CN101709097A - Olefin polymerization catalyst for coordinating [O-N-S] type tridentate ligand with titanium metal and preparation method thereof - Google Patents
Olefin polymerization catalyst for coordinating [O-N-S] type tridentate ligand with titanium metal and preparation method thereof Download PDFInfo
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- CN101709097A CN101709097A CN200910198316A CN200910198316A CN101709097A CN 101709097 A CN101709097 A CN 101709097A CN 200910198316 A CN200910198316 A CN 200910198316A CN 200910198316 A CN200910198316 A CN 200910198316A CN 101709097 A CN101709097 A CN 101709097A
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Abstract
The invention belongs to the technical field of chemical catalysts, in particular relates to an olefin polymerization catalyst for coordinating a [O-N-S] type tridentate ligand with titanium metal and a preparation method thereof. The expression of the catalyst is [L-Ti], wherein L expresses a ligand containing atoms of O, N and S capable of being coordinated with metals. The catalyst has unique and novel structure and higher catalytic activity for catalyzing vinyl polymerization, and can be prepared simply. The catalyst can be used as a component A and matched with a component B to be used for catalyzing vinyl polymerization to prepare high molecular weight polyethylene (HMWPE) products.
Description
Technical field
The invention belongs to the chemical catalyst technical field, be specifically related to a kind of olefin polymerization catalysis and preparation method thereof.
Background technology
The R and D of polyolefine synthesis technique are one of popular research topics of polymer chemistry and plastics industry.Polyolefine is the mainstay industry of modern macromolecular material industry, and olefin polymerization catalysis then is the core of polyolefine industry.Because the organo-metallic olefin polymerization catalysis not only can efficient catalytic olefinic polymerization under the condition of gentleness, and microtexture that can the cutting polymkeric substance, so can on molecular level, design the new function polyolefine material and improve existing polymer properties, so the research in this field is one of contemporary chemical forward position and focus always.Since nineteen fifty-three, olefin polymerization catalysis came out, Ziegler-Natta catalyst system, metallocene catalysis system and three important milestones of rear transition metal catalyst system have appearred in short 50 years.
After the Ziegler-Natta catalyst system came out, chemists had done a large amount of metallocene catalyst improvement work, and expectation can improve the reactive behavior of catalyzer, changed the character of resulting polymers, as tacticity, copolymerization performance and other microtextures.Recent years, non-metallocene catalyst, transition metal and late transition metal complex have caused concern widely before comprising, typical example is the 4th family's title complex that contains phenol oxygen imine ligand.As everyone knows, the 4th family's title complex that contains bis-phenol oxygen imine ligand in the molecule can be used as polyethylene and syndiotactic polypropylene catalyzer, and the polymkeric substance that obtains has high molecular, characteristics such as narrow molecular weight distribution.In addition, the substituting group on the reactive behavior of this class catalyzer and phenol oxygen base or the imido grpup has much relations.
2004, Gibson reported a phenomenon: contain the 4th family's title complex of phenol oxygen amine part, in the ligand structure of phenol oxygen amine additional have soft atom to electronics (S, in the time of P), such catalyzer has higher catalytic activity; And additionally in such part hard atom is arranged (O, when N) giving body, activity of such catalysts can reduce.Although people have had extensive studies to the title complex that contains salicylic alidehyde imine class part, seldom report for [O, N, S] three tooth dianion title complexs.The present invention will provide a kind of titanium catalyst and synthetic method and application of excellent performance.
Summary of the invention
The purpose of this invention is to provide a kind of catalytic activity height, olefin polymerization catalysis that synthesis technique is easy and preparation method thereof.
Olefin polymerization catalysis provided by the invention is a starting raw material by the phenol of 2-aminothiophenol, Paraformaldehyde 96, various replacements, makes the salicylic alidehyde imine of ligand L-2-thiophenyl through the series reaction step; The TiCl of ligand L and equimolar amount
4Or Ti (OPr
i)
4Instead, through the extraction, freezing, filter, drain, promptly obtain the titanium complex [L-Ti] of monokaryon or double-core.
Catalyzer expression formula provided by the invention is [L-Ti], L represent a kind of contain can with O, the N of metal-complexing, the part of S atom, concrete structure is as shown in the formula middle 2a, 2b, 2c, 3a is shown in 3b or the 3c.
