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CN101045764A - Alkene polymerization catalyst and preparation method and application thereof - Google Patents

Alkene polymerization catalyst and preparation method and application thereof Download PDF

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CN101045764A
CN101045764A CN 200710040016 CN200710040016A CN101045764A CN 101045764 A CN101045764 A CN 101045764A CN 200710040016 CN200710040016 CN 200710040016 CN 200710040016 A CN200710040016 A CN 200710040016A CN 101045764 A CN101045764 A CN 101045764A
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olefin polymerization
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CN100549043C (en
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金国新
汤光荣
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Fudan University
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Abstract

This invention relates to a [ O, N] type, double teeth ligand , two valence transition metal coordinative olefinic polymerization catalyzer, and its preparation method. The expression of this catalyst component is L2M, L express double teeth ligand which contain O, N atomi can co-ordinate with transition metal, M express two valence transition metal Ni or Cu; it takes 7 - hydroxy hydrindone with substituent group and aniline or substituted aniline as raw material, synthesize hydroxy hydrindone imine ligand possessing [ O, N] double dental, then ligand takes reaction with 0.5 times molar weight hydration hydration nickel acetate ( or nickel acetylacetonate) or hydration cupric acetate ( or acetic acid acetone cuprum), obtain corresponding catalyzer. This method is simple, stable to gas, used in catalyze norbornylene to polymerize polymer which posssess high catalytic activity, high molecular weight, high vitrification point.

