CN101134702A - Preparation method of alkene oligomer - Google Patents
Preparation method of alkene oligomer Download PDFInfo
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- CN101134702A CN101134702A CNA2007101215000A CN200710121500A CN101134702A CN 101134702 A CN101134702 A CN 101134702A CN A2007101215000 A CNA2007101215000 A CN A2007101215000A CN 200710121500 A CN200710121500 A CN 200710121500A CN 101134702 A CN101134702 A CN 101134702A
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Abstract
The present invention relates to olefin oligomer preparing process, and is especially olefin monomer polymerizing process under the action of supported or homogeneous metallocene catalyst. The olefin monomer polymerizing process includes the following steps: 1. mixing supported or homogeneous metallocene catalyst and cocatalyst in certain ratio inside organic solvent under the protection of nitrogen or inert gas to form the catalyst system; 2. adding organic solvent and olefin monomer into the catalyst system and reaction at 0-90 deg.c; and 3. terminating reaction with alcohol solution of hydrochloric acid, vacuum distillation to eliminate un-reacted monomer, heating to 160 deg.c and vacuum distillation to obtain olefin oligomer, and hydrogenation. The process can obtain olefin oligomer and copolymer with low molecular weight in monomer converting rate up to 95 % and yield of 2-5 polymerization degree oligomer not lower than 60 %.
Description
Technical field:
The invention belongs to macromolecule material preparation area, particularly loading type or homogeneous phase metallocene are the olefin monomer polymerizing process of catalyzer.
Background technology:
The oligopolymer of 1-decene has high viscosity (1.60 * 10
-5Pas, 100 ℃), high viscosity index (HVI), low pour point (being lower than-70 ℃), use temperature wide ranges, Heat stability is good, corrodibility be low, good with the mutual capacitive of mineral lubricating oils, reach characteristics such as nontoxic well with the common material consistency, be good lubricant base, be mainly used in automobile and shipping industry.
The neat polymeric catalyst system of catalysis alpha-olefin has homogeneous phase BF
3System (US Patent 5420073, USPatent 5357075), out-phase BF
3System (US Patent 4436948, US Patent 4218330), BF
3/ H
2O/O
2System (US Patent 4365105), BF
3Pneumonia can be caused, its recovery and processing must be paid attention to; Cr catalyst system (US Patent4 436948) generally is that the organic compound of Cr (II) is dissolved in the acetate, be carried on the silica gel, the productive rate of oligopolymer reach 90%. but the Cr compound that human toxicity is reached environmental pollution greatly is serious; Al compound system (US Patent5 922636) and domestic employing Ziegler-Natta system (European PolymerJ, 2005,41:2909; CN 02116911) oligomerisation of having studied 1-decene closes, and wherein, monomer conversion reaches 90%, and the oligopolymer productive rate of 2-5 aggressiveness is 54%.1-decene is part 1-decene generation double-bond isomerization in the oligomerisation process, influences the performance of 1-decene oligopolymer. Huang Qigu (JPoly Sci, PartA:Polym Chem, 2001,39:4068; Polymer Int.2001,50:45; J Polym Sci, PartA, Polym Chem, 1999,37:4497) adopt metallocene catalyst to study the alpha-olefine polymerizing behavior, resulting polymers is the high-molecular weight polyolefine, the catalyst activity height.Griselda (JPolym Sci, Part A:Poly Chem, 2003,41:2531) studied the copolymerization of metallocene catalyst catalysis 1-decene, ethene, propylene, find that 1-decene participates in improving polyethylene and polyacrylic performance after the copolymerization. the report that relevant employing metallocene catalyst catalysis 1-decene oligopolymer closes is less, we adopt homogeneous phase metallocene catalyst or carried metallocene catalyst, the catalyst system of forming with MAO has been studied the 1-decene oligomerisation and has been closed. its activity of such catalysts height, 1-decene three, tetrameric relative content height.This research all is very significant to the research and the polyolefin industry exploitation of the neat polymeric theoretical investigation of metallocene catalyst catalysis high alpha-olefin, synthetic lubricant base oil.
Summary of the invention:
The object of the present invention is to provide a kind of method of utilizing homogeneous phase metallocene catalyst or carried metallocene catalyst to realize olefinic monomer homopolymerization or copolymerization alkene oligomer, this method can efficiently obtain the low-molecular-weight homopolymer and the multipolymer of olefinic monomer.
