JPWO2014175199A1 - Catalyst composition and method for producing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst composition capable of exhibiting sufficient living radical polymerizability even when applied to polymerization of a nitrogen-containing vinyl monomer such as acrylonitrile. A catalyst composition according to the present invention includes (A) a transition metal complex, (B) an organic halide, and (C) a rare earth alkoxide. [Selection figure] None

Description

  The present invention relates to a catalyst composition, and more particularly to a catalyst composition suitably used for living radical polymerization of nitrogen-containing vinyl monomers such as acrylonitrile. The present invention also relates to a method for producing a polymer by living radical polymerization using the catalyst composition.

  Production of vinyl polymers using radical polymerization has long been carried out on an industrial scale as a method for producing various polymers such as polyvinyl acetate. In the case of the conventional production method, the growing radicals in a series of radical polymerization reactions are inactivated by side reactions such as recombination and disproportionation and side reactions such as chain transfer, so the molecular weight of the resulting vinyl polymer The distribution was wide, and it was difficult to control the molecular weight of the polymer, to control the molecular terminals of the polymer, and to synthesize block polymers.

  The living radical polymerization method has attracted attention as a measure for solving the technical problems in these conventional production methods. If living radical polymerization is used, it becomes possible to control the molecular weight, molecular weight distribution, molecular terminal, etc., and to obtain a block polymer. In particular, many studies have been made on monomers such as styrene and (meth) acrylate, and it is known that the primary structure of the polymer can be controlled to a certain degree of precision.

  As a catalyst system that enables such living radical polymerization, Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-137917) proposes a catalyst system composed of a transition metal complex, an organic halide, and a Lewis acid. In patent document 1, an iron carbonium complex etc. are illustrated as a specific example of a transition metal complex. Specific examples of the Lewis acid include aluminum alkoxide, titanium alkoxide, organoaluminum compound and the like. It has been introduced that the catalyst system of Patent Document 1 is particularly suitable for the polymerization of vinyl ester monomers such as vinyl acetate.

JP 2003-137717 A

  However, transition metal complexes, particularly iron carbonium complexes, do not have sufficient functional group resistance, and when used for the polymerization of nitrogen-containing vinyl monomers having a functional group containing a nitrogen atom such as acrylonitrile, It has been found by the present inventors that decomposition and deterioration are caused, living radical polymerizability is impaired, and control of the molecular weight, molecular weight distribution and molecular terminal of the resulting polymer may be difficult.

  Accordingly, an object of the present invention is to provide a catalyst composition capable of exhibiting sufficient living radical polymerizability even when applied to the polymerization of nitrogen-containing vinyl monomers such as acrylonitrile.

  As a result of intensive studies to solve the above problems, the present inventors can suppress the decomposition and deterioration of the transition metal complex by using a transition metal complex having a low functional group resistance together with a rare earth alkoxide as a Lewis acid, It has been found that the properties and structure of the resulting polymer can be controlled stably, and the present invention has been completed.

The gist of the present invention is as follows.
(1) (A) transition metal complex,
A catalyst composition comprising (B) an organic halide, and (C) a rare earth alkoxide.

(2) The catalyst composition according to (1), wherein the transition metal complex (A) is a transition metal complex having iron as a central metal.

(3) Transition metal complexes with iron as the central metal are dicarbonylcyclopentadienyl iron dimer, dicarbonylcyclopentadienyl iodoiron, dicarbonyl (pentamethylcyclopentadienyl) iron dimer, dicarbonyl (pentamethyl) The catalyst composition according to (2), selected from the group consisting of (cyclopentadienyl) iodoiron and dicarbonylindenyl iron dimer.

(4) The catalyst composition according to any one of (1) to (3), wherein the organic halide (B) is an organic iodide.

(5) The rare earth alkoxide (C) is an alkoxide of a rare earth element selected from the group consisting of praseodymium (Pr), neodymium (Nd), samarium (Sm), and erbium (Er) (1) to (4) The catalyst composition according to any one of the above.

