CN1200010C - Method for preparing vinyl monomer polymer using metallorene free-radical polymerization catalyst - Google Patents
Method for preparing vinyl monomer polymer using metallorene free-radical polymerization catalyst Download PDFInfo
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- CN1200010C CN1200010C CN 03130135 CN03130135A CN1200010C CN 1200010 C CN1200010 C CN 1200010C CN 03130135 CN03130135 CN 03130135 CN 03130135 A CN03130135 A CN 03130135A CN 1200010 C CN1200010 C CN 1200010C
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Abstract
The present invention relates to a method for preparing vinyl monomer polymers by metallocene radical polymerization catalysts. Vinyl monomer polymerization reaction is carried out in organic solvent under the existence of dicyclopentadienyl metallocene compound catalysts, initiators and inert gas. The proportion of the organic compound halide initiators and the catalysts is 1 to 3, argon shield is adopted, and the temperature for polymerization reaction is from 60 to 90 DGE C. General vinyl monomers can carry out active radical polymerization reaction, polymers with molecular weight within 1000 to 100000, controllable molecular weight and narrow molecular weight distribution and controllable polymers in a block structure, a graft structure, etc. can be obtained, and favorable conditions are created for the industrialization application of active radical polymerization reaction.
Description
Technical field
The present invention relates to a kind of novel active free radical polymerization catalyzer, particularly prepare the method for polymers of vinyl monomers with the metallocene catalysts for radical polymerization.
Background technology
Because living polymerization can be controlled the structure of macromolecular compound, the synthetic various useful special constructions and the macromolecular material of performance, its industrialization has huge social and economic benefit.In numerous living polymerization modes, radical living polymerization uses monomer scope wide with it, the implementation condition gentleness, helps many tangible advantages such as suitability for industrialized production, therefore has been subjected to people's great attention in this technology in recent years.Nineteen ninety-five American Krzysztof Matyjaszewski (J.Am.Chem.Soc.1995,117,5614) and Japanese Mitsuo Sawamoto (Macromolecules 1995,28,1721) taken the lead in reporting living free radical polymerization styrene catalyzed with transition-metal catalyst and methyl methacrylate, made transition metal-catalyzed active free radical polymerization become one of most active research field of Polymer Synthesizing in recent years.Up to now, existing a lot of transition-metal catalysts are used for living free radical polymerization (Krzysztof Matyjaszewski, Chem.Rev.2001,101,2921; Mitsuo Sawamoto, Chem.Rev.2001,101,3689).But, still there are many weakness in the present catalyzer of developing, and is lower as controllable molecular weight, and it is just out of hand that in a single day molecular weight reaches the level of industrial application, can not be used for the low activity monomer effectively simultaneously.The existence of these problems makes people still seek new catalyst system when improving existing catalyst system.
Metallocene compound is the highly stable organometallics of a class, and the polycomplexation merging that crooked sandwich metallocene IVB compounds of group has been widely used in alkene has realized suitability for industrialized production.For two luxuriant class metallocene compounds of classics, the existing report of the monomeric photopolymerization reaction of catalyzed ethylene base (Imoto, M. under the initiation of several halohydrocarbon; Ouchi, T.; Tanaka, T.J.Polym.Sci., Polym.Lett.Ed.1974,12,21; Tsubakiyama, K.; Fujisaki, S.J.Polym.Sci., Polym.Lett.Ed.1972,10,341; McGinniss, V.D.; Stevenson, D.Polym.Prepr.1974,15,302; Woo, H.-G.; Park, J.-Y.; Hong, L.-Y.; Yang, S.-Y.; You, H.; Ham, H.-S.Bull.Korean Chem.Soc.1996,17,412), but, polymerization is not controlled, molecular weight distribution is all more than 2.Korean Hee-Gweon Woo (Bull.Korean Chem.Soc.2002,23,1343) reported the catalyzing propone acid free radical thermopolymerization under the initiation of several halohydrocarbon of two luxuriant class metallocene compounds, but do not obtained the result of living polymerization, and speed of response is slow.Therefore, we openly use the achievement in research of sandwich two classical luxuriant class metallocene compound catalyzed ethylene base monomer reactivity radical polymerizations here.
Summary of the invention
The object of the present invention is to provide a kind ofly to prepare the method for polymers of vinyl monomers, can overcome above-mentioned shortcoming, thereby open class one zone not in the efficient catalyst of catalyzer in the past with the metallocene catalysts for radical polymerization.The present invention prepares the method for polymers of vinyl monomers, may command molecule amount and molecular weight distribution.
The present invention be in view of two luxuriant class metallocene compounds are organometallicss that a kind of metal center is in lower valency, but it be easy to and halohydrocarbon effect generation inverted electron transfer, form free radical, thereby realize active free radical polymerization.
