CN100549045C - A kind of method of preparing polynorborene by alkene polymerization catalytic - Google Patents
A kind of method of preparing polynorborene by alkene polymerization catalytic Download PDFInfo
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- CN100549045C CN100549045C CNB2007100400216A CN200710040021A CN100549045C CN 100549045 C CN100549045 C CN 100549045C CN B2007100400216 A CNB2007100400216 A CN B2007100400216A CN 200710040021 A CN200710040021 A CN 200710040021A CN 100549045 C CN100549045 C CN 100549045C
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Abstract
The invention belongs to chemical technology field, be specially a kind of method of preparing polynorborene by alkene polymerization catalytic.This method [O, N] title complex of type bitooth ligand and two valence state post transition metal coordinations carries out the addition polymerization of norbornylene as catalyst system A component, polyreaction is carried out under the condition of anhydrous and oxygen-free, concrete steps are, the chlorobenzene or the toluene solution that in nitrogen or argon atmosphere downhill reaction container, add the A component, stir and add the chlorobenzene solution of norbornylene and the chlorobenzene of certain volume, polyreaction certain hour down; The toluene solution that adds B component methylaluminoxane or modified methylaluminoxane then, initiated polymerization, methyl alcohol or the ethanolic soln with hcl acidifying comes stopped reaction then; Polymkeric substance is precipitated out with the solid form, filters, and water and methyl alcohol or washing with alcohol, vacuum-drying promptly gets required polynorbornene product.The inventive method can obtain the polymkeric substance of high molecular, high glass transition temperature, and polymkeric substance has good solubility.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of method of preparing polynorborene by alkene polymerization catalytic.
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.
Norbornylene has three kinds of polymerization methodses: ring-opening metathesis polymerization, positively charged ion or radical polymerization and addition polymerization.Nineteen fifty-five, people such as Anderson and Merckling have started the ring-opening metathesis polymerization of norbornylene, have kept two keys in the polymkeric substance of gained, can be processed into the material of different purposes by hydrogenation or means such as crosslinked.At present, the catalyst system that uses in the business-like ring-opening metathesis polymerization technology is RuCl
3/ HCl.And the positively charged ion of relevant norbornylene or radical polymerization are studied seldom, and this polymerization methods mainly obtains the oligopolymer of low-molecular-weight 2,7 connections.1963, Sartori etc. at first carried out the research with the catalyst system catalysis norbornylene addition polymerization of metal titanium, but catalytic activity is not high, and the resulting polymers molecular weight is low.At beginning of the nineties late 1980s, discoveries such as Kaminsky can be carried out addition polymerization by the catalysis norbornylene with metallocene/methylaluminoxane catalyst system, and the resulting polymers Heat stability is good does not melt processing difficulties but polymkeric substance is insoluble.Although the rear transition metal palladium catalyst is used to the polyaddition reaction of norbornylene more for a long time, the addition polymerization research that late transition metal catalyst is used for norbornylene on a large scale then starts from the nineties in 20th century.1993, Novak etc. reported that the title complex of first nickel is used for the addition polymerization research of norbornylene, and resulting polymers can be dissolved in the organic solvent well, and this provides huge convenience for the sign and the processing of polymkeric substance.Subsequently, the title complex of rear transition metal nickel, palladium and cobalt is used to the addition polymerization of norbornylene in a large number.2006, the title complex of rear transition metal copper also was used to the addition polymerization of norbornylene.Because the polynorbornene that addition polymerization obtains has a series of uniquenesses and interesting physicochemical property; the good solvability in halogenated aryl hydrocarbon for example; high chemical impedance; good ultraviolet impedance; low-k; high glass transition temperature; good light transmission; high specific refractory power and low-birefringence etc.; thereby this base polymer has excellent electric performance; extremely low water absorbability; good thermostability; higher tension fracture value; have very strong anti-ultraviolet radiation ability and excellent optical property; 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 objective of the invention is a kind ofly have high molecular, high glass transition temperature, and good solubility and unique physical chemical property are arranged, the preparation method of the polynorbornene that has wide range of applications.