(6) The catalyst composition according to any one of (1) to (5), wherein the rare earth alkoxide (C) is isopropoxide.

(7) A method for producing a polymer, wherein a living radical polymerization of a vinyl monomer is performed in the presence of the catalyst composition according to any one of (1) to (6) above.

(8) The method for producing a polymer according to (7), wherein the vinyl monomer contains a nitrogen-containing vinyl monomer.

(9) The method for producing a polymer according to (7) or (8), wherein the vinyl monomer contains a monomer selected from the group consisting of a conjugated diene compound and an aromatic vinyl compound.

  According to the present invention, even when applied to the polymerization of nitrogen-containing vinyl monomers such as acrylonitrile, a catalyst composition capable of exhibiting sufficient living radical polymerizability is provided, and such a catalyst composition is used. By polymerizing the vinyl monomer, even when a nitrogen-containing vinyl monomer such as acrylonitrile is polymerized, the decomposition and deterioration of the transition metal complex are suppressed, and the molecular weight, molecular weight distribution and The molecular end can be stably controlled.

  Hereinafter, the present invention will be described in more detail. The catalyst composition of the present invention includes a transition metal complex (component (A)), an organic halide (component (B)) as a polymerization initiator, and a rare earth alkoxide (component (C)) which is a Lewis acid as an activator. .

  As the central metal constituting the transition metal complex of component (A), Group 6 to 11 elements of the periodic table such as iron, ruthenium, rhodium, nickel, copper, etc. Edition "(1993)), and iron, ruthenium and copper are more preferred. Among these, iron complexes have low functional group resistance and are susceptible to decomposition and degradation by nitrogen-containing vinyl monomers. However, decomposition and degradation are suppressed in the catalyst system of the present invention, and the effects of the present invention are remarkably exhibited. Therefore, it can be particularly preferably used in the present invention. However, living radical polymerization is possible even with a metal complex such as ruthenium, rhodium, nickel, copper, and is not excluded in the present invention. Here, the “functional group resistance” of the complex refers to the property that the complex is not easily decomposed or deteriorated even when it comes into contact with a functional group other than a hydrocarbon group, particularly a nitrogen-containing functional group. Specifically, it is evaluated by a change in living polymerizability. Living polymerizability is evaluated by a ratio (ΔMn / ΔConv.) Of change in monomer conversion (ΔConv.) And change in number average molecular weight (ΔMn) by performing living radical polymerization under predetermined conditions. The higher this value, the higher the conversion of the monomer and the increase in the molecular weight, and the higher the living polymerizability.

As a specific example of the transition metal complex having iron as a central metal,
Dicarbonylcyclopentadienyl iron dimer [(FeCp (CO) ₂ ) ₂ ], dicarbonylcyclopentadienyl iodoiron [FeCpI (CO) ₂ ], dicarbonyl (pentamethylcyclopentadienyl) iron dimer [(FeCp ^* (CO) ₂ ) ₂ ], dicarbonyl (pentamethylcyclopentadienyl) iodoiron [FeCp ^* I (CO) ₂ ], dicarbonylindenyliron dimer [(FeInd (CO) ₂ ) ₂ )] and tri Iron carbonyl complexes such as carbonyl (cyclooctatetraene) iron;
Iron (II) acetate, iron (II) acetylacetonate, iron (II) phthalocyanine, 1,1'-diacetylferrocene, 1,1'-dimethylferrocene, dicyclopentadienyl iron and the like. In the above, Cp represents cyclopentadienyl, Cp ^* represents pentamethylcyclopentadienyl, and Ind represents indenyl.

Examples of the ruthenium complex include complexes composed of ruthenium compounds such as RuCp ^* Cl (PPh ₃ ) ₂ and RuCpCl (PPh ₃ ) ₂ and amines such as tributylamine.

