CN1165828A - Catalyst able to control polymerizing reaction and its application - Google Patents
Catalyst able to control polymerizing reaction and its application Download PDFInfo
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- CN1165828A CN1165828A CN 97106318 CN97106318A CN1165828A CN 1165828 A CN1165828 A CN 1165828A CN 97106318 CN97106318 CN 97106318 CN 97106318 A CN97106318 A CN 97106318A CN 1165828 A CN1165828 A CN 1165828A
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- halide
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Abstract
A catalyst for controllably synthesizing the polymer with predetermined chain structure, terminal functional group, molecular weight and molecular weight distribution is prepared from cuprous halide, orthophenanthroline and its derivatives, and is used for controllable polymerizations of styrene, acrylates, isobutylene and alkylvinylether triggered by halogen-contained compound. Its advantages are easy storage, low cost, simple and feasible polymerizing conditions and adapting different types of triggers.
Description
The invention belongs to the synthetic field of polymkeric substance, relate to a kind of synthetic catalyzer, can be used for the copolyreaction of the monomeric controllable polymerization reaction of vinylbenzene, esters of acrylic acid and conjugated dienes hydro carbons and they and other vinyl monomer with polymkeric substance of predetermined chain structure, predetermined functional end-group, predetermined molecular weight and molecular weight distribution.
As everyone knows, control by polyreaction being controlled chain structure, functional end-group, molecular weight and the molecular weight distribution that can realize polymerisate.At present, many documents and patent disclosure by polyreaction being controlled the synthetic predetermined chain structure that has, predetermined functional end-group, the catalyzer of predetermined molecular weight and molecular weight distribution is as document Webster.O.Science 251,887 (1991) etc.All there are many shortcomings in this type of catalyzer, as to the air instability, is difficult to preserve, and costs an arm and a leg.Document J.S., Wang; Maty-jaszewski, K.J.Am.Chem.Soc.117,5614 (1995). disclose a kind of catalyzer of forming by the mixture of cuprous chloride and adjacent two pyridines, but this catalyzer catalysis 1-chloro-1-diphenylphosphino ethane causes the body controllable polymerization of styrene monomer.But adjacent two pyridines of one of catalyst component of this catalyzer structurally have certain kindliness, to polymerization mechanism research, poly-platform reaction kinetics research and reaction are amplified research and are brought certain difficulty, and adjacent two pyridine prices are more expensive, catalysis initiated polymerization speed is slower, and is unfavorable to further industrialization.
The objective of the invention is to overcome the shortcoming that existing catalyzer exists, research and develop a kind of new polymerisation catalysts, the more effectively controlled polymerization reaction of this catalyzer, the polymkeric substance that can synthesize corresponding construction according to performance need, this catalyzer cost is lower simultaneously, thereby further lays the foundation for the industrial application of this catalyzer.
Design of the present invention is such:
The contriver is by studying for a long period of time, proposition is with cuprous halide and have the stiff molecule structure, the mixture of phenanthroline that has simultaneously the dinitrogen atom in molecular structure is as catalyzer, this catalyzer can cause the controllable polymerization reaction of vinyl monomer by the catalysis halide-containing, thereby realizes chain structure, functional end-group and the molecular weight of polymerisate and the controllability of distribution thereof.As prepare have predetermined molecular weight and molecular weight distribution, terminal be all kinds of simple function groups of halogen, bifunctional polymer, polyfunctional group star polymer and all kinds of block, grafting, alternating copolymer.
The present invention also is achieved in that
The said catalyzer of the present invention is the mixture of cuprous halide and phenanthroline and derivative thereof, and said cuprous halide is a cuprous chloride, a kind of in cuprous bromide and the cuprous iodide, and said phenanthroline derivative is the compound with following general structure:
Wherein, R is in hydrogen atom, halogen, aliphatics or aromatic substituents and all kinds of substituting group that contains non-carbon atom (as oxygen, sulphur, nitrogen etc.), molecular weight is less than 10,000, commonly used is 1,10-phenanthroline (phen), 4,7-phenylbenzene-1,10-phenanthroline etc., the mol ratio of phenanthroline and derivative thereof and cuprous halide is 0.5～5.
