CN101569865B - Ethylene oligomerization catalysis system - Google Patents
Ethylene oligomerization catalysis system Download PDFInfo
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- CN101569865B CN101569865B CN2008101053636A CN200810105363A CN101569865B CN 101569865 B CN101569865 B CN 101569865B CN 2008101053636 A CN2008101053636 A CN 2008101053636A CN 200810105363 A CN200810105363 A CN 200810105363A CN 101569865 B CN101569865 B CN 101569865B
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Abstract
The present invention relates to an ethylene oligomerization catalysis system comprising complex of the formula (I), organic aluminium compound and silane. In the formula (I), R and R' are both monosubstituted or polysubstituted groups on a benzene ring and are respectively alkyl of C1 to C6 and alkoxyl of C1 to C6, nitryl, Cl or Br, and the x is halogen. The ethylene oligomerization catalysis system is applied to the ethylene oligomerization reaction, has high linear Alpha-olefin selectivity and produces less accessory high polymer.
Description
Technical field
The present invention is a kind of olefin(e) oligomerization catalyst system and catalyzing, specifically, is the oligomerization catalysis system that a kind of ethylene oligomerization prepares linear alpha-alkene.
Background technology
The ethylene oligomerization reaction is important reaction in the petrochemical industry, and its product alpha-olefin is as a kind of important material of petroleum chemical industry, and purposes is very extensive, wherein C
6～C
10Alpha-olefin mainly as the comonomer of LLDPE (LLDPE), C
11～C
20Alpha-olefin be the good intermediate of making surfactant, plasticizer.C
20 +Alpha-olefin be again the raw material of making top-grade lubricating oil.
Zirconium-based catalyst is important ethylene oligomerisation catalyst, and mainly contain two types: a class is by Cp
2ZrCl
2And the Kaminsky type homogeneous catalyst of MAO (MAO) composition, this class catalyst is to the high poly-very high activity that has of alkene, but by improving reaction temperature, regulate the Al/Zr mol ratio in the catalyst system and selecting suitable co-catalyst, can make this class catalyst become the ethylene oligomerisation catalyst of high activity, high selectivity, US5043515 discloses bis cyclopentadienyl zirconium dichloride (Cp
2ZrCl
2)/aikyiaiurnirsoxan beta catalyst system and catalyzing can catalyzed ethylene generation oligomerisation when low Al/Zr mol ratio.This class catalyst is particularly suitable for the catalyzed ethylene oligomerisation and generates additive range C
4～C
8Or the C of abluent scope
10～C
20Alpha-olefin.This class catalyst also can be used for catalyzed ethylene and C in addition
3～C
10Olefin(e) oligomerization to generate carbon number be about 20 alpha-olefin.
Another kind of is zirconium chloride and zirconium alkoxide class catalyst, can the synthesizing low-carbon alpha-olefin with this class catalyst ethylene oligomerization.It is the method for Preparation of Catalyst linear alpha-alkene with the zirconium adducts that US4966874 discloses a kind of, and this method uses zirconium chloride and acetate to form adduct, cooperates with alkyl metal cpd to be used for ethylene oligomerization.US5260500 discloses a kind of alpha-olefin product, uses ZrCl
4For major catalyst, general formula are AlR
cO
dThe mixture of aluminum alkoxide and methyl alcohol or ethanol is a co-catalyst, is that solvent carries out the ethylene oligomerization reaction with the cyclohexane, and the product that obtains is mainly linear low-carbon alpha-alkene.
EP0578541 discloses and has a kind ofly prepared the catalyst of light alpha olefins by ethylene oligomerization, comprises that general formula is ZrX
xY
yO
zThe major catalyst of zirconium compounds, a kind of acetal or ketal and alkyl aluminum compound, ZrX
xY
yO
zIn, X is a chlorine or bromine, Y is RO-, (R)
2N-or RCOO-, wherein R is the alkyl with 1～30 carbon atom.Using above-mentioned catalyst oligomerizing ethylene to become the low-carbon (LC) oligomer, mainly is 1-butylene, 1-hexene, 1-octene, 1-decene, and the content of alpha-olefin＞98% wherein is except C
4, C
6Outside the selectivity height, can also reduce the poly amount of accessory substance during this catalyst ethylene oligomerization.
