CN116410780A - Synthesis method of high-viscosity metallocene poly alpha-olefin base oil, product and application thereof - Google Patents
Synthesis method of high-viscosity metallocene poly alpha-olefin base oil, product and application thereof Download PDFInfo
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- 229920013639 polyalphaolefin Polymers 0.000 title claims abstract description 57
- 239000002199 base oil Substances 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 46
- 238000006384 oligomerization reaction Methods 0.000 claims description 23
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000003607 modifier Substances 0.000 claims description 19
- 239000004711 α-olefin Substances 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000009977 dual effect Effects 0.000 claims description 10
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- HKQMTZGUFSJHMQ-UHFFFAOYSA-L C[SiH]C.Cl[Hf](Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[SiH]C.Cl[Hf](Cl)(C1C=CC=C1)C1C=CC=C1 HKQMTZGUFSJHMQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- -1 rac-ethylenebis (indenyl) zirconium dichloride Chemical compound 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- IZYHZMFAUFITLK-UHFFFAOYSA-N 1-ethenyl-2,4-difluorobenzene Chemical compound FC1=CC=C(C=C)C(F)=C1 IZYHZMFAUFITLK-UHFFFAOYSA-N 0.000 claims description 3
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 claims description 3
- DXLJGMQSQDKFKZ-UHFFFAOYSA-L [Cl-].[Cl-].C[Si](C)(C)C1(C=CC=C1)[Hf+2]C1(C=CC=C1)[Si](C)(C)C Chemical compound [Cl-].[Cl-].C[Si](C)(C)C1(C=CC=C1)[Hf+2]C1(C=CC=C1)[Si](C)(C)C DXLJGMQSQDKFKZ-UHFFFAOYSA-L 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 claims description 3
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical compound [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000539 dimer Substances 0.000 abstract description 24
- 230000003993 interaction Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 43
- 239000002994 raw material Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000010813 internal standard method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 238000011282 treatment Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 150000003754 zirconium Chemical class 0.000 description 5
- 239000003245 coal Substances 0.000 description 3
- 150000002362 hafnium Chemical class 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CJTHVCQBFBYORZ-UHFFFAOYSA-L 1-butylcyclopenta-1,3-diene;zirconium(2+);dichloride Chemical compound [Cl-].[Cl-].[Zr+2].CCCCC1=CC=CC1.CCCCC1=CC=CC1 CJTHVCQBFBYORZ-UHFFFAOYSA-L 0.000 description 1
- CPNALZXLUFBDPN-UHFFFAOYSA-N C=C.C1=CC2=CC=CC=C2C1[Zr]C1C2=CC=CC=C2C=C1 Chemical class C=C.C1=CC2=CC=CC=C2C1[Zr]C1C2=CC=CC=C2C=C1 CPNALZXLUFBDPN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QSZGOMRHQRFORD-UHFFFAOYSA-L [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Zr+2]C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Zr+2]C1C2=CC=CC=C2C=C1 QSZGOMRHQRFORD-UHFFFAOYSA-L 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a synthesis method of high-viscosity metallocene poly alpha-olefin base oil, a product and application thereof. The invention adopts a catalytic system of a composite metallocene-cocatalyst-regulator, and forms different catalytic active centers through the interaction of a mixed metallocene catalyst, a cocatalyst and the regulator, thereby achieving the purposes of controlling the viscosity of PAO products and reducing the selectivity of dimers.
Description
Technical Field
The invention relates to a synthesis method of high-viscosity metallocene poly alpha-olefin base oil, a product and application thereof.
Background
Group IV lubricant base oil, poly (alpha-olefin), PAO for short, is one of the best synthetic lubricant base oils prepared by polymerization (oligomerization) from C8-C12 alpha-olefins as raw materials. PAO is mainly based on its kinematic viscosity (mm) at 100 degrees Celsius 2 Per s) and expressed in KV (100 degrees celsius), PAOs can be classified into low-viscosity, medium-viscosity, and high-viscosity PAOs according to viscosity. Kinematic viscosity KV (100 ℃ C.) is less than or equal to 10mm 2 S is low-viscosity PAO, and the kinematic viscosity is 10mm 2 /s<KV (100 degree centigrade)<40mm 2 The viscosity/s is medium viscosity PAO, and the kinematic viscosity KV (100 ℃) is more than or equal to 40mm 2 And/s is high viscosity PAO.