The preparation method of the norbornylene that the present invention proposes, with [O, N] title complex of type bitooth ligand and two valence state post transition metal coordinations carries out the addition polymerization of norbornylene as catalyst system A component, polyreaction is carried out under the condition of anhydrous and oxygen-free, concrete steps are, the chlorobenzene or the toluene solution that in nitrogen or argon atmosphere downhill reaction container, add catalyst system A component, stir and add the chlorobenzene solution of norbornylene and the chlorobenzene of certain volume down, under 0-90 ℃ the polymerization temperature, kept 5-20 minute; The toluene solution that adds catalyst system B component methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) then, initiated polymerization, after polyreaction 1-300 minute, mixture is poured into coming stopped reaction in the methyl alcohol of the hcl acidifying of 5-20% volume or the ethanolic soln; Polymkeric substance is precipitated out with the solid form, filters, and solid water and methyl alcohol or washing with alcohol, vacuum-drying promptly gets required polynorbornene product.Catalyst system A component wherein: norbornylene: catalyst system B component=1: 3000-200000: 300-10000 (mol ratio).
Wherein the olefin polymerization catalyst system A component structure of [O, N] type bitooth ligand and two valence state post transition metal coordinations is:
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 for hydrogen, chlorine, methyl or sec.-propyl.
Among the present invention, the preparation method of catalyst system A component is as follows: with the 7-hydroxy indene ketone that contains substituted radical and aniline or substituted aniline is starting raw material, synthesize and have [O, N] the hydroxy indene kitimine part of bidentate, the hydration nickelous acetate or the acetylacetonate nickel of part and 0.5 times of molar weight then; Perhaps hydrated copper acetate or acetylacetone copper reaction just can obtain the A component in the corresponding catalyst system.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.
Above-mentioned catalyst system is made up of A component and B component two portions.A 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; The B component is expressed as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).
The olefin polymerization catalysis catalysis norbornylene polyaddition reaction of [O, N] type bitooth ligand and two valence state post transition metal coordinations with the experiment be example more specifically the preparation method be described below.
1) be example with [O, N] type bitooth ligand and two valence state rear transition metal Ni coordinate olefin polymerization catalysis: the norbornylene addition polymerization is carried out under the condition of anhydrous and oxygen-free.The chlorobenzene solution (0.1-2 μ mol) that adds catalyst system A component in nitrogen or the argon atmosphere downhill reaction container, stir and add the chlorobenzene solution (10-200mmol) of 2-30mL norbornylene and the chlorobenzene of 2-30mL down, under 0-90 ℃ the polymerization temperature, kept 5-20 minute; The toluene solution that adds 0.04-1.32mL (Al/Ni=10000-300) catalyst system B component methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) then, initiated polymerization, the polymerization reaction system cumulative volume remains on 10-100mL (different volumes useable solvents chlorobenzene is regulated), after polyreaction 1-300 minute, mixture is poured into coming stopped reaction in the methyl alcohol of the hcl acidifying of 5-20% volume or the ethanolic soln; Polymkeric substance is precipitated out with the solid form, filters, and solid polymer difference water and methyl alcohol or washing with alcohol 3 times were descended dry 25-45 hour at 50-80 ℃ in vacuum, promptly obtained required polynorbornene.The order of magnitude of catalytic activity is 10
7GPNBmol
-1Nih
-1, the molecular weight of polynorbornene is 10
6Gmol
-1
2) be example with [0, N] type bitooth ligand and two valence state rear transition metal Cu coordinate olefin polymerization catalysis: the norbornylene addition polymerization is carried out under the condition of anhydrous and oxygen-free.The chlorobenzene or the toluene solution (0.1-4 μ mol) that add catalyst system A component in nitrogen or the argon atmosphere downhill reaction container, stir and add the chlorobenzene solution (10-400mmol) of 2-30mL norbornylene and the chlorobenzene of 2-30mL down, under 0-90 ℃ the polymerization temperature, kept 5-20 minute, the toluene solution that adds 0.04-1.32mL (Al/Cu=10000-300) catalyst system B component methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) then, initiated polymerization, the polymerization reaction system cumulative volume remains on 10-100mL (different volumes useable solvents chlorobenzene is regulated), after polyreaction 1-300 minute, mixture is poured into coming stopped reaction in the methyl alcohol of the hcl acidifying of 5-20% volume or the ethanolic soln; Polymkeric substance is precipitated out with the solid form, filters, and solid polymer difference water and methyl alcohol or washing with alcohol 2-5 time were descended dry 25-45 hour at 50-80 ℃ in vacuum.The order of magnitude of catalytic activity is 10
4-10
5GPNBmol
-1Cuh
-1, the molecular weight of polynorbornene is 10
6Gmol
-1
Among the present invention, the consumption of catalyst system A component is 0.1-4 μ mol in the reaction system.
