CN113337311A - Ultra-high viscosity index poly-alpha-olefin base oil and preparation method and application thereof - Google Patents
Ultra-high viscosity index poly-alpha-olefin base oil and preparation method and application thereof Download PDFInfo
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- 229920013639 polyalphaolefin Polymers 0.000 title claims abstract description 53
- 239000002199 base oil Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000539 dimer Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000004711 α-olefin Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 17
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 14
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 10
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 10
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 3
- 238000006384 oligomerization reaction Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000010189 synthetic method Methods 0.000 claims 2
- DDDRMZMSFMQPPC-UHFFFAOYSA-L [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 Chemical compound [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 DDDRMZMSFMQPPC-UHFFFAOYSA-L 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 33
- 239000003921 oil Substances 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 77
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000002904 solvent Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- 229910052786 argon Inorganic materials 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000011056 performance test Methods 0.000 description 10
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 8
- NOQWABVRFAHTQD-UHFFFAOYSA-L [Cl-].[Cl-].C12=CC=CCC2CCC1[Zr+2]C1C2=CC=CCC2CC1 Chemical compound [Cl-].[Cl-].C12=CC=CCC2CCC1[Zr+2]C1C2=CC=CCC2CC1 NOQWABVRFAHTQD-UHFFFAOYSA-L 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229940069096 dodecene Drugs 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- -1 cyclopentadienyl-fluorenyl Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- 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
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- 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
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a PAO base oil with an ultrahigh viscosity index, and a preparation method and application thereof. The poly alpha-olefin synthetic oil viscosity index 155-223 comprises the following steps: an olefin monomer of C6-C12 reacts for a period of time under the action of metallocene catalyst/methylaluminoxane catalytic system, a terminating agent is added, and alpha-olefin dimer with a regular structure in a product is separated through water washing and alkali washing. The separated alpha-olefin dimer and an olefin monomer of C6-C12 are used as raw materials, react for a period of time under the action of a Ziegler-Natta catalyst system, and are added with a terminator for post-treatment to obtain the poly alpha-olefin synthetic oil containing the quaternary carbon structure.
Description
Technical Field
The invention relates to a preparation method of poly-alpha-olefin base oil with an ultrahigh viscosity index
Background
Poly alpha-olefin lube base oils (PAOs) are lube base oils obtained by polymerizing alpha-olefins under the action of a catalyst and hydrogenating the polymerized alpha-olefins, and are the most promising varieties of synthetic base oils. The lubricating oil base oil synthesized by the poly-alpha-olefin has the advantages of high viscosity index, excellent low-temperature performance, good high-temperature oxidation stability, environmental protection, energy consumption reduction, oil change period prolongation and the like, is widely applied to the fields of automobile industry, mechanical industry, aerospace industry and the like, and simultaneously, as the main components of the lubricating oil base oil are hydrocarbon substances, PAO can be mixed with mineral oil in any proportion and can meet the increasingly strict requirements of environmental protection regulations nowadays.
The catalysts currently used for the synthesis of PAO are mainly aluminium trichloride catalysts, Ziegler-Natta catalysts, metallocene catalysts and BF3The ionic liquid catalytic system and the related process are developed in recent years.
Metallocene catalysts have been a research hotspot in recent years and have been successfully applied to industrial production due to their single active center and high catalytic activity. The PAO molecules synthesized with metallocene catalysts have unique comb structures without the presence of upstanding side chains, which determines their higher regularity compared to conventional PAO products. US 09637791 discloses that bridged cyclopentadienyl-fluorenyl metallocene catalyst systems catalyze oligomerization of alpha-olefins and the product can be used as a lubricating oil without further hydrogenation.
Ziegler-Natta catalyst systems are typically used primarily for the production of medium and high viscosity lubricating oils. Because the Ziegler-Natta catalyst system has the characteristic of controllable central structure, the obtained PAO product has regular molecular structure and lower branching rate, and has excellent viscosity-temperature performance, but the low-temperature performance of the PAO product is poor due to regular long-chain molecules. US 311316 discloses the use of TiCl4And Al (iBu) as a catalytic system, and catalyzing 1-decene to prepare the poly-alpha-olefin lubricating oil, wherein the viscosity index of the obtained product is more than 135, and the pour point is less than minus 25 ℃.