The high-viscosity metallocene poly alpha-olefin (PAO) molecule synthesized by adopting the metallocene catalyst has a comb-shaped structure, a polymerization product has good uniformity, relatively narrow molecular weight distribution, and the PAO product has excellent flow property, shear stability, lower pour point and higher viscosity index. However, dimers are always produced during oligomerization of alpha-olefins using metallocene catalysts. Because of the low flash point of the dimer, it is necessary to remove it by distillation under reduced pressure as an unnecessary component in PAO, which affects the yield of the product and increases the cost of the final product. Therefore, in the research field of metallocene catalysis 1-decene oligomerization, how to regulate the activity of a metallocene catalyst system, control the viscosity range of PAO products, reduce the selectivity of dimers, improve the yield of base oil components and reduce the cost of PAO products is a technical problem to be solved.
Disclosure of Invention
The present invention has been made in order to solve, at least in part, the technical drawbacks existing in the prior art.
As one aspect of the invention, a method for synthesizing a high viscosity metallocene polyalphaolefin base oil is provided that uses a dual metallocene mixed catalyst-co-catalyst-modifier catalyst system.
In one embodiment, the dual metallocene mixed catalyst is compounded from a zirconium-based bridged metallocene and a hafnium-based metallocene.
In a specific embodiment, the cocatalyst is an aluminum alkyl or an aluminum alkyl/organoboron. Specifically, the alkyl aluminum is methylaluminoxane; the alkyl aluminum/organoboron is triisobutyl aluminum/[ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]。
In a specific embodiment, the modifier is an alkyl aluminum or organozinc, and the modifier is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride, dimethyl zinc, diethyl zinc, or diisopropyl zinc.
In a specific embodiment, the method comprises: (1) Carrying out polymerization reaction in a nitrogen or argon environment under certain conditions to obtain an oligomerization reaction product; (2) The oligomerization reaction product is hydrogenated to obtain the high-viscosity metallocene poly alpha-olefin base oil.
In a specific embodiment, the dual metallocene mixed catalyst comprises a metallocene a and a metallocene B, wherein the metallocene a is a bridged metallocene catalyst; metallocene B is a hafnium-based metallocene catalyst; the molar ratio of the metallocene A to the metallocene B is 10 to 0.5.
In a specific embodiment, the dual metallocene mixed catalyst, metallocene a is one of rac-ethylenebis (indenyl) zirconium dichloride, meso-ethylenebis (indenyl) zirconium dichloride, or rac-dimethylsilylbis (indenyl) zirconium dichloride; the metallocene B is one of dimethylsilyl bis (cyclopentadienyl) hafnium dichloride, bis (trimethylsilyl cyclopentadienyl) hafnium dichloride or bis (cyclopentadienyl) hafnium dichloride; the molar ratio of the metallocene A to the metallocene B is 6-1.
In a specific embodiment, the metallocene (A+B) is used in an amount of 0.001 to 0.01mol% and the molar ratio of cocatalyst to metallocene (A+B) is 1 to 500, [ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]The molar ratio of the modifier to the metallocene (A+B) is 1.5-1, and the molar ratio of the modifier to the metallocene (A+B) is 10-200.
In a specific embodiment, the metallocene (A+B) is used in an amount of 0.004 to 0.008mol%,the molar ratio of the cocatalyst to the metallocene (A+B) is 200-400, [ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]The molar ratio of the modifier to the metallocene (A+B) is 1.2-1, and the molar ratio of the modifier to the metallocene (A+B) is 50-100.
In a specific embodiment, the reaction temperature is 50-100 degrees celsius; the reaction pressure is 0-0.1 MPa; the polymerization time is 0.5-2 hours.
In a specific embodiment, the process uses a feedstock of 1-decene, 1-octene, mixed alpha-olefins in a fraction of 130-190 degrees celsius, mixed alpha-olefins in a fraction of 140-185 degrees celsius, or mixed alpha-olefins in a fraction of 140-210 degrees celsius.
As another aspect of the invention, it relates to the high viscosity metallocene polyalphaolefin base oils prepared by the above process.
As a further aspect of the invention, it relates to the use of the above-described high viscosity metallocene polyalphaolefin base oils in the preparation of lubricating oils.
As yet another aspect of the invention, it relates to a lubricating oil comprising the above-described high viscosity metallocene polyalphaolefin base oil.