Said catalyzer can the catalysis halide-containing causes the controllable polymerization of vinyl monomer, and the mol ratio of cuprous halide and halide-containing is 0.05～4.0 in the catalyzer.
Said halide-containing is the compound with one of following general structure:
Wherein, R is a hydrogen atom, halogen atom, and in aliphatics or aromatic substituents and all kinds of substituting group that contains non-carbon atom (as oxygen, sulphur, nitrogen, halogen etc.) one, molecular weight is less than 10,000; X is in chlorine, bromine, the iodine.
Commonly used has: tetracol phenixin, methyl chloroacetate, benzyl chloride, dibenzyl bromine, tribenzyl chlorine, p-methyl benzene sulfonic chloride, chlorallylene etc.
Said vinyl monomer is a series of vinyl monomers that contain two keys or conjugated double bond, and monomer commonly used is vinylbenzene, esters of acrylic acid, vinyl acetate, isoprene, divinyl, iso-butylene, alkyl vinyl ethers etc.
The general technology condition of polyreaction is as follows:
Halide-containing, catalyzer, vinyl monomer and solvent (also can not adding) are placed reactor, the argon filling of finding time repeatedly finds time to carry out polyreaction for several times under 0～150 ℃, polymerisate promptly gets required polymkeric substance with appropriate solvent dissolving, precipitation agent post precipitation.
To further illustrate the present invention by embodiment below, but embodiment does not limit protection scope of the present invention.
Embodiment one
Taking by weighing 39mg CuCl, 130mg phen joins in the ampere bottle, system vacuumizes after argon filling repeats four times, 6.0ml vinylbenzene and 0.041ml benzyl chloride reinject, react 2hr down at 140 ℃, monomer conversion is 80%, and a resulting end has the simple function group polymkeric substance of halogens chlorine atom through gel chromatography analysis (GPC), and molecular weight is 8925, molecular weight distribution (MWD) is 1.47, and the product predetermined molecular weight should be 9880.
Embodiment two
Take by weighing CuCl 40mg, phen 146mg and 55mg BrCH
2C
6H
4CH
2Br, system is found time after argon filling repeats four times, and the 5ml vinylbenzene that reinjects is 130 ℃ of reactions 11 hours down, monomer conversion 52%, resulting two ends have the bifunctional telechelic oligoner of bromine atoms, through gpc analysis, molecular weight Mn=11431, MWD=2.01, product predetermined molecular weight are 10952.
Embodiment three
Take by weighing 40mg CuCl, 60mg tribenzyl chlorine and 146mg phen, system finds time to inject 8ml vinylbenzene behind the argon filling four times repeatedly, and at 140 ℃ of reaction 20hr down, monomer conversion is 60%.Resulting arm tip has the trifunctional star polymer of bromine atoms, and through gpc analysis, molecular weight is 16300, MWD=1.41, product predetermined molecular weight 15800.
Embodiment four
Take by weighing 40mg CuCl, 146mg phen joins in the ampere bottle, and system is found time after argon filling repeats four times, inject 40mg vinylbenzene and 40 μ l benzyl chlorides, 140 ℃ down behind the reaction 1hr (this moment monomer conversion 40%, Mn=4130, MWD=1.70), then 0 ℃ of cooling, after taking out residual monomer with vacuum pump, add propionic acid alkene butyl ester 6ml, stop behind the repolymerization 4hr, butyl acrylate transformation efficiency 80%, products therefrom i.e. block polymer for being made up of polystyrene and polypropylene ester butyl ester.It is 15700 that GPC measures its molecular weight, MWD=1.52.
Embodiment five
Take by weighing 81mg CuCl, 29mg phen places the ampere bottle, find time repeatedly behind the argon filling four times, inject 2ml propylene ester methyl ester successively, 3ml IVE and 80 μ l tetracol phenixin, reaction is after 10 hours down in 50～60 ℃, and the methyl acrylate transformation efficiency is 100%, the IVE transformation efficiency is 30%, and products therefrom is the random alternating copolymer of being made up of propylene ester methyl ester and IVE.Molecular weight preset value 3520, GPC surveys to such an extent that molecular weight is 4050, and the content of IVE chain link is 35.3% in the H-NMR analyzing polymers.
