WO2004014848A1 - 有機テルル化合物、その製造方法、リビングラジカル重合開始剤、それを用いるポリマーの製造方法及びポリマー - Google Patents
有機テルル化合物、その製造方法、リビングラジカル重合開始剤、それを用いるポリマーの製造方法及びポリマー Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C395/00—Compounds containing tellurium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
Definitions
- the present invention relates to an organic tellurium compound and a method for producing the same. More specifically, it relates to a tellurium-based living radical polymerization initiator, a macro-living radical polymerization initiator using the same, a method for producing a living radical polymer and a block polymer, and these macro-living radical polymerization initiators and polymers.
- Living radical polymerization is a polymerization method that enables precise control of the molecular structure while maintaining the simplicity and versatility of radical polymerization, and has shown great power in the synthesis of new polymer materials.
- living radical polymerization Georges et al. Have reported living radical polymerization using TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) as an initiator. Kaihei 6—published 199916).
- the present invention relates to an organic tellurium compound represented by the formula (1).
- R 1 represents an alkyl group of ⁇ Cs.
- R 2 and R 3 represent a hydrogen atom or a C i Cs alkyl group.
- R 4 represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an oxycarbonyl group or a cyano group.
- the present invention provides a method for producing an organic tellurium compound represented by the formula (1), which comprises reacting a compound represented by the formula (2), a compound represented by the formula (3), and tellurium metal. According to the method.
- R 2 , R 3 and R 4 are the same as above.
- X represents a halogen atom.
- M represents an alkali metal, an alkaline earth metal, or a copper atom.
- m is 1, when M is an alkaline earth metal, m is 2, when M is a copper atom, m is 1 or 2.
- the present invention relates to an organic tellurium compound represented by the formula (1) that can be obtained by reacting a compound represented by the formula (2), a compound represented by the formula (3), and tellurium metal.
- the present invention relates to a living radical polymerization initiator represented by the formula (4).
- R 2 to R 4 are the same as above, and R 5 represents ( ⁇ to ( 8 represents an alkyl group, aryl group, substituted aryl group or aromatic heterocyclic group.)]
- the present invention relates to a method for producing a living radical polymer, comprising polymerizing a vinyl monomer using a compound of the formula (4) as a living radical polymerization initiator.
- the present invention relates to a living radical polymer obtained by subjecting a vinyl monomer to living radical polymerization using a living radical polymerization initiator represented by the formula (4).
- the present invention relates to a macro living radical polymerization initiator (macro initiator) comprising the above living radical polymer.
- the present invention relates to a method for producing a block copolymer, comprising polymerizing a vinyl monomer using the above macro living radical polymerization initiator (macro initiator) as a living radical polymerization initiator.
- macro living radical polymerization initiator macro initiator
- the present invention relates to a block copolymer obtainable by polymerizing a vinyl monomer using the above macro living radical polymerization initiator (macro initiator) as a living radical polymerization initiator.
- macro living radical polymerization initiator macro initiator
- the organic tellurium compound of the present invention is represented by the formula (1).
- R 1 represents an alkyl group of ( ⁇ to (: 8 ;
- R 2 and R 3 represent a hydrogen atom or C
- R 4 is an aryl group, a substituted aryl group, It represents a ring group, an oxycarbonyl group or a cyano group.
- R 1 The group represented by R 1 is specifically as follows.
- ( ⁇ -( ⁇ Alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n_butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n- Examples thereof include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, such as a pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. And a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
- R 2 and R 3 are specifically as follows.
- Examples of the C ⁇ Cs alkyl group include the same as the alkyl group represented by R 1 above.
- Each group represented by R 4 is specifically as follows.
- Aryl groups such as phenyl and naphthyl groups; substituted aryl groups such as phenyl groups having a substituent; naphthyl groups having a substituent; pyridyl groups as aromatic heterocyclic groups; Examples thereof include a furyl group and a chelyl group.