Description

A kind of olefin polymerization catalysis and its production and application
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to olefin polymerization catalysis of a class [O, N] type bitooth ligand and two valence state post transition metal coordinations and preparation method thereof.
Background technology
Go through semicentennial development, polyolefin industry has become the mainstay industry of modern macromolecular material industry, and polyolefin products has greatly promoted the development of human civilization ground.Make a general survey of the developing history of polyolefin industry, the upgrading of polyolefin products each time all is to finish under the situation of finding new olefin polymerization catalysis, that is to say that catalyzer is the constantly core and the prime mover of development of polyolefin industry.Since nineteen fifty-three, olefin polymerization catalysis came out, in 50 years, three epoch had been experienced in the development of olefin polymerization catalysis: Ziegler-Natta catalyst system, metallocene catalyst system and post-transition metal catalyst system.Over past ten years, academia both domestic and external and industry member all concentrate on post-transition metal catalyst system with the sight of research.This be since late transition metal catalyst for olefin polymerization have good stability, low price, good to all kinds of polar functional group tolerances, good advantages such as aggregation features are arranged.
Different polymerization methodses will cause the polynorbornene of gained to have different structures, character and purposes.Because the polynorbornene that addition polymerization obtains has a series of uniquenesses and interesting physicochemical property; the for example good solvability in halogenated aryl hydrocarbon, high chemical impedance, good ultraviolet impedance, low-k, high glass transition temperature, good light transmission, high specific refractory power and low-birefringence etc.; can be applied to microelectronic device and liquid-crystal display supercoat, also can be used as resistant to elevated temperatures protective material.Just because of this, the research of norbornylene addition polymerization has in recent years caused everybody extensive concern, especially late transition metal catalyst for olefin polymerization research and development in this respect.
Summary of the invention
The purpose of this invention is to provide a kind of stable in the air, that be easy to prepare, [O, N] type bitooth ligand of high catalytic activity and olefin polymerization catalysis of two valence state post transition metal coordinations and preparation method thereof.
The olefin polymerization catalysis that the present invention proposes, its component expression formula is L 2M, L represent to contain can with the O of post transition metal coordination, the bitooth ligand of N atom, M represents two valence state rear transition metal Ni and Cu, concrete structure is as follows:
Wherein: M is Ni or Cu; R 1A kind of in hydrogen, methyl or the tertiary butyl, R 2Be in hydrogen, methyl or the halogens any one, R 3Be in hydrogen or the methyl any one, R 4, R 5A kind of in hydrogen, chlorine, methyl or the sec.-propyl.
The present invention is a starting raw material with the 7-hydroxy indene ketone that contains substituted radical and aniline or substituted aniline, synthesize and have [O, N] the hydroxy indene kitimine part of bidentate, the hydration nickelous acetate (or nickel acetylacetonate) of part and 0.5 times of molar weight or hydrated copper acetate (or acetate acetone copper) reaction then just obtains corresponding catalyzer.These title complexs are stable in the air, can be dissolved in well in common organic solvent and the catalyst system after the effect of B component, become single site catalysts, have good catalytic activity under mild conditions.By changing the substituted radical on the part, can obtain the polynorbornene of different molecular weight with the addition polymerization of different activities catalysis norbornylene.
The preparation process of [O, N] type bitooth ligand and two valence state rear transition metal Ni or Cu coordinate olefin polymerization catalysis is as follows:
1, hydroxy indene kitimine part is synthetic
The structural formula of this part is:
Figure A20071004001600052
The synthesis step of part: under the environment of anhydrous and oxygen-free, get and contain substituent 7-hydroxy indene ketone, add excessive aniline or substituted aniline, under acid catalysis, reacted 44-50 hour, and just can obtain containing various substituent hydroxy indene kitimine parts.
Work as R 1=R 4=R 5During=H, above-mentioned reaction solvent for use is an absolute ethanol, and used acid is the formic acid of catalytic amount, and adds the 4A molecular sieve; To reflux during reaction; After reaction finishes, reaction mixture is filtered, concentrated filtrate then as eluent, as stationary phase, carries out column chromatography with silica gel with the mixing solutions of sherwood oil and ethyl acetate, just obtains hydroxy indene kitimine part;