The invention adopts a catalytic system of a composite metallocene-cocatalyst-regulator, and forms different catalytic active centers through the interaction of a mixed metallocene catalyst, a cocatalyst and the regulator, thereby achieving the purposes of controlling the viscosity of PAO products and reducing the selectivity of dimers.
The invention combines zirconium series bridged metallocene and hafnium series metallocene to form a mixed metallocene catalyst, and synthesizes high-viscosity PAO through interaction with a cocatalyst and a regulator, and has the advantages of high raw material conversion rate, controllable product kinematic viscosity, small dimer selectivity, high PAO product yield and the like. Wherein the conversion rate of raw materials is more than 97%, the selectivity of dimer is 0.1-10%, the yield of metallocene PAO base oil product is more than 90%, and the kinematic viscosity (100 ℃) is 40-100 mm 2 And/s, the viscosity index is more than 150, and the pour point is lower than-30 ℃.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus or methods used in the examples of the invention, the instruction not specifying the source of the supply, are all conventional products commercially available or available from the applicant.
Summary of the invention:
the invention synthesizes the high-viscosity PAO by adopting a catalytic system of a composite metallocene-cocatalyst-regulator. The invention combines zirconium series bridged metallocene and hafnium series metallocene to form a mixed metallocene catalyst, and different catalytic active centers are formed through interaction with a cocatalyst and a regulator, so that the purposes of controlling the viscosity of PAO products and reducing the selectivity of dimers are achieved.
The invention takes 1-decene, 1-octene or mixed alpha-olefin of 120-210 ℃ fraction as raw material, double metallocene as main catalyst, alkyl aluminum or alkyl aluminum/organoboron as cocatalyst, alkyl aluminum or organozinc as regulator, and carries out polymerization reaction under nitrogen or argon environment and certain condition, and the oligomerization reaction product is obtained through quenching, distillation and other post-treatment operations; the oligomerization reaction product is hydrogenated to obtain the metallocene PAO base oil.
In one embodiment, the main catalyst is a dual metallocene mixed catalyst comprising a metallocene A and a metallocene B, and the specific molecular structural formula is as follows:
wherein, the metallocene A is a bridged metallocene catalyst and comprises one of rac-ethylene bis (indenyl) zirconium dichloride, meso-ethylene bis (indenyl) zirconium dichloride or rac-dimethylsilyl bis (indenyl) zirconium dichloride; the metallocene B is a hafnium-based metallocene catalyst and comprises one of dimethylsilyl bis (cyclopentadienyl) hafnium dichloride, bis (trimethylsilyl cyclopentadienyl) hafnium dichloride or bis (cyclopentadienyl) hafnium dichloride; wherein the molar ratio of the metallocene A to the metallocene B is 10 to 0.5, preferably 6 to 1.
In one embodiment, the cocatalyst aluminum alkyl is methylaluminoxane; the cocatalyst alkyl aluminum/organoboron is triisobutyl aluminum/[ Me 2 NHPh][B(C 6 F 5 ) 4 ]The method comprises the steps of carrying out a first treatment on the surface of the The regulator is trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dimethylzinc, diethylzinc or diisopropylzinc.
In one embodiment, the metallocene (A+B) is used in an amount of 0.001 to 0.01mol% and the molar ratio of cocatalyst to metallocene (A+B) is 1 to 500, [ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]The molar ratio of the modifier to the metallocene (A+B) is 1.5-1, and the molar ratio of the modifier to the metallocene (A+B) is 10-200.
In one embodiment, the metallocene (A+B) is used in an amount of 0.004 to 0.008mol% and the molar ratio of cocatalyst to metallocene (A+B) is 200 to 400, [ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]The molar ratio of the modifier to the metallocene (A+B) is 1.2-1, and the molar ratio of the modifier to the metallocene (A+B) is 50-100.
In one embodiment, the reaction temperature is 50-100 degrees celsius, preferably 50-60 degrees celsius, 60-70 degrees celsius, 70-80 degrees celsius, 80-95 degrees celsius, 70-95 degrees celsius; the reaction pressure is 0-0.1 MPa, preferably 0-0.05 MPa; the polymerization time is 0.5 to 2 hours, preferably 0.5 to 1 hour.
