CN101240059A - Method for preparing norbornene open-loop translocation polymer or addition polymer - Google Patents
Method for preparing norbornene open-loop translocation polymer or addition polymer Download PDFInfo
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- CN101240059A CN101240059A CNA2008100343237A CN200810034323A CN101240059A CN 101240059 A CN101240059 A CN 101240059A CN A2008100343237 A CNA2008100343237 A CN A2008100343237A CN 200810034323 A CN200810034323 A CN 200810034323A CN 101240059 A CN101240059 A CN 101240059A
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Abstract
The invention pertains to chemical industry, particularly relates to a norbornene ring-opening metathesis polymer and preparation of addition polymer. Catalyst system is composed of two portions of A and B, A portion is trivalent iridium catalyst in half-sandwich structure, which is represented by formula Cp<SUP>*</SUP>IrL, wherein Cp<SUP>*</SUP> represents ligand of 1,2,3,4,5-Pentamethylcyclopentadiene, L represents bidentate ligand containing O, N heteroatom which is capable of coordinating with late transition metal; B portion is represented by methylaluminoxane (MAO) or modidied methylaluminoxane (MMAO). A portion of the invention is simple to prepare, stable in air. Purified norbornene ring-opening metathesis polymer and catalysate of addition polymer can be respectively obtained by regulating proportion of A and B portion.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the method that the novel half-sandwich three valence state iridium catalysts of a class prepare norbornene open-loop metathesis polymer and addition polymer.
Background technology
Norbornylene and derivative thereof can pass through 3 kinds of mode polymerizations, are respectively ring-opening metathesis polymerization, addition polymerization and cationoid polymerisation.Different polymerization methodses obtains having the norbornene polymer of different structure and character.Ring-opening metathesis polymerization has two kinds of catalyst system usually: a kind of is to form catalyst system with halogenide, oxide compound or the oxidation-halogenide of metals such as tungsten, molybdenum, rhenium, ruthenium and alkylating reagent and promotor; Another kind be after the catalyst system that constituted of transition metal carbene compound and some initiators.Still contain two keys in the resulting polymers chain, can fall by hydrogenation or the crosslinked material that is processed into different purposes.The addition polymerization mode of norbornylene has kept the twin nuclei in the monomer, opens the two keys in the monomer, is similar to traditional alkene addition polymerization.Catalyst system therefor mostly is luxuriant or the semi-metallocene title complex, and the catalyst system of some nickel, copper compound and promotor methylaluminoxane composition.Norbornylene addition homopolymer is a kind of polymkeric substance of unique properties; have excellent electric performance, extremely low water absorbability, good thermostability, higher tension fracture value and low-tension; metal had good adhesive; very strong anti-ultraviolet radiation ability; excellent optical property; in halogenated aryl hydrocarbon, have solvability preferably, be applied to microelectronic device, liquid-crystal display supercoat etc., also be used for resistant to elevated temperatures protective material.
It is reported that by the consumption that changes different promotors and regulate promotor, the title complex of some titaniums and cobalt can be used for preparing the polynorbornene mixture that contains ring-opening polymerization and addition polymerization product simultaneously.Yet, use to prepare these two kinds pure polynorbornene products respectively with a kind of catalyzer and also do not have report.
The rear transition metal iridic compound has been widely used in organic synthesis as a kind of effective catalyzer, as aldehyde ketone hydrogenation, alcohol dehydrogenase and some hydrocarbon activation and carbon carbon linked reaction.Along with people to the going deep into of late transition metal complex research, novel structure, the catalyzer of function novelty constantly comes out, the potential that enriches that complex of iridium shows aspect catalysis becomes the focus that people pay close attention to.
Summary of the invention
The purpose of this invention is to provide the method that a kind of novel half-sandwich three valence state iridium catalysts prepare norbornene polymer, by changing A in the catalyst system, B components contents ratio can be prepared the pure norbornene open-loop metathesis polymerization and the polymkeric substance of addition polymerization respectively.
Catalyst system is made up of A and B two portions, and A component expression formula is Cp
*IrL, Cp
*Expression pentamethyl-cyclopentadiene part, L represent to contain can with the heteroatomic bitooth ligand of O, N of post transition metal coordination, concrete structure is as follows:
Wherein: R
1Be one of hydrogen or sec.-propyl, R
2Be one of hydrogen or tertiary butyl.
The B component is expressed as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).
The present invention is to contain [the O of substituted radical, N] the hydroxy indene kitimine part of bidentate is starting raw material, pull out the lithium salts that hydrogen generates part with n-Butyl Lithium, the dimer with 0.5 equivalent pentamethyl-cyclopentadienyl iridium reacts again, 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 consumption of B component in catalyst system, can prepare pure norbornene open-loop metathesis polymer and addition polymer respectively.
