CN114075305A - Polyolefin lubricating oil base oil and preparation method thereof - Google Patents
Polyolefin lubricating oil base oil and preparation method thereof Download PDFInfo
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- 239000002199 base oil Substances 0.000 title claims abstract description 47
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 43
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 82
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000047 product Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000000314 lubricant Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 239000011951 cationic catalyst Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 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
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 2
- 150000001298 alcohols Chemical group 0.000 claims 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010626 work up procedure Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- -1 ethylene, propylene Chemical group 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VVNYDCGZZSTUBC-UHFFFAOYSA-N 5-amino-2-[(2-methylpropan-2-yl)oxycarbonylamino]-5-oxopentanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CCC(N)=O VVNYDCGZZSTUBC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
- C10M107/08—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing butene
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2205/026—Butene
- C10M2205/0265—Butene used as base material
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a polyolefin lubricating oil base oil and a preparation method thereof, wherein the method adopts a double-catalysis system and two-step polymerization reaction, and comprises the following steps: selecting a single component of 1-butene as a raw material; carrying out a first polymerization reaction on 1-butene by using a catalyst and an auxiliary agent to generate an intermediate reaction product; cooling the intermediate reaction product; performing a second polymerization reaction on the cooled intermediate reaction product by using another catalyst and an initiator to generate a reaction product; and carrying out product post-treatment on the reaction product to finally obtain the polyolefin lubricating oil base oil. The method takes the 1-butene single component with abundant resources as the raw material, thereby reducing the production cost of the polyolefin lubricating oil base oil; the polyolefin lubricating oil base oil prepared by the method has good viscosity-temperature performance and low-temperature flow performance.
Description
Technical Field
The invention relates to a preparation method of polyolefin lubricating oil base oil. In particular to a method for preparing polyolefin lubricating oil base oil by adopting a short-chain 1-butene single component as a raw material and carrying out two-step polymerization reaction by using a double-catalysis system.
Background
The polyolefin lube base oil (PAO) is a base oil obtained by polymerizing alpha-olefin (branched or unbranched) under the action of a catalyst and then hydrogenating, and is the most promising variety in synthetic base oil. Compared with mineral base oil, the high-viscosity oil has the advantages of high viscosity index, low pour point, good hydrolytic stability and oxidation stability, wide liquid phase range, small evaporation loss, low pour point, high viscosity index, good thermal oxidation stability and the like, can meet increasingly harsh OEM specifications, and meets the modern harsh energy-saving and environment-friendly requirements. Meanwhile, the oil can be used in fully synthetic or semi-synthetic oil with good blending property with mineral oil.
It is well known that alpha-olefins, particularly 1-decene, are preferred for producing high quality polyolefin lubricating oils. However, high-quality alpha-olefin is mainly obtained by an ethylene oligomerization process, and the production cost is high, the price is high, and the PAO price is high or low. The search for 1-decene substitutes to prepare high-performance lubricating oil base oil and widen the source of PAO raw materials is urgent. In the petrochemical industry, 1-butene is abundant in resources, mainly comes from ethylene cracking devices and refinery catalytic cracking devices, and respectively accounts for ethylene cracking C4(butadiene extraction early) about 20% of the total refiningCatalytic cracking of plants C4About 15% of the total weight of the product, and low resource utilization rate. Therefore, the development of 1-butene as the raw material for preparing the high-performance lubricating oil base oil by polymerization not only widens the raw material source of the PAO, reduces the production cost of the PAO and provides technical support for upgrading and updating of lubricating oil, but also is C4An important way for reasonably utilizing resources, and has obvious economic value and good application prospect.
The technology for preparing PAO by polymerizing 1-butene is researched more abroad, and mainly uses 1-butene and alpha-olefin for copolymerization, and a coordination polymerization catalytic system is adopted in the aspect of catalyst. Mobil corporation employed a modified Ziegler-Natta catalyst system with VOCl3As the main catalyst, (Et)2AlCl is a cocatalyst, and is used for conducting polymerization research on low-carbon mixed olefins (such as ethylene, propylene and 1-butene), wherein n-octane is a solvent, and Al: v is 9:1, the reaction temperature is 25 ℃, the reaction time is 4.5h, and the product is dewaxed after the reaction is finished to obtain the kinematic viscosity of 13.22mm at 100 DEG C2(ii) a PAO product having a viscosity index of 120,/s, and a pour point of-33 ℃.