- substituent of the aryl group having the above substituent examples include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by 1 COR 6 (RS ⁇ C Cs alkyl group, aryl group, C Cs alkoxy group, aryloxy group), sulfonyl group, trifluoromethyl group and the like.
- Preferred aryl groups are phenyl and trifluoromethyl-substituted phenyl. These substituents are preferably substituted one or two times, and are preferably in the para or ortho position.
- R 7 H, an alkyl group of C Cs, an aryl group
- the organic tellurium compound represented by the formula (1) is specifically as follows.
- organic tellurium compounds examples include (methyl terranyl monomethyl) benzene, (1-methyl terranyl ruethyl) benzene, (2-methyl terranyl methyl pill) benzene, and 1-methyl chlorinyl 4-benzene (methyl terranyl methyl) benzene.
- (methyl teranirumethyl) benzene, (1-methyl teraniruethyl) benzene, (2-methyl teraniru loop mouth pill) benzene, 2-methyl teraniru 2-methyl methyl propionate, 2-methyl teraniru 2 —Ethyl methylpropionate, 2-methylteranylpropionitrile, 2-methyl-2-methylteranylpropionitrile are good. . 2 008003
- the organic tellurium compound represented by the formula (1) can be produced by reacting the compound of the formula (2), the compound of the formula (3) and tellurium metal.
- the compound represented by the above formula (2) is specifically as follows.
- R 2 , R 3 and R 4 are the same as above.
- X represents a halogen atom.
- Each group represented by R 2 , R 3 and R 4 is as described above.
- Examples of the group represented by X include a halogen atom such as fluorine, chlorine, bromine or iodine. Preferably, chlorine and bromine are good.
- Specific compounds include benzyl chloride, benzyl bromide, 1-chloro-1-phenylethane, 1-bromo-1-phenylethane, 2-chloro-2-phenylpropane, 2-bromo-2-phenylpropane, and: Black mouth benzylic
- the compound represented by the above formula (3) is specifically as follows.
- M represents an alkali metal, an alkaline earth metal, or a copper atom.
- m is 1, when M is an alkaline earth metal, m is 2, when M is a copper atom, m is 1 or 2.
- R 1 The group represented by R 1 is as described above.
- Examples of the compound represented by M include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and copper. Preferably, lithium is used.
- Specific compounds include methyllithium, ethyllithium, n-butyllithium 8003
- the above manufacturing method is specifically as follows.
- the tellurium metal is suspended in the solvent.
- Solvents that can be used include polar solvents such as dimethylformamide (DMF) and tetrahydrofurash (THF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane, and ethers such as dialkyl ether. And the like.
- polar solvents such as dimethylformamide (DMF) and tetrahydrofurash (THF)
- aromatic solvents such as toluene and xylene
- aliphatic hydrocarbons such as hexane
- ethers such as dialkyl ether.
- the amount of the solvent to be used may be appropriately adjusted, but is usually 5 to 1 Om 1, preferably 7 to 8 ml per 1 g of metal tellurium.
- Compound (3) is slowly added dropwise to the above suspension, and the mixture is stirred.
- the reaction time varies depending on the reaction temperature and pressure, but is usually 5 minutes to 24 hours, preferably 10 minutes.
- the reaction temperature is between 20 ° C and 80 ° C, preferably between 15 ° C and
- the pressure is usually at normal pressure, but may be increased or decreased.
- the reaction time varies depending on the reaction temperature and pressure, but is usually 5 minutes to 24 hours, preferably 10 minutes to 2 hours.
- the reaction temperature is from ⁇ 20 ° C. to 80 ° C., preferably from 15 ° C. to 40 ° C., and more preferably room temperature.
- the pressure is usually set at normal pressure, but may be increased or decreased.