The present invention includes:
1) metallocene compound of two luxuriant sandwich structures with general formula (I) is as the catalyzer of living free radical polymerization:
Wherein: R is a hydrogen atom, or a kind of in identical or different aliphatics substituting group that contains 1 to 10 carbon or the aromatic substituents; Two adjacent R groups can Cheng Huan, comprises the aliphatics substituting group that contains 1 to 10 carbon, the indenyl or the tetrahydro indenyl of aromatic substituents, or fluorenyl or octahydrofluorenyl; M is a kind of in iron, cobalt, nickel, ruthenium, rhodium, vanadium, chromium, the manganese;
2) have (II) or (III) the general formula halogenated organic compounds as initiator:
Wherein: R
1, R
2And R
3Can be identical or different, be respectively hydrogen atom, contain aliphatics, aromatic substituents a kind of of 1 to 10 carbon; X is a kind of in chlorine, bromine, the iodine; Described initiator is in particular alpha-brominated ethyl isobutyrate or alpha-brominated ethylbenzene.
In the presence of above-mentioned catalyzer, initiator and rare gas element, in organic solvent, carry out the polymerization of vinyl monomer reaction.
Described vinyl monomer is a kind of in styrenic, α, beta-unsaturated esters class, ketone, amides, nitrile compounds or their derivative; Be in particular vinylbenzene or methyl methacrylate.
Catalyzer described in the described method for preparing polymers of vinyl monomers is the cobalt compounds particularly:
Organic solvent in the described method for preparing polymers of vinyl monomers is a toluene.
It is the reaction of initiator initiating polymerization of vinyl monomer that the said catalyzer of the present invention can be used for the halogenated organic compounds thing, and using method is as follows:
With catalyzer; initiator; monomer; solvent joins in the Schlenk reaction flask by proportioning; under liquid nitrogen freezing,, then under argon shield, in 60～90 ℃ of scopes, carried out polymerization in 24～100 hours repeatedly by vacuumizing, thaw, vacuumize deoxygenation; the polymkeric substance that obtains is handled with ordinary method, obtains the polymkeric substance that needs.
The catalyzer add-on is relevant with the initiator add-on, and add-on is:
Initiator: catalyzer=1～3 (mol ratio).
Of the present invention two luxuriant type metallocene catalysts conveniently are easy to get, and are easy to preserve.Adopt the used catalyzer of the present invention in the presence of radical polymerization initiator commonly used, can make general vinyl monomer (60～90 ℃) in the experimental temperature of broad carry out living free radical polymerization, obtain molecular weight in 1000～100000 scopes, molecular weight is controlled and the polymkeric substance of narrow molecular weight distribution (especially the polymethylmethacrylate molecular weight distribution can reach about 1.1), and the polymkeric substance of controllable structure such as block, grafting, for the industrial applications of living free radical polymerization has been created good condition.
Embodiment
Below will the present invention is further elaborated by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
The 57mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 5mL toluene, 6.858g vinylbenzene and the alpha-brominated ethyl isobutyrate of 62mg by injection technique, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 96 hours down at 60 ℃, and monomer conversion is 37.7%.The polymkeric substance that obtains is analyzed through gel permeation chromatography (GPC), and molecular weight is 16900, and molecular weight distribution (MWD) is 1.58, and the product predicted molecular weight is 7540.
Embodiment 2
The 57mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 5mL toluene, 6.314g vinylbenzene and the alpha-brominated ethyl isobutyrate of 60mg by injection technique, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 97 hours down at 70 ℃, and monomer conversion is 66.6%.The polymkeric substance that obtains is analyzed through gel permeation chromatography (GPC), and molecular weight is 26800, and molecular weight distribution (MWD) is 1.55, and the product predicted molecular weight is 13300.
Embodiment 3
The 57mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 5mL toluene, 6.151g vinylbenzene and the alpha-brominated ethyl isobutyrate of 62mg by injection technique, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 48 hours down at 80 ℃, and monomer conversion is 74.5%.The polymkeric substance that obtains is analyzed through gel permeation chromatography (GPC), and molecular weight is 32900, and molecular weight distribution (MWD) is 1.56, and the product predicted molecular weight is 14410.
Embodiment 4
The 57mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 5mL toluene, 6.237g vinylbenzene and the alpha-brominated ethyl isobutyrate of 59mg by injection technique, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 35 hours down at 90 ℃, and monomer conversion is 74.6%.The polymkeric substance that obtains is analyzed through gel permeation chromatography (GPC), and molecular weight is 29846, and molecular weight distribution (MWD) is 1.67, and the product predicted molecular weight is 14920.