The patents US4132663, US5188724 and US4163712 also use a Z-N catalytic system for olefin copolymerization, and as a result, the catalytic system is considered to have too high activity for low carbon number olefin, and the product is a high molecular weight polymer and has more isomerization.
The MargarettM.Wu uses diethyl bis (4,5,6, 7-tetrahydro-indenyl) zirconium chloride as a catalyst to catalyze ethylene and 1-butene, and the kinematic viscosity of the obtained product at 100 ℃ is 147-165 mm2Between s, a viscosity index of more than 164, a pour point of 23 ℃ and 24 ℃. Mobil corporation prepares bis-metallocene compounds to catalyze 1-butene and higher olefins (e.g., 1-C)12、1-C14Etc.) are copolymerized, toluene is taken as a solvent, the reaction temperature is 60 ℃, the reaction time is 6 hours, and the kinematic viscosity at 100 ℃ is 212mm2(ii) a high viscosity index PAO product of viscosity index 166. The China northeast petroleum university uses bis (tetramethyl cyclopentadienyl) zirconium dichloride as a catalyst to catalyze the copolymerization of 1-butene and long-chain alpha-olefin. The concentration of the catalyst bis (tetramethylcyclopentadienyl) zirconium dichloride is 0.2748mmol/L, the reaction temperature is 70 ℃, the molar ratio of aluminum to zirconium is 100, and the reaction temperature is 1-C4＝/1-C12Under the condition of 13 molar ratio, the kinematic viscosity at 100 ℃ can be synthesized to be 67.08mm2A polyolefin synthetic oil having a viscosity index of 121 and a pour point of-21 ℃. The research on the preparation of PAO by the copolymerization of butene-1 and long-chain olefin is also carried out in universities such as Tianjin scientific and technical university, and the PAO with excellent comprehensive performance is obtained. Both of these methods require two reactants as the basis for catalysis, thereby increasing production costs.
Disclosure of Invention
The invention aims to provide polyolefin lubricating oil base oil with low production cost and excellent performance.
The preparation method of the polyolefin lubricating oil base oil provided by the invention adopts abundant 1-butene as a raw material to obtain the polyolefin lubricating oil base oil with the kinematic viscosity of 19-30 mm at 100 DEG C2The polyolefin lubricant base oil adopts TiCl containing double promoters as the catalyst4Complex catalyst and BF3An initiator catalytic system, the degree of polymerization and the degree of isomerization of a polymerization product are adjustable through the synergistic effect of the two catalytic systems and the bidirectional adjustment of two-step polymerization reaction, the structural regularity of the obtained product is moderate, the comprehensive performance of the product is improved, and the prepared lubricating oil base oil has excellent viscosity-temperature performance and low-temperature flow performance.
In order to achieve the above object, the present invention provides a method for preparing a polyolefin lubricant base oil, which comprises a two-step polymerization reaction using a dual catalyst system, the method comprising the steps of:
(1) selecting a single component of 1-butene as a raw material;
(2) carrying out a first polymerization reaction on 1-butene by using a catalyst and an auxiliary agent to generate an intermediate reaction product;
(3) cooling the intermediate reaction product obtained in the step (2);
(4) performing a second polymerization reaction on the intermediate reaction product cooled and cooled in the step (3) by using another catalyst and an initiator to generate a reaction product;
(5) and (4) carrying out product post-treatment on the reaction product obtained in the step (4) to finally obtain the polyolefin lubricating oil base oil.
In one embodiment, in step (2), the catalyst is a Ziegler-Natta catalyst system and the promoter is a mixture of two aluminum alkyls.
Preferably, the auxiliaries are two selected from triethylaluminium, monoethylaluminium dichloride and diethyl aluminium chloride.