The properties of the PAO product are determined by the degree of polymerization and molecular weight distribution of the oligomeric product, and in general, the product viscosity and thermal stabilityThe number of carbon atoms of the PAO molecules increases, and the more side chain structures and the relatively shorter straight chain segments are beneficial to the good flowability of the PAO at low temperature. Star-branched PAOs containing quaternary carbons are believed to have the best lube performance, i.e., structures with long branches in the middle of the alkane segments, such as trimers of 1-decene. CN 107304237 adopts two polymerization steps, the dosage of Ziegler-Natta catalyst, Al/Ti molar ratio and reaction time of polymerization reaction are strictly controlled in the first step, the polymerization degree is controlled, poly alpha-olefin with high regular molecular structure is obtained, and BF with high branching property is added in the second step3Catalyst by controlling BF3The addition amount of the catalytic system, the proportion of the main catalyst and the cocatalyst in the catalytic system and the polymerization time are used for polymerizing the reaction product in the first step and the residual monomers to obtain a molecular structure with a long branched chain and a regular molecular main chain structure, so that the product is ensured to have good viscosity-temperature characteristics, and the problem of poor low-temperature performance of the product is solved. But BF3Acid gas HF is easily generated when meeting water, equipment is corroded, a series of environmental problems are caused, the catalyst is difficult to separate and cannot be recycled, and a large amount of production waste liquid which is difficult to treat is generated, so that the production cost is increased.
In the process of preparing polyalphaolefin lubricant base oil by using alpha-olefin as raw material, alpha-olefin dimer produced by polymerization is not suitable as an effective component for producing PAO, and has a problem of high volatility, so that dimer is selected to be removed after polymerization is completed. This not only increases the cost of the process, but also results in a large loss of economic value. Therefore, a method for recycling the alpha-olefin dimer is needed, and the alpha-olefin dimer generated in the polymerization process is used as a raw material to polymerize the alpha-olefin dimer into PAO which has excellent performance and can be used as lubricating oil base oil.
Disclosure of Invention
The invention aims to obtain poly alpha-olefin lubricating oil base oil containing quaternary carbon structural components with excellent performance by using alpha-olefin monomers and alpha-olefin dimers with regular structures separated from alpha-olefin polymerization products catalyzed by a metallocene catalyst system as raw materials and catalyzing by a Ziegler-Natta catalyst system. Therefore, the method not only solves the problem of recycling the dimer, but also obtains PAO with excellent viscosity-temperature performance and low-temperature fluidity and different kinematic viscosity grades through the change of the ratio of the dimer to the monomer.
In order to achieve the above object, the present invention provides a method for preparing a synthetic poly-alpha-olefin oil containing a quaternary carbon structure, comprising the steps of: c6-C12The alpha-olefin monomer reacts for a period of time under the action of a metallocene catalyst/methylaluminoxane catalytic system, and alpha-olefin dimer with a regular structure in the product is separated through water washing and alkali washing after a terminator is added. To separate alpha-olefin dimer and C6-C12The alpha-olefin monomer is used as a raw material, reacts for a period of time under the action of a Ziegler-Natta catalyst system, and is added with a terminator for post-treatment to obtain the poly alpha-olefin synthetic oil containing the quaternary carbon structure.
Water and alkali washing of the product
In the method provided by the invention, no special requirements are required for the washing and alkaline washing processes of the alpha-olefin, a separating funnel can be adopted, the washing solution adopts deionized water, and the alkaline washing solution adopts an aqueous solution of sodium hydroxide.
Separation of alpha-olefin dimers
In the method provided by the invention, no special requirement is required for the separation process of the alpha-olefin dimer, and the separation process can adopt normal and reduced pressure distillation equipment commonly used in the field as long as the separation of the alpha-olefin dimer can be realized.
