalytic system composed of the above catalyst and the hydrogenation catalyst can realize the direct preparation of highly branched alkanes from inexpensive olefins such as ethylene, propylene and butylene.
• the hyperbranched alkane refers to an aliphatic hydrocarbon having a methyl group number of from 100 to 500 and a bromine number of less than 0.5 g/100 g per 1000 methylene groups in the polymer chain.
• this method consists of the following two steps.
• the metal complex is a complex of compound I with divalent nickel or palladium, preferably a nickel complex of the formula ⁇ .
• the cocatalyst is a reagent capable of promoting the catalytic reaction, and may be an alkyl aluminum compound or an organic boron reagent.
• the alkyl aluminum compound includes any compound containing a carbon-aluminum bond, including methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), triethyl aluminum, triisobutyl aluminum. , diethyl aluminum chloride, ethyl aluminum dichloride, and the like.
• the molar ratio of the promoter aluminum to the nickel or palladium in the catalyst is 10-5000; the methylaluminoxane or the aluminum alkyl reagent can be used as a co-catalyst to assist the nickel or palladium complex to catalyze the polymerization of the olefin to obtain an oily polyolefin, and
• the structure of the aluminoxane or the aluminum alkyl reagent does not affect the promotion, but the degree of branching or molecular weight of the resulting polymer may vary depending on the structure of the promoter, wherein methylaluminoxane The best results were obtained with diethylaluminum chloride and ethylaluminum dichloride.
• A1C1 3 alone or in combination with an alkyl aluminum compound can also be a pro-catalytic effect.
• the highly branched polyolefins (e.g., polyethylene) of the present invention can be hydrogenated to form highly branched alkanes.
• the structure of the highly branched polyolefin (e.g., polyethylene) is determined by comparing the molecular weight measured by 13 C NMR and high temperature GPC with the actual molecular weight measured by high temperature laser light scattering.
• the polymer obtained in Example 41 has a molecular weight of 4570 g/mol as measured by GPC, and the molecular weight measured by laser light scattering is 46,400 g/mol, thereby demonstrating that the structure of the highly branched polyethylene is spheroidal. .
• the hyperbranched alkane has a molecular weight of between 500 and 500,000 g/mol and is a clear, transparent oil.
• the hyperbranched alkane means that the alkane has a spheroidal or dendritic structure, ie, R 8 R 9 CH(CH 2 ) n CHR 1Q R u or R 8 R 9 R 1Q C(CH 2 ) n CHR
• the contact time of ethylene with nickel or palladium complex and alkyl aluminum compound in an inert solvent in step 1 may vary from 0.5 hours to 72 hours, and the reaction temperature ranges from 0 to - At 100 degrees, the pressure (referred to as gauge pressure) varies from 0.1 to 3 Mpa (l-30 atmospheres).
• the hyperbranched oily polyethylene obtained in the step 1 is reacted with a reducing agent or the oily polyethylene is contacted with hydrogen under the action of one or more reducing catalysts to obtain a highly branched oily alkane mixture.
• the bromine number is below 0.5 g/100 g.
• the reduction catalyst may be any catalyst which can promote the hydrogenation process, preferably from hydrogenation catalysts such as Pd/C, Pd(OH) 2 , Pt0 2 , ruthenium, nickel, ruthenium, etc., and the reduction reagent includes any conventional reagent capable of reducing double bonds.
• hydrogenation catalysts such as Pd/C, Pd(OH) 2 , Pt0 2 , ruthenium, nickel, ruthenium, etc.
• the reduction reagent includes any conventional reagent capable of reducing double bonds.
• step of step (1) and step (2) further comprises the step of: separating the oily polyethylene.
• the hydrogenation reaction is simultaneously carried out in the step (1).
• the step (2) may be carried out in an inert solvent or directly with an oily polyethylene as a solvent; the step (1) may be carried out in an inert solvent or in an oily polyethylene as a solvent.
• the step (2) can also be accomplished as follows: a) when performing the step (1), simultaneously introducing hydrogen gas to directly obtain a highly branched oily alkane; b) after performing the step (1), not performing Treating, introducing hydrogen into the polymerization system to obtain a highly branched oily alkane; c) after carrying out the step (1), without treatment, directly adding one or more reduction catalysts to the polymerization system for hydrogenation, thereby obtaining Highly branched oily alkane; d) After carrying out step (1), the oily polyethylene is separated and subjected to a hydrogenation reaction.