- the proportions of metal tellurium, compound (2) and compound (3) used are 0.5 to 1.5 mol 1 for compound (2) and 0.5 to 1.5 mol for compound (3) based on lmo 1 of metal tellurium. 5 mo 1, preferably compound (2) 0.8 to 1.2 mol, compound
- (3) is preferably set to 0.8 to 1.2mo1.
- the living radical polymerization initiator of the present invention is a compound represented by the formula (4).
- R 2 to R 4 are the same as above, and R 5 represents ( ⁇ to ( 8 represents an alkyl group, aryl group, substituted aryl group or aromatic heterocyclic group.)]
- the alkyl group represented by R 5 the same alkyl groups and groups represented by R 1 can ani gel.
- Ariru group a substituted Ariru group, the aromatic heterocyclic group, can be exemplified the same groups as those indicated above R 4.
- the living radical polymerization initiator represented by the formula (4) specifically includes, in addition to the compound specifically represented by the formula (1), (phenylteranilumethyl) benzene, (1-phenylteraniruruethyl) benzene, (2-phenyl terra loop pill) Benzene and the like.
- the living radical polymerization initiator represented by the formula (4) is a compound of the formula (1) except that a compound represented by the formula (7) is used instead of the compound represented by the formula (3). It can be manufactured by the same method as the manufacturing method.
- the compound (7) include, in addition to the compound (3), phenyllithium, p-chlorophenylphenyl, p-methoxyphenyllithium, p-nitrophenyllithium and the like. .
- phenyllithium is good.
- the vinyl monomer used in the present invention is not particularly limited as long as it is capable of radical polymerization, and examples thereof include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) propyl acrylate, and ( (Meth) acrylic esters such as (meth) butyl acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, Evening) Cyclohexyl acrylate, methylcyclohexyl (meth) acrylate, (Me) Isopolnyl acrylate, (meth) cyclododecyl acrylate, etc., unsaturated monomers containing cycloalkyl group, (meth) acrylic acid, maleic acid Carboxyl group-containing unsaturated monomers such as methyl, fumaric acid, itaconic acid, citraconic acid, crotonic acid, and maleic anhydride; N, N-dimethylamin
- (meth) acrylic acid ester monomers tertiary amine-containing unsaturated monomers, styrene monomers, acrylamide, and ⁇ , ⁇ -dimethylacrylamide are preferred.
- Preferred (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Particularly preferred are methyl (meth) acrylate and butyl (meth) acrylate.
- Preferred tertiary amine-containing unsaturated monomers include N, N-dimethylaminoethyl '(meth) acrylamide and 2- (dimethylamino) ethyl (meth) acrylic acid.
- Preferred styrene-based monomers include styrene, permethylstyrene, o-methylstyrene, p-methylstyrene, ⁇ -methoxystyrene, p_t-butylstyrene, p-n-butylstyrene, p-chlorostyrene, and p-styrenesulfo. Acid or an alkali metal salt thereof (sodium salt, potassium salt, etc.). Particularly preferred are styrene, p-methoxystyrene and p-chlorostyrene.
- (meth) acrylic acid” is a general term for “acrylic acid” and “methacrylic acid”.
- the above manufacturing method is specifically as follows.
- a vinyl monomer and a living radical polymerization initiator represented by the formula (4) of the present invention are mixed.
- the inert gas include nitrogen, argon, and helium.
- argon and nitrogen are used, and nitrogen is particularly preferable.
- the amounts of the vinyl monomer and the living radical polymerization initiator may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the obtained living radical polymer.
- the amount of the system monomer is 5 to 100,000 equivalents, preferably 50 to 5,000 equivalents.
- the reaction is usually performed without a solvent, but a solvent generally used in radical polymerization may be used. Solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), 2002/008003
- Examples include acetone, black form, carbon tetrachloride, tetrahydrofuran (THF), and ethyl acetate.
- D.MF tetrahydrofuran
- ethyl acetate Preferably, D.MF is good.
- the amount of the solvent used may be appropriately adjusted.
