CN104926963A - Method for synthesizing poly alpha-olefin base oil through 1-butene oligomerization - Google Patents

Method for synthesizing poly alpha-olefin base oil through 1-butene oligomerization Download PDF

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CN104926963A
CN104926963A CN201510363006.XA CN201510363006A CN104926963A CN 104926963 A CN104926963 A CN 104926963A CN 201510363006 A CN201510363006 A CN 201510363006A CN 104926963 A CN104926963 A CN 104926963A
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butylene
base oil
poly alpha
oligomerisation reaction
olefin base
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徐用军
贺强
任合刚
闫义彬
丁琦
董卫涛
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention relates to a method of adopting metallocene catalyst oligomerization to synthesize poly alpha-olefin base oil, in particular to a method for synthesizing the poly alpha-olefin base oil through 1-butene oligomerization, and solves the problem that catalysts used in existing 1-butene oligomerization are low in catalysis efficiency and low in product selectivity. The method includes: under protection of nitrogen, sequentially adding metallocene catalyst, cocatalyst solution, hydrogen and monomer 1-butene liquid into a reactor; enabling oligomerization to occur at temperature of 0-90 DEG C; flashing out monomer which is not in reaction to obtain the poly alpha-olefin base oil. The catalyst used for preparing the poly alpha-olefin base oil is high in catalysis efficiency, catalysis activity of the catalyst can reach 0.8x106-7.6x106g/(molZr.h), and product selectivity is realized by controlling polymerization process conditions like reaction temperature and hydrogen concentration.

Description

The method of 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil
Technical field
The present invention relates to a kind of method adopting metallocene catalyst catalysis 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil.
Background technology
Poly-alpha olefins (Poly-alpha-olefin, PAO) is one of important ucon oil.Have heat-resistant quality, oxidation stability and shear stability good, liquid range is wide, and condensation point is low, viscosity index advantages of higher.Usually, 100 DEG C of kinematic viscosity are less than or equal to 10mm 2the lubricating oil of/s is called low viscosity oil, is more than or equal to 40mm 2/ s is called heavy oil, therebetween be called medium viscosity oil.PAO can be used as engine oil, compressor oil, gear oil, aviation wet goods.Medium viscosity PAO lubricating oil can be produced by the method that low viscosity and high viscosity PAO are in harmonious proportion, but the medium viscosity PAO that shear stability and volatile performance are not so good as directly synthesis is good.
The production technique of PAO base oil is divided into two large steps substantially: the first step is prepare linear alpha-alkene intermediate feed used, but is all the decene produced by various ethylene oligomerization processing method substantially; Second step decene synthesizes PAO base oil further.As for catalyzer used, be 2 ~ 10mm for the 100 DEG C of kinematic viscosity preparing consumption maximum 2the PAO product of/s, the catalyzer of use is with BF 3be main, with various alcohols and water etc. for promotor.These homogeneous catalysts are industrially successfully applied, and obtain good economic benefit.As Japanese Patent JP08505888 discloses a kind of method that cationoid polymerisation prepares lubricant base, with AlCl 3, BF 3deng Lewis acid as catalyzer, prepare poly decene.The method, owing to adopting homogeneous system, makes AlCl in product 3, BF 3higher etc. the content of halides, the product of low halides cannot be produced, BF 3not only price is more expensive but also due to the corrodibility of fluorine, causes a series of environmental problem.And catalyzer is difficult to be separated, and cannot reclaim use, create a large amount of reluctant production waste liquid, improve production cost.
Chinese invention patent 201210323278.3 relates to a kind of modification aluminum trichloride catalyst of gamma-aluminium oxide carrier load, this supported catalyst is used for 1-decene oligomerisation, the severe corrosive of aluminum trichloride catalyst and strong toxicity can be overcome, easily and product separation, the large amount of sewage in traditional technology and problem of environmental pollution is avoided; Gained poly-alpha olefins yield is greater than 60 ω %, oligopolymer 100 DEG C of kinematic viscosity 10.0 ~ 25.0mm 2/ s, oligopolymer cl content is less than 2.0 ω %.