In one embodiment, in step (4), the other catalyst is BF3Cationic catalyst system, and initiator alcohol.
Preferably, the initiator is isopropanol.
In one embodiment, in the Ziegler-Natta catalyst system, TiCl4The dosage (based on the added mass of the olefin monomer) is 1 wt% -10 wt%, the molar ratio of Al to Ti is 0.5-5: 1, and the molar ratio of two aluminum alkyls is 1: 1.
Preferably, TiCl4The dosage is 3 wt% -5 wt%.
In one embodiment, BF3In cationic catalytic systems, BF3The dosage is 0.1 MPa-0.8 MPa (system partial pressure), and the dosage of the initiator (based on the mass of the materials of the first polymerization reaction) is 0.2-4%.
Preferably, BF3The dosage is 0.2MPa to 0.5MPa, and the dosage of the initiator is 0.5 percent to 2.0 percent.
In one embodiment, in the step (2), the reaction temperature of the first polymerization reaction is 50 ℃ to 100 ℃, and the reaction time is 0.5h to 3 h.
Preferably, the reaction temperature is 60-90 ℃, and the reaction time is 1.0-2 h.
In one embodiment, in the step (4), the reaction temperature of the second polymerization reaction is 10 ℃ to 30 ℃, and the reaction time is 0.5h to 4 h.
Preferably, the reaction temperature is 15-25 ℃, and the reaction time is 1.0-2.5 h.
In one embodiment, in step (5), the product post-treatment is to wash the reaction product to neutrality with sodium hydroxide solution, and then to distill under reduced pressure to remove the oligomeric components below 320 ℃.
In one embodiment, the preparation process is carried out under a nitrogen atmosphere.
The invention also provides the polyolefin lubricating oil base oil prepared by the preparation method.
In one embodiment, the polyolefin lubricant base oil has a kinematic viscosity at 100 ℃ of 19 to 30mm2/s，。
The invention takes the 1-butene single component with rich resources as the raw material, widens the raw material source for generating the polyolefin lubricating oil base oil, reduces the production cost of the polyolefin lubricating oil base oil, provides technical support for the upgrading and updating of lubricating oil, and simultaneously provides C4An important way for reasonably utilizing resources, and has obvious economic value and good application prospect.
The invention adopts Ziegler-Natta/dual-cocatalyst and BF3The initiator is a catalytic system, and the polymerization degree and the isomerization degree of the polyolefin lubricating oil base oil which is a polymerization product are adjustable through the synergistic effect of the two catalytic systems and the bidirectional adjustment of two-step polymerization reaction, so that the structural regularity of the obtained product is moderate, and the comprehensive performance of the product is improved. The kinematic viscosity at 100 ℃ generated by the reaction of the preparation method of the polyolefin lubricating oil base oil is 19-30 mm2The polyolefin lubricating oil base oil has high viscosity index, low pour point, good viscosity-temperature performance and low-temperature flow performance and is an excellent lubricating oil component.
Detailed Description
The preparation method of the polyolefin lubricating oil base oil specifically comprises the following steps:
selecting a single component of 1-butene as a raw material;
step (2), the preparation method of the invention can be carried out in an autoclave type reactor, and firstly, the alkyl aluminum double-promoter and TiCl are added41-butene (liquid phase feed) to carry out a first polymerization reaction, and controlling the reaction conditions to obtain an intermediate reaction product.
Furthermore, before the start of the first polymerization reaction, the autoclave reactor is pretreated: firstly, washing an autoclave type reactor by 300ml of refined cyclohexane, wherein the washing temperature is 100 ℃, the washing time is 0.5h, discharging the liquid after washing, and then blowing the polymerization reaction kettle by high-purity nitrogen to ensure that air and trace water in the polymerization reaction kettle are removed; after nitrogen purging, cooling to a preset reaction condition by using circulating water, adding a cocatalyst and a main catalyst, introducing a quantitative raw material 1-butene (weight loss weighing method), starting stirring, setting a reaction temperature, and controlling the reaction temperature by using a cooling system. After reacting for a certain time, discharging unreacted monomers, transferring the product into a 500mL round-bottom flask, terminating with 10% acidified ethanol, filtering, washing with alkali and water, collecting and weighing for later use.