A kind of olefinic monomer oligomerisation prepares the method for alkene oligomer, it is characterized in that, the step of this method is as follows:
(1) under nitrogen or protection of inert gas, at 0-90 ℃, homogeneous phase metallocene catalyst or carried metallocene catalyst and promotor are stirred in organic solvent by a certain percentage, make catalyst system after making their thorough mixing;
Above-mentioned metallocene catalyst is meant to have general formula L
1MX
3Mono-metallocene compound or have general formula L
1L
2MX
2The dicyclopentadiene metallic compound, wherein M is transition metal Ti, Zr or Hf, preferred Ti; X is C1 or Br; Two ligand L
1And L
2Be cyclopentadienyl, indenyl, fluorenyl or derivatives thereof, the substituting group number on the cyclopentadiene ring can be chosen 0～5 integer, L wantonly
1And L
2Between also can be randomly by C
1-4Alkylidene abutment is linked together, or randomly is linked together by siloxanes abutment or amido;
Above-mentioned carried metallocene catalyst is meant metallocene catalyst is loaded on the carrier that carrier comprises inorganic oxide or butter, as SiO
2, Al
2O
3, MgCl
2Or AlCl
3, preferred SiO
2Or MgCl
2
Above-mentioned homogeneous phase metallocene catalyst is meant the metallocene catalyst that does not load on the carrier;
Above-mentioned promotor is alkylaluminoxane or aluminum alkyls, wherein alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta or ethyl aikyiaiurnirsoxan beta, the preferred triethyl aluminum of aluminum alkyls, diethyl aluminum chloride or triisobutyl aluminium;
The mol ratio of homogeneous phase metallocene catalyst or loaded metallocene catalysis and promotor is 1: 50-5000, preferred 1: 100-600;
(2) add organic solvent and monomer in above-mentioned catalyzer, temperature of reaction is between 0-90 ℃, and preferred 20-80 ℃, the reaction times is 5-1000 minute, preferred 80-600 minute;
Above-mentioned organic solvent is toluene, hexane, pentane, heptane, octane, nonane, decane or their mixture, preferred toluene or hexane, and the consumption of solvent is unrestricted;
Above-mentioned monomer is meant C
4-C
30Alpha-alkene or their mixture, preferred decylene-1, octene-1, hexene-1, butene-1, laurylene-1, tetradecene-1 or their mixture;
(3) after certain back time of reaction, with alcohol hydrochloric acid solution termination reaction, unreacted monomer is removed in underpressure distillation, is warming up to 160 ℃, and underpressure distillation goes out oligopolymer, adopts general method of hydrotreating hydrogenation again, i.e. aliphatic double bond Ni catalytic hydrogenation method.
Beneficial effect of the present invention is, the productive rate height of the alkene oligomer by method preparation of the present invention: monomer conversion can reach 95%, and the oligopolymer productive rate of 2-5 aggressiveness is not less than 60%.
Embodiment:
In embodiment, metallocene catalyst adopts prior art synthetic (referring to document DCBreslow and N R Newburg.J of the America Chemical Society, 1957,79:5073; DC Breslow and N R Newburg.J of the America Chemical Society.1959,81:81.).
Embodiment is the specific examples that adopts for detailed description the present invention, but should be not limited to following embodiment when practical application.
Embodiment 1-4
After exsiccant 500ml high-pressure reactor vacuumized deoxygenation dehumidifying, at 20 ℃, under nitrogen protection with 100ml toluene (solvent), with SiO
2Loading type titanocene dichloride (Cp for carrier
2TiCl
2) 1.0 * 10
-2Mmol, methylaluminoxane (MAO) 0.65ml (10%g/V toluene solution) adds in the reactor, and the Al/Ti mol ratio is 110, stirs 10 minutes.Add 40ml monomer decylene-1, rose to the certain temperature polymerization 1 hour.Use alcohol hydrochloric acid solution termination reaction afterwards, unreacted monomer is removed in underpressure distillation, is warming up to 160 ℃, and underpressure distillation goes out oligopolymer, weighs.High-pressure hydrogenation in the presence of the Ni-Pd catalyzer.Calculate catalyzer to polyolefine (comprising polymkeric substance and oligopolymer) catalytic activity (PAO) according to the output of monomeric consumption and oligopolymer.