WO80/00224 discloses the catalyst system and catalyzing that a kind of ethylene oligomerization is produced high-carbon alpha-olefin, comprises a kind of aliphatic acid zirconates and organo-aluminum compound, shows high polymerization activity in the ethylene oligomerization process, but the high polymer that produces is more.
CN101007856A discloses a kind of load type bimetallic polyethylene catalyst and preparation method thereof, comprises being carried on magnesium chloride support TiX
4, expression formula is L
mZrX
4-mNonmetallocene and organo-aluminum compound, described L is
Remove the ligand groups that forms behind the proton.This catalyst is applicable to ethylene polymerization, has advantages of high catalytic activity, and the polyethylene product of preparation has wider molecular weight distribution.
Summary of the invention
The purpose of this invention is to provide a kind of ethylene oligomerization catalysis system, this system is used for preparing alpha-olefin by ethane oligomerisation, has high polymerization activity and linear alpha-alkene selectivity.
Ethylene oligomerization catalysis system provided by the invention comprises complex, organo-aluminum compound and the silane of (I) expression formula that has formula,
In the described formula (I), R and R ' are single the replacement or multi-substituent on the phenyl ring, are selected from hydrogen, C respectively
1～C
6Alkyl, C
1～C
6Alkoxyl, nitro, Cl or Br, described X is selected from halogen.
Ethylene oligomerization catalysis system provided by the invention is the electron donor of oligomerisation process with silane, and the method for preparing alpha-olefin is simple, polymerization activity is high, can effectively improve the content of linear alkene in the oligomerisation product, and effectively suppresses the generation of high polymer.
The specific embodiment
Buddhist alkali is that the zirconium complex of part is a major catalyst to the west of the present invention, with the organo-aluminum compound is co-catalyst, and in system, add the silane electron donor and form catalyst system and catalyzing of the present invention, make the selectivity height of the linear alpha-alkene of its oligomerization product that is used for ethylene oligomerization reaction generation, the high polymer accessory substance is few.
The complex of the major catalyst of catalyst system and catalyzing of the present invention for having formula (I) structure, in the formula (I), R and R ' are single the replacement or multi-substituent on the phenyl ring, preferred hydrogen, C respectively
1～C
4Alkyl, C
1～C
3Alkoxyl, more preferably hydrogen, methyl, ethyl, propyl group or isopropyl; Described X is a chlorine.
The preferred formula of the present invention (I) complex has: (salicylidene aniline)-zirconium dichloride, (salicylidene 2, the 6-diisopropyl aniline)-zirconium dichloride, (salicylidene 2, the 4-dimethylaniline)-and zirconium dichloride, (salicylidene 2,6-dimethylaniline)-zirconium dichloride, (salicylidene 2,4-diethylaniline)-zirconium dichloride.
The preparation method of described zirconium complex is: salicylaldehyde derivatives and anil such as are pressed at mol ratio fully react under reflux temperature, product is cooled to-10～0 ℃ and makes and separate out crystal, obtain the salicylidene anil after washing, drying.Salicylidene anil and NaH are fully reacted in 0～40 ℃ in the oxolane medium, add ZrCl again
4In 60～80 ℃ of reactions, the ZrCl of adding
4With the mol ratio of salicylidene anil be 1: 1.5～2.5, filter reaction back, solids is drying to obtain the complex of formula (I) after with the alkane washing.
Co-catalyst in the catalyst system and catalyzing of the present invention is an organo-aluminum compound, and its general formula is AlR "
nX
3-n, R " is selected from C in the formula
1～C
20Alkyl, alkoxyl, aryl, aryloxy group; X is selected from halogen, preferred chlorine or bromine, more preferably chlorine; N is 0＜n≤3.
The present invention can use one or more organo-aluminum compound to be co-catalyst, and preferred organo-aluminum compound is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminium chloride or ethyl aluminum dichloride.
The present invention adds the silane electron donor in catalyst system, the expression formula of described silane is R
1R
2Si (OR
3)
2, R in the formula
1, R
2And R
3Be selected from C respectively
1～C
8Alkyl or cycloalkyl, preferred C
1～C
6Alkyl or cycloalkyl.Preferred silane is diisopropyl dimethoxy silane or cyclohexyl methyl dimethoxy silane.Described silane can be a kind of, also can be two or more.