• the above reaction can be carried out in an inert solvent, preferably an alcohol, an alkane, an aromatic hydrocarbon and a halogenated hydrocarbon, wherein in the step (1), a C 5 - C 12 saturated hydrocarbon such as hexane, heptane or a halogenated hydrocarbon such as two is preferable.
• a C 5 - C 12 saturated hydrocarbon such as hexane, heptane or a halogenated hydrocarbon such as two is preferable.
• Preferred in the step (2) are C 5 - C 12 saturated hydrocarbons such as hexane, heptane; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloro Ethane; aromatic hydrocarbons such as toluene and xylene.
• the catalyst system can also efficiently catalyze the polymerization of propylene and butene to obtain an oily polymer, or contact with any combination of ethylene, propylene or butene to achieve the above catalytic reaction. Oily polymer.
• the ethylene, propylene or butene system contains some other C 5 -C 12 olefins, such as hexene and octene, the above-mentioned catalytic polymerization results are not affected, and the obtained polymer is still oily and has a high degree of support.
• the polymer is a dendritic or spherical, spheroidal polymer which can also obtain highly branched alkanes by hydrogenation step (2).
• the step of step (1) and step (2) further comprises the step of: separating the oily polyethylene.
• the above The operation of directly obtaining a highly branched alkane by ethylene is equally applicable to these olefins, that is, in another preferred embodiment, the hydrogenation reaction is simultaneously carried out in the step (1); in another preferred embodiment, the step (2) may be The hydrogenation reaction is carried out in an inert solvent or directly as an oily polyolefin; the step (1) can be carried out in an inert solvent or in an oily polyolefin as a solvent.
• olefins used in the present invention may have a double bond at the end group or an internal olefin, and do not affect the catalytic effect.
• the internal olefin refers to a double bond at any position other than the terminal group.
• the internal olefin of the same olefin may be a mixture of a plurality of isomers or a single internal olefin, for example, for butene.
• 2-C4 a mixture of one or more isomers may be used at the same time without affecting the above polymerization. Oily olefin polymer and oily hydrocarbon mixture
• the catalyst disclosed in the present invention can be applied to various ethylene, propylene, butene polymerization process equipment and conventional reduction process equipment which have been used in the industry. It can be used under heterogeneous conditions using homogeneous conditions or after loading on an organic or inorganic carrier.
• the invention also provides an oily ethylene polymer and a process for the preparation thereof.
• the oily polyethylene of the present invention is highly branched; and the high branching means that the number of methyl groups corresponding to 1000 methylene groups (CH 2 ) in the polyethylene is from 100 to 500.
• a representative preparation method includes the steps of:
• composition of the present invention is used as an olefin polymerization catalyst at a temperature ranging from 0 to 100 ° C and a pressure (gauge pressure)
• a cocatalyst is also present in the step; more preferably, the cocatalyst is selected from the group consisting of: an aluminum alkyl reagent
• step (a) is carried out under a polymerization solvent selected from the group consisting of toluene, n-hexane, dichloromethane,
• the cocatalyst may be an alkyl aluminoxane MAO (or a modified alkyl aluminoxane)
• MMAO aluminum alkyl or organoboron reagent.
• the molar ratio of the promoter to the catalyst in nickel or palladium is from 1 to 5000.
• the resulting polymer contains a large number of branches, and the total number of branches can be quantitatively analyzed by 13 C NMR by judging the signals (integral areas) of C3 ⁇ 4 and C3 ⁇ 4. Further, since the mode of terminating the catalytic cycle is the elimination of ⁇ -tellurium of the metal, it is inevitable that the polymer chain contains a double bond, and the resulting oily polyolefin mixture has high unsaturation.
• the oily polymer obtained by catalyzing ethylene polymerization using a nickel catalyst has a bromine number of 38 g/100 g.
• the step (a) in the representative preparation method may further be that the complex of the present invention is in the presence of an olefin polymerization catalyst at 0-100 ° C, and the pressure (gauge pressure) varies from 0.1 to 3 Mpa (l). -30 atmospheres), catalytically polymerizing propylene, butene or any combination of ethylene, propylene, butene, and other C 5 -C 12 olefins to form an oily polyolefin.