Other conditions are constant, change polymerization temperature, specifically see Table 1:
Table 1
| The embodiment numbering | Catalytic activity/Kg PAO/mol Ti.h | Polymerization temperature/℃ | Monomer conversion % | Oligopolymer productive rate (%) |
| 1 2 3 4 | 170 187 210 200 | 40 50 60 70 | 80.4 87.6 95.2 90.1 | 52 56 63 60 |
Embodiment 5-9
Polymerization temperature is 60 ℃, and other conditions and embodiment 1 change the Al/Ti molar ratio decylene-1, neat polymeric influence are seen Table 2 together:
Table 2
| The embodiment numbering | Al/Ti ratio mol/mol | Catalytic activity/kg PAO/molTi.h | Monomer conversion % | Oligopolymer productive rate (%) |
| 5 6 7 8 9 | 80 100 110 120 150 | 175 200 210 190 186 | 78.6 85.5 96.1 90.5 89.1 | 61.2 61.7 63.8 60.5 59.3 |
Embodiment 10-14
Polymerization temperature is 60 ℃, and other conditions and embodiment 1 are same, and different metallocene catalysts see Table 3 to decylene-1, neat polymeric influence:
Table 3
| The embodiment numbering | Metallocene catalyst | Catalytic activity/kg PAO/mol Ti (Zr) .h | Monomer conversion (%) | Oligopolymer productive rate (%) |
| 10 11 12 13 14 | CpTiCl 3 Cp 2ZrCl 2 Me2C(Ind )2Cl2 Me2Si(Ind )2Cl2 Me2C(Flu )2Cl2 | 176 210 220 205 225 | 96.0 95.1 90.1 91.4 90.6 | 65.9 66.3 67.2 65.1 62.4 |
Embodiment 15-19
Polymerization temperature is 60 ℃, and other conditions and embodiment 1 are same, and the homogeneous phase metallocene catalyst sees Table 4 to decylene-1, neat polymeric influence:
Table 4
| The embodiment numbering | Metallocene catalyst | Catalytic activity/kgPAO/mol Ti (Zr) .h | Monomer conversion (%) | Oligopolymer productive rate (%) |
| 15 16 17 18 19 | CpTiCl 3Cp 2ZrCl 2Me2C(Ind)2 TiCl2 Me2Si(Ind)2 ZrCl2 Me2C(Flu)2 TiCl2 | 180 220 235 210 210 | 92.8 96.8 97.2 92.5 92.5 | 66.5 63.1 62.8 66.4 60.8 |
Embodiment 20-24
Polymerization temperature is 60 ℃, and other conditions and embodiment 1 are same, carried metallocene catalyst Cp
2TiCl
2Neat polymeric influence sees Table 5 to/SiO2 to different alkene:
Table 5
| The embodiment numbering | Monomer | Catalytic activity/kg PAO/mol Ti.h | Monomer conversion (%) | Oligopolymer productive rate (%) |
| 20 21 22 23 24 | Octene-1 laurylene-1 hexene-1 C 5 ＝-C 9 ＝Mix monomer C 9 ＝-C 13 ＝Mix monomer | 210 180 250 230 220 | 97.1 85.2 98.3 95.8 93.2 | 55.2 69.2 50.7 58.2 63.4 |
Claims (9)
1. an olefin oligomer preparing process is characterized in that, the step of this method is as follows:
(1) under nitrogen or protection of inert gas, at 0-90 ℃, homogeneous phase metallocene catalyst or carried metallocene catalyst and promotor are stirred in organic solvent by a certain percentage, make catalyst system after making their thorough mixing;
Above-mentioned metallocene catalyst is meant to have general formula L
1MX
3Mono-metallocene compound or have general formula L
1L
2MX
2The dicyclopentadiene metallic compound, wherein M is transition metal Ti, Zr or Hf, X is Cl or Br; Two ligand L
1And L
2Be cyclopentadienyl, indenyl, fluorenyl or derivatives thereof, the substituting group number on the cyclopentadiene ring can be chosen 0～5 integer, L wantonly
1And L
2Between also can be randomly by C
1-4Alkylidene abutment is linked together, or randomly is linked together by siloxanes abutment or amido;
Above-mentioned carried metallocene catalyst is meant metallocene catalyst is loaded on the carrier that carrier comprises inorganic oxide or butter, as SiO
2, Al
2O
3, MgCl
2Or AlCl
3
Above-mentioned homogeneous phase metallocene catalyst is meant the metallocene catalyst that does not load on the carrier;
Above-mentioned promotor is alkylaluminoxane or aluminum alkyls;
The mol ratio of above-mentioned homogeneous phase metallocene catalyst or loaded metallocene catalysis and promotor is 1: 50-5000;
(2) add organic solvent and monomer in above-mentioned catalyst system, temperature of reaction is between 0-90 ℃, and the reaction times is 5-1000 minute;
Organic solvent in step (1) and (2) is toluene, hexane, pentane, heptane, octane, nonane, decane or their mixture;
Above-mentioned monomer is meant C
4-C
30Alpha-alkene or their mixture;
(3) behind the reaction certain hour, with alcohol hydrochloric acid solution termination reaction, unreacted monomer is removed in underpressure distillation, is warming up to 160 ℃, and underpressure distillation goes out oligopolymer, adopts the method for hydrotreating hydrogenation again.