  As a copper complex, copper compounds such as cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, cuprous perchlorate, Alkylamines such as tributylamine; polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetraamine; amines such as 2,2′-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof A complex.

Among these, iron carbonyl complexes are preferable, and in particular, dicarbonylcyclopentadienyl iron dimer, dicarbonylcyclopentadienyl iodoiron, dicarbonyl (pentamethylcyclopentadienyl) iron dimer, dicarbonyl (pentamethylcyclopenta). Dienyl) iodoiron and dicarbonylindenyliron dimer are preferably used because the effects of the present invention are remarkably exhibited.
These transition metal complexes can be used alone or in combination of two or more.

  The organic halide of component (B) functions as a polymerization initiator. Examples of such organic halides include organic fluorides, organic chlorides, organic bromides, organic iodides, and more specifically, products obtained by the addition reaction of hydrogen halides with alkenes, monohalogenated alkyls. , Dihalogenated alkyl, trihalogenated alkyl, halogenated acetonitrile, halogenated acetic acid, halogenated acetamide and the like.

  Examples of the hydrogen halide used in the addition reaction between hydrogen halide and alkene include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like. Specific examples of the alkene include vinyl esters such as vinyl acetate. Monomeric monomers; methacrylic acid ester monomers such as methyl methacrylate and ethyl methacrylate; acrylic acid ester monomers such as methyl acrylate.

  In the present invention, the product obtained by the addition reaction of hydrogen halide and alkene is a commercial product as long as it has the same chemical structure as the product other than the product obtained by adding hydrogen halide to alkene. May be used, or may be obtained by other reactions.

  Further, a commercial product having the same chemical structure as the product obtained by the addition reaction between hydrogen bromide and a specific alkene is brought into contact with an iodide salt such as sodium iodide, so that the bromine atom in the commercial product is replaced with an iodine atom. It is also possible to prepare a compound having the same chemical structure as that of a product obtained by addition reaction of hydrogen iodide with a specific alkene.

Examples of the monohalogenated alkyl include iodomethane, iodoethane, iodopropane, and iodobutane.
Examples of the dihalogenated alkyl include diiodomethane, 1,2-diiodoethane, chloroiodomethane, 1,6-diiodohexane, and the like.
Examples of the trihalogenated alkyl include iodoform and the like, and alkyl halides obtained by substituting iodine of these iodides with fluorine, chlorine, bromine and the like.

  Examples of the halogenated acetonitrile include iodoacetonitrile. Examples of the halogenated acetic acid include iodoacetic acid, and examples of the halogenated acetamide include iodoacetamide. Moreover, the compound which substituted the iodine of these iodide with fluorine, chlorine, bromine, etc. is mention | raise | lifted.

Among organic halides, from the viewpoint of stably performing living radical polymerization, organic iodides are preferable, products obtained by addition reaction of hydrogen iodide and alkene are more preferable, and hydrogen iodide and (meth) acrylic acid ester The product of the addition reaction of is particularly preferred.
These organic halides can be used alone or in combination of two or more.

  The amount of the organic halide of the component (B) in the catalyst composition is appropriately determined according to the molecular weight of the target polymer, but if the amount of the organic halide is too small, control of the primary structure of the polymer. Since it is difficult to obtain a polymer if the amount is too large, it is preferably added in a proportion of 0.00005 to 0.2 mol with respect to 1 mol of the vinyl monomer used for the polymerization. More preferably, it is added at a ratio of 1 mol.

  The rare earth alkoxide as the Lewis acid of the component (C) functions as an activator. Such a rare earth alkoxide is not particularly limited as long as it has a rare earth element and an alkoxy group. From the viewpoint of suppressing decomposition and deterioration of the metal complex, rare earth elements include praseodymium (Pr), neodymium (Nd), and samarium. Alkoxides containing (Sm) or erbium (Er) are preferred, and monoalkoxides, dialkoxides, trialkoxides, and tetraalkoxides may be used. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 4, and isopropoxide is particularly preferably used.