- the amount of the solvent is preferably 0.01 to 1 ml, preferably 0.05 to 0.5 ml per 1 g of the vinyl monomer.
- the mixture is stirred.
- the reaction temperature and the reaction time may be appropriately adjusted depending on the molecular weight or the molecular weight distribution of the obtained living radical polymer.
- the mixture is stirred at 60 to 150 ° C for 5 to 100 hours.
- the mixture is stirred at 80 to 120 for i 0 to 30 hours.
- the reaction is usually performed at normal pressure, but may be performed under pressure or under reduced pressure.
- the solvent used and the remaining monomers are removed under reduced pressure by a conventional method to take out the desired polymer, or the desired product is isolated by reprecipitation using a desired polymer-insoluble solvent.
- any treatment method can be used as long as the object is not hindered.
- the living radical ___ polymerization initiator of the present invention can perform excellent control of molecular weight and control of molecular weight distribution under extremely mild conditions.
- the molecular weight of the living radical polymer obtained in the present invention can be adjusted by the reaction time and the amount of the organic tellurium compound, a living radical polymer having a number average molecular weight of 500 to 1,000,000,000 can be obtained. In particular, it is suitable for obtaining a living radical polymer having a number average molecular weight of 1,000 to 50,000.
- the terminal group of the living radical polymer obtained in the present invention may be an alkyl group derived from an organic tellurium compound, an aryl group, a substituted aryl group, an aromatic heterocyclic group or an oxy group. 2 008003
- the living radical polymer obtained in the present invention can be used as a macro living radical polymerization initiator (macro iniche—Yuichi).
- an A-B diblock copolymer such as styrene-butyl acrylate or an A-B-A triple block copolymer such as styrene-butyl acrylate-styrene is used. It is possible to obtain an A—B—C triplep copolymer such as a polymer and styrene-butyl acrylate methyl methacrylate.
- the living radical polymerization initiator of the present invention can control a variety of different types of vinyl monomers, and there is highly reactive tellurium at the growth terminal of the living radical polymer obtained by the living radical polymerization initiator. It is due to doing.
- the method for producing the block copolymer is specifically as follows.
- styrene and a compound represented by the formula (4) of the present invention are used in the same manner as in the above-mentioned method for producing a living radical polymer.
- the method includes mixing the living radical polymerization initiator shown to produce polystyrene, and then mixing butyl acrylate to obtain a styrene-butyl acrylate copolymer.
- A—B—A triblock copolymer or A—B—C triblock copolymer after producing the A—B diblock copolymer by the above method, the vinyl monomer (A) or A method in which a vinyl monomer (C) is mixed to obtain an A—B—A triblock copolymer or an A—B-C triblock copolymer.
- the reaction of the next block may be started as it is However, once the reaction is completed, purification may be performed before starting the reaction of the next block.
- the block copolymer can be isolated by a usual method. BEST MODE FOR CARRYING OUT THE INVENTION
- the organic tellurium compound was identified from the results of —NMR, 2 H—NMR, 13 C—NMR, IR and MS.
- the molecular weight and molecular weight distribution of the living radical polymer were determined using GPC (gel permeation chromatography) based on the molecular weight of a polystyrene standard sample.
- the measuring instruments used are as follows. .
- N-methyl-2-vinylpyrrol (vinyl monomer used in Example 26) 13.5 g (12 Ommo 1) of potassium tert-butoxide The suspension was suspended in 200 ml of methyl terephthalate, and 42.9 g (12 Ommo 1) of methyltriphenylphosphonium bromide was added. The yellow suspension was refluxed for 1 hour. The mixed solution was cooled to room temperature, and 10.9 g (10 Ommo 1) of 1-methyl-2-pyrrolealdehyde was slowly added thereto (for 10 minutes), followed by refluxing for 1 hour.