Post-treatment process
In the method provided by the invention, the post-treatment comprises washing, alkali washing, distillation and hydrogenation of reaction products, and the washing solution in the washing and alkali washing processes can use deionized water and sodium hydroxide aqueous solution, and the distillation process can adopt normal and reduced pressure distillation equipment commonly used in the field as long as separation of different products such as unpolymerized monomers, dimers, solvents and the like can be realized. Similarly, there is no special requirement for the hydrogenation process, and common hydrogenation catalysts, equipment, process conditions, etc. can be used as long as the hydrogenation purpose of the product can be achieved.
Characterization of Quaternary carbon structures
The method for characterizing the quaternary carbon structure in the poly alpha-olefin synthetic oil containing the quaternary carbon structure prepared by the method provided by the invention comprises the following steps13C NMR of the product13The presence or absence of quaternary carbon peaks on the C NMR spectrum was used to determine the presence or absence of quaternary carbon structures in the product.
The method for synthesizing the poly alpha-olefin is characterized in that the metallocene catalyst is a non-bridged metallocene catalyst or a bridged metallocene catalyst, and preferably the non-bridged metallocene catalyst is selected from one of zirconocene dichloride, bisindenyl zirconium dichloride and the like; preferably, the bridged metallocene catalyst is selected from one of dimethylsilicon-bridged bis (tetrahydroindenyl) zirconium dichloride, ethyl-bridged bis indenyl zirconium dichloride, and the like.
The method for synthesizing the poly-alpha-olefin is characterized in that the main catalyst of the Ziegler-Natta catalyst system is TiCl4。
The method for synthesizing the poly-alpha-olefin is characterized in that a cocatalyst of the Ziegler-Natta catalyst system is one of triethylaluminum, diethyl aluminum chloride and the like.
The method for synthesizing the poly-alpha-olefin is characterized in that the addition quality of olefin dimer and monomer is taken as the reference, and TiCl in the Ziegler-Natta catalyst system4The mass consumption is 2-6%.
The synthesis method of the poly alpha-olefin is characterized in that the molar ratio of Al to Ti in the Ziegler-Natta catalyst system is 1:5-5: 1.
The synthesis method of the poly alpha-olefin is characterized in that the reaction temperature in the Ziegler-Natta catalyst system is 40-80 ℃.
The synthesis method of the poly alpha-olefin is characterized in that the reaction time in the Ziegler-Natta catalyst system is 120-360 min.
The method for synthesizing the poly alpha-olefin is characterized in that the olefin monomer of C6-C12 is one of 1-hexene, 1-octene, 1-decene and 1-dodecene.
The synthesis method of the poly alpha-olefin is characterized in that the terminating agent is 2-5% of hydrochloric acid ethanol solution.
The method is characterized in that an organic solvent is used in the polymerization process of the metallocene/methylaluminoxane and the Ziegler-Natta catalyst system, and the organic solvent is one selected from toluene, cyclohexane, normal hexane and tetrahydrofuran.
Compared with the prior art, the preparation method of the poly alpha-olefin base oil containing the quaternary carbon structure has the beneficial effects that:
(1) alpha-olefin dimer with regular structure and C separated from alpha-olefin polymerization product by using metallocene catalyst/methylaluminoxane catalytic system6-C12The alpha-olefin monomer is used as a raw material to prepare the poly alpha-olefin synthetic oil containing the quaternary carbon structure, and alpha-olefin dimers which are not effective components of the lubricating oil are utilized, so that the utilization rate is improved, the cost is reduced, and the economic benefit is increased.
(2) The poly-alpha-olefin prepared by the preparation method has higher viscosity index and low-temperature fluidity, and the technological process is simple and convenient to operate.
(3) The preparation method can prepare PAO with different kinematic viscosity grades by changing the proportion of the alpha-olefin dimer and the alpha-olefin monomer, meets more requirements and has strong operability.
