CN1176953C - Beta-diketoimide titanium olefin polymer catalyst - Google Patents

Beta-diketoimide titanium olefin polymer catalyst

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CN1176953C
CN1176953C CNB021589216A CN02158921A CN1176953C CN 1176953 C CN1176953 C CN 1176953C CN B021589216 A CNB021589216 A CN B021589216A CN 02158921 A CN02158921 A CN 02158921A CN 1176953 C CN1176953 C CN 1176953C
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phenyl
trifluoromethyl
titanium
beta
olefin polymerization
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CN1424334A (en
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李悦生
李晓芳
戴可
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention discloses a beta-diketoimide titanium olefin polymer catalyst which has the structure disclosed in the specification, wherein R1 can be trifluoromethyl, tertiary butyl, phenyl, furyl or thienyl; R2 can be methyl or trifluoromethyl; R3 is phenyl. Under the action of neutral lewis acids, such as methylaluminoxane or modified methylaluminoxane, etc., the catalyst can catalyze the polymerization of ethylene, the copolymerization of ethylene and norborene and the copolymerization of ethylene and alpha-olefin.

Description

A kind of beta-diketon imines titanium olefin polymerization catalysis
Technical field
The present invention relates to a kind of beta-diketon imines titanium olefin polymerization catalysis.
The invention still further relates to the preparation method of above-mentioned beta-diketon imines titanium olefin polymerization catalysis.
The invention still further relates to the application of above-mentioned beta-diketon imines titanium olefin polymerization catalysis in catalyzed ethylene polymerization, ethene and norbornylene copolymerization, ethene and alpha-olefin copolymer close.
Polyolefine is the important macromolecular material of a class, accounts for 50% of plastics, is widely used in industry, agricultural, national defence, communications and transportation and the daily life.Catalyzer is the core of polyolefin industry development, is the key of control polyolefin structure and performance.Traditional Ziegler-Natta catalyst is widely used in the industrial production of isotatic polypropylene, high density polyethylene(HDPE) and linear low density polyethylene, but its structural controllability and copolymerized ability are relatively poor.In order to overcome above-mentioned shortcoming, people have been developed the metallocene catalyst of a class high reactivity, high structural controllability.Metallocene catalyst is the agent of monomer reactivity centers catalyse, be widely used in the industrial production of syndiotactic polypropylene, syndiotactic polystyrene, linear low density polyethylene and long-chain branched polyethylene, but the copolymerized ability of metallocene catalyst still awaits improving, for example when metallocene catalysis ethene and styrene copolymerized poor effect, catalyzed ethylene and norbornylene copolymerization, the reactivity ratio of norbornylene is lower etc.Therefore, " luxuriant back " (Post-metallocene) olefin polymerization catalysis causes people's great interest, wishes to develop the better or stronger olefin polymerization catalysis of copolymerized ability of structural controllability.
Recently, people such as Japanese scientist Fujita has reported salicylic alidehyde imine titanium with high catalytic activity, (J.Am.Chem.Soc.2001,123:6847-6856), but its catalyzed alkene copolymerization is indifferent for catalyzer for zirconium type " luxuriant back ".For overcoming this shortcoming, the invention discloses a kind of beta-diketon imines titanium olefin polymerization catalysis, it has advantages such as the high and copolymerization ability of easy to prepare and catalytic activity is strong.
The purpose of this invention is to provide a kind of beta-diketon imines titanium olefin polymerization catalysis.
Another purpose of the present invention provides the preparation method of above-mentioned beta-diketon imines titanium olefin polymerization catalysis.
A further object of the present invention provides above-mentioned beta-diketon imines titanium olefin polymerization catalysis under the effect of methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), the application during catalyzed ethylene polymerization, ethene and norbornylene copolymerization, ethene and alpha-olefin copolymer close.
Under the effect of formic acid, in alcoholic solution, carry out the condensation reaction of beta-diketone compounds and aniline, obtain the western Buddhist alkali shown in the following formula,
Figure C0215892100051
Under the condition of anhydrous and oxygen-free, carry out the reaction of above-mentioned western Buddhist alkali and n-Butyl Lithium, the negative ion part that obtains being shown below,
Figure C0215892100052
Under the anhydrous and oxygen-free condition, carry out the coordination reaction of above-mentioned negative ion part and titanium tetrachloride, the titanium complex that obtains being shown below:
R in the formula 1Can be trifluoromethyl, the tertiary butyl, phenyl, furyl or thienyl; R 2Can be methyl or trifluoromethyl; R 3Be phenyl.