Among the present invention, the methyl alcohol of hcl acidifying or the proportioning of ethanolic soln are that the volume ratio of hydrochloric acid and alcohol is 5-20%, i.e. alcohol/dense HCl=100/5-100/20 (volume ratio).
Among the present invention, solid polymer is water and methyl alcohol or washing with alcohol 2-5 time respectively, 50-80 ℃ following vacuum-drying 25-45 hour.
Among the present invention, the polymerization temperature scope is 0-90 ℃, and the polymerization time scope is 1-300 minute.
Among the present invention, B component in the catalyst system/A component=300-10000 (mol ratio).
The present invention adopts the class [O with high catalytic activity, N] the olefin polymerization catalyst system A component of type bitooth ligand and two valence state post transition metal coordinations, the polynorbornene product that has obtained high molecular, high glass transition temperature, good solubility and unique physical chemical property have been arranged, have wide range of applications.
Embodiment
Embodiment 1 part 7-hydroxyl-3, the preparation of 4-dimethyl indone-1-phenyl imine
At N
2Down, 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 48 hours.After reaction finishes, filter, collect filtrate, use anhydrous Mg
2SO
4Drying concentrates, and crosses silicagel column with the mixing solutions of sherwood oil and ethyl acetate as eluent, obtains yellow solid 2.3g, productive rate 80%.
Embodiment 2 part 7-hydroxyls-3, the preparation of 4-dimethyl indone-1-(2, the 6-di-isopropyl) phenyl imine
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 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 1.54g, productive rate 40%.
The preparation of embodiment 3 and metal Ni coordinate olefin polymerization catalysis
Ni (OAc) with 0.122g (0.49mmol)
24H
2The 7-hydroxyl-3 of O and 0.245g (0.98mmol), 4-dimethyl indone-1-phenyl imine 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 4 and metal Ni coordinate olefin polymerization catalysis
Ni (OAc) with 0.122g (0.49mmol)
24H
2The 7-hydroxyl-3 of O and 0.327g (0.98mmol), 4-dimethyl indone-1-(2, the 6-di-isopropyl) phenyl imine joins in the dehydrated alcohol of 20mL 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 5 and metal Cu coordinate olefin polymerization catalysis
Cu (OAc) with 0.098g (0.49mmol)
2H
2The 7-hydroxyl-3 of O and 0.245g (0.98mmol), 4-dimethyl indone-1-phenyl imine 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 6 and metal Cu coordinate olefin polymerization catalysis
Cu (OAc) with 0.098g (0.49mmol)
2H
2The 7-hydroxyl-3 of O and 0.327g (0.98mmol), 4-dimethyl indone-1-(2, the 6-di-isopropyl) phenyl imine joins in the dehydrated alcohol of 25mL reflux 5 hours.After the cooling, filter, collect solid, dry under vacuum.Obtain brown solid 0.246g, productive rate 78%.