The concrete preparation method of the catalyst system A component of [O, N] bitooth ligand and three valence state half-sandwich iridium catalyzer and rare ring-opening polymerization polymer of norborneol and addition polymer is as follows:
Synthesizing of 1 hydroxy indene kitimine part
Its structural formula is
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 48 hours.Then reaction system is carried out aftertreatment, just can obtain containing various substituent hydroxy indene kitimine parts.
Work as R
1=R
2During=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.Carry out aftertreatment after reaction finishes, be about to reaction mixture and filter, 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 can obtain hydroxy indene kitimine part.
Work as substituent R
1, R
2In have one above-mentioned reaction solvent for use be a toluene when the hydrogen atom, used acid is excessive TiCl
4Temperature of reaction is 90 ℃.Reaction is carried out aftertreatment after finishing, and is about to reaction solution and pours 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.
The preparation of 2 hydroxy indene kitimine parts and half-sandwich iridium coordinate olefin polymerization catalyst system A component
Under-78 ℃, hydroxy indene kitimine part is dissolved in the anhydrous tetrahydro furan, dropwise adds the hexane solution of the n-Butyl Lithium of monovalent, be warming up to room temperature gradually, continue to stir after 2 hours, solution is transferred to 0.5 equivalent [Cp
*IrCl (μ-Cl)]
2Tetrahydrofuran solution in, stirred 8 hours, staticly settle, remove by filter the LiCl precipitation, drain, wash with normal hexane, the toluene recrystallization obtains solid, under vacuum dry 24 hours then, just can obtain [O, N] bitooth ligand and iridium coordinate half-sandwich olefin polymerization catalyst system A component.
3, the preparation of norbornene open-loop metathesis polymer and addition polymer
Under the anhydrous and oxygen-free condition, the chlorobenzene solution that in reaction vessel, adds catalyst system A component in argon gas or the nitrogen atmosphere, the chlorobenzene solution of norbornylene and solvent chlorobenzene, under 0-130 ℃ the polymerization temperature, kept 5-20 minute, the toluene solution that adds catalyst system B component methylaluminoxane or modified methylaluminoxane then, initiated polymerization; When the mol ratio of adjusting B component and A is 5-30, system causes the ring-opening metathesis polymerization of norbornylene, when the mol ratio of adjusting B component and A component is 30-1000, system causes the addition polymerization of norbornylene, polymerization reaction time is 10-720 minute, then mixture is poured into coming stopped reaction in the methyl alcohol of hcl acidifying or the ethanolic soln, hydrochloric acid and methyl alcohol or alcoholic acid volume ratio are 5-20%, polymkeric substance is precipitated out with the solid form, filter, solid polymer water and methyl alcohol or washing with alcohol, vacuum-drying.
Half-sandwich three valence state iridium catalyst catalysis norbornene open-loop metathesis polymerizations
The norbornene open-loop metathesis polymerization carries out under the condition of anhydrous and oxygen-free.The chlorobenzene solution (1-50 μ mol) that adds catalyst system A component in argon gas or the nitrogen atmosphere downhill reaction container, stir and add the norbornylene chlorobenzene solution (0.63g/mL) of 1-20mL and the chlorobenzene of 2-30mL down, under 0-130 ℃ the polymerization temperature, kept 5-20 minute, the toluene solution that adds 0.003-1mL (Al/Ir=5-30) catalyst system B component methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) then, initiated polymerization, the polymerization reaction system cumulative volume remains on 5-100mL (different volumes useable solvents chlorobenzene is regulated), after polyreaction 10-720 minute, mixture is poured into coming stopped reaction in the methyl alcohol of hcl acidifying or the ethanolic soln, the consumption of hydrochloric acid is the 5-20% of methyl alcohol or ethanol volume, polymkeric substance is precipitated out with the solid form, filter, solid polymer is respectively with methyl alcohol or washing with alcohol 2-5 time, in vacuum at drying at room temperature 12-45 hour.The order of magnitude of high catalytic activity is 10
4GPEBmol
-1Irh
-1, the polynorbornene productive rate is 10-60%, the molecular weight of polynorbornene is 10
4Gmol
-1
Half-sandwich three valence state iridium catalyst catalysis norbornylene addition polymerizations
The norbornylene addition polymerization is carried out under the condition of anhydrous and oxygen-free.The chlorobenzene solution (1-50 μ mol) that adds catalyst system A component in argon gas or the nitrogen atmosphere downhill reaction container, stir and add the norbornylene chlorobenzene solution (0.63g/mL) of 1-20mL and the chlorobenzene of 2-30mL down, under 0-130 ℃ the polymerization temperature, kept 5-20 minute, the toluene solution that adds 1-33mL (Al/Ir=30-1000) catalyst system B component methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) then, initiated polymerization, the polymerization reaction system cumulative volume remains on 6-100mL (different volumes useable solvents chlorobenzene is regulated), after polyreaction 10-300 minute, mixture is poured into coming stopped reaction in the methyl alcohol of hcl acidifying or the ethanolic soln, the hydrochloric acid consumption is the 5-20% of methyl alcohol or ethanol volume, polymkeric substance is precipitated out with the solid form, filter, solid polymer is respectively with methyl alcohol or washing with alcohol 2-5 time, in vacuum at drying at room temperature 12-45 hour.The order of magnitude of high catalytic activity is 10
4GPEBmol
-1Irh
-1, the molecular weight of polynorbornene is 10
5Gmol
-1
Among the present invention, the consumption of catalyst system A component is 1-50 μ mol in the reaction system.