2. preparation method according to claim 1 is characterized in that, general formula is L
1MX
3Mono-metallocene compound or general formula be L
1L
2MX
2The dicyclopentadiene metallic compound, wherein M is transition metal Ti.
3. a kind of olefinic monomer oligomerisation according to claim 1 prepares the method for alkene oligomer, it is characterized in that, in the step (2), temperature is 20-80 ℃, and the reaction times is 80-600 minute.
4. preparation method according to claim 1 is characterized in that, the carrier of carried metallocene catalyst is SiO
2Or MgCl.
5. preparation method according to claim 1 is characterized in that, described promotor is methylaluminoxane, ethyl aikyiaiurnirsoxan beta, triethyl aluminum, diethyl aluminum chloride or triisobutyl aluminium.
6. preparation method according to claim 1 is characterized in that, described organic solvent is toluene or hexane.
7. according to the described preparation method of claim 1, it is characterized in that described monomer is decylene-1, octene-1, hexene-1, butene-1, laurylene-1, tetradecene-1 or their mixture.
8. preparation method according to claim 1 is characterized in that, the mol ratio preferred 1 of homogeneous phase metallocene catalyst or loaded metallocene catalysis and promotor: 100-600.
9. preparation method according to claim 1 is characterized in that: described method of hydrotreating is an aliphatic double bond Ni catalytic hydrogenation method.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967456A (en) * | 2017-04-14 | 2017-07-21 | 上海欧勒奋生物科技有限公司 | A kind of method prepared by top-grade lubricating oil PAO4 |
| CN109937215A (en) * | 2016-11-18 | 2019-06-25 | 出光兴产株式会社 | Process for producing alpha-olefin oligomer |
| 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 |
| WO2021083238A1 (en) * | 2019-10-28 | 2021-05-06 | 南京中科康润新材料科技有限公司 | Processing method for directly synthesizing high-performance base oil by means of polymerization of low-carbon olefin |
| CN116410780A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Synthesis method of high-viscosity metallocene poly alpha-olefin base oil, product and application thereof |
| CN116554924A (en) * | 2022-01-30 | 2023-08-08 | 中国石油天然气股份有限公司 | Preparation method of medium-high viscosity lubricating oil base oil |
-
2007
- 2007-09-07 CN CNA2007101215000A patent/CN101134702A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109937215A (en) * | 2016-11-18 | 2019-06-25 | 出光兴产株式会社 | Process for producing alpha-olefin oligomer |
| CN109937215B (en) * | 2016-11-18 | 2022-06-17 | 出光兴产株式会社 | Process for producing alpha-olefin oligomer |
| CN106967456A (en) * | 2017-04-14 | 2017-07-21 | 上海欧勒奋生物科技有限公司 | A kind of method prepared by top-grade lubricating oil PAO4 |
| 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 |
| CN111286385B (en) * | 2018-12-06 | 2022-03-29 | 中国石油天然气股份有限公司 | Synthetic method of lubricating oil base oil |
| WO2021083238A1 (en) * | 2019-10-28 | 2021-05-06 | 南京中科康润新材料科技有限公司 | Processing method for directly synthesizing high-performance base oil by means of polymerization of low-carbon olefin |
| CN116410780A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Synthesis method of high-viscosity metallocene poly alpha-olefin base oil, product and application thereof |
| CN116554924A (en) * | 2022-01-30 | 2023-08-08 | 中国石油天然气股份有限公司 | Preparation method of medium-high viscosity lubricating oil base oil |
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Open date: 20080305 |