For achieving the above object, the structure of beta-diketon imines titanium olefin polymerization catalysis provided by the invention is as follows:
Figure C0215892100062
R in the formula 1Can be trifluoromethyl, the tertiary butyl, phenyl, furyl or thienyl; R 2Can be methyl or trifluoromethyl.
Embodiment
Embodiment 1
In exsiccant 100mL reaction flask, add 1,1,1-three fluoro-2,4-diacetylmethane 5.0g (32mmol), aniline 6.1g (64mmol), methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 30h.The cooling reaction solution has clear crystal to separate out.Filter crystal, wash several with cold sherwood oil after, 60 ℃ of vacuum-drying 48h, De Xifo alkali (C 11H 10F 3NO) 3.0g, yield 41%.
Embodiment 2
In exsiccant 100mL reaction flask, add 1,1,1-three fluoro-5,5-dimethyl-2,4-diacetylmethane 5.88g (30mmol), aniline 4.19g (45mmol), methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 30h.The cooling reaction solution steams excess ethanol, residuum column chromatography (ethyl acetate/petroleum ether=1/100), De Xifo alkali (C 14H 16F 3NO) 4.56g, yield 56%.
Embodiment 3
In exsiccant 100mL reaction flask, add 1-phenyl-2,4-dimethyl diketone 1.62g (10mmol), aniline 1.9g (20mmol), methyl alcohol 15mL, formic acid 0.6mL, room temperature reaction 30h.The cooling reaction solution has light yellow crystal to separate out.Filter crystal, wash for several times with cold methanol after, 60 ℃ of vacuum-drying 48h, De Xifo alkali (C 16H 15NO) 1.9g, yield 80%.
Embodiment 4
In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-phenyl-1,3-dimethyl diketone 5.0g (23mmol), aniline 4.4g (46mmol), methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 30h.The cooling reaction solution steams excess ethanol, and residuum column chromatography (ethyl acetate/petroleum ether=1/100) gets flaxen western Buddhist alkali lye body (C 16H 12F 3NO) 4.5g, yield 67%.
Embodiment 5
With 4,4,4-three fluoro-1-furyls-1,4,4 in 3-dimethyl diketone 4.74g (23mmol) alternate embodiment 4,4-three fluoro-1-phenyl-1, the 3-dimethyl diketone, operation gets flaxen western Buddhist alkali lye body (C with embodiment 4 14H 10F 3NO 2) 3.8g, yield 59%.
Embodiment 6
With 4,4,4-three fluoro-1-thienyls-1,4,4 in 3-dimethyl diketone 5.11g (23mmol) alternate embodiment 4,4-three fluoro-1-phenyl-1, the 3-dimethyl diketone, operation gets flaxen western Buddhist alkali lye body (C with embodiment 4 14H 10F 3NOS) 4.1g, yield 60%.
Embodiment 7
Under nitrogen protection; add western Buddhist alkali 1.0g (4.4mmol) and the ether 20mL that embodiment 1 obtains in exsiccant 100mL reaction flask, stirring at room reaction 5min is cooled to-78 ℃; (3.0mL 4.8mmol) joins in the reaction flask within 5min with the hexane solution of 1.60M n-Butyl Lithium.Solution is by the colourless scarlet that becomes, and reactant is raised to stirring at room 4h.Add TiCl after getting a Schlenk bottle drying 40.15mL (1.4mmol), down the above-mentioned lithium salt solution that obtains is joined in 30min in the Schlenk bottle at-78 ℃.Reactant is at stirring at room 12h.After the vacuum filtration, filtrate concentrating obtained black solid, add dry ether 20mL and stir 10min, after the vacuum filtration, filtrate is concentrated, gets black solid.Add methylene dichloride (5mL) and hexane (10mL) again and stir 1h, filter, vacuum-drying gets sorrel title complex 0.67g, yield 53%.
Embodiment 8
The western Buddhist alkali that obtains in western Buddhist alkali 1.20g (4.4mmol) alternate embodiment 1 with embodiment 2 preparations, operation get sorrel title complex 0.83g, yield 57% with embodiment 7.
Embodiment 9
The western Buddhist alkali that obtains in western Buddhist alkali 1.04g (4.4mmol) alternate embodiment 1 with embodiment 3 preparations, operation get sorrel title complex 0.91g, yield 63% with embodiment 7.
Embodiment 10
The western Buddhist alkali that obtains in western Buddhist alkali 1.28g (4.4mmol) alternate embodiment 1 with embodiment 4 preparations, operation get sorrel title complex 0.88g, yield 57% with embodiment 7.
Embodiment 11
The western Buddhist alkali that obtains in western Buddhist alkali 1.24g (4.4mmol) alternate embodiment 1 with embodiment 5 preparations, operation get sorrel title complex 0.82g, yield 55% with embodiment 7.
Embodiment 12
The western Buddhist alkali that obtains in western Buddhist alkali 1.31g (4.4mmol) alternate embodiment 1 with embodiment 6 preparations, operation get sorrel title complex 0.93g, yield 61% with embodiment 7.
Embodiment 13
Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add successively absolute toluene 50mL, MMAO n-heptane solution (2.0M, 1mL), after stirring 5 minutes under 25 ℃, the titanium complex 0.58mg (1 μ mol is dissolved in 1mL toluene) that adds embodiment 7 preparations stirs polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filter washing with alcohol 2 times, vacuum-drying, get linear polyethylene 0.18g, activity is 1.1 * 10 6GPE/mol TiH, 137 ℃ of fusing points, weight-average molecular weight is 160,000, molecular weight distribution 1.37.
Embodiment 14