Chinese invention patent 201310279379.X relates to one gama-alumina (γ-Al 2o 3) nickel (the II)-organoaluminum of load is catalyzer, tertiary butyl chloride is promotor, with iso-butylene and C 8~ C 12alpha-olefin be raw material, oligomerisation reaction under temperature 50 C ~ 80 DEG C, hydrogen partial pressure 0.25 ~ 0.4MPa, reaction pressure 0.5 ~ 1.0MPa condition, then carries out hydrogenation to oligopolymer, obtains PAO base oil.C in gained PAO base oil 8~ C 12alpha-olefin content 60 ~ 81 ω %, base oil number-average molecular weight is less than 550, and molecular weight distribution is less than 15,100 DEG C of kinematic viscosity 8.8 ~ 28.0mm 2/ s, viscosity index is 121 ~ 147, and pour point is-38 DEG C ~-52 DEG C, and bromine number is less than 0.050 bromine g/100gPAO.
But no matter be homogeneous phase or heterogeneous PAO production technique, PAO is substantially by C 8above alpha-olefin oligomerisation obtains, and C 8above alpha-olefin needs to be obtained by ethylene oligomerization technique, limits the raw material sources of PAO base oil; And ethylene oligomerization technique prepares C 10and above alpha-olefin yield is low, preparation cost is high, the corresponding production cost adding PAO base oil.
Along with the development of petrochemical industry, the attention of people is gradually from the C that the higher ethene of current interest rate or propylene feedstocks turn to utilization ratio lower 4alkene.Catalytic cracking unit and a large amount of C of ethylene cracker coproduction 4cut, divinyl wherein, iso-butylene are after effectively utilizing, and the 1-butylene of about 77% is burnt together with butane as civil liquefied gas.Therefore, C is effectively utilized 4the Chemicals that 1-butylene in cut carrys out production high added value have great importance.
Current 1-butylene oligomerisation reaction catalyzer mainly contains solid phosphoric acid catalyst, loaded catalyst, zeolite molecular sieve etc.And commercial process extensively adopts phosphoric acid/diatom scholar catalyzer, though this type of catalyzer is through repeatedly improving, still there is the phosphoric acid salt that phosphoric acid and acid carrier effect generate and catalyst agglomeration can be made to cause blocking the technical barrier of reactor.
US Patent No. 4100220 and US4463211 report 1-butylene oligomerisation reaction, by adopting cation exchange resin catalyst, but the oligomerization product that the method mainly exists higher molecular weight blocks reaction channel, and catalyst activity reduction is very fast, the resin temperature tolerance of synthesis is poor, thus limits it and produces and application.
US Patent No. 5304615 and European patent EP 0558187 patent reports with C 4mixture is raw material, wherein mainly comprises 1-butylene, 2-butylene, iso-butylene and butane etc., adopts imidazole type or pyridine type ionic liquid catalyzer to react.The method possesses raw material sources advantage widely, and the molecular weight of polymerisate is comparatively large, and generally its molecular-weight average is about 600-1000.But the method is not suitable for producing C 8, C 12, C 16deng very low-molecular-weight product.
Chinese patent CN 1721375A reports and adopts MCM-56 molecular sieve catalyst to prepare C for the oligomerisation of catalysis 1-butylene 8the method of alkene, the method can solve the lower and problem that selectivity of product is poor of the easy argillization of catalyzer in conventional art, catalytic activity, but still there is the comparatively harsh problem of reaction conditions.
Open a kind of employing SO in Chinese patent CN 104324734A 4 2-/ γ-Al 2o 3-Fe 2o 3catalyzer is applicable to 1-butylene oligomerisation reaction synthesis C 8and C 12preparation method, there is when this catalyzer is used for 1-butylene oligomerisation reaction high reactivity, feature that target product selectivity is high, but this catalyzer is not suitable for synthesis is more than or equal to C 16above product.
Summary of the invention:
The object of the invention is the lower and problem that selectivity of product is poor of catalytic efficiency in order to solve existing 1-butylene oligomerisation reaction used catalyst, and a kind of method adopting metallocene catalyst catalysis 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil is provided.
The method of 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil of the present invention realizes according to the following steps:
Under nitrogen protection, metallocene catalyst, promotor solution, hydrogen and monomer 1-butylene liquid is added successively in tank reactor, at the temperature of 0 ~ 90 DEG C, carry out oligomerisation reaction 0.5 ~ 4h, then flash off unreacted monomer 1-butylene, obtain poly-alpha olefins base oil;
The structural formula of wherein said metallocene catalyst is as follows:
(I) R in structural formula 1, R 2, R 3, R 4, R 5, R 6for-H ,-CH 3,-C 2h 5,-C 3h 7,-C 4h 9,-C 5h 11,-C 6h 13or-C 8h 17;
Described promotor is one or both the mixture in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine di-isopropyl aluminium, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, methylaluminoxane.