• the present invention also provides a high-branched oily alkane mixture which is a hydrogenated product of the oily polyolefin of the present invention.
• the oily polyolefin comprises an oily polyethylene, an oily polypropylene, an oily polybutene or an oily copolymer obtained by a catalyst under the action of a catalyst.
• the oily alkane mixture of the present invention has a molecular weight of from 500 to 500,000 g/mol, and a methyl group (CH3) per 1000 methylene groups (CH2) of from 100 to 500.
• the hyperbranched alkane has a spheroidal or dendritic structure,
• R 8 -R 12 has the structure of R 13 R 14 CH(CH 2 ) m CHR 15 R 16 or R 13 R 14 R 15 C(CH 2 ) n CHR 15 R 16 R 17 , R 13 -R 17 Structure having R 18 R 19 CH(CH 2 ) X CHR 2 °R 21 or R 18 R 19 R 2 °C(CH 2 ) X CHR 2 °R 21 R 22 , R 18 , R 19 , R 20 R 21 And R 22 is hydrogen, a linear or branched alkane, and n, m and X are each an integer of from 1 to 500, preferably an integer of from 1 to 300, more preferably an integer of from 1 to 100.
• Such hyperbranched alkane mixtures of the present invention have a high viscosity index of from about 100 to about 300, preferably from about 150 to about 300; a pour point of from about -50 to about -10 ° C, while at 100 ° C.
• the viscosity is from about 5 to about 100 cSt.
• the alkane mixture is an oily polymer having a molecular weight of from about 500 to about 500,000 g/mol and a degree of branching BI of at least 0.20.
• a distinguishing feature of the alkane mixture of the present invention is that the number of methyl groups per 1000 methylene groups is from about 100 to about 500, preferably from 200 to 400. This feature makes the alkane mixture of the present invention microscopically different from a general linear polymer, and more like a spheroidal or dendritic structure, and thus more suitable as a base oil for lubricating oils.
• the alkane mixture of the present invention contains from about 20 to about 100 ethyl branches, from about 2 to about 50 propyl branches, from about 20 to about 100 butyl branches, from about 2 to about 50 per 100 methyl branches.
• the oily alkane mixture of the present invention has a low bromine number and can satisfy the requirements of the base oil.
• an oily polymer obtained by catalyzing ethylene polymerization using a nickel catalyst has a bromine number of 38 g/100 g, and its bromine number is reduced to 0.38 g/100 g after hydrogenation.
• the performance is significantly better than that of a commercially available PAO base oil.
• the viscosity index (Viscosity index) of the commercial PAO is 139, and a highly branched oil of the present invention is disclosed.
• the Viscosity index of alkanes can be as high as 261.
• such highly branched saturated alkanes may be added with various additives or reinforcing agents, such as antifreeze, and in addition, such highly branched saturated alkanes may also be used as additives to improve the resin.
• Processability for example as a plasticizer in the processing of polymers.
• Both the terminal olefin or the internal olefin can be directly used for this purpose, so that the internal olefin is also better utilized.
• the highly branched alkane of the present invention has a low bromine number, a high viscosity index, and can be used as a base oil or processing aid for advanced lubricating oils.
• the second step was to replace the aniline with 2,6-dichloroaniline, and the other operating conditions were the same to obtain an orange solid.
• v(cm _1 ) 3052, 2960, 2923, 2865, 1674, 1640, 1602, 1463, 1433, 1242, 1077, 1033, 831, 779, 760, 730; C 30 H 26 C1 2 N2 (484.45) : Anal.Calc. C 74.22, H 5.40, N 5.77; Found C 73.99, H 5.39, N 5.65.
• Example 3
• v (cm _1) 3058, 2960, 2922, 2865, 1677, 1640, 1594, 1547, 1462, 1425, 1282, 1241, 1080, 1032, 925, 831, 792, 778, 759, 725 C 30 H 26 Br 2 N 2 (574.35): Anal. Calc. C 62.74, H 4.56, N 4.88; Found C 62.69, H 4.60, N 4.73.
• Example 5 8.30-6.