In one embodiment, the metallocene PAO product has an kinematic viscosity (100 ℃) of 40 to 100mm 2 /s、40～50mm 2 /s、40～60mm 2 /s、50～60mm 2 /s、60～70mm 2 /s、70～80mm 2 /s、80～90mm 2 /s、80～100mm 2 /s or 90-100 mm 2 /s。
In one embodiment, the feedstock is 1-decene, 1-octene, mixed alpha-olefins in a fraction of 130-190 degrees celsius, mixed alpha-olefins in a fraction of 140-185 degrees celsius, or mixed alpha-olefins in a fraction of 140-210 degrees celsius.
In a word, the present inventionThe invention combines zirconium series bridged metallocene and hafnium series metallocene to form a mixed metallocene catalyst, and synthesizes high-viscosity PAO through interaction with a cocatalyst and a regulator, and has the advantages of high raw material conversion rate, small dimer selectivity, high oligomerization reaction yield, controllable kinematic viscosity range of metallocene PAO products and the like. Wherein, the conversion rate of the raw materials is more than 97%, the selectivity of the dimer is 0.1-10%, and the yield of oligomerization products is more than 90%. The kinematic viscosity (100 ℃) of the metallocene PAO product is 40-100 mm 2 And/s, the viscosity index is more than 150, and the pour point is lower than-30 ℃.
The process equipment or devices not specifically identified in the examples below are all conventional in the art. In the examples provided herein, experimental runs were all conducted under nitrogen or argon using Schlenk techniques. The starting materials used in the examples were obtained from commercial sources and subjected to anhydrous anaerobic treatment according to laboratory routine procedures unless otherwise specified. The preparation of the metallocene catalyst solution used in the examples was carried out in a glove box. Other materials, if not stated, may be used directly without further purification treatment. The mixed alpha-olefins are coal-based alpha-olefin mixtures derived from a high temperature fischer-tropsch process.
In the method provided by the invention, no special requirements are imposed on the post-treatment, distillation and hydrogenation processes of the reaction product, and the post-treatment process of the reaction product can adopt the common process technologies such as filtration, distillation solvent, vacuum drying and the like in the field; the distillation process can adopt normal pressure or reduced pressure distillation equipment commonly used in the field, so long as the separation of low-boiling substances such as solvent, unpolymerized monomers, dimers and the like from the products can be realized; similarly, the hydrogenation process has no special requirement, and common hydrogenation catalysts, equipment, process conditions and the like can be adopted as long as the purpose of product hydrogenation can be achieved.
The test method for each viscosity-temperature property of the metallocene PAO base oil (product) in the examples is as follows:
a. petroleum product kinematic viscosity measurement and kinematic viscosity calculation methods: GB/T265-88
b. Petroleum product viscosity index calculation method: GB/T1995-1998
c. Petroleum product pour point determination: GB/T3535-2006
The inventor uses bis (n-butylcyclopentadiene) zirconium dichloride as a main catalyst to catalyze the polymerization of alpha-olefin produced by coal based on the Chinese patent document No. CN105062555A, and obtains the low-viscosity PAO. A large amount of dimers are formed in the reaction system.
The inventor uses a series of ethylene bis (indenyl) zirconium compounds to carry out oligomerization of 1-decene based on the Chinese patent document No. CN104672264A, thus obtaining low-viscosity PAO. The dimer selectivity is 20-80%, and the 1-decene conversion rate is lower and is less than 90%.
The inventor is based on CN105885929A Chinese patent literature, adopts a dual metallocene catalyst system consisting of a zirconium series bridged metallocene catalyst and a zirconium series non-bridged metallocene catalyst, takes alpha-olefin prepared by coal as a polymerization raw material, and obtains a low-viscosity PAO product through polymerization reaction. The dimer selectivity is higher and the product yield is lower.
Example 1
Preparing a mixed metallocene catalyst system M: rac-ethylenebis (indenyl) zirconium dichloride (metallocene a) (10.0 mg,0.024 mmol) and dimethylsilylbis (cyclopentadienyl) hafnium dichloride (metallocene B) (3.5 mg,0.008 mmol) were dissolved in 10mL toluene (molar ratio of metallocene a to metallocene B3:1, (a+b) total amount 0.0086 mol%) to which 6.0mL methylaluminoxane/toluene solution (1.5M) (cocatalyst/(metallocene (a+b)) =281) was added and stirred at room temperature for 20 minutes, then 2mL triethylaluminum/toluene solution (1M) (regulator/(metallocene (a+b)) =62) was added and the reaction was continued with stirring at room temperature for 30 minutes for use.