The present invention carries out the mild condition of 1-butylene oligomerisation reaction, low to equipment cost, and not easily blocks reactor, and the catalyst efficiency preparing poly-alpha olefins base oil is high, and catalytic activity can reach 0.8 × 10 6~ 7.6 × 10 6g/ (molZrh).And the present invention regulates the selectivity of product by the space steric effect of this body structure of catalyst ligand and electronic effect and polymerization process condition (as temperature of reaction and density of hydrogen etc.).The kinematic viscosity of the polybutene-1 liquid prepared 100 DEG C time is 12 ~ 95mm 2/ s, viscosity index is 112 ~ 170, and pour point is-20 DEG C ~-60 DEG C.The control of this catalyst system combined process condition, makes polybutene-1 completely in liquid state, produces, therefore can not block reactor without high-molecular weight polymer.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the polybutene-1 liquid that embodiment one obtains;
Fig. 2 is the nucleus magnetic hydrogen spectrum figure A of the polybutene-1 liquid that embodiment one obtains;
Fig. 3 is the nucleus magnetic hydrogen spectrum figure B of the polybutene-1 liquid that embodiment one obtains;
Fig. 4 is the nuclear-magnetism carbon spectrogram A of the polybutene-1 liquid that embodiment two obtains;
Fig. 5 is the nuclear-magnetism carbon spectrogram B of the polybutene-1 liquid that embodiment two obtains.
Embodiment
Embodiment one: the method for present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
Under nitrogen protection, metallocene catalyst, promotor solution, hydrogen and monomer 1-butylene liquid (liquid 1-butylene) is added successively in tank reactor, oligomerisation reaction 0.5 ~ 4h is carried out at the temperature of 0 ~ 90 DEG C, then flash off unreacted monomer 1-butylene, obtain poly-alpha olefins base oil;
The structural formula of wherein said metallocene catalyst is as follows:
(I) R in structural formula 1, R 2, R 3, R 4, R 5, R 6for-H ,-CH 3,-C 2h 5,-C 3h 7,-C 4h 9,-C 5h 11,-C 6h 13or-C 8h 17;
Described promotor is one or both the mixture in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine di-isopropyl aluminium, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, methylaluminoxane.
Present embodiment is due to the characteristic of metallocene catalyst, and during polyreaction, chainpropagation constant and chain transfer constant differ less, therefore achieve oligomerisation reaction.
Present embodiment adopts metallocene catalyst catalysis 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil, this catalyzer has the advantages that activity is high, selectivity of product is controlled when being used for 1-butylene oligomerisation, thus utilizes this catalyzer to carry out 1-butylene oligomerisation reaction synthesis C 8to C 120polybutene-1 liquid.The structural formula of primary product is as follows:
Embodiment two: present embodiment and embodiment one are two (1-butyl-3-methyl cyclopentadienyl) zirconium dichlorides unlike described metallocene catalyst, two (1-butyl-2-methyl-cyclopentad ienyl) zirconium dichloride, two (1-isobutyl--3-methyl cyclopentadienyl) zirconium dichloride, two (1-octyl group-3-butyl cyclopentadienyl) zirconium dichloride, two (n-butyl cyclopentadienyl) zirconium dichloride, two (methyl cyclopentadienyl) zirconium dichloride, two (t-butyl cyclopentadienyl) zirconium dichloride, two (isobutylcyclopentadienyl) zirconium dichloride or two (n-octyl cyclopentadienyl) zirconium dichloride.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are methylaluminoxane unlike described promotor.Other step and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are that 1:300 ~ 3000 add metallocene catalyst and promotor unlike the mol ratio by zirconium and aluminium.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are 0 ~ 1MPa unlike the partial pressure range of hydrogen.Other step and parameter identical with one of embodiment one to four.
Hydrogen described in present embodiment is as molecular weight regulator.
Embodiment six: one of present embodiment and embodiment one to five carry out oligomerisation reaction 2 ~ 3h unlike at the temperature of 0 ~ 90 DEG C.Other step and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six carry out oligomerisation reaction 2 ~ 3h unlike at the temperature of 40 ~ 80 DEG C.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven are 5000 ~ 50000g/gCat unlike the add-on of monomer 1-butylene liquid.Other step and parameter identical with one of embodiment one to seven.