Drawings
The poly alpha-olefin base oil provided by the invention contains quaternary carbon structures, and the chemical shift of the quaternary carbon is about 30.95ppm, as shown in figure 1; the composition spectrum of the polyalphaolefin base oil is shown in FIG. 2.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
Example 1:
a250 mL three-necked flask was replaced several times with argon to remove water vapor and oxygen, 50mL of 1-decene and 30mL of toluene as a solvent were injected into the reactor with a syringe, the temperature was raised to 50 ℃ with stirring, 50. mu. moL of dimethylsilicon-bridged bis (tetrahydroindenyl) zirconium dichloride was added, and the molar ratio of Al/Zr was 300Adding methylaluminoxane, reacting for 3 hours, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, and separating out 1-decene dimer. A250 mL three-necked flask was replaced several times with argon to remove water vapor and oxygen, 50mL of the separated 1-decene dimer and 25mL of 1-decene monomer were injected into the reactor with a syringe, and 50mL of solvent n-hexane was added to the reactor, stirred and warmed to 60 deg.C, and 1.3mL of TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 0.5, reacting for 4 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product contained quaternary carbon structural components.
Example 2:
replacing a 250mL three-necked flask with argon for several times to remove water vapor and oxygen, injecting 50mL of 1-decene and 30mL of solvent toluene into a reactor by using an injector, stirring and heating to 50 ℃, adding 50 mu moL of dimethyl silicon bridged bis (tetrahydroindenyl) zirconium dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, reacting for 4 hours, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, and separating out 1-decene dimer. A250 mL three-necked flask was replaced several times with argon to remove water vapor and oxygen, 50mL of the separated 1-decene dimer and 50mL of 1-decene monomer were injected into the reactor with a syringe, and 50mL of solvent n-hexane was added to the reactor, stirred and warmed to 60 ℃ and 1.7mL of TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 0.5, reacting for 4 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product contained quaternary carbon structural components.
Example 3:
replacing 250mL three-necked flask with argon for several times to remove water vapor and oxygen, injecting 50mL 1-decene and 30mL toluene solvent into the reactor with a syringe, stirring, heating to 70 deg.C, and addingAdding 50 mu moL of dimethyl silicon bridged bis (tetrahydroindenyl) zirconium dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, reacting for 3 hours, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, and separating out 1-decene dimer. A500 mL three-necked flask was replaced with argon several times to remove water vapor and oxygen, 50mL of the separated 1-decene dimer and 100mL of 1-decene monomer were injected into the reactor with a syringe, and 50mL of n-hexane as a solvent, and the temperature was raised to 60 ℃ with stirring, and 2.6mL of TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 0.5, reacting for 4 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product contained quaternary carbon structural components.
Example 4:
replacing a 250mL three-necked flask with argon for several times to remove water vapor and oxygen, injecting 50mL of 1-decene and 30mL of solvent toluene into a reactor by using an injector, stirring and heating to 50 ℃, adding 50 mu moL of dimethyl silicon bridged bis (tetrahydroindenyl) zirconium dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, reacting for 3 hours, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, and separating out 1-decene dimer. A500 mL three-necked flask was replaced with argon several times to remove water vapor and oxygen, 75mL of the separated 1-decene dimer and 150mL of 1-decene monomer were injected into the reactor with a syringe, and 50mL of n-hexane as a solvent, and the temperature was raised to 60 ℃ with stirring, and 3.4mL of TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 0.5, reacting for 4 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product contained quaternary carbon structural components.
Example 5:
a 250mL three-necked flask was replaced several times with argon to remove water vapor, oxygen,injecting 50mL of 1-hexene and 30mL of solvent toluene into a reactor by using an injector, stirring and heating to 60 ℃, adding 50 mu moL of ethyl bridged bis-indenyl zirconium dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, reacting for 3 hours, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, and separating out 1-hexene dimer. A250 mL three-necked flask was replaced with argon several times to remove water vapor and oxygen, 50mL of the separated 1-hexene dimer and 50mL of 1-decene monomer were injected into the reactor with a syringe, and 50mL of toluene as a solvent were added to the reactor, stirred and warmed to 40 ℃ and 0.86mL of TiCl was added4Adding triethylaluminum according to the Al/Ti molar ratio of 0.2, reacting for 2h, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product contained quaternary carbon structural components.