Work as substituent R 1, R 4And R 5In have one above-mentioned reaction solvent for use be a toluene when the hydrogen atom, used acid is excessive TiCl 4Temperature of reaction is 85-90 ℃; After reaction finished, reaction solution was poured Na into 2CO 3Saturated aqueous solution, separatory concentrates organic phase, as eluent, as stationary phase, carries out column chromatography with silica gel with the mixing solutions of sherwood oil and ethyl acetate, just can obtain hydroxy indene kitimine part;
2, the preparation of the Ni coordinate olefin polymerization catalysis of [O, N] bitooth ligand and two valence states
With Ni (OAc) 24H 2O or Ni (AcAc) 2Join in the dehydrated alcohol with the hydroxy indene kitimine part of twice molar weight, backflow 3-5 hour, produce solid, filter, collect solid, washing, under vacuum dry 20-28 hour then, just can obtain the Ni or the Cu coordinate olefin polymerization catalysis of [O, N] bitooth ligand and two valence states.
3, the preparation of the Cu coordinate olefin polymerization catalysis of [O, N] bitooth ligand and two valence states
With Cu (OAc) 2H 2O or Cu (AcAc) 2Join in the dehydrated alcohol with the hydroxy indene kitimine part of twice molar weight, backflow 3-5 hour, produce solid, filter, collect solid, washing, under vacuum dry 24 hours then, just can obtain the Cu coordinate olefin polymerization catalysis of [O, N] bitooth ligand and two valence states.
The solids wash solvent for use is sherwood oil, normal hexane, dehydrated alcohol and methyl alcohol etc., washs to get final product for 2-3 time.
Method for preparing catalyst of the present invention is simple, to air-stable, is used for the addition polymerization of catalysis norbornylene and has high reactivity, can obtain high molecular, high glass transition temperature, the polynorbornene product of good solubility is arranged.
Among the present invention, when above-mentioned catalyzer is used for the norbornylene addition polymerization,, be used with B component methylaluminoxane (MAO) or modified methylaluminoxane (MHAO) as catalyst system A component.
Description of drawings
Fig. 1 is the crystalline structure figure with Ni coordinate olefin polymerization catalysis.
Fig. 2 is the crystalline structure figure with Cu coordinate olefin polymerization catalysis
Embodiment
The preparation of embodiment 1 part 7-hydroxyindan-1-(N-phenylimine)
At N 2Down, 1.68g (11.4mmol) 7-hydroxy indene ketone and 1.4mL (15.0mmol) aniline are added in the there-necked flask of 100mL, add the 30mL absolute ethanol then, 0.1mL formic acid, 0.7g 4A molecular sieve.Reflux 48 hours.After reaction finishes, filter, collect filtrate, use anhydrous Mg 2S0 4Drying concentrates, and crosses silicagel column with the mixing solutions of sherwood oil and ethyl acetate as eluent, obtains orange 1.53g, productive rate 60%.
Embodiment 2 part 7-hydroxy-3, the preparation of 4-dimethylindan-1-(N-phenylimine)
Under N2, with 2.0g (11.4mmol) 7-hydroxyl-3,4-dimethyl indone and 1.4mL (15.0mmol) aniline is added in the there-necked flask of 100mL, adds the 30mL absolute ethanol then, 0.1mL formic acid, 0.7g 4A molecular sieve.Reflux 45 hours.After reaction finishes, filter, collect filtrate,, concentrate, cross silicagel column as eluent, obtain yellow solid 2.3g, productive rate 80% with the mixing solutions of sherwood oil and ethyl acetate with anhydrous Mg2SO4 drying.
Embodiment 3 part 7-hydroxy-3,4-dimethylindan-1-(N-2, preparation 6-diisopropylphenylimine)
At N 2In 30min, will be dissolved with 1.3mL (11.4mmol) TiCl down, 4The 30mL toluene solution add and to contain 8.6mL (45.4mmol) 2, in the 40mL toluene solution of 6-diisopropyl aniline.Reaction mixture is heated to 90 ℃ then, adds 7-hydroxyl-3 behind the 30min again, 4-dimethyl indone 2g (11.4mmol).Under this temperature, reacted 50 hours.After reaction finished, reaction solution was poured Na into 2CO 3Saturated aqueous solution, separatory, the anhydrous Mg of organic phase 2SO 4Drying concentrates, and crosses silicagel column with the mixing solutions of sherwood oil and ethyl acetate as eluent, obtains red solid 1.54g, productive rate 40%.
Embodiment 4 part 7-hydroxy-3, the preparation of 4-dimethyl-6-tert-butylindan-1-(N-phenylimine)
At N 2In 30min, will be dissolved with 1.3mL (11.4mmol) TiCl down, 4The 30mL toluene solution add and to contain in the 40mL toluene solution of 4.3mL (45.4mmol) aniline.Reaction mixture is heated to 90 ℃ then, adds 7-hydroxyl-3 behind the 30min again, 4-dimethyl-6-tertiary butyl indone 2.63g (11.4mmol).Under this temperature, reacted 44 hours.After reaction finished, reaction solution was poured Na into 2CO 3Saturated aqueous solution, separatory, the anhydrous Mg of organic phase 2SO 4Drying concentrates, and crosses silicagel column with the mixing solutions of sherwood oil and ethyl acetate as eluent, obtains orange red solid 2.75g, productive rate 45%.