In the catalyst system of the present invention, the mol ratio of used silane and formula (I) complex is 1～20: 1, preferred 2～12: 1, and the mol ratio of zirconium in aluminium and formula (I) complex in the organo-aluminum compound in the described system, be that aluminium/zirconium mol ratio is 10～1000: 1, preferred 50～500: 1.
The temperature of using catalyst system and catalyzing of the present invention to carry out the catalyzed ethylene oligomerisation is 20～120 ℃, preferred 60～80 ℃, and pressure is 1.0～6.0MPa, preferred 2.0～4.0MPa.Described ethylene oligomerization suits to carry out in organic solvent, and described organic solvent is selected from C
6～C
8Aromatic hydrocarbons, halogenated aryl hydrocarbon or C
3～C
20Alkane, the preferred benzene,toluene,xylene of described aromatic hydrocarbons, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene; The preferred butane of alkane, pentane, hexane, cyclohexane or heptane.Described solvent is benzene or toluene more preferably.
Below by example in detail the present invention.
Example 1
(1) preparation zirconium complex
10mL (0.1mol) salicylide and 8.7mL (0.1mol) aniline are added in the there-necked flask of band return duct of 25mL nitrogen protection, be solvent with the absolute ethyl alcohol, and drip several glacial acetic acid, 60 ℃ of back flow reaction 3 hours, color is from the light yellow dark-brown that becomes.Be cooled to-5 ℃ of a large amount of crystal of generation, filter, with solids hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets pressed powder 12.1g, is salicylidene aniline.
In the there-necked flask of the band return duct of nitrogen protection, add 3.0g (15mmol) salicylidene aniline and 0.36g (15mmol) NaH, 25 ℃ of reactions are 1 hour in 30mL oxolane medium.Add 1.77g (7.5mmol) ZrCl
4, be warming up to 50 ℃ of reactions 3 hours.Filter under the nitrogen protection, solid hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets pressed powder 3.9g, is salicylidene aniline zirconium dichloride.
Its elementary analysis measured value (theoretical value), quality % is as follows:
C56.29(56.31)，H3.58(3.61)，N5.07(5.03)，Zr12.58(12.63)。
(2) ethylene oligomerization
With 1 liter of stainless steel cauldron nitrogen replacement three time that agitator is housed, again with ethene displacement three times, the toluene and the concentration that add 100 milliliters of dryings successively are the hexane solution of the aluminium diethyl monochloride of 0.9M, and it is 300: 1 that the consumption of co-catalyst should make the Al/Zr mol ratio, stir it is uniformly dispersed.With the toluene of 100 milliliters of dryings with 1.0 * 10
-4The salicylidene aniline zirconium dichloride and 5.0 * 10 of mole
-4The diisopropyl dimethoxy silane of mole is sent into reactor by charge pipe, stirs it is uniformly dispersed.Be warming up to 80 ℃, feed ethene to still pressure and be 3.0MPa, polymerisation 1 hour.After reaction finishes, calculate catalyst activity according to autoclave weight difference before and after the reaction and be: 4770g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 2
Method by example 1 is carried out ethylene oligomerization, and different is that the amount that diisopropyl dimethoxy silane adds is 1.0 * 10
-3Mole, calculate catalyst activity according to autoclave weight difference before and after the reaction and be: 3794g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 3
Method by example 1 is carried out ethylene oligomerization, and different is that the organic silane compound that adds is a cyclohexyl methyl dimethoxy silane, and addition is 5.0 * 10
-4Mole.Calculating catalyst activity according to autoclave weight difference before and after the reaction is: 4500g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 4
Method by example 1 is carried out ethylene oligomerization, and different is that the organic silane compound that adds is a cyclohexyl methyl dimethoxy silane, and addition is 1.0 * 10
-3Mole.Calculating catalyst activity according to autoclave weight difference before and after the reaction is: 3681g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 5
Method by example 1 is carried out ethylene oligomerization, and different is to add diisopropyl dimethoxy silane and cyclohexyl methyl dimethoxy silane, and addition is 5.0 * 10
-4Mole.Calculating catalyst activity according to autoclave weight difference before and after the reaction is: 4038g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 6
Method by example 1 is carried out ethylene oligomerization, and the alkyl aluminum that different is adds such as is at the aluminium diethyl monochloride and the triethyl aluminum of mol ratio.Calculating catalyst activity according to autoclave weight difference before and after the reaction is: 5126g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 7
Method by example 1 is carried out ethylene oligomerization, and different is that the alkyl aluminum that adds is a sesquialter ethyl aluminium chloride.Calculating catalyst activity according to autoclave weight difference before and after the reaction is: 4586g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 8
(1) preparation zirconium complex
With 10mL (0.1mol) salicylide and 12.4mL (0.1mol) 2; in the there-necked flask of the band return duct of 4-dimethylaniline adding 25mL nitrogen protection, be solvent with the absolute ethyl alcohol, and drip several glacial acetic acid; 60 ℃ of back flow reaction 3 hours, color is from the light yellow dark-brown that becomes.Be cooled to-5 ℃ of a large amount of crystal of generation, filter, with solids hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets pressed powder 13.8g, is salicylidene 2, the 4-dimethylaniline.