Obviously, according to catalyzer disclosed by the invention and embodiment, relevant professional can carry out omnibearing control to the polymerization of all kinds of vinyl monomers easily, thereby prepare have predetermined molecular weight and molecular weight distribution, terminal be polymerisate halogen, that have other chain structures, as graft copolymer, segmented copolymer, degree of passing polymkeric substance and branch-shape polymer etc.
Claims (5)
- One kind can the controlled polymerization catalyst for reaction, it is characterized in that the mixture of forming by cuprous halide and phenanthroline and derivative thereof.
- 2. the described catalyzer of root claim 1 is characterized in that the ratio of phenanthroline in the catalyzer and derivative and cuprous halide is 0.5～5 (mol ratio).
- 3. according to the described Application of Catalyst of claim 1, it is characterized in that this catalyzer can be used for the polymerization that the catalysis halide-containing causes vinyl monomer, said halide-containing is the compound with one of following general structure: Wherein, R is a hydrogen atom, halogen atom, and in aliphatics or aromatic substituents and all kinds of substituting group that contains non-carbon atom (as oxygen, sulphur, nitrogen, halogen etc.) one, molecular weight is less than 10,000; X is in chlorine, bromine, the iodine; Halide-containing commonly used is in tetracol phenixin, methyl chloroacetate, benzyl chloride, dibenzyl bromine, tribenzyl chlorine, p-methyl benzene sulfonic chloride, the chlorallylene;Said vinyl monomer is the vinyl monomer that contains two keys or conjugated double bond, and monomer commonly used is vinylbenzene, esters of acrylic acid, vinyl acetate, isoprene, divinyl, iso-butylene, alkyl vinyl ethers.
- 4. according to the described application of claim 3, it is characterized in that the mol ratio 0.05～4.0 of the CuCl in the catalyzer and halide-containing in the polyreaction.
- 5. according to claim 3,4 described application, it is characterized in that the temperature that catalyzer uses is 0～150 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97106318 CN1165828A (en) | 1997-03-13 | 1997-03-13 | Catalyst able to control polymerizing reaction and its application |
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| CN 97106318 CN1165828A (en) | 1997-03-13 | 1997-03-13 | Catalyst able to control polymerizing reaction and its application |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6111022A (en) * | 1996-07-10 | 2000-08-29 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
| US6121371A (en) * | 1998-07-31 | 2000-09-19 | Carnegie Mellon University | Application of atom transfer radical polymerization to water-borne polymerization systems |
| US6288186B1 (en) * | 1996-08-22 | 2001-09-11 | Carnegie Mellon University | Rate enhancement of nitroxyl radical-mediated polymerization |
| US6407187B1 (en) | 1995-03-31 | 2002-06-18 | Carnegie Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
| CN1098864C (en) * | 1998-08-12 | 2003-01-15 | 华东理工大学 | Polymerization catalyst containing active free radical of Lewis acid and its use |
| US6538091B1 (en) | 1995-11-15 | 2003-03-25 | Carnegie Mellon University | Atom or group transfer radical polymerization |
| US6541580B1 (en) | 1995-03-31 | 2003-04-01 | Carnegie Mellon University | Atom or group transfer radical polymerization |
| US7678869B2 (en) | 1997-03-11 | 2010-03-16 | Carnegie Mellon University | Atom or group transfer radical polymerization |
| US7795355B2 (en) | 2004-03-05 | 2010-09-14 | Carnegie Mellon University | Preparation of functional polymers |
| US7893173B2 (en) | 2005-08-26 | 2011-02-22 | Carnegie Mellon University | Polymerization process with catalyst reactivation |
| US8252880B2 (en) | 2007-05-23 | 2012-08-28 | Carnegie Mellon University | Atom transfer dispersion polymerization |
| US8273823B2 (en) | 2005-08-23 | 2012-09-25 | Carnegie Mellon University | Atom transfer radical polymerization in microemulsion and true emulsion polymerization processes |