Add-on described in present embodiment refers to the ratio adding butylene quality and catalyst levels, and namely the catalyzer of unit mass adds the 1-butylene of 5000 ~ 50000g.
Embodiment nine: present embodiment and embodiment eight are 10000 ~ 30000g/gCat unlike the add-on of monomer 1-butylene liquid.Other step and parameter identical with embodiment eight.
Embodiment one: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 4mg two (1-butyl-3-methyl cyclopentadienyl) zirconium dichloride, 3ml methylaluminoxane, hydrogen (dividing potential drop 0.1MPa) and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 0.5h is carried out at the temperature of 60 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 61.2g water white transparency oligomerization product polybutene-1 liquid.
The present embodiment metallocene catalyst used is purchased from Xi Paike chemical reagent company limited.
The catalytic efficiency of the present embodiment catalyzer is 7.6 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 61.2wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 25mm 2/ s, viscosity index is 138, and pour point is-32 DEG C, and weight-average molecular weight is 1452g/mol.Viscosity described in the present embodiment utilizes determination of ubbelohde viscometer, obtains test data according to GB/T 265-1988 petroleum products kinematic viscosity assay method and kinetic viscosity computing method.
Embodiment two: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 6mg two (1-butyl-3-methyl cyclopentadienyl) zirconium dichloride, 3ml methylaluminoxane and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 2h is carried out at the temperature of 80 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 90g water white transparency oligomerization product polybutene-1 liquid.
The catalytic efficiency of the present embodiment catalyzer is 1.8 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 90wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 12mm 2/ s, viscosity index is 158, and pour point is-48 DEG C, and weight-average molecular weight is 580g/mol.
Embodiment three: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 6mg two (1-butyl-3-methyl cyclopentadienyl) zirconium dichloride, 6ml methylaluminoxane, hydrogen (dividing potential drop 0.1MPa) and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 3h is carried out at the temperature of 80 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 60g water white transparency oligomerization product polybutene-1 liquid.
The catalytic efficiency of the present embodiment catalyzer is 0.8 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 60wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 55mm 2/ s, viscosity index is 112, and pour point is-20 DEG C, and weight-average molecular weight is 2365g/mol.
Embodiment four: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 4mg two (n-butyl cyclopentadienyl) zirconium dichloride, 6ml methylaluminoxane, hydrogen (dividing potential drop 0.5MPa) and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 2h is carried out at the temperature of 40 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 80g water white transparency oligomerization product polybutene-1 liquid.
The catalytic efficiency of the present embodiment catalyzer is 4.0 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 80wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 35mm 2/ s, viscosity index is 140, and pour point is-41 DEG C, and weight-average molecular weight is 1800g/mol.
Embodiment five: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 4mg two (isobutylcyclopentadienyl) zirconium dichloride, 2ml methylaluminoxane, hydrogen (dividing potential drop 0.5MPa) and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 1h is carried out at the temperature of 60 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 50g water white transparency oligomerization product polybutene-1 liquid.
The catalytic efficiency of the present embodiment catalyzer is 5.0 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 50wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 20mm 2/ s, viscosity index is 120, and pour point is-25 DEG C, and weight-average molecular weight is 890g/mol.
Embodiment six: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 4mg two (isobutylcyclopentadienyl) zirconium dichloride, 2ml methylaluminoxane and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 3h is carried out at the temperature of 45 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 60g water white transparency oligomerization product polybutene-1 liquid.
The catalytic efficiency of the present embodiment catalyzer is 6.0 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 60wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 95mm 2/ s, viscosity index is 170, and pour point is-55 DEG C, and weight-average molecular weight is 4370g/mol.
Embodiment seven: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 4mg two (isobutylcyclopentadienyl) zirconium dichloride, 3ml methylaluminoxane, hydrogen (dividing potential drop 0.02MPa) and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 1h is carried out at the temperature of 50 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 58g water white transparency oligomerization product polybutene-1 liquid.
The catalytic efficiency of the present embodiment catalyzer is 5.3 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 58wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 86mm 2/ s, viscosity index is 145, and pour point is-45 DEG C, and weight-average molecular weight is 3860g/mol.