Such catalyzer is the homogeneous phase single site catalysts, has medium catalytic activity under the condition of gentleness, and long catalytic life, greater than 2h.By changing the substituted radical on the part, can obtain the polyethylene of different molecular weight with different active catalytic.
Above-mentioned [O^N^S] type tridentate ligand and titanium metal coordinate olefin polymerization catalysis preparation process are as follows:
(1) substituted salicylic aldehydes preparation
Its structural formula is:
Wherein, (a) R
1=H, R
2=H; (b) R
1=Me, R
2=H; (c) R
1=
tBu, R
2=Me
N
2Protection adds 60-80mL exsiccant toluene down successively in 250mL three neck round-bottomed flasks, phenol of replacement (10.0-100.0mmol) and tri-n-butylamine (4.0-40.0mmol) stir 30-60min.Drip anhydrous stannic chloride (0.26-2.60g) from constant pressure funnel, behind the stirring at normal temperature 30-60min, get light yellow turbid solution.Add Paraformaldehyde 96 0.82-8.20g, fully stir and be warming up to 80-110 ℃, continue heated and stirred 8-12h.TLC follows the tracks of detection, and substrate disappears, and reacts completely.The cooling reaction solution is poured in the 0.5-1L water, is divided into two-layer (upper strata is an oily matter, and lower floor is a water), adds 10-25mL 2N HCl and makes it acidifying, and adjusting PH is 1-3.Use the 50-100mL extracted with diethyl ether, obtain yellow thick liquid.Anhydrous sodium sulfate drying spends the night, after rotary evaporation removes behind the ether underpressure distillation or recrystallization, purified substituted salicylic aldehydes, productive rate about 70%.
(2) preparation of the salicylic alidehyde imine of 2-thiophenyl:
Its structural formula is:
Wherein, (a) R
1=H, R
2=H; (b) R
1=Me, R
2=H; (c) R
1=
tBu, R
2=Me
N
2Protection adds different salicylic aldehyde (4.78-47.8mmol), the 30-50mL dehydrated alcohols that replace down successively in 100mL three neck round-bottomed flasks, be heated to 80-100 ℃.From constant pressure funnel to the ethanolic soln that wherein slowly drips the 2-aminothiophenol (4.78-47.8mmol, 10-20mL ethanol).Backflow 2-3h, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, obtain pale yellow crystals.Filter, washing with alcohol is drained the final vacuum drying, gets purified ligand.Productive rate about 85%.
(3) [O^N^S] type tridentate ligand and titanium metal coordinate olefin polymerization catalysis preparation:
Its structural formula is:
The preparation of catalyzer 2a-2c is carried out under the protection of and high-purity argon gas anhydrous in anaerobic.The part that 0.5-1mmol is made by step (2) is dissolved in the dry toluene that the 15-20 milliliter handled, and at room temperature stirs 5min.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1-2mmol Ti (OPr
i)
4Toluene solution in (toluene, 10-20mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the orange settled solution.Drain, the tangerine solid of gained is with small amount of toluene or n-hexane dissolution.Freezing, get orange-yellow crystal.Filter fast, drain under the vacuum.Get pure target product, productive rate 73%-80%.
Carry out under the protection of the preparation of catalyzer 3a-3c and high-purity argon gas anhydrous in anaerobic.The part of 0.5-1mmol is dissolved in the dry toluene that the 15-30 milliliter handled, at room temperature stirs 5-10min.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1-2mmol TiCl
4Toluene solution in (toluene, 10mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the scarlet turbid solution.Filter, the normal hexane washing is drained, and gets the dark red solid of pure target product, productive rate 60%-70%.