• the second step was to replace the aniline with p-methoxyaniline, and the other operating conditions were the same to obtain an orange-red solid.
• 1H NMR (300 MHz, CDC1 3 ): ⁇ 7.94-6.61 (13H, m), 3.00-2.52 (2H, m), 1.26-0.91 (12H, d); 13 C NMR (75 MHz, CDC1 3 ): 161.3, 154.7, 146.9, 141.4, 135.5, 131.2, 129.4, 129.1, 129.0, 128.3, 128.0, 127.6, 126.7, 124.5, 123.8, 123.7, 123.6, 123.2, 118.5, 117.7, 77.0, 28.3, 23.5, 23.4 , 23.1, 22.3; Anal. Calcd. C 76.84, H 5.62, N 5.78; Found C 76.63, H 5.62, N 5.73.
• the second step was to replace the aniline with N,N-dimethylaniline, and the other operating conditions were the same to obtain an orange-red solid.
• 1H NMR (300 MHz, CDCI3): ⁇ 8.18-6.58 (13 H, m), 3.04 (8H, m), 1.22- 0.91 (12H, d); 13 C NMR (75 MHz, CDCI3): 161.8 , 159.2, 148.3, 147.4, 141.0, 135.6, 129.5, 129.2, 128.7, 128.3, 127.5, 124.1, 123.4, 123.3, 123.0, 120.7, 112.9, 77.0, 40.8, 28.3, 28.2, 23.7, 23.4, 23.3.
• the second step was to replace the aniline with p-chloroaniline, and the other operating conditions were the same to obtain an orange-red solid.
• 1H NMR (300 MHz, CDC1 3 ): ⁇ 8.17-6.60 (13H, m), 3.01-2.97 (2H, m), 1.23-0.93 (12H, d); 13 C NMR (75 MHz, CDC1 3 ): 161.4, 160.9, 150.1, 147.0, 131.1, 141.2, 129.5, 129.4, 129.1, 128.9, 128.4, 128.2, 127.8, 127.5, 124.4, 124.1, 123.7, 123.5, 123.1, 119.8, 119.2, 77.4, 77.0, 28.2 , 23.5, 23.4, 23.3, 23.1; Anal. Calcd. C 79.89, H 6.03, N 6.21; Found C 79.82, H 6.13, N 6.07.
• ⁇ 8.38 (1 ⁇ , d), 8.06-7.98 (3 H, d), 7.70-7.63 (2 H, m), 7.50 (1 H, t), 7.38 (1 H, t), 7.18 (2 H, d), 7.10 ( 1 H, m), 2.66 (2 H, m), 1.28-1.04 (12 H, d).
• the second step was carried out by replacing 2,6-dichloroaniline with 2,6-dibromoaniline to obtain a ligand L1j.
• Example 14 According to the synthesis method of Example 8, the second step was carried out by replacing o-isopropylaniline with o-trifluoromethylaniline to obtain a ligand Llm.
• 1H NMR (300 MHz, CDC1 3 ): 5 8.27 - 6.62 (12H, m).
• Example 14
• the second step was carried out by replacing o-isopropylaniline with o-tert-butylaniline to obtain a ligand Lln.
• 1H NMR (300 MHz, CDC1 3 ): ⁇ 8.26-6.50 (12 ⁇ , m), 1.33-1.02 (9 ⁇ , m); Anal.Calc. C 56.70, H 3.45, N 4.56; Found C 56.56, H 3.33, N 4.32.
• Example 16 According to the synthesis method of Example 1, the second step was carried out by substituting p-trifluoromethylaniline for aniline to obtain a ligand Llo.
• 1H NMR (300 MHz, CDCI3): ⁇ 7.94-6.61 (13 H, m), 3.00-2.52 (2 H, m), 1.26-0.91 (12 H, d);
• Example 17 According to the synthesis method of Example 1, the second step was to replace the aniline with 3,5-ditrifluoromethylaniline to obtain the ligand Llp.