Polymerization reaction: the 250 ml Schlenk flask was evacuated/purged 3 times with nitrogen. Anhydrous anaerobic treated 1-decene (70 mL,51.9g,370 mmol) was added under nitrogen blanket. The reaction system is heated to 80 ℃ and stirred for 15 minutes, and then the pre-prepared mixed metallocene catalyst system M is added to start the reaction. The reaction was carried out under nitrogen atmosphere at normal pressure for 1 hour, sampled, and analyzed by gas chromatography internal standard method, the conversion of the raw material was 99.1%, and the dimer selectivity was 0.6%.The reaction was stopped, cooled to room temperature, quenched by the addition of 5% ethanol hydrochloride (10 mL), stirred for a further 30 min, filtered through celite to give a crude product solution, and the solvent, unreacted 1-decene and dimer low boiling components were distilled off under reduced pressure to give an oligomerization product (49.2 g) in 94.8% yield. Hydrogenation of oligomerization products is carried out in a 500 ml high-pressure reaction kettle, the hydrogenation catalyst is nickel catalyst, the reaction temperature is 130 ℃, the reaction pressure is 4MPa, the reaction time is 4 hours, the metallocene PAO products are obtained after post treatment, and the kinematic viscosity (100 ℃) is measured to be 75.4mm 2 Viscosity index 216, pour point-42 degrees celsius.
Examples 2 to 6
The reaction steps and operations are the same as in example 1, except that the feed alpha-olefin is different from example 1:
examples 7 to 8
The reaction steps and operations are the same as in example 1, except that the metallocene A is different from example 1:
examples 9 to 10
The reaction steps and operations are the same as in example 1, except that the metallocene B is different from example 1:
examples 11 to 14
The reaction procedure and operation are as in example 1, except that the molar ratio of metallocene A to B is different from example 1:
example 15
The reaction procedure and operation were as in example 1, except that the cocatalyst was triisobutylaluminum/[ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]1M triisobutylaluminum (6.4 mL,6.4 mmol) was added thereto, [ Me ] 2 NHPh][B(C 6 F 5 ) 4 ](38.4mg,0.048mmol)([Me 2 NHPh][B(C 6 F 5 ) 4 ]The molar ratio to the metallocene catalyst (A+B) was 1.5. After the reaction is finished, detecting by a gas chromatography internal standard method, wherein the raw material conversion rate is 98.8%, and the dimer selectivity is 0.6%; the oligomerization product yield is 93.6%; the kinematic viscosity (100 ℃) of the metallocene PAO product is 64.4mm 2 Viscosity index 213, pour point-42 degrees celsius.
Examples 16 to 18
The reaction procedure and operation were as in example 15, except that the modifier was different from example 15:
examples 19 to 20
The reaction procedure and operation were as in example 15, except for [ Me 2 NHPh][B(C 6 F 5 ) 4 ]Different from the molar ratio of the metallocene catalyst (A+B):
examples 21 to 26
The reaction steps and operations are the same as in example 1, except that the regulator is different from example 1:
examples 27 to 31
The reaction steps and operations are the same as in example 1, except that the total amount of metallocene (A+B) used is different from example 1:
examples 32 to 38
The reaction procedure and operation are as in example 1, except that the molar ratio of cocatalyst to metallocene (A+B) is different from example 1:
examples 39 to 42
The reaction procedure and operation are as in example 1, except that the molar ratio of modifier to metallocene (A+B) is different from example 1:
example 43
The reaction procedure and operation were the same as in example 1, except that argon was used as a protective atmosphere. After the reaction is finished, detecting by a gas chromatography internal standard method, wherein the raw material conversion rate is 98.8%, and the dimer selectivity is 0.7%; the oligomerization product yield is 95.0%; through detection, the kinematic viscosity (100 ℃) of the metallocene PAO product is 78.5mm 2 S, viscosity index 217, pour point-39 degrees celsius.
Examples 44 to 48
The reaction steps and operations were the same as in example 1, except that the reaction temperature was different from example 1:
examples 49 to 50
The reaction steps and operations were the same as in example 1, except that the reaction pressure was different from example 1:
examples 51 to 52
The reaction steps and operations were the same as in example 1, except that the reaction time was different from example 1:
example 53
The reaction steps and operations were the same as in example 1, except that the reaction temperature was 60 degrees celsius. After the reaction is finished, the raw material conversion rate is 99.1 percent and the dimer selectivity is 0.7 percent by gas chromatography internal standard method detection; the oligomerization product yield is 95.0%; through detection, the kinematic viscosity (100 ℃) of the metallocene PAO product is 80.1mm 2 S, viscosity index 219, pour point-39 degrees celsius.