Embodiment 5 part 7-hydroxy-3, the preparation of 4-dimethylindan-1-(N-2-methylphenylimine)
At N 2In 30min, will be dissolved with 1.3mL (11.4mmol) TiCl down, 4The 30mL toluene solution add and to contain in the 40mL toluene solution of 4.9mL (45.4mmol) 2-aminotoluene.Reaction mixture is heated to 90 ℃ then, adds 7-hydroxyl-3 behind the 30min again, 4-dimethyl indone 2g (11.4mmol).Under this temperature, reacted 48 hours.After reaction finished, reaction solution was poured Na into 2CO 3Saturated aqueous solution, separatory, the anhydrous Mg of organic phase 2SO 4Drying concentrates, and crosses silicagel column with the mixing solutions of sherwood oil and ethyl acetate as eluent, obtains red solid 2.98g, productive rate 53%.
The preparation of embodiment 6 and metal Ni coordinate olefin polymerization catalysis
Ni (OAc) with 0.122g (0.49mmol) 24H 2The 7-hydroxy-3 of O and 0.245g (0.98mmol), 4-dimethylindan-1-(N-phenylimine) joins in the dehydrated alcohol of 20mL, reflux 5 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain green solid 0.164g, productive rate 60%.
The preparation of embodiment 7 and metal Ni coordinate olefin polymerization catalysis
Ni (OAc) with 0.122g (0.49mmol) 24H 2The 7-hydroxy-3 of O and 0.327g (0.98mmol), (N-2 6-diisopropylphenylimine) joins in the dehydrated alcohol of 20mL 4-dimethylindan-1-, reflux 3 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown xanchromatic solid 0.236g, productive rate 75%.
The preparation of embodiment 8 and metal Ni coordinate olefin polymerization catalysis
Ni (OAc) with 0.122g (0.49mmol) 24H 2The 7-hydroxy-3 of O and 0.258g (0.98mmol), 4-dimethylindan-1-(N-2-methylphenylimine) joins in the dehydrated alcohol of 20mL, reflux 3 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown xanchromatic solid 0.233g, productive rate 81%.
The preparation of embodiment 9 and metal Ni coordinate olefin polymerization catalysis
Ni (OAc) with 0.122g (0.49mmol) 24H 2The 7-hydroxy-3 of O and 0.300g (0.98mmol), 4-dimethyl-6-tert-butylindan-1-(N-phenylimine) joins in the dehydrated alcohol of 20mL, reflux 3.5 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown xanchromatic solid 0.234g, productive rate 71%.
The preparation of embodiment 10 and metal Cu coordinate olefin polymerization catalysis
Cu (OAc) with 0.098g (0.49mmol) 2H 2The 7-hydroxy-3 of O and 0.300g (0.98mmol), 4-dimethyl-6-tert-butylindan-1-(N-phenylimine) joins in the dehydrated alcohol of 20mL, reflux 3 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown solid 0.222g, productive rate 67%.
The preparation of embodiment 11 and metal Cu coordinate olefin polymerization catalysis
Cu (OAc) with 0.098g (0.49mmol) 2H 2The 7-hydroxy-3 of O and 0.245g (0.98mmol), 4-dimethylindan-1-(N-phenylimine) joins in the dehydrated alcohol of 20mL, reflux 3 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown solid 0.170g, productive rate 72%.
The preparation of embodiment 12 and metal Cu coordinate olefin polymerization catalysis
Cu (OAc) with 0.098g (0.49mmol) 2H 2The 7-hydroxy-3 of O and 0.258g (0.98mmol), 4-dimethylindan-1-(N-2-methylphenylimine) joins in the dehydrated alcohol of 25mL, reflux 3.5 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown solid 0.235g, productive rate 81%.
The preparation of embodiment 13 and metal Cu coordinate olefin polymerization catalysis
With Cu (OAc) 2H2O of 0.098g (0.49mmol) and the 7-hydroxy-3 of 0.327g (0.98mmol), (N-2 6-diisopropylphenylimine) joins in the dehydrated alcohol of 25mL 4-dimethylindan-1-, reflux 5 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown solid 0.246g, productive rate 78%.
Embodiment 14 and the addition polymerization of metal Ni coordinate olefin polymerization catalysis catalysis norbornylene
Under N2, add the Ni title complex 0.2 μ mol that is dissolved in the chlorobenzene by preparation among the embodiment 7, be dissolved in the norbornene monomer 0.91g in the chlorobenzene, methylaluminoxane (MAO) 0.6mL.The maintenance cumulative volume is 10mL.At 40 ℃ of following polymerization 10min.Stop polyreaction with the ethanol that contains 10%HCl, filter, in a vacuum in 60 ℃ of dryings 30 hours, weighing obtains the 0.69g polymkeric substance with white solid.Catalytic activity is 2.07 * 107gPNBmol-1Nih-1.
Embodiment 15 and the addition polymerization of metal Cu coordinate olefin polymerization catalysis catalysis norbornylene
Under N2, add the Cu title complex 1.0 μ mol that are dissolved in the chlorobenzene by preparation among the embodiment 13, be dissolved in the norbornene monomer 0.95g in the chlorobenzene, methylaluminoxane (MAO) 0.5mL.The maintenance cumulative volume is 10mL.At 30 ℃ of following polymerization 60min.Stop polyreaction with the ethanol that contains 10%HCl, filter, in a vacuum in 60 ℃ of dryings 30 hours, weighing obtains the 0.11g polymkeric substance with white solid.Catalytic activity is 1.1 * 105gPNBmol-1Cuh-1.