(4) above-mentioned catalyzer is used for the reaction of normal pressure catalyzed ethylene polymerization, and concrete steps are as follows:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition.Catalyzer is made into the solution of 0.005-0.01mol/L in advance with the toluene dissolving.The toluene solution that in polymerization bottle, adds 1-10 μ mol catalyst A component under the ethene atmosphere with syringe successively, add 30-40mL toluene under the violent stirring, under the 0-100 ℃ of temperature, preferred 10-60 ℃, keep 5-10min, the toluene solution initiated polymerization that adds a certain amount of catalyst B component, the mol ratio of A component and B component is 500: 1-3000: 1.The cumulative volume of reaction system generally remains on 50mL (adjusting of different volumes useable solvents toluene), behind the reaction 30min-120min, pours mixture in the acidifying ethanolic soln (ethanol/HCl
Conc=95: 5).Fully stirred 4-6 hour,, and use washing with alcohol, 80 ℃ of following vacuum-drying 24 hours polymer filtration.The active amt level is 10
4-10
6G PE/ (mol Tih), the molecular weight of polyethylene order of magnitude is 10
6G/mol.
(5) above-mentioned catalyzer high pressure catalyzed ethylene polymerization reaction, concrete steps are as follows
Earlier autoclave is treated to the reaction system of anhydrous and oxygen-free, is warming up to temperature of reaction.By substituting gas, make it to be the ethene atmosphere.Syringe adds the toluene solution of 1-10 μ mol catalyst A component successively in polymerization reaction kettle, intense mechanical stirs and adds 30-40mL toluene down, under 0-100 ℃ of temperature, preferred 10-60 ℃, keep 5-10min, the toluene solution that adds a certain amount of catalyst B component, initiated polymerization, the mol ratio of A component and B component is 500: 1-3000: 1.Be forced into 7atm, reaction 30-120min.Close steel cylinder, venting, making it is a normal atmosphere.With acidifying ethanolic soln (ethanol/HCl
Conc=95: 5) stop polymerization.Pour mixture in the acidifying ethanolic soln (ethanol/HCl
Conc=95: 5).Fully stirred 4-6 hour,, and use washing with alcohol, 80 ℃ of following vacuum-drying 24 hours polymer filtration.The active amt level is 10
5G PE/ (mol Tih), the molecular weight of polyethylene order of magnitude is 10
7G/mol.
Catalyst of the present invention is active high, and synthesis technique is easy, can obtain High molecular weight polyethylene.
In the reaction of above-mentioned catalyzed ethylene polymerization, the catalyst A component is [O, N, S] type tridentate ligand provided by the invention and titanium metal coordinate catalyzer, the catalyst B component is methylaluminoxane (being designated as MAO) or modified methylaluminoxane (being designated as MMAO).
Description of drawings
Fig. 1 is the crystalline structure of 2a.
Fig. 2 is the crystalline structure of 2b.
Fig. 3 is the crystalline structure of 2c.
Embodiment
Embodiment 1:
The preparation of part (E)-2-((2-mercaptophenylimino) methyl) phenol (La)
N
2Protection adds salicylic aldehyde (47.8mmol), 30mL dehydrated alcohol down successively in 100mL three neck round-bottomed flasks, be heated to 80 ℃.From constant pressure funnel to the ethanolic soln that wherein slowly drips the 2-aminothiophenol (47.8mmol, 15mL ethanol).Backflow 2h, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, obtain pale yellow crystals.Filter, washing with alcohol is drained the final vacuum drying, gets purified ligand 9.30g.Productive rate about 85%.
Embodiment 2:
The preparation of part (E)-2-((2-mercaptophenylimino) methyl)-6-methylphenol (Lb):
N
2Protection adds 3-cresotinic acid aldehyde (47.8mmol), 30mL dehydrated alcohol down successively in 100mL three neck round-bottomed flasks, be heated to 90 ℃.From constant pressure funnel to the ethanolic soln that wherein slowly drips the 2-aminothiophenol (47.8mmol, 10mL ethanol).Backflow 2-4h, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, obtain light yellow cotton-shaped crystal.Filter, washing with alcohol is drained the final vacuum drying, gets purified ligand 10.2g.Productive rate about 88%.
Embodiment 3:
The preparation of part (E)-2-tert-butyl-6-((2-mercaptophenylimino) methyl)-4-methylphenol (Lc):
N
2Protection adds the 3-tertiary butyl-5-cresotinic acid aldehyde (47.8mmol), 50mL dehydrated alcohol down successively in 100mL three neck round-bottomed flasks, be heated to 80 ℃.From constant pressure funnel to the ethanolic soln that wherein slowly drips the 2-aminothiophenol (47.8mmol, 10mL ethanol).Backflow 2-4h, TLC follows the tracks of detection, and substrate disappears, and reacts completely.Be cooled to room temperature, obtain yellow crystals.Filter, washing with alcohol is drained the final vacuum drying, gets purified ligand 12.1g.Productive rate about 85%.