And (3) cooling the intermediate reaction product obtained in the step (2).
And (5) emptying the reaction kettle, discharging the materials, and performing subsequent treatment.
And (4) carrying out a second polymerization reaction on the intermediate reaction product cooled and cooled in the step (3) by using another catalyst and an initiator to generate a reaction product.
More specifically, firstly, sequentially adding the intermediate reaction product cooled and cooled in the step (3) and an initiator (based on the mass of materials) into a 1L high-pressure reaction kettle, starting stirring, and simultaneously setting the reaction temperature; then introducing catalyst BF3Gas, the amount of addition (pressure of the reaction vessel) was controlled, and the reaction temperature was controlled using a cooling system. After a certain time of reaction, unreacted catalyst was discharged and recovered, and the product was transferred to a 500mL round bottom flask.
And (5) carrying out product post-treatment on the reaction product obtained in the step (4) to finally obtain the polyolefin lubricating oil base oil.
More specifically, washing the reaction product obtained in the step (4) to be neutral by using a sodium hydroxide solution with the mass fraction of 5%, and distilling under reduced pressure after washing treatment to remove oligomeric components below 320 ℃, thereby obtaining the polyolefin lubricating oil base oil product to be tested.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the contents of the present invention, and those equivalents may fall within the scope of the present invention defined by the claims appended to the present application.
Example 1
Carrying out polymerization reaction by adopting the steps, firstly carrying out pretreatment of a reaction kettle, and then starting a first polymerization reaction: 0.33ml of AlEt was added to the polymerization reactor in order2Cl and 0.36ml Al (Et)3，2g TiCl4And 200g of 1-butene (liquid phase injection), heating to control the reaction temperature to be 50 ℃, reacting for 1.0h, stopping stirring, cooling to room temperature, flashing unreacted monomers, filling nitrogen for replacement for 4 times, discharging the materials into 50ml of acidified ethanol (10%), terminating the polymerization reaction, removing impurities, putting the materials into a second reaction kettle, controlling the reaction temperature to be 10 ℃, and sequentially adding 0.2% of methanol initiator (based on the mass of the materials), BF, and30.1MPa, controlling the reaction time for 1.0h, transferring the product into a 500mL round-bottom flask, washing the product to be neutral by using a sodium hydroxide solution with the mass fraction of 5%, distilling off oligomeric components below 320 ℃ after water washing treatment, measuring the viscosity, the viscosity index and the pour point of the obtained product, and obtaining the product with the kinematic viscosity of 19.18mm at 100 DEG C2The viscosity index was 127 and the pour point was-36 ℃.
Example 2
The same polymerization procedure as in example 1 was used: 7ml of AlEt are added in turn to the polymerization reactor2Cl and 7ml Al (Et)3，20g TiCl4And 200g of 1-butene, the reaction temperature was controlled at 60 ℃ by heating, the reaction was carried out for 0.5h, stirring was stopped, and after the reaction, a second polymerization and a product work-up were carried out as in example 1, under conditions such that 0.5% propanol initiator (based on the mass of the material) and BF were added30.2MPa, the polymerization temperature is 20 ℃, and the time is 2 h. The kinematic viscosity at 100 ℃ of the product obtained is 20.17mm2The viscosity index was 131 and the pour point was-36 ℃.
Example 3
The same polymerization procedure as in example 1 was used: 7ml of AlEt are added in turn to the polymerization reactor2Cl and 7ml Al (Et)3，20g TiCl4And 200g of 1-butene, heating to control the reaction temperature to 70 ℃, reacting for 1h, stopping stirring, carrying out a second polymerization reaction and product post-treatment after the reaction is finished according to the method of example 1, wherein the second polymerization reaction condition is that ethanol is added to introduce0.5% of hair agent (based on the mass of the material), BF30.2MPa, the polymerization temperature is 25 ℃, and the time is 3 h. The kinematic viscosity at 100 ℃ of the product obtained is 19.45mm2The viscosity index was 125 and the pour point was-39 ℃.