Preferred rare earth alkoxides include praseodymium triisopropoxide, neodymium triisopropoxide, samarium triisopropoxide and erbium triisopropoxide.
These rare earth alkoxides can be used alone or in combination of two or more.

  The content ratio of each component in the catalyst composition is not necessarily limited. However, when the ratio of the component (A) to the component (B) is too small, the polymerization tends to be slow, and conversely, the content is too large. Since the molecular weight distribution of the obtained polymer tends to be wide, the molar ratio of component (A) / component (B) is preferably in the range of 0.05 / 1 to 3/1. Further, if the ratio of the component (C) to the component (B) is too small, the polymerization tends to be slow, and conversely if it is too large, the molecular weight distribution of the resulting polymer tends to be widened, so the component (B) / The molar ratio of component (C) is preferably in the range of 1 / 0.05 to 1/5.

  The catalyst composition can be usually prepared by mixing the transition metal complex of component (A), the organic halide of component (B) and the rare earth alkoxide of component (C) immediately before use. In addition, the transition metal complex of component (A), the organic halide of component (B), and the rare earth alkoxide of component (C) are stored separately and added separately to the polymerization reaction system. The catalyst composition may be prepared by mixing in the catalyst.

  In addition to the components (A) to (C), the catalyst composition of the present invention may contain a radical generator in order to accelerate the polymerization. Examples of the radical generator used include radical generators such as azo compounds, organic peroxides, and nonpolar radical generators.

  Specific examples of the azo compound include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile. 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis- (2 -Amidinopropane) dihydrochloride, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile, 1-((1-cyano-1-methylethyl) azo) formamide and the like.

  Specific examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (T-butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5 Dialkyl peroxides such as di (t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane and 1,1-di (t-hexylperoxy) ) Cyclohexane, 1,1-di (t-butylperoxy)- Peroxyketals such as 2-methylcyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di ( Peroxycarbonates such as isopropylperoxy) dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl Cyclic peroxides such as -3,6,9-trimethyl-1,4,7-triperoxonane and 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; It is done.

  Specific examples of the nonpolar radical initiator include, for example, 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1 1,1-triphenyl-2-phenylethane and the like. These radical generators can be used alone or in combination of two or more.

  These radical generators may be contained in a proportion of 50 parts by mass or less with respect to 100 parts by mass in total of the components (A) to (C).

  In the method for producing a polymer according to the present invention, a living radical polymerization of a vinyl monomer is performed in the presence of the catalyst composition. Here, the polymer is used in a concept including a homopolymer, a multi-component copolymer of two or more, and includes a multi-block copolymer such as a diblock and a triblock, and a random copolymer. Further, it may be a gradient polymer in which the monomer composition continuously changes in the polymer chain, and may be a graft polymer, a star polymer, or a polymer having various special structures. Good.

  The vinyl monomer is not particularly limited as long as living radical polymerization is possible. However, the catalyst composition of the present invention uses a specific rare earth alkoxide to improve the functional group resistance of a transition metal complex, particularly an iron complex, contained in the catalyst composition, suppress decomposition and deterioration, and obtain the obtained heavy weight. Since the effect that the molecular weight, molecular weight distribution, and molecular terminal of the coalescence can be stably controlled is exhibited, it can be preferably applied to the polymerization of a vinyl monomer having a functional group that tends to impair the resistance of the transition metal complex.

  The functional group that tends to impair the resistance of the transition metal complex is a nitrogen-containing functional group. Examples of the nitrogen-containing vinyl monomer having a nitrogen-containing functional group include nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile having a nitrile group; dimethylaminoethyl acrylate having an amino group, dimethylaminoethyl methacrylate, or And amino group-containing vinyl monomers such as vinylpyridine having a pyridine structure.