| US8367051B2 (en) | 2006-10-09 | 2013-02-05 | Carnegie Mellon University | Preparation of functional gel particles with a dual crosslink network |
| US8404788B2 (en) | 2004-03-05 | 2013-03-26 | Carnegie Mellon University | Atom transfer radical polymerization process |
| US8865797B2 (en) | 2007-05-23 | 2014-10-21 | Carnegie Mellon University | Hybrid particle composite structures with reduced scattering |
| US9533297B2 (en) | 2012-02-23 | 2017-01-03 | Carnegie Mellon University | Ligands designed to provide highly active catalyst complexes |
| US9644042B2 (en) | 2010-12-17 | 2017-05-09 | Carnegie Mellon University | Electrochemically mediated atom transfer radical polymerization |
| US9982070B2 (en) | 2015-01-12 | 2018-05-29 | Carnegie Mellon University | Aqueous ATRP in the presence of an activator regenerator |
| US10072042B2 (en) | 2011-08-22 | 2018-09-11 | Carnegie Mellon University | Atom transfer radical polymerization under biologically compatible conditions |
-
1997
- 1997-03-13 CN CN 97106318 patent/CN1165828A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6407187B1 (en) | 1995-03-31 | 2002-06-18 | Carnegie Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
| US6512060B1 (en) | 1995-03-31 | 2003-01-28 | Carnegie Mellon University | Atom or group transfer radical polymerization |
| US6541580B1 (en) | 1995-03-31 | 2003-04-01 | Carnegie Mellon University | Atom or group transfer radical polymerization |
| US6538091B1 (en) | 1995-11-15 | 2003-03-25 | Carnegie Mellon University | Atom or group transfer radical polymerization |
| US7572874B2 (en) | 1995-11-15 | 2009-08-11 | Carnegie Mellon University | Processes based on atom (or group) transfer radical polymerization and novel (co)polymers having useful structures and properties |
| US6162882A (en) * | 1996-07-10 | 2000-12-19 | Carnegie Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
| US6111022A (en) * | 1996-07-10 | 2000-08-29 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
| US6288186B1 (en) * | 1996-08-22 | 2001-09-11 | Carnegie Mellon University | Rate enhancement of nitroxyl radical-mediated polymerization |
| US7678869B2 (en) | 1997-03-11 | 2010-03-16 | Carnegie Mellon University | Atom or group transfer radical polymerization |
| US6121371A (en) * | 1998-07-31 | 2000-09-19 | Carnegie Mellon University | Application of atom transfer radical polymerization to water-borne polymerization systems |
| CN1098864C (en) * | 1998-08-12 | 2003-01-15 | 华东理工大学 | Polymerization catalyst containing active free radical of Lewis acid and its use |
| US7795355B2 (en) | 2004-03-05 | 2010-09-14 | Carnegie Mellon University | Preparation of functional polymers |
| US8404788B2 (en) | 2004-03-05 | 2013-03-26 | Carnegie Mellon University | Atom transfer radical polymerization process |
| US8273823B2 (en) | 2005-08-23 | 2012-09-25 | Carnegie Mellon University | Atom transfer radical polymerization in microemulsion and true emulsion polymerization processes |
| US7893173B2 (en) | 2005-08-26 | 2011-02-22 | Carnegie Mellon University | Polymerization process with catalyst reactivation |
| US8367051B2 (en) | 2006-10-09 | 2013-02-05 | Carnegie Mellon University | Preparation of functional gel particles with a dual crosslink network |
| US8252880B2 (en) | 2007-05-23 | 2012-08-28 | Carnegie Mellon University | Atom transfer dispersion polymerization |
| US8865797B2 (en) | 2007-05-23 | 2014-10-21 | Carnegie Mellon University | Hybrid particle composite structures with reduced scattering |
| US9644042B2 (en) | 2010-12-17 | 2017-05-09 | Carnegie Mellon University | Electrochemically mediated atom transfer radical polymerization |
| US10072042B2 (en) | 2011-08-22 | 2018-09-11 | Carnegie Mellon University | Atom transfer radical polymerization under biologically compatible conditions |
| US9533297B2 (en) | 2012-02-23 | 2017-01-03 | Carnegie Mellon University | Ligands designed to provide highly active catalyst complexes |
| US9982070B2 (en) | 2015-01-12 | 2018-05-29 | Carnegie Mellon University | Aqueous ATRP in the presence of an activator regenerator |
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