• 1H NMR (300 MHz, CDCI3): ⁇ 8.08-6.47 (12 ⁇ , m), 2.98-2.48 (2 ⁇ , m), 1.24-0.88 (12 ⁇ , m); 13 C NMR (75 MHz, CDCI3) : 162.3, 161.1, 153.2, 152.8, 146.7, 146.3, 141.5, 140.8, 135, 4, 134.3, 133.4, 133.0, 132.7, 131.9, 131.6, 130.8, 130.0, 129.5, 129.1, 128.9, 128.5, 128.1, 128.0, 127.7 , 124.7, 124.6, 124.5, 123.9, 123.6, 123.5, 123.3, 123.2, 120.4, 119.2, 117.8, 116.3, 77.0, 28.4, 23.6, 23.5, 22.8, 22.6.
• Example 17 Example 17
• the second step was to replace the aniline with o-phenoxymethylene aniline to obtain a ligand L1q.
• Example 39 was repeated except that the complex la was replaced with the complex lb (2 ⁇ ), and 0.22 mL (0.9 mol/L) of a toluene solution of a promoter ethylaluminum chloride was added.
• the polyethylene bromide value is 33 g/100 g, and the molecular weight of the material is 50,000 g/molo.
• Example 39 was repeated except that the complex la was replaced with the complex lc (2 mol).
• Example 39 was repeated except that the complex la was replaced with the complex le(5 ⁇ ).
• Example 39 was repeated except that the complex la was replaced with the complex lf (5 ⁇ ).
• Example 39 was repeated, except that the complex la was replaced with the complex lg (5 ⁇ ).
• Example 39 was repeated except that the complex la was replaced with the complex lh (5 ⁇ ).
• Example 39 was repeated, except that the complex la was replaced with the complex ⁇ (1 ⁇ ), and the polymerization time was 5 min. Results: 4.2 g of oily polyethylene was obtained with a catalytic efficiency of 5.0*10 7 g/mol.h.atm. The 1000 methylene groups of polyethylene correspond to a methyl number of 200, and the molecular weight of the product is 110,000 g/mol.
• Example 48
• Example 39 was repeated, except that the complex la was replaced with the complex lj (l ⁇ ).
• Oily polyethylene 10.0 g was obtained with a catalytic efficiency of 4.0*10 6 g/mol.h.atm.
• the 1000 methylene groups of polyethylene correspond to a methyl number of 200.
• the bromine number is 30 g / 100 g and the molecular weight of the product is 120,000 g/mol.
• Example 49
• Example 39 was repeated except that the complex la was replaced with the complex lk (5 ⁇ ).
• Example 39 was repeated except that the complex la was replaced with the complex 11 (5 ⁇ ).
• Example 39 was repeated except that the complex la was replaced with the complex lm (5 ⁇ ).
• Example 39 was repeated except that the complex la was replaced with the complex 1 ⁇ (5 ⁇ ).
• Example 39 was repeated, except that the complex la was replaced with the complex 1 ⁇ (5 ⁇ ).
• the catalytic efficiency of oily polyethylene was 2.0* 10 6 g/mol.h.atm.
• the 1000 methylene groups of polyethylene correspond to a methyl number of 280 and a bromine number of 55 g/100 g.
• Example 39 was repeated, except that the complex la was replaced with the complex 1 ⁇ (5 ⁇ ).
• Example 39 was repeated except that the complex la was replaced with the complex lq (5 ⁇ ).
• Example 39 was repeated except that the complex la was replaced with the complex lr (5 ⁇ ), and the promoter MMAO 0.30 mL (1.9 mol/L) was added.
• Example 39 was repeated except that the complex la was replaced with the complex lj (5 ⁇ ) and the solvent was changed to toluene.
• the catalytic efficiency of the oily polymer is 5* 10 6 g/mol.h.atm, the bromine number is 40 g/100 g, and the molecular weight of the product is 200,000 g/mol o
• Example 58 (solvent: n-hexane)
• Example 39 was repeated, except that the complex 1a) was replaced with the complex 1_)' (5 ⁇ 0 1), and the solvent was changed to n-hexane.
• Example 59 solvent: chlorobenzene
• Example 39 was repeated except that the complex la was replaced with the complex lj (5 ⁇ ) and the solvent was changed to chlorobenzene.
• Example 60 solvent dichloromethane
• Example 39 was repeated, except that the complex la was replaced with the complex lj (5 ⁇ ), and the solvent was changed to dichlorocarb. The temperature was changed to 20 °C.