Comparative example 1
The procedure and operation were as in example 1, except that the main catalyst was single metallocene rac-ethylenebis (indenyl) zirconium dichloride in an amount of 0.0086mol%. After the reaction is finished, detecting by a gas chromatography internal standard method, wherein the raw material conversion rate is 95.2%, and the dimer selectivity is 1.5%; the oligomerization product yield is 90.3%; the kinematic viscosity (100 ℃) of the metallocene PAO product is 161.1mm 2/ s, viscosity index 239, pour point-24 ℃.
Although it can be prepared by using metalloceneThe PAO with high viscosity is prepared, but the reaction controllability is poor, the accurate regulation and control of the PAO viscosity is difficult to realize, and the kinematic viscosity (100 ℃) of the obtained product is often more than 100mm 2/ s. For example, using rac-Et (1-Ind) 2 ZrCl 2 MAO catalytic system (chemical reaction engineering and Process 2015,31 (2): 164.), rac-Me 2 Si(1-Ind) 2 ZrCl 2 /Al(i-Bu) 3 Catalytic system of organic boride (petroleum refining and chemical industry, 2017,48 (1): 61.). Carried out 1-decene oligomerization research, and the kinematic viscosity (100 ℃ C.) was mainly 147-900 mm 2 The high viscosity PAO per second has low product yield of only 90-93%.
Comparative examples 2 to 6
The reaction procedure and operation were the same as in comparative example 1, except that the metallocene catalyst was different from comparative example 1:
comparative example 7
The reaction procedure and operation were the same as in comparative example 1, except that the amount of the main catalyst used was 0.0005mol%. After the reaction is finished, detecting by a gas chromatography internal standard method, wherein the raw material conversion rate is 59.2%, and the dimer selectivity is 0.1%; the oligomerization product yield is 52.6%; through detection, the kinematic viscosity (100 ℃) of the metallocene PAO product is 261.1mm 2 S, viscosity index 274, pour point-21 degrees celsius.
Comparative example 8
The reaction procedure and operation were the same as in comparative example 1, except that the amount of the main catalyst used was 0.0007mol%. After the reaction is finished, the raw material conversion rate is 62.7 percent and the dimer selectivity is 0.1 percent by gas chromatography internal standard method detection; the oligomerization product yield is 57.4%; through detection, the kinematic viscosity (100 ℃) of the metallocene PAO product is 248.7mm 2 Viscosity index 262, pour point-21 degrees celsius.
Comparative example 9
The reaction procedure and operation were the same as in comparative example 1, except that the amount of the main catalyst used was 0.001mol%. Reaction completionThen, the gas chromatography internal standard method is adopted to detect, the conversion rate of raw materials is 69.8 percent, and the dimer selectivity is 0.2 percent; the oligomerization product yield was 62.2%; through detection, the kinematic viscosity (100 ℃) of the metallocene PAO product is 240.8mm 2 Viscosity index 268, pour point-24 degrees celsius.
Comparative example 10
The reaction procedure and operation were the same as in comparative example 1, except that the amount of the main catalyst used was 0.008mol%. After the reaction is finished, detecting by a gas chromatography internal standard method, wherein the raw material conversion rate is 94.1 percent, and the dimer selectivity is 1.5 percent; the oligomerization product yield is 90.1%; through detection, the kinematic viscosity (100 ℃) of the metallocene PAO product is 163.1mm 2 Viscosity index 241, pour point-24 degrees celsius.
Comparative example 11
The reaction procedure and operation were the same as in comparative example 1, except that no cocatalyst was added to the reaction mixture as in comparative example 1. After the reaction is finished, the raw material conversion rate is 0% by detection of a gas chromatography internal standard method, and no polymerization reaction occurs.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (18)
1. A method for synthesizing high-viscosity metallocene poly alpha-olefin base oil, which is characterized in that a catalytic system of a dual metallocene mixed catalyst-cocatalyst-regulator is used.