Example 6:
replacing a 250mL three-necked bottle with argon for several times to remove water vapor and oxygen, injecting 50mL of 1-octene and 30mL of solvent toluene into a reactor by using an injector, stirring and heating to 40 ℃, adding 50 mu moL of dimethyl silicon bridged bis (tetrahydroindenyl) zirconium dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction after the reaction is carried out for 5 hours, and separating 1-octene dimer after the obtained product is washed by water and alkali. A250 mL three-necked flask was replaced with argon several times to remove water vapor and oxygen, 50mL of the separated 1-octene dimer and 50mL of 1-dodecene monomer were injected into the reactor with a syringe, and 50mL of toluene solvent were added to the reactor, stirred and heated to 50 ℃ and 1.3mL of TiCl was added4Adding ethyl aluminium dichloride according to the Al/Ti molar ratio of 2, reacting for 3 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under normal and reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the table 113C NMR confirmed that the product contained quaternary carbon structural components.
Example 7:
replacing a 250mL three-necked flask with argon for several times to remove water vapor and oxygen, injecting 50mL of 1-dodecene and 30mL of solvent toluene into a reactor by using an injector, stirring and heating to 80 ℃, adding 50 mu moL of dimethyl silicon bridged bis (tetrahydroindenyl) zirconium dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, reacting for 3 hours, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, and separating out 1-dodecene dimer. A250 mL three-necked flask was replaced several times with argon to remove water vapor and oxygen, 50mL of the separated 1-dodecene dimer and 50mL of 1-hexene monomer were injected into the reactor with a syringe, and 50mL of toluene as a solvent were added to the reactor, stirred and warmed to 70 ℃ and 2.2mL of TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 3, reacting for 5 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under normal and reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product contained quaternary carbon structural components.
Example 8:
replacing a 250mL three-necked bottle with argon for several times to remove water vapor and oxygen, injecting 50mL of 1-decene and 30mL of solvent toluene into a reactor by using an injector, stirring and heating to 60 ℃, adding 50 mu moL of bisindenyl zirconium dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, reacting for 4 hours, adding an ethanol solution of 5% hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, and separating 1-decene dimer. A250 mL three-necked flask was replaced several times with argon to remove water vapor and oxygen, 50mL of the separated 1-decene dimer and 50mL of 1-octene monomer were injected into the reactor with a syringe, and 50mL of toluene solvent were added to the reactor, stirred and warmed to 70 ℃ and 2.6mL of TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 5, reacting for 6 hours, adding 3% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under normal and reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product contained quaternary carbon structural components.
Comparative example 1:
a250 mL three-necked flask was replaced several times with argon to remove water vapor and oxygen, 50mL 1-decene monomer and 50mL n-hexane solvent were injected into the reactor with a syringe, the temperature was raised to 60 ℃ with stirring, and 0.86mL TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 0.5, reacting for 4 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product had no quaternary carbon structure.
Comparative example 2:
replacing a 250mL three-necked bottle with argon for several times to remove water vapor and oxygen, injecting 50mL of 1-decene and 30mL of solvent toluene into a reactor by using an injector, stirring and heating to 50 ℃, adding 50 mu moL of zirconocene dichloride, adding methylaluminoxane according to the Al/Zr molar ratio of 300, adding an ethanol solution of 5% hydrochloric acid after reacting for 3 hours to terminate the reaction, and separating 1-decene dimer after washing and alkaline washing the obtained product. The 250mL three-necked flask was replaced several times with argon to remove water vapor and oxygen, 50mL of the separated 1-decene dimer and 50mL of the solvent n-hexane were injected into the reactor with a syringe, the temperature was raised to 60 ℃ with stirring, and 0.86mL of TiCl was added4Adding diethyl aluminum chloride according to the Al/Ti molar ratio of 0.5, reacting for 4 hours, adding 5% ethanol solution of hydrochloric acid to terminate the reaction, washing the obtained product with water and alkali, removing the solvent under reduced pressure, removing unreacted monomer and dimer, hydrogenating to obtain a product, collecting the product, and performing performance test, wherein the product passes through the steps shown in Table 113C NMR confirmed that the product had no quaternary carbon structure.
TABLE 1
As can be seen from table 1, the polyalphaolefin synthetic oil provided by the present invention has excellent viscosity-temperature properties and low-temperature fluidity, and polyalphaolefin synthetic oils of different kinematic viscosity grades can be prepared by varying the ratio of dimer to monomer.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the method of the present invention, and these modifications and decorations should be regarded as being within the protection scope of the present invention.
Claims (4)
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