The titanium complex that obtains in titanium complex 0.66mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 8 preparations, operation get linear polyethylene 0.19g with embodiment 13, and activity is 1.14 * 10 6GPE/mol TiH, 135 ℃ of fusing points, weight-average molecular weight is 150,000, molecular weight distribution 1.39.
Embodiment 15
The titanium complex that obtains in titanium complex 0.70mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 9 preparations, operation get linear polyethylene 0.22g with embodiment 13, and activity is 1.32 * 10 6GPE/mol TiH, 139 ℃ of fusing points, weight-average molecular weight is 160,000, molecular weight distribution 1.35.
Embodiment 16
Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add successively absolute toluene 80mL, MMAO n-heptane solution (2.0M, 5mL), after stirring 5 minutes under 25 ℃, the titanium complex 3.00mg (1 μ mol is dissolved in 5mL toluene) that adds embodiment 10 preparations stirs polyreaction 30min down, reactant is poured in the ethanolic soln of 300mL 1% hydrochloric acid, filter washing with alcohol 2 times, vacuum-drying, get linear polyethylene 0.02g, activity is 8.1 * 10 4GPE/mol TiH.
Embodiment 17
Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add successively absolute toluene 60mL, MAO n-heptane solution (2.0M, 2mL), after stirring 5 minutes under 25 ℃, the titanium complex 1.36mg (2 μ mol are dissolved in 2mL toluene) that adds embodiment 11 preparations stirs polyreaction 10min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filter washing with alcohol 2 times, vacuum-drying, get linear polyethylene 0.12g, activity is 3.6 * 10 5GPE/mol TiH.
Embodiment 18
The titanium complex that obtains in titanium complex 1.40mg (2 μ mol the are dissolved in 2mL toluene) alternate embodiment 11 with embodiment 12 preparations, operation get linear polyethylene 0.24g with embodiment 17, and activity is 7.2 * 10 5GPE/mol TiH, 136 ℃ of fusing points, weight-average molecular weight is 130,000, molecular weight distribution 1.43.
Embodiment 19
Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add absolute toluene 50mL, norbornylene 5g successively, the n-heptane solution (2.0M of MMAO, 1mL), after stirring 5 minutes under 25 ℃, add titanium complex 0.58mg (the 1 μ mol of embodiment 7 preparations, be dissolved in 1mL toluene), stir polyreaction 15min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filter, washing with alcohol 2 times, vacuum-drying gets cyclic olefine copolymer 0.82g, and activity is 3.3 * 10 6GPolym/mol TiH, 146 ℃ of second-order transition temperatures, weight-average molecular weight are 14.6 ten thousand.
Embodiment 20
The titanium complex that obtains in titanium complex 0.66mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 8 preparations, operation get cyclic olefine copolymer 0.63g with embodiment 19, and activity is 2.52 * 10 6GPolym/mol TiH, 138 ℃ of fusing points, weight-average molecular weight is 150,000.
Embodiment 21
The titanium complex that obtains in titanium complex 0.70mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 9 preparations, operation get cyclic olefine copolymer 0.44g with embodiment 19, and activity is 1.76 * 10 6GPolym/mol TiH, 142 ℃ of fusing points, weight-average molecular weight is 13.8 ten thousand.
Embodiment 22
The titanium complex that obtains in titanium complex 0.68mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 11 preparations, operation get cyclic olefine copolymer 0.11g with embodiment 19, and activity is 4.4 * 10 5GPolym/mol TiH.
Embodiment 23
The titanium complex that obtains in titanium complex 0.70mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 11 preparations, operation get cyclic olefine copolymer 0.26g with embodiment 19, and activity is 1.1 * 10 6GPolym/mol TiH, 142 ℃ of fusing points, weight-average molecular weight is 12.4 ten thousand.
Embodiment 24
Under the ethene atmosphere, in exsiccant 100mL polymerization bottle, add absolute toluene 50mL, 1-hexene 2mL successively, the n-heptane solution (2.0M of MMAO, 1mL), after stirring 5 minutes under 25 ℃, add titanium complex 0.58mg (the 1 μ mol of embodiment 7 preparations, be dissolved in 1mL toluene), stir polyreaction 15min down, reactant is poured in the ethanolic soln of 200mL 1% hydrochloric acid, filter, washing with alcohol 2 times, vacuum-drying gets linear low density polyethylene 0.12g, and activity is 4.8 * 10 5GPolym/mol TiH, 126 ℃ of fusing points, weight-average molecular weight is 13.6 ten thousand.
Embodiment 25
The titanium complex that obtains in titanium complex 0.66mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 8 preparations, operation get linear low density polyethylene 0.11g with embodiment 24, and activity is 4.4 * 10 5GPolym/mol TiH, 123 ℃ of fusing points, weight-average molecular weight is 13.1 ten thousand.
Embodiment 26
The titanium complex that obtains in titanium complex 0.70mg (1 μ mol the is dissolved in 1mL toluene) alternate embodiment 7 with embodiment 9 preparations, operation get linear low density polyethylene 0.13g with embodiment 24, and activity is 5.2 * 10 5GPolym/mol TiH, 124 ℃ of fusing points, weight-average molecular weight is 14.1 ten thousand.