Embodiment 5
The 57mg dicyclopentadienylcobalt placed the 100mL Schlenk reaction flask that stirs magneton is housed, add 5mL toluene, 6.087g vinylbenzene and the alpha-brominated phenylethane of 57mg by injection technique, system by freezing-vacuumize-freezing three times to circulate, charge into argon gas at last.Reaction system was reacted 24 hours down at 80 ℃, and monomer conversion is 40.4%.The polymkeric substance that obtains is analyzed through gel permeation chromatography (GPC), and molecular weight is 21900, and molecular weight distribution (MWD) is 1.43, and the product predicted molecular weight is 7980.
Embodiment 6
The 57mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 1 of 5mL by injection technique, 4-dioxane, 6.358g vinylbenzene and the alpha-brominated ethyl isobutyrate of 60mg, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 72 hours down at 80 ℃, and monomer conversion is 69.2%.Analyze through gel permeation chromatography (GPC), molecular weight is 35500, and molecular weight distribution (MWD) is 1.55, and the product predicted molecular weight is 14300.
Embodiment 7
The 57mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 5mL toluene, 7.047g methyl methacrylate and the alpha-brominated ethyl isobutyrate of 60mg by injection technique, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 24 hours down at 70 ℃, and monomer conversion is 81.7%.The polymkeric substance that obtains is analyzed through gel permeation chromatography (GPC), and molecular weight is 80600, and molecular weight distribution (MWD) is 1.14, and the product predicted molecular weight is 18700.
Embodiment 8
The 57mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 10mL toluene, 6.539g methyl methacrylate and the alpha-brominated ethyl isobutyrate of 63mg by injection technique, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 24 hours down at 80 ℃, and monomer conversion is 97.8%.Analyze through gel permeation chromatography (GPC), molecular weight is 56300, and molecular weight distribution (MWD) is 1.35, and the product predicted molecular weight is 19800.
Embodiment 9
The 19mg dicyclopentadienylcobalt is placed the 100mL Schlenk reaction flask that the stirring magneton is housed, add 5mL toluene, 6.522g methyl methacrylate and the alpha-brominated ethyl isobutyrate of 60mg by injection technique, system by freezing-vacuumize-freezing three times the circulation, charge into argon gas at last.Reaction system was reacted 24 hours down at 80 ℃, and monomer conversion is 74.3%.Analyze through gel permeation chromatography (GPC), molecular weight is 176000, and molecular weight distribution (MWD) is 1.64, and the product predicted molecular weight is 15750.
Claims (7)
1, a kind of method for preparing polymers of vinyl monomers is characterized in that this method comprises:
1) metallocene compound of two luxuriant sandwich structures with general formula (I) is as the catalyzer of living free radical polymerization:
Wherein: R is a hydrogen atom, or contains a kind of in the aliphatics substituting group of 1 to 10 carbon, can be identical or different between the R; Two adjacent R groups can Cheng Huan, promptly comprises the substituent indenyl of aliphatics or the tetrahydro indenyl that contain 1 to 10 carbon, or fluorenyl or octahydrofluorenyl; M is a cobalt;
2) have (II) or (III) the general formula halogenated organic compounds as initiator:
Wherein: R
1, R
2And R
3Can be identical or different, be respectively hydrogen atom, contain the aliphatic a kind of of 1 to 10 carbon; X is a kind of in chlorine, the bromine or iodine;
In the presence of above-mentioned catalyzer, initiator and rare gas element, in organic solvent, carry out the polymerization of vinyl monomer reaction, the preparation polymers of vinyl monomers; Initiator: catalyzer=1～3: 1, mol ratio.
2, the method for preparing polymers of vinyl monomers according to claim 1 is characterized in that described vinyl monomer is a styrenic.
3, the method for preparing polymers of vinyl monomers according to claim 1 is characterized in that described vinyl monomer is vinylbenzene or methyl methacrylate.
4, the method for preparing polymers of vinyl monomers according to claim 1 is characterized in that described catalyzer is the cobalt compounds:
5, the method for preparing polymers of vinyl monomers according to claim 1 is characterized in that described initiator is alpha-brominated ethyl isobutyrate or alpha-brominated ethylbenzene.
6, the method for preparing polymers of vinyl monomers according to claim 1 is characterized in that described organic solvent is a toluene.
7, the method for preparing polymers of vinyl monomers according to claim 1; the mol ratio that it is characterized in that described halogenated organic compounds initiator and catalyzer is 1～3: 1; argon shield, polymerization reaction time 24～100 hours, temperature is 60～90 ℃.
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| CN 03130135 CN1200010C (en) | 2003-06-18 | 2003-06-18 | Method for preparing vinyl monomer polymer using metallorene free-radical polymerization catalyst |
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| CN 03130135 CN1200010C (en) | 2003-06-18 | 2003-06-18 | Method for preparing vinyl monomer polymer using metallorene free-radical polymerization catalyst |
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| CN1200010C true CN1200010C (en) | 2005-05-04 |
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