- Methyl-2-benzenesulfonylmethyl acrylate obtained above 1.29 g (5.lmmo 1), triptyltin hydride 2.75 ml (10.2 mmo 1), azobisbutyronitrile (AIBN) 33.4 mg (0.2 Ommo 1) benzene 2.
- the 6 ml solution was heated to reflux for 1 hour. After the solvent was distilled off, the obtained product was purified by silica gel chromatography to obtain 1.34 g of ethyl 2-triptylsylmethyl acrylate in a yield of 65%.
- Example 2 (1) Synthesis of 1-chloro-4-1 (1 -methylterarinylethyl) benzene 4.08 g (32 mmo 1) of metal tellurium was suspended in 50 ml of THF, and 42 ml (35 mmo 1) of methyllithium (same as above) was added to 0 ml. The solution was slowly added dropwise at 20 ° C (20 minutes). The reaction solution was stirred until the metal tellurium completely disappeared (10 minutes). To this reaction solution, 7.68 g (35 mmo 1) of 1- (1-bromoethyl) -4-chlorobenzene (obtained in Synthesis Example 1) was added at room temperature, and the mixture was stirred for 1.5 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain 3.59 g (12.7 mmol: yield: 36%) of a brown oil.
- Example 2 The same operation as in Example 1 was carried out except that methyllithium was changed to 53.0 ml of phenyllithium (same as above) (1.06M dimethyl ether solution, 55 mmo 1). %).
- Example 2 The same operation as in Example 1 was carried out except for changing to I), to obtain 7.30 g (yield 50%) of a yellow oil.
- Example 7 100 18 96 9200 1.17
- Example 8 200 20 87 18400 1.18
- Example 9 300 23 85 25 200 1.22
- Example 10 400 27 78 29 500 1.17
- Example 11 500 27 78 35 700 1.21
- Example 12 800 27 80 52 600 1.30
- Example 13 1000 29 84 62 600 1.37
- Example 14
- Example 17 In a glove box purged with nitrogen, 1.04 g (1 Ommo 1) of styrene and 19.7 mg (0.1 Ommo 1) of 2-methylteranylpropionitrile synthesized in Example 6 were blended and mixed at 100 ° C. The reaction was carried out at C for 11 hours. After completion of the reaction, the mixture was dissolved in 5 ml of chloroform, and the solution was poured into 25 Oml of hexane under stirring. The precipitated polymer was collected by suction filtration and dried to obtain 1.01 g (yield 97%) of polystyrene. According to GPC analysis, Mn was 11000 and PD was 1.21.
- N-methyl-2-vinylvirol (synthesis 1.07 g (1 Ommo 1) and 24.8 mg (0.1 Ommo 1) of benzene (1-methyl terrenylethyl) synthesized in Example 1 were blended.
- the reaction was performed at 00 ° C for 20 hours.
- the mixture was dissolved in 5 ml of chloroform, and the solution was poured into 25 ml of hexane under stirring.
- the precipitated polymer was subjected to suction filtration and dried to obtain 1.02 g (yield 95%) of poly N-methyl-2-pinylpyrrole.
- the polymer was purified by preparative GPC and analyzed by NMR, which revealed that 61% of the polymer end groups had been converted to acrylic ester groups.
- an organic tellurium compound and a method for producing the same are provided.
- the organic tellurium compound is useful as a living radical polymerization initiator, and enables precise control of molecular weight and molecular weight distribution under mild conditions.
- the living radical polymer obtained by polymerization is capable of converting a terminal group into another functional group, whereby the living radical polymer obtained in the present invention is a macro living radical polymerization initiator (ma. It can be used as a clone initiator).