Example 4
The same polymerization procedure as in example 1 was used: 16ml of AlEt are added in turn to the polymerization kettle2Cl and 18ml Al (Et)3，10g TiCl4And 200g of 1-butene, the reaction temperature is controlled to be 80 ℃, the reaction is carried out for 2 hours, the stirring is stopped, after the reaction is finished, the second polymerization reaction and the product post-treatment are carried out according to the method of the example 1, and the second polymerization reaction condition is that 1 percent of isopropanol initiator (based on the mass of the materials) and BF are added30.4MPa, the polymerization temperature is 25 ℃, and the time is 2.5 h. The kinematic viscosity at 100 ℃ of the product obtained is 20.89mm2The viscosity index was 128 and the pour point was-36 ℃.
Example 5
The same polymerization procedure as in example 1 was used: 16ml of AlEt are added in turn to the polymerization kettle2Cl and 18ml Al (Et)3，20g TiCl4And 200g of 1-butene, the reaction temperature is controlled to be 90 ℃ by heating, the reaction is carried out for 2h, the stirring is stopped, after the reaction is finished, the second polymerization reaction and the product post-treatment are carried out according to the method of the example 1, and the second polymerization reaction conditions are that a propanol initiator (based on the mass of the materials) is added for 2 percent, and BF is added30.5MPa, the polymerization temperature is 15 ℃, and the time is 3 h. The kinematic viscosity at 100 ℃ of the product obtained is 20.43mm2Viscosity index 138 and pour point-33 ℃.
Example 6
The same polymerization procedure as in example 1 was used: 7.8ml of AlEtCl were added in succession to the polymerization vessel2And 7.3ml of Al (Et)3，20g TiCl4And 200g of 1-butene, the reaction temperature was controlled at 80 ℃ by heating, the reaction was carried out for 2 hours, stirring was stopped, and after the reaction, a second polymerization and a product work-up were carried out as in example 1, under conditions such that 0.5% isopropanol initiator (based on the mass of the material) and BF were added30.2MPa, the polymerization temperature is 15 ℃, and the time is 2 h. The kinematic viscosity at 100 ℃ of the product obtained is 29.75mm2(ii) a viscosity index of 139 and a pour point of-36 ℃.
Example 7
The same polymerization procedure as in example 1 was used: 5.9ml of AlEtCl were added in succession to the polymerization vessel2And 7.0ml of Al (Et)2Cl，6g TiCl4And 200g of 1-butene, the reaction temperature was controlled at 80 ℃ by heating, the reaction was carried out for 2 hours, stirring was stopped, a second polymerization and a product work-up were carried out after the reaction as in example 1, under conditions such that 4% of ethanol initiator (based on the mass of the material) and BF were added30.8MPa, the polymerization temperature is 10 ℃, and the time is 1 h. The kinematic viscosity at 100 ℃ of the product obtained is 23.14mm2Viscosity index 138 and pour point-39 ℃.
Example 8
The same polymerization procedure as in example 1 was used: 0.32ml of AlEtCl was added to the polymerization reactor in succession2And 0.30ml of Al (Et)2Cl，2g TiCl4And 200g of 1-butene, the reaction temperature was controlled at 90 ℃ by heating, the reaction was carried out for 3 hours, stirring was stopped, and after the reaction, a second polymerization and a product work-up were carried out as in example 1, under conditions such that 3.0% by mass of methanol initiator (based on the mass of the material) and BF were added30.5MPa, the polymerization temperature is 15 ℃, and the time is 2 h. The kinematic viscosity at 100 ℃ of the product obtained is 25mm2(ii) a viscosity index of 131 and a pour point of-39 ℃.