Claims (7)

1. beta-diketon imines titanium olefin polymerization catalysis, it has following structure:
R in the formula 1Can be trifluoromethyl, the tertiary butyl, phenyl, furyl or thienyl; R 2Can be methyl or trifluoromethyl; R 3Be phenyl.
2. according to the described beta-diketon imines of claim 1 titanium olefin polymerization catalysis, wherein, R 1Can be phenyl, the tertiary butyl or trifluoromethyl; R 2Be methyl or trifluoromethyl, R 3Be phenyl.
3. according to the described beta-diketon imines of claim 1 titanium olefin polymerization catalysis, wherein, R 1Can be phenyl or trifluoromethyl; R 2Be methyl or trifluoromethyl, R 3Be phenyl.
4. according to the described beta-diketon imines of claim 1 titanium olefin polymerization catalysis, wherein, R 1It is phenyl; R 2Be trifluoromethyl, R 3It is phenyl.
5. according to the described beta-diketon imines of claim 1 titanium olefin polymerization catalysis, wherein, R 1It is trifluoromethyl; R 2Be methyl, R 3It is phenyl.
6. according to the described beta-diketon imines of claim 1 titanium olefin polymerization catalysis, under the effect of methylaluminoxane or modified methylaluminoxane, catalyzed ethylene polymerization, ethene and norbornylene copolymerization, ethene and alpha-olefin copolymer close.
7. method for preparing the described beta-diketon imines of claim 1 titanium olefin polymerization catalysis:
Under the effect of formic acid, in alcoholic solution, carry out the condensation reaction of beta-diketone compounds and aniline, obtain the western Buddhist alkali shown in the following formula,
Figure C021589210003C1
Under the condition of anhydrous and oxygen-free, carry out the reaction of above-mentioned western Buddhist alkali and n-Butyl Lithium, the negative ion part that obtains being shown below,
Under the anhydrous and oxygen-free condition, carry out the coordination reaction of above-mentioned negative ion part and titanium tetrachloride, the titanium complex that obtains being shown below:
Figure C021589210003C3
R in the formula 1Can be trifluoromethyl, the tertiary butyl, phenyl, furyl or thienyl; R 2Can be methyl or trifluoromethyl; R 3Be phenyl.
CNB021589216A 2002-12-27 2002-12-27 Beta-diketoimide titanium olefin polymer catalyst Expired - Fee Related CN1176953C (en)

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JP2008510001A (en) * 2004-08-18 2008-04-03 コーネル・リサーチ・ファンデーション・インコーポレイテッド Alkene polymerization using β-ketoiminato metal complex
CN100384893C (en) * 2005-07-22 2008-04-30 中国科学院上海有机化学研究所 Halogen substituent ketoimine front transient metal titanium complex, synthesis method and uses
CN100424100C (en) * 2006-05-25 2008-10-08 中国科学院长春应用化学研究所 Beta-ketimine vanadium olefinic polymerization catalyst, and its preparing method and use
CN100406479C (en) * 2006-05-25 2008-07-30 中国科学院长春应用化学研究所 Beta-diketone monoimine vanadium catalyst containing trifluoromethyl radical for olefinic polymerization and its preparation method and uses
CN101177463B (en) * 2007-12-06 2010-05-26 中国科学院长春应用化学研究所 Supported beta-diketone enamine vanadium olefin poly catalyst as well as preparation method and application thereof
CN103183624B (en) * 2011-12-30 2017-04-19 中国科学院上海有机化学研究所 Catalyst used for olefine polymerization or copolymerization and preparation method thereof
CN112608065B (en) * 2019-12-13 2022-07-15 科之杰新材料集团(贵州)有限公司 Liquid alkali-free accelerator for sprayed concrete and preparation method thereof
CN115806642A (en) * 2023-02-03 2023-03-17 天津大学 Preparation method of transparent ultrahigh molecular weight cycloolefin copolymer

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