JPH11158206A - Living radical polymerization initiator system and preparation of polymer by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a polymer having a narrow molecular weight distribution in a relatively short time while controlling the molecular weight and suppressing side reactions by living radical polymerizing a radical-polymerizable monomer using a living radical polymerization initiator system comprising a specific metal complex, a specific halogen compound and a Lewis base. SOLUTION: A living radical polymerization initiator system is used, which comprises (A) a metal complex comprising a central metal selected from metals of the group 10 in the periodic table and both carbon monoxide and phosphorus compounds as legends coordinating to the central metal; (B) a compound having at least one of a halogenated sulfonyl group and a halogen atom linking to a carbon atom having no unsaturated bonds; and (C) a Lewis base. As the metal complex of component A, for example, dicarbonylbis (triphenylphosphine) nickel is preferred. Component B includes, for example, carbon tetrachloride, trichloromethanesulfonyl chloride and the like. Component C includes trialkoxyaluminum, titanium tetrachloride and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a living radical polymerization initiator system, and more particularly, to a living radical polymerization initiator capable of easily obtaining a living polymer having a narrow molecular weight distribution in a relatively short time while controlling the molecular weight. The present invention relates to an initiator system and a method for producing a polymer using the initiator system.

[0002]

2. Description of the Related Art Various living radical polymerization methods have been proposed as methods for producing a polymer having a narrow molecular weight distribution from a monomer capable of radical polymerization such as a vinyl compound while controlling the molecular weight. For example, the iniferter method (Mak
romol. Chem. , Rapid Commu
n. , Vol. 3,127 (1982)), iodine transfer polymerization method (Contemporary Topics i).
n Polymer Science, Vol. 4,7
64 (1984); Polymer Prep. Ja
p. , Vol. 43 (2), 255 (1994); Ma
cromolecules, Vol. 28,2093
(1995)), a method using a stabilized radical (USP
4,581,429 (1986); Macromole
cules, Vol. 26, 2987 (1993);
J. Am. Chem. Soc. , Vol. 116, 11
185 (1994)), a method using a transition metal complex (M
acromolecules, Vol. 28,1721
(1995); Am. Chem. Soc. , Vo
l. 117, 5614 (1995); Am. Che
m. Soc. , Vol. 116, 7943 (199
4); JP-A-8-41117) and the like have been proposed.

[0003] Among these methods, the method using a transition metal complex has a wide range of polymerizable monomers, relatively easy control of the molecular weight, and enables synthesis of a block copolymer. It is known as a highly versatile living radical polymerization method. Among them, in the method described in JP-A-8-41117, according to the examples, as the central metal, a Group 8 element of the periodic table (Chemical Handbook) Chlorine and triphenylphosphine were simultaneously coordinated to ruthenium selected from the Periodic Table described in Basic Edition I, 4th revised edition (edited by the Chemical Society of Japan, 1993), which corresponds to Group 8-10 elements. A metal complex, and carbon tetrachloride as a halogenated hydrocarbon,
In the presence of a living radical polymerization initiator system using bis (2,6-di-t-butylphenoxy) methylaluminum in combination as a Lewis acid, the unsaturated carboxylic acid monomer is subjected to living radical polymerization to reduce the molecular weight. A polymer with a narrow molecular weight distribution is obtained while controlling.

[0004]

However, in living radical polymerization, since the growing species are unstable radicals, it is necessary to keep the concentration of active radicals in the polymerization system low in order to maintain the living property. There is a problem that it takes a long time to complete the polymerization as compared with free radical polymerization. It is conceivable to carry out the polymerization at a high temperature in order to shorten the polymerization time. However, if the polymerization temperature is excessively increased, there is a concern that a side reaction may be induced. In the living radical polymerization method described in JP-A-8-41117 using a living radical polymerization initiator system composed of a metal complex or the like having ruthenium as a central metal, the above bis (2,2) is used as a Lewis acid.
When 6-di-t-butylphenoxy) methylaluminum is used, the polymerization reaction rate is increased, but the side reaction cannot be suppressed, and the polymer obtained by the side reaction is Therefore, it has a bimodal molecular weight distribution curve. Also, in the living radical polymerization method described in the same publication, depending on the type of Lewis acid used,
As a result, there is a problem that the polymerization time becomes longer and the production efficiency of the polymer cannot be sufficiently improved.