Embodiment 4: with [O^N^S] type tridentate ligand La coordinate oxo bridge connection double-core titanium olefin polymerization catalysis μ-O-Ti[O, N, S]
H(OPri)
2}
2Preparation (2a):
Carry out under the protection of Preparation of catalysts and high-purity argon gas anhydrous in anaerobic.(1mmol 0.229g) is dissolved in 15 milliliters the dry toluene of processing, at room temperature stirs 5min with the ligand L a among the embodiment 1.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1mmol Ti (OPr
i)
4In the toluene solution (0.3mL) (toluene, 10mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the orange settled solution.Drain the tangerine solid of gained.In toluene/normal hexane mixed solvent, freezing, get orange-yellow crystal.Filter fast, drain under the vacuum.Get pure target product 0.29g, productive rate 73%.Its crystalline structure is seen shown in Figure 1.
Embodiment 5: with [O^N^S] type tridentate ligand Lb coordinate sulphur bridge connection double-core titanium olefin polymerization catalysis μ-S-Ti[O, N, S]
Me(OPr
i)
2}
2Preparation (2b):
Carry out under the protection of Preparation of catalysts and high-purity argon gas anhydrous in anaerobic.(1mmol 0.243g) is dissolved in 15 milliliters the dry toluene of processing, at room temperature stirs 8min with the ligand L b among the embodiment 2.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1mmol Ti (OPr
i)
4In the toluene solution (0.3mL) (toluene, 10mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the orange settled solution.Drain the tangerine solid of gained.Recrystallization in normal hexane, freezing, get orange-yellow crystal.Filter fast, drain under the vacuum.Get pure target product 0.32g, productive rate 80%.Its crystalline structure is seen shown in Figure 2.
Embodiment 6: with [O^N^S] type tridentate ligand Lc coordinate monokaryon titanium olefin polymerization catalysis Ti[O, N, S]
TBu(OPr
i)
2Preparation (2c):
Carry out under the protection of Preparation of catalysts and high-purity argon gas anhydrous in anaerobic.(1mmol 0.299g) is dissolved in 18 milliliters the dry toluene of processing, at room temperature stirs 6min with the ligand L c among the embodiment 3.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1mmol Ti (OPr
i)
4In the toluene solution (0.3mL) (toluene, 10mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the orange settled solution.Drain the tangerine solid of gained.Recrystallization in normal hexane, freezing, get orange-yellow crystal.Filter fast, drain under the vacuum.Get pure target product 0.35g, productive rate 75%.Its crystalline structure is seen shown in Figure 3.
Embodiment 7: with [O^N^S] type tridentate ligand La coordinate oxo bridge connection double-core titanium olefin polymerization catalysis μ-O-Ti[O, N, S]
HCl
2}
2Preparation (3a):
Carry out under the protection of Preparation of catalysts and high-purity argon gas anhydrous in anaerobic.(1mmol 0.229g) is dissolved in 15 milliliters the dry toluene of processing, at room temperature stirs 8min with the ligand L a among the embodiment 1.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1mmol TiCl
4In the toluene solution (1.0mL) (toluene, 10mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the scarlet turbid solution.Filter, the pure target product 0.24g of the dark red solid of gained, productive rate 70% are drained in normal hexane washing 2 times.
Embodiment 8: with [O^N^S] type tridentate ligand Lb coordinate sulphur bridge connection double-core titanium olefin polymerization catalysis μ-S-Ti[O, N, S]
MeCl
2}
2Preparation (3b):
Carry out under the protection of Preparation of catalysts and high-purity argon gas anhydrous in anaerobic.(1mmol 0.243g) is dissolved in 20 milliliters the dry toluene of processing, at room temperature stirs 10min with the ligand L b among the embodiment 1.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1mmol TiCl
4In the toluene solution (1.0mL) (toluene, 10mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the scarlet turbid solution.Filter, the pure target product 0.22g of the dark red solid of gained, productive rate 65% are drained in the normal hexane washing.