Example 9
The same polymerization procedure as in example 1 was used: 19.5ml of AlEtCl were added in succession to the polymerization vessel2And 16.5ml of Al (Et)2Cl，10g TiCl4And 200g of 1-butene, the reaction temperature was controlled at 100 ℃ by heating, the reaction was carried out for 1.5h, stirring was stopped, and after the reaction, a second polymerization and a product work-up were carried out as in example 1, under conditions such that 0.2% propanol initiator (based on the mass of the material) and BF were added30.3MPa, the polymerization temperature is 25 ℃, and the time is 3 h. The kinematic viscosity at 100 ℃ of the product obtained is 22.56mm2Viscosity index of 142 and pour point of-36 ℃.
Example 10
The same polymerization procedure as in example 1 was used: 19.5ml of AlEtCl were added in succession to the polymerization vessel2And 16.5ml of Al (Et)2Cl，10g TiCl4And 200g of 1-butene, the reaction temperature was controlled at 100 ℃ by heating, the reaction was carried out for 1.5h, stirring was stopped, and after the reaction, a second polymerization and a product work-up were carried out as in example 1, under conditions such that 0.2% of initiator (based on the mass of the material) and BF were added30.3MPa, the polymerization temperature is 30 ℃, and the time is 4 h. The kinematic viscosity at 100 ℃ of the product obtained is 26.69mm2Viscosity index of 137 and pour point of-33 ℃.
Comparative example 1
Using the same polymerization method as in the first polymerization of example 1, 7.8ml of AlEtCl was successively charged into a polymerization vessel2Or 7.3ml Al (Et)3，6g、10g TiCl4And 200g of 1-butene, raising the temperature to control the reaction temperature to be 80 ℃, reacting for 2 hours, stopping stirring, carrying out product post-treatment and removing oligomerization components according to the method of the embodiment 1 after the reaction is finished, and obtaining the product with the kinematic viscosity of 30.75 and 32.43mm at 100 DEG C2The viscosity index was 120 in each case and the pour point was-15 ℃.
Comparative example 2
Using the same polymerization method as in the second polymerization reaction of example 1, 0.2%, 0.5%, 2%, 4%, 200g of 1-butene as a starting material (based on the mass of the starting material) as an initiator was sequentially added to a polymerization reactor to control BF3The partial pressure is 0.2MPa and 0.4MPa, the reaction temperature is 25 ℃, the reaction time is controlled to be 2h, and the kinematic viscosity of the obtained product at 100 ℃ is lower than 4.75mm2The viscosity index was 85, the pour point was-42 ℃.
The above examples 1 to 10 are the polyolefin lubricant base oils prepared by the two-step polymerization reaction using the dual catalyst system in the preparation method of the polyolefin lubricant base oil of the present invention, and the kinematic viscosity at 100 ℃ is 19 to 30mm2Is between/s. Comparative examples 1 and 2 are preparation methods in which only one catalyst is used and only the first polymerization reaction or the second polymerization reaction is carried out, and it can be seen by comparison that the polyolefin lubricating base oil prepared by comparative example 1 or 2 does not have a kinematic viscosity at 100 ℃ ofWithin the scope of the invention, it is significantly higher or lower than the invention, and the viscosity index is too low and the pour point is higher.
In the use process of the lubricating oil, the kinematic viscosity, the viscosity index and the pour point are important evaluation indexes of the quality of the lubricating oil. The higher the viscosity index is, the smaller the degree of change of the viscosity of the lubricating oil along with the problem is, the less sensitive the lubricating oil to the temperature is, and the wider the applicable environment temperature is; lower pour points indicate that the lubricant can accommodate lower temperatures and flow at lower ambient temperatures.
The method takes a single component of 1-butene with rich resources as a raw material, and can prepare the product with the kinematic viscosity of 19-30 mm at 100 ℃ by adopting a double-catalysis system and a two-step polymerization reaction method2The preparation method reduces the production cost of the polyolefin lubricant base oil, and the prepared polyolefin lubricant base oil has the characteristics of high viscosity index and low pour point, so that the polyolefin lubricant base oil has good viscosity-temperature performance and low-temperature flow performance and is an excellent lubricant component.