Embodiment 7 and the addition polymerization of metal Ni coordinate olefin polymerization catalysis catalysis norbornylene
At N
2Down, add the Ni title complex 0.2 μ mol that is dissolved in the chlorobenzene, be dissolved in the norbornene monomer 0.91g in the chlorobenzene, methylaluminoxane (MAO) 0.6mL by preparation among the embodiment 4.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 * 10
7GPNBmol
-1Nih
-1, the polymkeric substance viscosity-average molecular weight is 1.32 * 10
6Gmol
-1
Embodiment 8 and the addition polymerization of metal Ni coordinate olefin polymerization catalysis catalysis norbornylene
At N
2Down, add the Ni title complex 0.2 μ mol that is dissolved in the chlorobenzene, be dissolved in the norbornene monomer 0.91g in the chlorobenzene, methylaluminoxane (MAO) 1.0mL by preparation among the embodiment 3.The maintenance cumulative volume is 10mL.At 35 ℃ 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 0.53g polymkeric substance with white solid.Catalytic activity is 1.95 * 10
7GPNBmol
-1Nih
-1, the polymkeric substance viscosity-average molecular weight is 1.53 * 10
6Gmol
-1
Embodiment 10 and the addition polymerization of metal Cu coordinate olefin polymerization catalysis catalysis norbornylene
At N
2Down, add the Cu title complex 1.0 μ mol that are dissolved in the chlorobenzene, be dissolved in the norbornene monomer 0.95g in the chlorobenzene, methylaluminoxane (MAO) 0.7mL by preparation among the embodiment 5.The maintenance cumulative volume is 10mL.At 40 ℃ 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 0.95 * 10
5GPNBmol
-1Cuh
-1, the polymkeric substance viscosity-average molecular weight is 1.23 * 10
6Gmol
-1
Embodiment 10 and the addition polymerization of metal Cu coordinate olefin polymerization catalysis catalysis norbornylene
At N
2Down, add the Cu title complex 1.0 μ mol that are dissolved in the chlorobenzene, be dissolved in the norbornene monomer 0.95g in the chlorobenzene, methylaluminoxane (MAO) 0.5mL by preparation among the embodiment 6.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 * 10
5GPNBmol
-1Cuh
-1, the polymkeric substance viscosity-average molecular weight is 1.03 * 10
6Gmol
-1
Claims (3)
1, a kind of method of preparing polynorborene by alkene polymerization catalytic, it is characterized in that with [O, N] title complex of type bitooth ligand and two valence state post transition metal coordinations carries out the addition polymerization of norbornylene as catalyst system A component, polyreaction is carried out under the condition of anhydrous and oxygen-free, concrete steps are: the chlorobenzene or the toluene solution that add catalyst system A component in nitrogen or argon atmosphere downhill reaction container, stir the chlorobenzene solution and the chlorobenzene that add norbornylene down, under 0-90 ℃ the polymerization temperature, kept 5-20 minute; The toluene solution that adds catalyst system B component methylaluminoxane or modified methylaluminoxane then, initiated polymerization, after polyreaction 1-300 minute, mixture is poured into coming stopped reaction in the methyl alcohol of the hcl acidifying of 5-20% volume or the ethanolic soln; Polymkeric substance is precipitated out with the solid form, filters, and solid water and methyl alcohol or washing with alcohol, vacuum-drying promptly gets polynorbornene; Wherein:
Catalyst system A component: norbornylene: the mol ratio of catalyst system B component is 1: 3000-200000: 300-10000, mole;
Catalyst system A component structure is:
Here: M is Ni or Cu; R
1A kind of in hydrogen, methyl or the tertiary butyl, R
2For in hydrogen, methyl or the halogens any one, R
3For in hydrogen or the methyl any one, R
4, R
5A kind of in hydrogen, chlorine, methyl or the sec.-propyl.
2, the method for preparing polynorborene by alkene polymerization catalytic according to claim 1, it is characterized in that M is Ni in the catalyst system A component, the consumption of described A component is 0.1-2 μ mol, and content is that the chlorobenzene solution add-on of the norbornylene of 10-20mmol is 2-30mL; The toluene solution add-on of described B component is 0.04-1.32mL; 50-80 ℃ of described vacuum-drying temperature; Be 25-45 hour time of drying.
3, the method for preparing polynorborene by alkene polymerization catalytic according to claim 1, it is characterized in that M is Cu in the catalyst system A component, described A amounts of components is 0.1-4 μ mol, and content is that the chlorobenzene solution add-on of the norbornylene of 10-400mmol is 2-30mL; The toluene solution add-on of B component is 0.04-1.32mL; 50-80 ℃ of described vacuum-drying temperature; Be 25-45 hour time of drying.
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| 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 |
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| CN105542078B (en) * | 2016-03-10 | 2018-03-09 | 宁波工程学院 | Norborneol alkenes, phenylethylene and tetrafluoroethylene triple catalyst for copolymerization and method for ternary polymerization |
| WO2021066756A2 (en) * | 2019-09-30 | 2021-04-08 | Ptt Global Chemical Public Company Limited | Catalyst composition for cyclic carbonate production from co2 and olefins |
| US20220379290A1 (en) * | 2019-09-30 | 2022-12-01 | Ptt Global Chemical Public Company Limited | Catalyst composition for cyclic carbonate production from co2 and epoxides |
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| 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 |
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