  Moreover, as a vinyl monomer, the various monomer used for living radical polymerization other than the said nitrogen-containing vinyl monomer can also be used, and it can also use together with the said nitrogen-containing vinyl monomer. Examples of such monomers include conjugated diene compounds, aromatic vinyl compounds, and acrylic compounds.

Examples of the conjugated diene compound include butadiene and isoprene.
Aromatic vinyl compounds include styrene, α-methyl styrene, p-methyl styrene, m-methyl styrene, o-methyl styrene, p-ethyl styrene, p-isopropyl styrene, t-butyl styrene, 2,4-dimethyl styrene. 1,5-dimethylstyrene, p-chloromethylstyrene, p- (2-chloroethyl) styrene, vinyltoluene, vinylbenzoic acid, methyl vinylbenzoate, chloromethylstyrene, hydroxymethylstyrene, divinylbenzene A mass is given. The aromatic vinyl compound may be a naphthalene monomer such as vinyl naphthalene.

  Examples of the acrylic compound include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n- (meth) acrylate Octyl, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esthetics such as phenyl acid and stearyl (meth) acrylate System monomers; and the like. In addition, (meth) acryl is used in the meaning including both acryl and methacryl.

In addition to the above, vinyl acetate, vinyl pivalate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl n-caproate, vinyl isocaproate, vinyl octoate, vinyl laurate, vinyl palmitate, vinyl stearate, Vinyl esters such as vinyl trimethyl acetate, vinyl chloroacetate, vinyl trichloroacetate, vinyl trifluoroacetate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl Vinyl ketones such as ketone and isopropenyl vinyl ketone can also be used.
These vinyl monomers can be used alone or in combination of two or more.

  The catalyst composition of the present invention has high functional group resistance, suppresses decomposition and degradation of the transition metal complex, and maintains living radical polymerizability. Therefore, the polymerization of vinyl monomers including nitrogen-containing vinyl monomers is particularly preferred. Although it can be preferably applied to a system, even a vinyl monomer polymerization system that does not contain a nitrogen-containing vinyl monomer exhibits sufficient living radical polymerizability.

  In the present invention, in the presence of a catalyst composition comprising a transition metal complex (component (A)), an organic halide (component (B)) as a polymerization initiator, and a rare earth alkoxide (component (C)) as an activator. The polymer is obtained by living radical polymerization of the vinyl monomer. The vinyl monomer may be added to the polymerization reaction system from the beginning, or may be added sequentially as the polymerization proceeds.

  The molecular weight of the polymer obtained by the production method of the present invention is preferably 500 to 1,000,000 (number average molecular weight) because if the molecular weight is too small, the function as a polymer is difficult to be exhibited, and if it is too large, handling becomes difficult. , 1000 to 500,000 (number average molecular weight) is more preferable. Here, the molecular weight of the polymer can be adjusted by adjusting the amount of the organic halide of the component (B) contained in the catalyst composition with respect to the vinyl monomer. Specifically, increasing the amount of organic halide used can reduce the molecular weight of the polymer, and conversely reducing the amount of organic halide used can increase the molecular weight of the polymer.

  As a polymerization method used in the production method of the present invention, a conventionally known method can be used, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these, from the viewpoint of reducing chain transfer and controlling the polymerization more precisely, a solution polymerization method or a bulk polymerization method with a very high vinyl monomer concentration is preferably used. In the solution polymerization method, the vinyl monomer concentration is preferably 10% by weight or more, and more preferably 20% by weight or more. Moreover, you may superpose | polymerize continuously using an extruder.

  Examples of solvents that can be used when the solution polymerization method is employed include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene; methylene chloride, chloroform Halogenated hydrocarbon solvents such as chlorobenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; acetonitrile, pro Nitrile solvents such as pionitrile and benzonitrile; acetate solvents such as ethyl acetate and butyl acetate; cyclic ester solvents such as γ-butyrolactone and ε-caprolactone; Examples include, but are not limited to, cyclic carbonate solvents such as ethylene carbonate and propylene carbonate; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; aprotic polar solvents such as dimethyl sulfoxide; It is not a thing.