Embodiment 9: with [O^N^S] type tridentate ligand Lc coordinate monokaryon titanium olefin polymerization catalysis Ti[O, N, S]
TBuCl
2Preparation (2c):
Carry out under the protection of Preparation of catalysts and high-purity argon gas anhydrous in anaerobic.(1mmol 0.299g) is dissolved in 15 milliliters the dry toluene of processing, at room temperature stirs 10min with the ligand L c among the embodiment 1.Under-78 ℃ of conditions, it slowly is transferred to bridge contains 1mmol TiCl
4In the toluene solution (1.0mL) (toluene, 10mL).Slowly rise to room temperature, and at room temperature continue to stir after 12-16 hour, get the scarlet turbid solution.Filter, the pure target product 0.23g of the dark red solid of gained, productive rate 60% are drained in normal hexane washing 2 times.
Embodiment 10: the reaction of normal pressure catalyzed ethylene polymerization:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition.Catalyzer is made into the solution of 0.005-0.01mol/L in advance with the toluene dissolving.The toluene solution that in polymerization bottle, adds 1-10 μ mol catalyst A component under the ethene atmosphere with syringe successively, add 30-40mL toluene under the violent stirring, under 0-60 ℃ of temperature, keep 5-10min, the toluene solution initiated polymerization that adds a certain amount of catalyst B component MAO, the mol ratio of A component and B component is 500: 1-3000: 1.The cumulative volume of reaction system generally remains on 50mL (adjusting of different volumes useable solvents toluene), behind the reaction 30min-120min, pours mixture in the acidifying ethanolic soln (ethanol/HCl
Conc=95: 5).Fully stirred 4-6 hour,, and use washing with alcohol, 80 ℃ of following vacuum-drying 24 hours polymer filtration.The active amt level is 10
4-10
6G PE/ (mol Tih), the molecular weight of polyethylene order of magnitude is 10
6G/mol.
Embodiment 11: the reaction of high pressure catalyzed ethylene polymerization:
Earlier autoclave is treated to the reaction system of anhydrous and oxygen-free, is warming up to temperature of reaction.By substituting gas, make it to be the ethene atmosphere.Syringe adds the toluene solution of 10 μ mol catalyst A components successively in polymerization reaction kettle, intense mechanical stirs and adds 40mL toluene down, under 0-60 ℃ of temperature, keep 5-10min, the toluene solution that adds a certain amount of catalyst B component MAO, initiated polymerization, the mol ratio of A component and B component is 500: 1-3000: 1.Be forced into 7atm, reaction 30-120min.Close steel cylinder, venting, making it is a normal atmosphere.With acidifying ethanolic soln (ethanol/HCl
Conc=95: 5) stop polymerization.Pour mixture in the acidifying ethanolic soln (ethanol/HCl
Conc=95: 5).Fully stirred 4-6 hour,, and use washing with alcohol, 80 ℃ of following vacuum-drying 24 hours polymer filtration.The active amt level is 10
5G PE/ (mol Tih), the molecular weight of polyethylene order of magnitude is 10
7G/mol.