In the there-necked flask of the band return duct of nitrogen protection, add 3.4g (15mmol) salicylidene 2,4-dimethylaniline and 0.36g (15mmol) NaH, 25 ℃ of reactions are 1 hour in 30mL oxolane medium.Add 1.77g (7.5mmol) ZrCl
4, be warming up to 50 ℃ of reactions 3 hours.Filter under the nitrogen protection, solid hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets pressed powder 4.9g, is (salicylidene 2,4-dimethylaniline)-zirconium dichloride.
Its elementary analysis measured value (theoretical value), quality % is as follows:
C，58.96(59.00)；H，4.61(4.59)；N，4.56(4.59)；Zr，14.97(14.95)。
(2) ethylene oligomerization
With 1 liter of stainless steel cauldron nitrogen replacement three time that agitator is housed, with ethene displacement three times, add the toluene of 100 milliliters of dryings successively again, concentration is the hexane solution of the aluminium diethyl monochloride of 0.9M, making the Al/Zr mol ratio is 300: 1, stirs it is uniformly dispersed.With the toluene of 100 milliliters of dryings with 1.0 * 10
-4(salicylidene 2,4-the dimethylaniline)-zirconium dichloride and 5.0 * 10 of mole
-4The diisopropyl dimethoxy silane of mole is sent into reactor by charge pipe, stirs it is uniformly dispersed.Be warming up to 80 ℃, feed ethene to still pressure and be 3.0MPa, polymerisation 1 hour.After reaction finishes, calculate catalyst activity according to autoclave weight difference before and after the reaction and be: 3260g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Example 9
(1) preparation zirconium complex
With 10mL (0.1mol) salicylide and 18.9mL (0.1mol) 2; in the there-necked flask of the band return duct of 6-diisopropyl aniline adding 25mL nitrogen protection, be solvent with the absolute ethyl alcohol, and drip several glacial acetic acid; 60 ℃ of back flow reaction 3 hours, color is from the light yellow dark-brown that becomes.Be cooled to-5 ℃ of a large amount of crystal of generation, filter, with solids hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets pressed powder 19.3g, is salicylidene 2, the 6-diisopropyl aniline.
In the there-necked flask of the band return duct of nitrogen protection, add 4.2g (15mmol) salicylidene 2,6-diisopropyl aniline and 0.36g (15mmol) NaH, 25 ℃ of reactions are 1 hour in 30mL oxolane medium.Add 1.77g (7.5mmol) ZrCl
4, be warming up to 50 ℃ of reactions 3 hours.Filter under the nitrogen protection, solid hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets pressed powder 5.7g, is (salicylidene 2,6-diisopropyl aniline)-zirconium dichloride.
Its elementary analysis measured value (theoretical value), quality % is as follows:
C，63.21(63.15)；H，6.01(6.09)；N，3.86(3.88)；Zr，16.49(16.46)。
(2) ethylene oligomerization
With 1 liter of stainless steel cauldron nitrogen replacement three time that agitator is housed, with ethene displacement three times, add the toluene of 100 milliliters of dryings successively again, concentration is the hexane solution of the aluminium diethyl monochloride of 0.9M, making the Al/Zr mol ratio is 300: 1, stirs it is uniformly dispersed.With the toluene of 100 milliliters of dryings with 1.0 * 10
-4(salicylidene 2,6-the diisopropyl aniline)-zirconium dichloride and 5.0 * 10 of mole
-4The diisopropyl dimethoxy silane of mole is sent into reactor by charge pipe, stirs it is uniformly dispersed.Be warming up to 80 ℃, feed ethene to still pressure and be 3.0MPa, polymerisation 1 hour.After reaction finishes, calculate catalyst activity according to autoclave weight difference before and after the reaction and be: 2928g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Comparative Examples 1
Method by example 1 is carried out ethylene oligomerization, and different is not add diisopropyl dimethoxy silane.Calculating catalyst activity according to autoclave weight difference before and after the reaction is: 5818g/gZrh sees Table 1 with the product carbon number distribution of gas Chromatographic Determination.