  Among these, the use of cyclic ester solvents such as γ-butyrolactone and ε-caprolactone; cyclic carbonate solvents such as ethylene carbonate and propylene carbonate can be preferably used because the polymerization reaction is accelerated. A solvent can be used individually or in mixture of 2 or more types.

In the production method of the present invention, at the start of the polymerization reaction, a vinyl monomer, a solvent, a rare earth alkoxide (component (C)), and a transition metal complex (component) in an atmosphere of an inert gas such as nitrogen. It is preferable to prepare a mixture comprising (A)) and add an organic halide (component (B)) thereto.
The polymerization temperature is usually 10 to 120 ° C, preferably 25 to 100 ° C.

  After completion of the polymerization, for example, the polymerization reaction system is cooled to 0 ° C. or lower, preferably about −78 ° C., or a polymerization inhibitor is added to stop the polymerization reaction. Thereafter, the produced polymer is obtained by a conventional method. For example, if desired, the polymer solution is diluted with a solvent such as toluene and then poured into methanol, and the precipitate is washed several times and dried under reduced pressure at room temperature to obtain the desired polymer. Can do.

  In the living radical polymerization in the present invention, the carbon-halogen bond in the organic halide of component (B) is activated by the transition metal complex of component (A) and the rare earth alkoxide which is a Lewis acid of component (C), Polymerization proceeds in such a manner that a vinyl monomer is inserted during bonding. This type of polymerization is supported by the fact that many of the growth terminals of the polymer obtained are halogen elements. Therefore, it is possible to introduce a functional group into the starting terminal of the polymer obtained by using an organic halide having a functional group as the component (B). It is also possible to convert the halogen element at the growth end to another functional group by utilizing the reactivity of the halogen element at the growth end.

  Thus, the terminal functional group introduced into the target polymer can be used for synthesis of a macromonomer, synthesis of a block copolymer, a crosslinking point, and the like. Further, the block copolymer obtained in this way exhibits novel physical properties that cannot be obtained with a homopolymer. For example, a diblock copolymer is useful as a compatibilizing agent and the like, and an ABA type triblock copolymer is useful as a thermoplastic elastomer and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples. In the following Examples and Comparative Examples, unless otherwise specified, all operations were performed under a dry nitrogen gas atmosphere, and reagents were collected from the container with a syringe and added to the reaction system. The solvent and monomer were purified by distillation and further blown with dry nitrogen gas.

Further, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymers in the following Examples and Comparative Examples are determined by gel permeation chromatography (GPC) measurement. It was.
Tetrahydrofuran (THF) is used as an eluent, and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko KK are used and are shown in terms of polystyrene.

The monomer conversion rate was determined based on ¹ H-NMR measurement using JNM-LA500 manufactured by JEOL as a measuring device, CDCl ₃ as a solvent, n-hexane as an internal standard substance, and the unreacted unit in the polymerization solution. Calculation was performed by measuring the amount of the monomer.

Living polymerizability was evaluated according to the following criteria.
(Living polymerizability)
The difference between Mn 9 hours after the start of the polymerization reaction and Mn in the middle of the polymerization reaction (at any time when the conversion rate is about 15% to 50%) was calculated using Conv. (%) And Conv. The value divided by the difference in (%) was used as an index of living property. A polymerization system showing 30 or more was judged to have good living polymerizability, and less than 30 was judged to have poor living polymerizability.

Reference example (production of ethyl methacrylate hydride (2-iodoisobutyrate))
61 g of sodium iodide (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed and put into a three-necked flask purged with argon, and after thoroughly drying, 250 ml of acetone was added to dissolve sodium iodide. 12.5 ml of ethyl 2-bromoisobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd .: a commercial product having the same chemical structure as ethyl methacrylate hydrobromide) was added to the solution and reacted at 65 ° C. for 24 hours. A halogen exchange reaction was performed.