Claims (3)
1. [O^N^S] type tridentate ligand and titanium metal coordinate olefin polymerization catalysis is characterized in that expression formula is [L-Ti], L represent a kind of contain can with the O of metal-complexing, N, the tridentate ligand of S atom, the 2a that its structure is shown below, 2b, 2c, 3a, 3b, a kind of among the 3c:
2. preparation method of olefin polymerization catalysis according to claim 1 is characterized in that concrete steps are as follows:
Phenol by 2-aminothiophenol, Paraformaldehyde 96, various replacements is starting raw material, makes the salicylic alidehyde imine of ligand L-2-thiophenyl through the series reaction step; Ti (the OPr of ligand L and equimolar amount
i)
4Or TiCl
4The reaction, through the extraction, freezing, filter, drain, obtain titanium complex [(the Ti-L) (OPr of monokaryon and double-core
i)
2]
x[(Ti-L) Cl
2]
x, x=1.2; Entire reaction course is as follows:
3. the application of olefin polymerization catalysis as claimed in claim 1 in the preparation polyethylene is characterized in that:
(1) step of normal pressure catalyzed ethylene polymerization reaction is as follows:
Vinyl polymerization carries out under the anhydrous and oxygen-free condition; Catalyzer dissolves with toluene in advance, be made into the solution of 0.005-0.01mol/L, the toluene solution that in polymerization bottle, adds 1-10 μ mol catalyst A component under the ethene atmosphere with syringe successively, stir and add 30-40mL toluene down, under 0-100 ℃, keep 5-10min, add the toluene solution initiated polymerization of a certain amount of catalyst B component, the mol ratio of A component and B component is 500: 1-3000: 1; The cumulative volume of reaction system remains on 50mL, behind the reaction 30min-120min, mixture is poured in the acidifying ethanolic soln into ethanol/HCl
Conc=95: 5; Stirred 4-6 hour, and, and used washing with alcohol, 80 ℃ of following vacuum-drying 24 hours polymer filtration; The active amt level is 10
4-10
6G PE/ (mol Tih), the molecular weight of polyethylene order of magnitude is 10
6G/mol;
(2) step of high pressure catalyzed ethylene polymerization reaction is as follows:
Earlier autoclave is treated to the reaction system of anhydrous and oxygen-free, is warming up to temperature of reaction; By substituting gas, make it to be the ethene atmosphere; Syringe adds the toluene solution of 1-10 μ mol catalyst A component successively in polymerization reaction kettle, stir and add 30-40mL toluene down, under 0-100 ℃, keep 5-10min, the toluene solution that adds the catalyst B component, initiated polymerization, the mol ratio of A component and B component is 500: 1-3000: 1; Be forced into 7atm, reaction 30-120min; Close steel cylinder, venting, making it is a normal atmosphere; Stop polymerization, ethanol/HCl with the acidifying ethanolic soln
Conc=95: 5; Mixture is poured in the acidifying ethanolic soln into ethanol/HCl
Conc=95: 5; Stirred 4-6 hour, and, and used washing with alcohol, 80 ℃ of following vacuum-drying 24 hours polymer filtration; The active amt level is 10
5G PE/ (mol Tih), the molecular weight of polyethylene order of magnitude is 10
7G/mol;
Wherein said catalyst A component is the described olefin polymerization catalysis of claim 1, and the B component is methylaluminoxane or modified methylaluminoxane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030719A (en) * | 2013-01-08 | 2013-04-10 | 上海化工研究院 | ONS (Organometallics) type salicylaldimine binuclear metallic alkene catalyst and preparation method thereof |
| CN104994948A (en) * | 2013-02-27 | 2015-10-21 | 三井化学株式会社 | Catalyst for olefin multimerization and method for producing olefin multimer in presence of catalyst for olefin multimerization |
| CN108368268A (en) * | 2015-12-17 | 2018-08-03 | 汉高股份有限及两合公司 | Titanium complex as sulphurized catalyst |
-
2009
- 2009-11-05 CN CN200910198316A patent/CN101709097A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030719A (en) * | 2013-01-08 | 2013-04-10 | 上海化工研究院 | ONS (Organometallics) type salicylaldimine binuclear metallic alkene catalyst and preparation method thereof |
| CN103030719B (en) * | 2013-01-08 | 2015-12-09 | 上海化工研究院 | ONS type salicylic alidehyde imine dinuclear metal alkene catalyst and preparation method |
| CN104994948A (en) * | 2013-02-27 | 2015-10-21 | 三井化学株式会社 | Catalyst for olefin multimerization and method for producing olefin multimer in presence of catalyst for olefin multimerization |
| US9616421B2 (en) | 2013-02-27 | 2017-04-11 | Mitsui Chemicals, Inc. | Catalyst for olefin multimerization and method for producing olefin multimer in presence of catalyst for olefin multimerization |
| CN108368268A (en) * | 2015-12-17 | 2018-08-03 | 汉高股份有限及两合公司 | Titanium complex as sulphurized catalyst |
| CN108368268B (en) * | 2015-12-17 | 2021-03-19 | 汉高股份有限及两合公司 | Titanium complexes as sulfidation catalysts |
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Application publication date: 20100519 |