Embodiment eight: the method for the present embodiment 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil realizes according to the following steps:
1L fully-closed mechanical stirring stainless steel cauldron high pure nitrogen is replaced 5 times; under high pure nitrogen protection; 4mg two (isobutylcyclopentadienyl) zirconium dichloride, 2ml methylaluminoxane, hydrogen (dividing potential drop 0.08MPa) and 100g monomer 1-butylene liquid is added successively in tank reactor; oligomerisation reaction 1h is carried out at the temperature of 60 DEG C; flash off unreacted monomer 1-butylene after reaction terminates, obtain 50g water white transparency oligomerization product polybutene-1 liquid.
The catalytic efficiency of the present embodiment catalyzer is 5.0 × 10 6g/ (molZrh), 1-butylene transformation efficiency is 50wt%, and the kinematic viscosity that polybutene-1 liquid is 100 DEG C is 70mm 2/ s, viscosity index is 140, and pour point is-52 DEG C, and weight-average molecular weight is 2925g/mol.

Claims (9)

  1. The method of 1.1-butene oligomerization Reactive Synthesis poly-alpha olefins base oil, it is characterized in that following these steps to realize:
    Under nitrogen protection, metallocene catalyst, promotor solution, hydrogen and monomer 1-butylene liquid is added successively in tank reactor, at the temperature of 0 ~ 90 DEG C, carry out oligomerisation reaction 0.5 ~ 4h, then flash off unreacted monomer 1-butylene, obtain poly-alpha olefins base oil;
    The structural formula of wherein said metallocene catalyst is as follows:
    (I) R in structural formula 1, R 2, R 3, R 4, R 5, R 6for-H ,-CH 3,-C 2h 5,-C 3h 7,-C 4h 9,-C 5h 11,-C 6h 13or-C 8h 17;
    Described promotor is one or both the mixture in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine di-isopropyl aluminium, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, methylaluminoxane.
  2. 2. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 1, it is characterized in that described metallocene catalyst is for two (1-butyl-3-methyl cyclopentadienyl) zirconium dichloride, two (1-butyl-2-methyl-cyclopentad ienyl) zirconium dichloride, two (1-isobutyl--3-methyl cyclopentadienyl) zirconium dichloride, two (1-octyl group-3-butyl cyclopentadienyl) zirconium dichloride, two (n-butyl cyclopentadienyl) zirconium dichloride, two (methyl cyclopentadienyl) zirconium dichloride, two (t-butyl cyclopentadienyl) zirconium dichloride, two (isobutylcyclopentadienyl) zirconium dichloride or two (n-octyl cyclopentadienyl) zirconium dichloride.
  3. 3. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 1, is characterized in that described promotor is methylaluminoxane.
  4. 4. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 1, is characterized in that by the mol ratio of zirconium and aluminium be that 1:300 ~ 3000 add metallocene catalyst and promotor.
  5. 5. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 1, is characterized in that the partial pressure range of hydrogen is 0 ~ 1MPa.
  6. 6. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 1, is characterized in that carrying out oligomerisation reaction 2 ~ 3h at the temperature of 0 ~ 90 DEG C.
  7. 7. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 6, is characterized in that carrying out oligomerisation reaction 2 ~ 3h at the temperature of 40 ~ 80 DEG C.
  8. 8. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 1, is characterized in that the add-on of monomer 1-butylene liquid is 5000 ~ 50000g/gCat.
  9. 9. the method for 1-butylene oligomerisation reaction synthesizing poly alpha-olefin base oil according to claim 8, is characterized in that the add-on of monomer 1-butylene liquid is 10000 ~ 30000g/gCat.
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CN110407965A (en) * 2019-06-10 2019-11-05 河南省君恒实业集团生物科技有限公司 A kind of method that the polymerization of low-carbon alkene one-step method prepares PAO
WO2021083307A1 (en) * 2019-10-30 2021-05-06 中国石油化工股份有限公司 METHOD FOR PREPARING HIGH VISCOSITY INDEX POLY-α-OLEFIN
CN113136254A (en) * 2021-04-16 2021-07-20 华东理工大学 1-decene oligomer base oil with narrow composition distribution as well as preparation method and application thereof
CN113150826A (en) * 2021-04-16 2021-07-23 华东理工大学 Poly alpha-olefin base oil with low viscosity and high viscosity index and preparation method thereof
CN115991804A (en) * 2021-10-20 2023-04-21 中国石油化工股份有限公司 Poly-1-butene and preparation method thereof

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