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Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02753239A EP1541550B1 (en) | 2002-08-06 | 2002-08-06 | Organic tellurium compound, process for producing the same, living radical polymerization initiator, process for producing polymer with the same, and polymer |
DE60229446T DE60229446D1 (de) | 2002-08-06 | 2002-08-06 | Organische tellurverbindung, verfahren zu deren herstellung, initiator für die lebende radikalische polymerisation, verfahren zur herstellung eines polymers unter anwendung desselben, und polymer |
CNB02829422XA CN1307153C (zh) | 2002-08-06 | 2002-08-06 | 有机碲化合物、其制备方法、活性自由基聚合引发剂、使用其的聚合物的制备方法以及聚合物 |
CA2494816A CA2494816C (en) | 2002-08-06 | 2002-08-06 | Organic tellurium compound, process for producing the same, living radical polymerization initiator, process for producing polymer with the same, and polymer |
AU2002313917A AU2002313917B2 (en) | 2002-08-06 | 2002-08-06 | Organic tellurium compound, process for producing the same, living radical polymerization initiator, process for producing polymer with the same, and polymer |
US10/523,824 US7276569B2 (en) | 2002-08-06 | 2002-08-06 | Organic tellurium compound, process for producing the same, living radical polymerization initiator, process for producing polymer with the same, and polymer |
AT02753239T ATE411282T1 (de) | 2002-08-06 | 2002-08-06 | Organische tellurverbindung, verfahren zu deren herstellung, initiator für die lebende radikalische polymerisation, verfahren zur herstellung eines polymers unter anwendung desselben, und polymer |
JP2004527297A JP4464821B2 (ja) | 2002-08-06 | 2002-08-06 | 有機テルル化合物、その製造方法、リビングラジカル重合開始剤、それを用いるポリマーの製造方法及びポリマー |
PCT/JP2002/008003 WO2004014848A1 (ja) | 2002-08-06 | 2002-08-06 | 有機テルル化合物、その製造方法、リビングラジカル重合開始剤、それを用いるポリマーの製造方法及びポリマー |
US11/878,901 US7662899B2 (en) | 2002-08-06 | 2007-07-27 | Organic tellurium compound, process for producing the same, living radical polymerization initiator, process for producing polymer with the same, and polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2002/008003 WO2004014848A1 (ja) | 2002-08-06 | 2002-08-06 | 有機テルル化合物、その製造方法、リビングラジカル重合開始剤、それを用いるポリマーの製造方法及びポリマー |
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US10523824 A-371-Of-International | 2002-08-06 | ||
US11/878,901 Division US7662899B2 (en) | 2002-08-06 | 2007-07-27 | Organic tellurium compound, process for producing the same, living radical polymerization initiator, process for producing polymer with the same, and polymer |
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WO2004014848A1 true WO2004014848A1 (ja) | 2004-02-19 |
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US (2) | US7276569B2 (ja) |
EP (1) | EP1541550B1 (ja) |
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CN (1) | CN1307153C (ja) |
AT (1) | ATE411282T1 (ja) |
AU (1) | AU2002313917B2 (ja) |
CA (1) | CA2494816C (ja) |
DE (1) | DE60229446D1 (ja) |
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Also Published As
Publication number | Publication date |
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AU2002313917A1 (en) | 2004-02-25 |
US7276569B2 (en) | 2007-10-02 |
AU2002313917B2 (en) | 2007-07-12 |
CA2494816A1 (en) | 2004-02-19 |
US20050245714A1 (en) | 2005-11-03 |
CN1307153C (zh) | 2007-03-28 |
CN1649838A (zh) | 2005-08-03 |
DE60229446D1 (de) | 2008-11-27 |
US7662899B2 (en) | 2010-02-16 |
US20080004366A1 (en) | 2008-01-03 |
EP1541550A1 (en) | 2005-06-15 |
CA2494816C (en) | 2010-01-26 |
EP1541550A4 (en) | 2006-01-11 |
JP4464821B2 (ja) | 2010-05-19 |
ATE411282T1 (de) | 2008-10-15 |
JPWO2004014848A1 (ja) | 2005-12-02 |
EP1541550B1 (en) | 2008-10-15 |
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