After filtering the obtained reaction product, distilled water and diethyl ether were added to the filtrate, and only the organic layer was extracted using a separatory funnel. The obtained organic layer was washed successively with an aqueous sodium thiosulfate solution, an aqueous sodium chloride solution and distilled water, and then only the organic layer was extracted and dried under reduced pressure. The resulting reaction product was further purified by distillation under reduced pressure, and then dried under reduced pressure at 60 ° C. and 1.33 × 10 ³ Pa to obtain the desired hydrogen iodide of ethyl methacrylate (2-iodoisobutyric acid). Ethyl).

(Manufacture of other organic halides)
In the above, sodium chloride was used in place of sodium iodide and reacted with ethyl 2-bromoisobutyrate to obtain a hydrogen chloride of ethyl methacrylate. Further, instead of ethyl 2-bromoisobutyrate, methyl 2-bromopropionate (manufactured by Wako Pure Chemical Industries, Ltd .: a commercial product having the same chemical structure as hydrobromide of methyl acrylate), sodium iodide and By making it react, the hydroiodide of methyl acrylate was obtained.

Example 1
In a nitrogen atmosphere, toluene is used as a solvent in a 30 mL glass reaction vessel, an organic halide (ethyl iodide hydride) is 60 mmol / l, a transition metal complex (dicarbonylcyclopentadienyl iron dimer (manufactured by Aldrich) )) Is 10 mmol / l, rare earth alkoxide (samarium triisopropoxide (Aldrich)) is 100 mmol / l, isoprene (Wako Pure Chemical Industries) is 3 mol / l, and acrylonitrile (Wako Pure Chemical Industries) is 3 mol / l, n-hexane (manufactured by Wako Pure Chemical Industries, Ltd.) as an internal standard substance is uniformly mixed so as to be 150 mmol / l to prepare a polymerization reaction solution, and the reaction solution is heated to 80 ° C. Polymerization was started.

  After reacting for 9 hours, the polymerization solution was cooled to −78 ° C. to stop the polymerization, and the volatile matter was distilled off under reduced pressure to obtain a random (isoprene-acrylonitrile) copolymer. The total conversion of isoprene and acrylonitrile was 65%, and the polymer produced had Mn = 9,000 and Mw / Mn = 1.60 from GPC measurement (polystyrene conversion). Living polymerizability was good.

(Examples 2 to 19)
A predetermined amount of vinyl monomer, organic halide, transition metal complex, and rare earth alkoxide shown in Table 1 were used, and other solvents, experimental operations, and experimental conditions were initiated in accordance with the same operations as in Example 1. After reacting for a period of time, the polymerization solution was cooled to −78 ° C. to terminate the polymerization. The obtained polymerization solution was processed in the same manner as in Example 1, and the total conversion rate of vinyl monomers and GPC (polystyrene conversion) were measured. These measurement results are shown in Table 1.

(Example 20)
Under nitrogen atmosphere, 30 mL glass reaction vessel, toluene as solvent, 60 mmol / l ethyl methacrylate hydride, chloropentamethylcyclopentadienylbistriphenylphosphine ruthenium (RuCp ^* Cl (PPh ₃ ) ₂ ) (Aldrich) 10 mmol / l, Tributylamine (Tokyo Kasei Kogyo) 100 mmol / l, Samarium triisopropoxide (Aldrich) 100 mmol / l, Isoprene (Wako Pure Chemical Industries) 3 mol / l The polymerization reaction solution was prepared by uniformly mixing so that acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was 3 mol / l and n-hexane (manufactured by Wako Pure Chemical Industries, Ltd.) was 150 mmol / l as an internal standard substance. The reaction solution was heated to 80 ° C. to initiate polymerization.