An object of the present invention is to solve the above-mentioned problems of the prior art. When a radical polymerizable monomer is subjected to living radical polymerization, a polymer having a narrow molecular weight distribution can be controlled while controlling the molecular weight. It is an object of the present invention to suppress side reactions so that the reaction can be obtained in a relatively short time.

[0006]

Means for Solving the Problems The present inventors, as a central metal, have used Group 10 elements of the Periodic Table (Chemical Handbook, Basic Edition I, Rev. 4).
Edition (see The Chemical Society of Japan, 1993)), a metal complex in which carbon monoxide and a phosphorus compound are simultaneously coordinated to a metal selected from the metal and a carbon having no sulfonyl halide group or unsaturated bond. The present inventors have found that the above object can be achieved by using a living radical polymerization initiator system composed of a compound having at least one of a halogen atom and a Lewis acid, thereby completing the present invention.

That is, the present invention provides the following component (A):
(B) and (C): (A) a metal complex in which carbon monoxide and a phosphorus compound are simultaneously coordinated as ligands to a central metal selected from Group 10 elements of the periodic table; A living radical polymerization initiator system, comprising: a compound having at least one of a halogenated sulfonyl group and a halogen atom bonded to a carbon atom having no unsaturated bond; and (C) a Lewis acid.

The present invention also provides a method for producing a polymer, comprising subjecting a radically polymerizable monomer to living polymerization in the presence of the above-mentioned living radical polymerization initiator system.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The living radical polymerization initiator system of the present invention has at least one of component (A) a metal complex, component (B) a sulfonyl halide group and a halogen atom bonded to a carbon atom having no unsaturated bond. Compound,
And component (C) a Lewis acid. The term "unsaturated bond" used for the component (B) includes not only a usual double bond and triple bond, but also a double bond used for convenience in describing an aromatic ring.

The metal complex of the component (A) is represented by the following formula 10
The complex is a complex in which at least one of carbon monoxide and at least one of phosphorus compounds are simultaneously coordinated as ligands to a central metal selected from group elements. By using this metal complex, the living radical polymerization reaction rate can be increased.

Here, the elements of Group 10 of the periodic table include:
Nickel, palladium or platinum can be mentioned, and nickel can be preferably mentioned. By using a Group 10 element of the periodic table as the central metal, a polymer having a narrow molecular weight distribution and a unimodal molecular weight distribution curve, which has been difficult in the conventional case using ruthenium as the central metal, It becomes possible to produce at a living radical polymerization rate.

Further, by coordinating carbon monoxide and a phosphorus compound simultaneously as a ligand which coordinates with a central metal selected from Group 10 elements of the periodic table to form a complex,
The living radical polymerization rate can be increased as compared with the case where any of them is replaced with chlorine or the like.

Examples of the phosphorus compound of the ligand are preferably trialkylphosphines such as triethylphosphine and tributylphosphine, triarylphosphines such as triphenylphosphine and trinaphthylphosphine, and trialkylphosphites such as tributylphosphite.
Examples include triaryl phosphites such as triphenyl phosphite, bisphosphinoalkanes such as 1,2-bis (diphenylphosphino) ethane, and phosphaalkenes. Of these, triphenylphosphine is more preferable.

The central metal of the metal complex of the component (A) may be coordinated with a ligand other than carbon monoxide and a phosphorus compound. The ligand is not particularly limited. However, examples thereof include alkene, alkyne, carbene, alkyl, aryl, acyl, halogen, hydrogen and the like.