Among the present invention, the consumption that is used for the catalyst system B component of norbornene open-loop metathesis polymerization is B component/A component=5-30 (mole number)
Among the present invention, the consumption that is used for the catalyst system B component of norbornylene addition polymerization is B component/A component=30-1000 (mole number)
Among the present invention, the methyl alcohol of hcl acidifying or the proportioning of ethanolic soln are that hydrochloric acid and methyl alcohol or alcoholic acid volume ratio are 5-20%, i.e. alcohol/dense HCl=95/5-80/20 (volume ratio).
The present invention adopts the norbornene open-loop metathesis polymerization and the addition polymerization catalyst system A component of the novel half-sandwich three valence state iridium catalysts with special catalytic performance, realized using with two kinds of polymerization methodses of a kind of catalyst system catalysis norbornylene, obtained the norbornene open-loop metathesis polymer and the addition polymer of intermediate molecular weight.
Description of drawings
Fig. 1 is the crystalline structure figure with metal Ir coordinate olefin polymerization catalysis precursor.
Embodiment
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%.
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%.
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 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 orange red solid 2.75g, productive rate 45%.
The preparation of embodiment 4 and the agent of metal Ir coordinate norbornene polymerization catalyst
Under-78 ℃ with part, (C
6H
5) N=CC
2H
3(CH
3) C
6H
2(CH
3) OH 0.11g (0.41mmol) is dissolved in the anhydrous tetrahydro furan, dropwise add 0.28mL (1.6M, the 0.45mmol) hexane solution of n-Butyl Lithium, be warming up to room temperature gradually after, continue to stir 2 hours, solution is transferred to 0.16g (0.2mmol) [Cp
*IrCl (μ-Cl)]
2Tetrahydrofuran solution in, stirred 8 hours, staticly settle, remove by filter LiCl precipitation, drain, with the normal hexane washing, the toluene recrystallization obtains solid, under vacuum dry 24 hours then, output 0.20g, productive rate 80%.
The preparation of embodiment 5 and the agent of metal Ir coordinate norbornene polymerization catalyst
Under-78 ℃ with part, [C
6H
3-i-(C
3H
7)
2-2,6] N=CC
2H
3(CH
3) C
6H
2(CH
3) OH 0.144g (0.41mmol) is dissolved in the anhydrous tetrahydro furan, dropwise add 0.28mL (1.6M, the 0.45mmol) hexane solution of n-Butyl Lithium, be warming up to room temperature gradually after, continue to stir 2 hours, solution is transferred to 0.16g (0.2mmol) [Cp
*IrCl (μ-Cl)]
2Tetrahydrofuran solution in, stirred 8 hours, staticly settle, remove by filter LiCl precipitation, drain, with the normal hexane washing, the toluene recrystallization obtains solid, under vacuum dry 24 hours then, output 0.25g, productive rate 87%.
The preparation of embodiment 6 and the agent of metal Ir coordinate norbornene polymerization catalyst
Under-78 ℃ with part, (C
6H
5) N=CC
2H
3(CH
3) C
6H
2(CH
3) (C
4H
9) OH 0.132g (0.41mmol) is dissolved in the anhydrous tetrahydro furan, dropwise add 0.28mL (1.6M, the 0.45mmol) hexane solution of n-Butyl Lithium, be warming up to room temperature gradually after, continue to stir 2 hours, solution is transferred to 0.16g (0.2mmol) [Cp
*IrCl (μ-Cl)]
2Tetrahydrofuran solution in, stirred 8 hours, staticly settle, remove by filter LiCl precipitation, drain, with the normal hexane washing, the toluene recrystallization obtains solid, under vacuum dry 24 hours then, output 0.23g, productive rate 81%.