Claims (17)
1. A preparation method of polyolefin lubricating oil base oil is characterized in that a double-catalysis system is adopted, and two-step polymerization reaction is carried out, and the preparation method comprises the following steps:
(1) selecting a single component of 1-butene as a raw material;
(2) carrying out a first polymerization reaction on 1-butene by using a catalyst and an auxiliary agent to generate an intermediate reaction product;
(3) cooling the intermediate reaction product obtained in the step (2);
(4) performing a second polymerization reaction on the intermediate reaction product cooled and cooled in the step (3) by using another catalyst and an initiator to generate a reaction product;
(5) and (4) carrying out product post-treatment on the reaction product obtained in the step (4) to finally obtain the polyolefin lubricating oil base oil.
2. The method of claim 1, wherein in step (2), the catalyst is a Ziegler-Natta catalyst system and the adjuvant is a mixture of two aluminum alkyls.
3. The method of claim 2, wherein the adjuvant is two selected from triethylaluminum, monoethylaluminum dichloride, and diethyl aluminum dichloride.
4. The process for preparing a polyolefin lubricant base oil according to claim 1, characterized in that in step (4), the other catalyst is BF3The cationic catalyst system, the initiator is alcohols.
5. The method of claim 4, wherein the initiator is isopropanol.
6. The method of claim 2, wherein TiCl is added to the Ziegler-Natta catalyst system4The dosage (based on the added mass of the olefin monomer) is 1 wt% -10 wt%, the molar ratio of Al to Ti is 0.5-5: 1, and the molar ratio of the two aluminum alkyls is 1: 1.
7. The method of preparing the polyolefin lubricant base oil of claim 6, wherein the TiCl is4The dosage is 3 wt% -5 wt%.
8. The method of preparing a polyolefin lubricant base oil of claim 4, wherein the BF is prepared by3In cationic catalytic systems, BF3The dosage is 0.1 MPa-0.8 MPa (system partial pressure), and the dosage of the initiator (based on the mass of the materials of the first polymerization reaction) is 0.2-4%.
9. The method of making a polyolefin lubricant base oil of claim 8, wherein the BF is performed3The dosage is 0.2MPa to 0.5MPa, and the dosage of the initiator is 0.5 percent to 2.0 percent.
10. The method for preparing polyolefin lubricant base oil according to claim 1, wherein in the step (2), the reaction temperature of the first polymerization reaction is 50 ℃ to 100 ℃ and the reaction time is 0.5h to 3 h.
11. The method of claim 10, wherein the reaction temperature is 60 ℃ to 90 ℃ and the reaction time is 1.0h to 2 h.
12. The method for preparing polyolefin lubricant base oil according to claim 1, wherein in the step (4), the reaction temperature of the second polymerization reaction is 10 ℃ to 30 ℃ and the reaction time is 0.5h to 4 h.
13. The method of claim 12, wherein the reaction temperature is 15 ℃ to 25 ℃ and the reaction time is 1.0h to 2.5 h.
14. The method of claim 1, wherein in step (5), the product is post-treated by washing the reaction product to neutrality with sodium hydroxide solution and then distilling under reduced pressure to remove oligomeric components below 320 ℃.
15. The method of claim 1, wherein the method is performed under a nitrogen atmosphere.
16. A polyolefin lubricant base oil produced by the production method according to any one of claims 1 to 15.
17. The polyolefin lubricant base oil of claim 16, wherein the kinematic viscosity at 100 ℃ is 19 to 30mm2/s。
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| US4420647A (en) * | 1982-04-26 | 1983-12-13 | Texaco Inc. | Semi-synthetic lubricating oil composition |
| CN111286385A (en) * | 2018-12-06 | 2020-06-16 | 中国石油天然气股份有限公司 | Synthetic method of lubricating oil base oil |
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| CN115637184A (en) * | 2022-11-15 | 2023-01-24 | 国家能源集团宁夏煤业有限责任公司 | PAO base oil and preparation method thereof |
| CN115637184B (en) * | 2022-11-15 | 2024-02-13 | 国家能源集团宁夏煤业有限责任公司 | PAO base oil and preparation method thereof |
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