• Example 39 was repeated except that the complex la was replaced with the complex lj (5 ⁇ ), and the promoter MMAO 0.30 mL (1.9 mol/L) was added.
• Example 39 was repeated except that the complex lj (5 ⁇ ) was used to replace the complex la, and a promoter MAO 0.30 mL (1.5 mol/L) was added.
• Example 39 was repeated except that the polymerization temperature was changed to 80 °C.
• Example 39 was repeated except that the polymerization temperature was changed to 20 °C.
• Example 65 was repeated, the ethylene pressure was changed to 5 atm, the solvent was changed to toluene, and the polymerization temperature was changed to 100 °C.
• Example 39 was repeated, except that the complex Lla was changed to the complex lt, and a cocatalyst MMAO 0.30 mL (1.9 mol/L) was added.
• Example 39 was repeated except that the complex Lla was changed to the complex lu, and a promoter MAO of 0.30 mL (1.5 mol/L) was added.
• Example 39 was repeated, except that the complex Lla was changed to the complex lv.
• Example 70 was repeated, and nickel perchlorate was changed to nickel trifluoromethanesulfonate.
• Example 70 was repeated, changing nickel perchlorate to (COD)Ni.
• the second step was carried out by replacing the aniline with o-thiophenylaniline to obtain a ligand L1w.
• Example 39 was repeated, and an ethylene polymerization experiment was carried out using the complex lw instead of la to obtain 2.5 g of an oily polyethylene having an activity of 1.0*10 6 g/mol.h.atm.
• Examples 78-82 are comparative examples made using the catalysts in the literature, under which the ethylene obtained only solid polyethylene under the same conditions as in Examples 39, 63, 64, 57, 62.
• the ligand Lis was used in place of Lla, and other operating conditions were the same as in Example 18 to give a reddish brown complex with a yield of 80%.
• Example 80 In a 200 mL polymerization bottle, purge the gas three times with nitrogen, then vacuum once, change the ethylene, add 25 mL of solvent DCE under ethylene atmosphere, and add 0.30 mL (0.9 mol/L) of cocatalyst diethylaluminum chloride. At 80 ° C, 1 atm, add the complex ls (5 ⁇ ), polymerize for 30 min, the reaction is finished, cut off the ethylene, the reaction solution is poured into acidified ethanol, solid polyethylene is precipitated, filtered, and the solid is vacuum dried to obtain 1.5 g, catalytic efficiency 0.6*10 6 g/m O lhatm.
• Example 80 (compared to Example 64)
• Example 84 Similar to Example 1, the first step was carried out by replacing 2,6-diisopropylaniline with 2,6-diphenylaniline, and the second step was carried out to obtain a ligand Llx. Anal. Calcd. C 89.23, H 4.99, N 5.78; Found C 82.50, H 6.24, N 5.30.
• Example 84 Anal. Calcd. C 89.23, H 4.99, N 5.78; Found C 82.50, H 6.24, N 5.30.
• Example 84 Anal. Calcd. C 89.23, H 4.99, N 5.78; Found C 82.50, H 6.24, N 5.30.
• Example 39 was repeated, substituting the complex lx for la, to obtain an oily polyethylene of 7.6 g, an activity of 3.1 * 10' g/mol.h. atm, and a methyl group corresponding to 1000 methylene groups of 160.
• Example 86
• Example 87 According to the method of Example 1, the second step was carried out by substituting p-nitroaniline for aniline to obtain ligand Lly.
• Example 87 Example 87
• Example 89 Similar to the reaction conditions of Example 39, the complex ly was used instead of la, and propylene was used instead of ethylene to obtain 8.0 g of oily polypropylene, and the activity was 3.2*10 6 g/mol.h.atm, and 1000 methylene groups of polyethylene corresponded. The methyl number is 260 and the molecular weight is 1500.
• Example 89
• Compound 19 is a control compound. Hydrogenation to prepare oily hyperbranched terpene hydrocarbons (oily terpene hydrocarbon mixtures)
• Example 47 In a 50 mL egg-shaped bottle, 2.5 g of the highly branched oily polyethylene obtained in Example 47 was added, and Pd/C 50 mg was added. 10 mL of n-hexane, after three times of gas exchange, react at room temperature overnight under normal pressure hydrogen atmosphere. The sampled nuclear magnetic hydrogen spectrum was found to have been completely hydrogenated, hydrogenation was stopped, filtered through a short silica gel column, and the filtrate was concentrated to obtain an oily hyperbranched alkane. The bromine number is 0.31 g/100 g. The corresponding number of methyl groups in 1000 methylene groups was 230, the viscosity index VI was 261, and the kinematic viscosity at 100 ° C was 7.9 cSt.