  After reacting for 9 hours, the polymerization solution was cooled to −78 ° C. to stop the polymerization, and the volatile matter was distilled off under reduced pressure to obtain a random (isoprene-acrylonitrile) copolymer. The total conversion rate of isoprene and acrylonitrile was 43%, and the produced polymer had Mn = 4,100 and Mw / Mn = 1.52 from GPC measurement (polystyrene conversion). Living polymerizability was good.

(Example 21)
Under a nitrogen atmosphere, toluene was used as a solvent in a 30 mL glass reaction vessel, ethyl methacrylate hydride was 60 mmol / l, copper (I) bromide (Aldrich) 10 mmol / l, tris (2-pyridylmethyl) ) Amine (Aldrich) 30 mmol / l, Samarium triisopropoxide (Aldrich) 100 mmol / l, Isoprene (Wako Pure Chemical Industries) 3 mol / l, Acrylonitrile (Wako Pure Chemical Industries) 3 mol / l, n-hexane (manufactured by Wako Pure Chemical Industries, Ltd.) as an internal standard substance is uniformly mixed so as to be 150 mmol / l to prepare a polymerization reaction solution, and the reaction solution is heated to 80 ° C. Polymerization was started.

  After reacting for 9 hours, the polymerization solution was cooled to −78 ° C. to stop the polymerization, and the volatile matter was distilled off under reduced pressure to obtain a random (isoprene-acrylonitrile) copolymer. The total conversion rate of isoprene and acrylonitrile was 39%, and the polymer produced had Mn = 3,800 and Mw / Mn = 1.49 from GPC measurement (polystyrene conversion). Living polymerizability was good.

(Comparative Examples 1-3)
A predetermined amount of vinyl monomer, organic halide, transition metal complex and Lewis acid shown in Table 2 were used. Other solvents, experimental operations and experimental conditions were the same as those in Example 1, and polymerization was started. After reacting for a period of time, the polymerization solution was cooled to −78 ° C. to terminate the polymerization. The obtained polymerization solution was processed in the same manner as in Example 1, and the total conversion rate of vinyl monomers and GPC (polystyrene conversion) were measured. These measurement results are shown in Table 1. Living polymerizability was poor.

As can be seen from Tables 1 and 2, when the rare earth alkoxide was used as the Lewis acid, the conversion rate of the vinyl monomer was improved and the polymerization activity was improved in the same transition metal complex. Also, good living polymerizability was shown.

In the above table, Cp represents cyclopentadienyl, Cp ^* represents pentamethylcyclopentadienyl, Ind represents indenyl, and ⁱ Pr represents isopropyl.

Claims (9)

(A) transition metal complex,
A catalyst composition comprising (B) an organic halide and (C) a rare earth alkoxide.   The catalyst composition according to claim 1, wherein the transition metal complex (A) is a transition metal complex having iron as a central metal.   Transition metal complexes with iron as the central metal are dicarbonylcyclopentadienyl iron dimer, dicarbonylcyclopentadienyl iodoiron, dicarbonyl (pentamethylcyclopentadienyl) iron dimer, dicarbonyl (pentamethylcyclopentadiene). The catalyst composition of claim 2 selected from the group consisting of (enyl) iodoiron and dicarbonylindenyl iron dimer.   The catalyst composition according to any one of claims 1 to 3, wherein the organic halide (B) is an organic iodide.   5. The rare earth alkoxide (C) is an alkoxide of a rare earth element selected from the group consisting of praseodymium (Pr), neodymium (Nd), samarium (Sm), and erbium (Er). The catalyst composition.   The catalyst composition according to any one of claims 1 to 5, wherein the rare earth alkoxide (C) is isopropoxide.   The manufacturing method of a polymer which performs living radical polymerization of a vinyl monomer in presence of the catalyst composition in any one of Claims 1-6.   The method for producing a polymer according to claim 7, wherein the vinyl monomer contains a nitrogen-containing vinyl monomer.   The method for producing a polymer according to claim 7 or 8, wherein the vinyl monomer contains a monomer selected from the group consisting of a conjugated diene compound and an aromatic vinyl compound.