Table 1
Claims (8)
1. an ethylene oligomerization catalysis system is made up of complex, organo-aluminum compound and silane with formula (I) expression formula,
In the described formula (I), R and R ' are single the replacement or multi-substituent on the phenyl ring, are selected from hydrogen, C respectively
1～C
6Alkyl, C
1～C
6Alkoxyl, nitro, Cl or Br, described X is selected from halogen, the expression formula of described silane is R
1R
2Si (OR
3)
2, R in the formula
1, R
2And R
3Be selected from C respectively
1～C
8Alkyl or cycloalkyl.
2. according to the described catalyst system and catalyzing of claim 1, it is characterized in that described R and R ' are selected from hydrogen, C respectively
1～C
4Alkyl, C
1～C
3Alkoxyl, X is a chlorine.
3. according to the described catalyst system and catalyzing of claim 1, it is characterized in that described R and R ' are respectively hydrogen, methyl, ethyl, propyl group or isopropyl.
4. according to the described catalyst system and catalyzing of claim 1, it is characterized in that described organo-aluminum compound general formula is AlR "
nX
3-n, R " is selected from C in the formula
1～C
20Alkyl, alkoxyl, aryl, aryloxy group; X is selected from halogen, and n is 0＜n≤3.
5. according to the described catalyst system and catalyzing of claim 4, it is characterized in that described organo-aluminum compound is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminium chloride or ethyl aluminum dichloride.
6. according to the described catalyst system and catalyzing of claim 1, it is characterized in that the mol ratio of described silane and formula (I) complex is 1～20: 1.
7. according to the described catalyst system and catalyzing of claim 1, it is characterized in that the aluminium/zirconium mol ratio in the described system is 10～1000: 1.
8. according to the described catalyst system and catalyzing of claim 1, it is characterized in that described silane is diisopropyl dimethoxy silane or cyclohexyl methyl dimethoxy silane.
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| CN103724146B (en) * | 2013-12-20 | 2016-06-15 | 浙江大学 | A kind of reduce the method for content of polyethylene wax in ethylene oligomerization reaction |
| CN104693233B (en) * | 2015-03-23 | 2017-10-24 | 武汉科技大学 | Titanium complex, preparation method and purposes containing many nitro substituent Phenoxy-imine ligands |
| CN109201117B (en) * | 2017-07-06 | 2021-11-16 | 中国石油化工股份有限公司 | Supported ethylene oligomerization catalyst, and preparation method and application thereof |
| CN114247476B (en) * | 2020-09-25 | 2023-05-26 | 北京化工大学 | Zirconium-based catalytic system and method for preparing linear alpha-olefin by catalyzing ethylene oligomerization |
| CN113880881B (en) * | 2021-10-20 | 2023-11-17 | 中化泉州石化有限公司 | Synthesis of rigid organic phosphine ligand and application of rigid organic phosphine ligand in ethylene oligomerization |
| CN113996343A (en) * | 2021-11-19 | 2022-02-01 | 中化泉州石化有限公司 | Catalyst composition for preparing 1-octene |
| CN114160211B (en) * | 2021-12-20 | 2024-01-16 | 天津科技大学 | Catalyst system for selective trimerization and tetramerization of ethylene and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104647A (en) * | 1986-06-17 | 1988-05-11 | 阿莫科公司 | The alpha-olefin polymerization catalyst system that contains good properties-correcting agent composition |
| CN101007856A (en) * | 2006-01-27 | 2007-08-01 | 中国石油化工股份有限公司 | Load type bimetallic polyethylene catalyst and preparation method thereof |
-
2008
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104647A (en) * | 1986-06-17 | 1988-05-11 | 阿莫科公司 | The alpha-olefin polymerization catalyst system that contains good properties-correcting agent composition |
| CN101007856A (en) * | 2006-01-27 | 2007-08-01 | 中国石油化工股份有限公司 | Load type bimetallic polyethylene catalyst and preparation method thereof |
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