At N
2Down, add the half-sandwich Ir title complex 5 μ mol that are dissolved in the chlorobenzene, be dissolved in the norbornene monomer 1.36g in the chlorobenzene, methylaluminoxane (MAO) 0.017mL by preparation among the embodiment 5.The maintenance cumulative volume is 5mL.At 60 ℃ of following polymerization 15min.Stop polyreaction with the ethanol that contains 10%HCl, filter, with white solid dry 24 hours in a vacuum, weighing obtained the 0.056g polymkeric substance, and catalytic activity is 4.48 * 10
4GPNBmol
-1Irh
-1
At N
2Down, add the Ir title complex 1 μ mol that is dissolved in the chlorobenzene, be dissolved in the norbornene monomer 1.36g in the chlorobenzene, methylaluminoxane (MAO) 2mL by preparation among the embodiment 5.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 0.028g polymkeric substance with white solid.Catalytic activity is 2.8 * 10
4GPNBmol
-1Irh
-1
Claims (3)
1, the preparation method of a kind of norbornene open-loop metathesis polymer or addition polymer, it is characterized in that concrete steps are as follows: under the anhydrous and oxygen-free condition, the chlorobenzene solution that in reaction vessel, adds catalyst system A component in argon gas or the nitrogen atmosphere, the chlorobenzene solution of norbornylene and solvent chlorobenzene, under 0-130 ℃ the polymerization temperature, kept 5-20 minute, and added the toluene solution of catalyst system B component methylaluminoxane or modified methylaluminoxane then, initiated polymerization; When the mol ratio of adjusting B component and A was 5-30, system caused the ring-opening metathesis polymerization of norbornylene, and when the mol ratio of adjusting B component and A component was 30-1000, system caused the addition polymerization of norbornylene; Polymerization reaction time is 10-720 minute, then mixture is poured into coming stopped reaction in the methyl alcohol of hcl acidifying or the ethanolic soln, hydrochloric acid and methyl alcohol or alcoholic acid volume ratio are 5-20%, polymkeric substance is precipitated out with the solid form, filter, solid polymer water and methyl alcohol or washing with alcohol, vacuum-drying;
Wherein, in the catalyst system, the A component is three valence state iridium catalysts of half-sandwich, and its expression formula is Cp
*IrL, Cp
*Expression pentamethyl-cyclopentadiene part, L represent to contain can with [O, N] heteroatoms bitooth ligand of post transition metal coordination, concrete structure is as follows:
Wherein: R
1Be one of hydrogen or sec.-propyl, R
2Be one of hydrogen or tertiary butyl.
2, a kind of preparation method as claimed in claim 1, the preparation process that it is characterized in that the catalyst A component is: to contain [the O of substituted radical, N] the hydroxy indene kitimine part of bidentate is starting raw material, in tetrahydrofuran (THF), pull out the lithium salts that hydrogen generates part with n-Butyl Lithium, dimer with 0.5 equivalent pentamethyl-cyclopentadienyl iridium reacts again, promptly obtains the A component in the corresponding catalyst system.
3, preparation method as claimed in claim 1 is characterized in that solid polymer water and methyl alcohol respectively, and perhaps water and washing with alcohol number of times are 2-5 time, and the vacuum-drying temperature is 50-80 ℃, and the time is 12-45 hour.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544711B (en) * | 2009-05-07 | 2011-11-02 | 复旦大学 | Non-bridging semi-sandwich chromium olefinic polymerization catalyst, preparation method thereof and application thereof |
| CN109824737A (en) * | 2019-03-20 | 2019-05-31 | 上海应用技术大学 | A kind of half sandwich complex of iridium and its preparation and application |
-
2008
- 2008-03-06 CN CNA2008100343237A patent/CN101240059A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544711B (en) * | 2009-05-07 | 2011-11-02 | 复旦大学 | Non-bridging semi-sandwich chromium olefinic polymerization catalyst, preparation method thereof and application thereof |
| CN109824737A (en) * | 2019-03-20 | 2019-05-31 | 上海应用技术大学 | A kind of half sandwich complex of iridium and its preparation and application |
| CN109824737B (en) * | 2019-03-20 | 2021-03-05 | 上海应用技术大学 | Half-sandwich iridium complex and preparation and application thereof |
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Open date: 20080813 |