Claims (3)

1, a kind of olefin polymerization catalysis, the component expression formula that it is characterized in that this catalyzer is L 2M, L represent to contain can with post transition metal coordination 0, the bitooth ligand of N atom, M represents two valence state rear transition metal Ni or Cu, concrete structure is:
Figure A2007100400160002C1
Wherein: M is Ni or Cu; R 1A kind of in hydrogen, methyl or the tertiary butyl, R 2Be in hydrogen, methyl or the halogens any one, R 3Be in hydrogen or the methyl any one, R 4, R 5A kind of in hydrogen, chlorine, methyl or the sec.-propyl;
2, a kind of preparation method of olefin polymerization catalysis as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) hydroxy indene kitimine part is synthetic: under the environment of anhydrous and oxygen-free, get and contain substituent 7-hydroxy indene ketone, add excessive aniline or substituted aniline, under acid catalysis, reacted 44-50 hour, and obtained containing various substituent hydroxy indene kitimine parts; Its structural formula is as follows:
Figure A2007100400160002C2
Wherein: M is Ni or Cu; R 1A kind of in hydrogen, methyl or the tertiary butyl, R 2Be in hydrogen, methyl or the halogens any one, R 3Be in hydrogen or the methyl any one, R 4, R 5A kind of in hydrogen, chlorine, methyl or the sec.-propyl;
Work as R 1=R 4=R 5During=H, above-mentioned reaction solvent for use is an absolute ethanol, and used acid is the formic acid of catalytic amount, and adds the 4A molecular sieve; To reflux during reaction; After reaction finishes, reaction mixture is filtered, concentrated filtrate then as eluent, as stationary phase, carries out column chromatography with silica gel with the mixing solutions of sherwood oil and ethyl acetate, just obtains hydroxy indene kitimine part;
Work as substituent R 1, R 4And R 5In have one above-mentioned reaction solvent for use be a toluene when the hydrogen atom, used acid is excessive TiCl 4Temperature of reaction is 85-90 ℃; After reaction finished, reaction solution was poured Na into 2CO 3Saturated aqueous solution, separatory concentrates organic phase, as eluent, as stationary phase, carries out column chromatography with silica gel with the mixing solutions of sherwood oil and ethyl acetate, just can obtain hydroxy indene kitimine part;
(2) Preparation of catalysts: with Ni (OAc) 24H 2O or Ni (AcAc) 2Join in the dehydrated alcohol with the hydroxy indene kitimine part of twice molar weight, backflow 3-5 hour, produce solid, filter, collect solid, washing, under vacuum dry 20-28 hour then, perhaps obtain the Ni coordinate olefin polymerization catalysis of [O, N] bitooth ligand and two valence states; Perhaps with Cu (OAc) 2H 2O or Cu (AcAc) 2Join in the dehydrated alcohol with the hydroxy indene kitimine part of twice molar weight, backflow 3-5 hour, produce solid, filter, collect solid, washing, under vacuum dry 20-28 hour then, obtain the Cu coordinate olefin polymerization catalysis of [O, N] bitooth ligand and two valence states.
3, the application of coordination olefin polymerization catalysis as claimed in claim 1 in producing polynorbornene.
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Cited By (7)

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CN101245117B (en) * 2008-02-28 2011-05-18 复旦大学 Method for producing verelite with [O,N] type catalyst of bidentate ligand coordinated with post-transition metal
CN102504056A (en) * 2011-10-09 2012-06-20 南昌大学 N,O-double ligand metal catalyst with stereo structure and preparation method
RU2487898C1 (en) * 2012-02-28 2013-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" Method of producing norbornene oligomers with terminal double bond
RU2487896C1 (en) * 2012-03-11 2013-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" Method for addition polymerisation of norbornene
RU2487895C1 (en) * 2012-02-28 2013-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" Method for addition polymerisation of norbornene
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101245117B (en) * 2008-02-28 2011-05-18 复旦大学 Method for producing verelite with [O,N] type catalyst of bidentate ligand coordinated with post-transition metal
CN102504056A (en) * 2011-10-09 2012-06-20 南昌大学 N,O-double ligand metal catalyst with stereo structure and preparation method
CN102504056B (en) * 2011-10-09 2014-07-16 南昌大学 N,O-double ligand metal catalyst with stereo structure and preparation method
RU2487898C1 (en) * 2012-02-28 2013-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" Method of producing norbornene oligomers with terminal double bond
RU2487895C1 (en) * 2012-02-28 2013-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" Method for addition polymerisation of norbornene
RU2487896C1 (en) * 2012-03-11 2013-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" Method for addition polymerisation of norbornene
CN103265564A (en) * 2013-05-13 2013-08-28 中南民族大学 Beta-ketimine coordinated binuclear copper complex as well as preparation method and application thereof
CN103265564B (en) * 2013-05-13 2016-04-06 中南民族大学 The dicopper complex4-amino-3 of beta-ketimine coordination, Preparation method and use
CN114585632A (en) * 2019-09-30 2022-06-03 Ptt全球化学股份有限公司 Catalyst composition for the manufacture of cyclic carbonates from CO2 and olefins

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