• the polymer nuclear magnetic carbon spectrum is shown in Figure 1.
• the product has a molecular weight of about 110,000 g/mol.
• the product had a pour point of -15 ° C, a flash point of 194 ° C, and an evaporation loss of 3.8 (%WA ⁇ ).
• Example 93 (no solvent)
• Example 94 In a 50 mL egg-shaped bottle, 2.5 g of the highly branched oily polyethylene obtained in Example 47 was added, Pd/C 50 mg was added, and the gas was exchanged three times, and then reacted at room temperature overnight under an atmospheric hydrogen atmosphere to sample a nuclear magnetic resonance spectrum. It was found that the starting material had been completely hydrogenated, the hydrogenation was stopped, and the mixture was filtered through a short silica gel column, and the filtrate was concentrated to give an oily hyperbranched alkane having a bromine number of 0.33 g/100 to 1000 methylene groups corresponding to a methyl group of 260.
• Example 94 Example 94
• Example 92 was repeated, replacing Pd/C with Pd(OH) 2 . Results: The oily polyethylene bromine number was 0.39 g/100 g. Example 95
• Example 92 was repeated, and the hydrogenated substrate was changed to the oily polyethylene obtained in Example 48.
• Example 92 was repeated, and the hydrogenated substrate was changed to the oily polyethylene obtained in Example 41.
• Example 39 when ethylene was changed to propylene, an oily polypropylene was obtained.
• Example 92 was repeated to change the hydrogenated substrate to an oily polypropylene.
• Example 98 The bromine value of the oily hyperbranched alkane was 0.10 g/100 g, the product pour point was -40 ° C, and the flash point was 190 °C.
• Example 39 when ethylene was changed to butene, an oily polybutene was obtained. Hydrogenation under the same conditions as in the above Example 92 using a highly branched oily polybutene gave an oily hyperbranched alkane having a bromine value of 0.49 g / 100 g.
• Example 99
• the oily polybutene 3.2 g was obtained by the procedure of Example 39 using the complex li instead of la catalyzed 1-butene polymerization.
• the oily polybutene was hydrogenated under the same conditions as in the above Example 92 to obtain an oily hyperbranched alkane having a bromine value.
• This oily alkane has a pour point of -15 ° C, a flash point of 200 ° C and a viscosity index VI of 195.
• Example 100
• Example 101 The copolymerization of ethylene and 1-hexene (10%) was catalyzed by the complex la according to the method of Example 39 to obtain an oily polymerization. 5.8 g. This oily polymer was hydrogenated under the same conditions as in the above Example 92 to give an oily, highly branched alkane having a bromine value of 0.31 g / 100 g. The oily alkane had a pour point of -17 ° C, a flash point of 193 ° C and a viscosity index VI of 186.
• Example 101 Example 101
• Example 47 was repeated.
• the olefin polymerization catalyst was contacted with ethylene, hydrogen gas was simultaneously introduced, and the hydrogenation was completed completely, and the filtrate was concentrated under reduced pressure to obtain a highly branched oily alkane having a bromine number of 0.48 g / 100 g, 1000
• the methylene group has a methyl number of 320, a viscosity index of 189, a pour point of -26 ° C, and a flash point of 190 ° C.
• Example 102
• Example 47 was repeated, after the olefin polymerization catalyst was contacted with ethylene for 30 min, no treatment was carried out, Pd/C 50 mg was added, hydrogen gas was introduced, and the hydrogenation was completed completely, and the filtrate was concentrated under reduced pressure to obtain a highly branched oily alkane.
• the number of methyl groups corresponding to 1000 methylene groups in the oily hyperbranched alkane is 260.