2. The method of claim 1, wherein the dual metallocene mixed catalyst is compounded from a zirconium-based bridged metallocene and a hafnium-based metallocene.
3. The process of claim 1 wherein the cocatalyst is an aluminum alkyl or an aluminum alkyl/organoboron.
4. A process according to claim 3, wherein the alkyl aluminium is methylaluminoxane; the alkyl aluminum/organoboron is triisobutyl aluminum/[ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]。
5. The method of claim 1, wherein the modifier is an aluminum alkyl or an organozinc.
6. The method of claim 5, wherein the modifier is trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dimethylzinc, diethylzinc, or diisopropylzinc.
7. The method of claim 1, wherein the method comprises: (1) Carrying out polymerization reaction in a nitrogen or argon environment under certain conditions to obtain an oligomerization reaction product; (2) The oligomerization reaction product is hydrogenated to obtain the high-viscosity metallocene poly alpha-olefin base oil.
8. The process of any of claims 1-7, wherein the dual metallocene mixed catalyst comprises a metallocene a and a metallocene B, wherein the metallocene a is a bridged metallocene catalyst; metallocene B is a hafnium-based metallocene catalyst; the molar ratio of the metallocene A to the metallocene B is 10 to 0.5.
9. The process of claim 8 wherein the dual metallocene mixed catalyst, metallocene a is one of rac-ethylenebis (indenyl) zirconium dichloride, meso-ethylenebis (indenyl) zirconium dichloride or rac-dimethylsilylbis (indenyl) zirconium dichloride; the metallocene B is one of dimethylsilyl bis (cyclopentadienyl) hafnium dichloride, bis (trimethylsilyl cyclopentadienyl) hafnium dichloride or bis (cyclopentadienyl) hafnium dichloride; the molar ratio of the metallocene A to the metallocene B is 6-1.
10. The process of claim 8, wherein the metallocene (A+B) is used in an amount of from 0.001 to 0.01mol%, co-catalystThe molar ratio of the catalyst to the metallocene (A+B) is 1-500, [ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]The molar ratio of the modifier to the metallocene (A+B) is 1.5-1, and the molar ratio of the modifier to the metallocene (A+B) is 10-200.
11. The process according to claim 8, wherein the metallocene (A+B) is used in an amount of 0.004 to 0.008mol% and the molar ratio of cocatalyst to metallocene (A+B) is 200 to 400, [ Me ] 2 NHPh][B(C 6 F 5 ) 4 ]The molar ratio of the modifier to the metallocene (A+B) is 1.2-1, and the molar ratio of the modifier to the metallocene (A+B) is 50-100.
12. The method of claim 8, wherein the reaction temperature is 50-100 degrees celsius; the reaction pressure is 0-0.1 MPa; the polymerization time is 0.5-2 hours.
13. The method of claim 12, wherein the reaction temperature is 50-60 degrees celsius, 60-70 degrees celsius, 70-80 degrees celsius, 80-95 degrees celsius, or 70-95 degrees celsius; the reaction pressure is 0-0.05 MPa; the polymerization time is 0.5 to 1 hour.
14. The method of claim 8, wherein the high viscosity metallocene polyalphaolefin base oil has an kinematic viscosity of 40 to 100mm at 100 degrees celsius 2 /s、40～50mm 2 /s、40～60mm 2 /s、50～60mm 2 /s、60～70mm 2 /s、70～80mm 2 /s、80～90mm 2 /s、80～100mm 2 /s or 90-100 mm 2 /s。
15. The process of claim 8 wherein the feedstock used in the process is 1-decene, 1-octene, mixed alpha-olefins in a fraction of 130-190 degrees celsius, mixed alpha-olefins in a fraction of 140-185 degrees celsius, or mixed alpha-olefins in a fraction of 140-210 degrees celsius.
16. The high viscosity metallocene polyalphaolefin base oil made by the process of any one of claims 1-15.
17. Use of the high viscosity metallocene polyalphaolefin base oil of claim 16 in the preparation of a lubricating oil.
18. A lubricating oil comprising the high viscosity metallocene polyalphaolefin base oil of claim 16.
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| CN101134702A (en) * | 2007-09-07 | 2008-03-05 | 北京化工大学 | Preparation method of alkene oligomer |
| CN108929186A (en) * | 2017-05-27 | 2018-12-04 | 中国石油天然气股份有限公司 | Method for preparing high viscosity index lubricating oil base oil |
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