• Example 47 after the olefin polymerization catalyst was contacted with ethylene for 30 minutes, the atmosphere was replaced with hydrogen without treatment, and the reaction was carried out under a hydrogen atmosphere until the hydrogenation was completed, and the filtrate was concentrated under reduced pressure to obtain a highly branched oily alkane. , bromine number is 0.34 g / 100 go Example 104
• Example 92 was repeated, and the hydrogenated substrate was changed to the oily polyethylene obtained in Example 63.
• Example 92 was repeated, and the hydrogenated substrate was changed to the oily polyethylene obtained in Example 49.
• the oily polymer was hydrogenated under the same conditions as in the above Example 92 to obtain an oily hyperbranched alkane containing an alcoholic hydroxy group.
• the bromine value was 0.30 g/100 g, and the oily alkane had a pour point of -30 ° C and a flash point of 193. °C, viscosity index VI is 180.
• Example 111
• the oily alkane polymer having a specific methyl group is not given in Examples 92 to 112, and it is determined that the number of methyl groups per 1000 methylene groups is from 160 to 350.
• the product pour point was determined by reference to the pour point standard method of ASTM D97 petroleum based oil.
• the color is measured by referring to the ASTM D 1500 standard method.
• the density at 15.6 ° C was measured by the ASTM D 4052 standard method.
• the kinematic viscosity at 100 ° C and 40 ° C measured according to the ASTM D 445 standard method.
• the bromine is determined according to the standard method of ASTM D 92.
• the flash point was determined according to the standard method of ASTM D 1 159.
• the acidity was measured by the standard method of ASTM D 664.
• the results are shown in Table 2.
• the results show that the oily hyperbranched alkanes of the present invention are comparable to commercially available PAO or Group III base oils in pour point, flash point, chromaticity, and evaporation loss, but have a higher viscosity index than existing products and can be larger. Maintaining viscosity over the temperature range is more suitable as a base oil for lubricating oils.
• Example 92 the polymerization was carried out by amplifying to obtain an oil as a base oil, and 0.2% by weight to 0.5% by weight of a methacrylate copolymer or a polyacrylate was added based on the mass thereof, and uniformly mixed to obtain a lubricating oil.
• the pour point is -32 ° C to -40 ° C.
• Example 115 According to Example 92, the oil was amplified by amplifying to obtain an oil as a base oil, and an acrylic high carbon alcohol ester and an acrylonitrile copolymer (500 mg/L oil) were added, and uniformly mixed to obtain a lubricating oil, and the pour point of the lubricating oil was lowered to - 20 ° C - 30 ° C
• Example 116
• Example 97 the polymerization was amplified to obtain an oil as a base oil, and based on the mass thereof, 0.02 wt% of 6 6-di-tert-butyl ⁇ -dimethylamino-p-cresol was added as an antioxidant additive, and 0.5 wt% of 2 wt was added.
• Example 117 Example 117
• Example 97 the polymerization was carried out by amplification to obtain an oil as a base oil, and based on the mass thereof, 1 wt% to 5 wt% of polyalkenyl succinimide or monoalkenyl succinimide or dialkenyl butyl group was added.
• Diimide as a dispersant, 0.8wt% - 1.3wt% high base value synthetic calcium sulfonate or 2wt% _3wt% calcium alkylsalicylate as a cleaning agent, 0.1wt% - 0.5wt% methyl silicone polymerization
• an anti-foaming agent a condensate of 0.4 wt% to 0.6 wt%/ ⁇ with an epoxide is used as an anti-emulsifier, and uniformly mixed to obtain a lubricating oil.
• Example 90 the oil was amplified by amplifying to obtain an oil as a base oil, and based on the mass thereof, 0.1% by weight to 1.0% by weight of the alkylnaphthalene was uniformly mixed to obtain a lubricating oil.
• Example 119
• Example 97 the oil was amplified by amplifying to obtain an oil as a base oil, and 0.3 W t ° / acid ester was added as a friction modifier based on the mass thereof, and uniformly mixed to obtain a lubricating oil.
• Example 120
• Example 97 the polymerization was carried out by amplifying to obtain an oil as a base oil, and based on the mass thereof, 0. 2 wt o / / was added.
• the zinc dialkyl dithiophosphate is used as an anti-oxidation anti-corrosion agent, and is uniformly mixed to obtain a lubricating oil.
• Example 121
• Example 97 the polymerization was amplified to obtain an oil as a base oil, and based on the mass thereof,

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