Specific examples of the metal complex of component (A) as described above include dicarbonylbis (triphenylphosphine) nickel, dicarbonylbis (tributylphosphine) nickel, and dicarbonylbis (triphenylphosphite) nickel. , Bromobiscarbonylbis (triphenylphosphine) nickel, dibromocarbonylbis (triethylphosphine) nickel, carbonyltris (triphenylphosphine) palladium, carbonylchlorobis (triethylphosphine) baradium tetrafluoroborate, carbonyltris (triphenylphosphine) Platinum, dicarbonylbis (triphenylphosphine) platinum, carbonylchlorobis (triphenylphosphine) platinum, carbonyldichloro (triethylphosphine) Fin) platinum, dibromo carbonyl (triethylphosphine) platinum, bromo (carbonyl) methyl (triphenylphosphine) can be exemplified platinum or the like.

In the present invention, the compound of the component (B) is
It has at least one of a halogenated sulfonyl group and a halogen atom bonded to a carbon atom having no unsaturated bond. This compound is cleaved between a carbon atom having no unsaturated bond and a halogen atom bonded thereto or between an S atom and a halogen atom of a sulfonyl halide group by the action of the metal complex of the component (A). Thus, it is considered to have a function of generating radical active species and initiating polymerization.

Preferred compounds of component (B) include compounds of formula (B1) or (B2)

[0019]

Embedded image CX ¹ X ² X ³ X ⁴ (B1) RSO ₂ X (B2) (in the formula (B1) or (B2), X and X ¹ each represent a halogen atom, and X ² , X ³ and X ⁴ is each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an aryl group which may be substituted, and a hetero atom-containing organic group; A good alkyl group or an optionally substituted aryl group).

In the above formula (B1), examples of the halogen atom for X ¹ include iodine, bromine and chlorine.

X ² , X ³ and X ⁴ may be the same or different from each other because they are independently selected groups. Here, examples of the halogen atom of X ² , X ³ and X ⁴ include iodine, bromine and chlorine. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and the like, and these are an ester group, a ketone group, an ether group, It may be substituted with a thioester group, thioether group, imino group, amide group, halogen atom or the like. Examples of the aryl group include a phenyl group, a naphthyl group, a pyranyl group, a furanyl group, a pyridyl group, and the like. , An amide group, a halogen atom or the like. The hetero atom-containing organic group is an organic group having 1 to 10 carbon atoms containing a hetero atom such as oxygen, nitrogen, sulfur and the like, and is an ester, ketone, ether, thioester, thioether, imine,
An organic group having an amide bond or the like can be given.

Specific examples of the compound of the above formula (B1) include carbon tetrachloride, bromotrichloromethane, dichlorodibromomethane, chlorotribromomethane, carbon tetrabromide, iodotrichloromethane, dichlorodiiodomethane, Chlorotriiodomethane, methane tetraiodide, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, chloroform, dichloromethane, methyl chloride, bromoform, dibromomethane, methyl bromide,
Iodoform, diiodomethane, methyl iodide, 1,
1,1-trichloroethane, 1,1-dichloroethane,
Ethyl chloride, 2,2-dichloropropane, isopropyl chloride, t-butyl chloride, 1,1,1-tribromoethane, 1,1-dibromoethane, ethyl bromide, 2,2-dibromopropane, isoprobromide Building, t-butyl bromide,
1,1,1-triiodoethane, 1,1-diiodoethane, ethyl iodide, 1,1-diiodoethane, ethyl iodide, 2,2-diiodopropane, isopropyl iodide, t-butyl iodide, Bromo-1,1-dichloroethane, 1-chloro-1,1-dibromoethane, 1-bromo-1-chloroethane, 1-iodo-1,1-dichloroethane, 1-chloro-1,1-diiodoethane, 2-
Chloro-2-iodopropane, 1-iodo-1,1-dibromoethane, 2-bromo-2-iodopropane, 1-
Phenylethyl bromide, 2,2-dichloroacetophenone, ethyl 2-bromobutyrate, dimethyl 2-bromo-2-methylmalonate, benzyl chloride, benzyl bromide, benzyl iodide, allyl chloride, allyl bromide, allyl iodide,
Xylylene dichloride, xylylene dibromide, xylylene diiodide and the like can be mentioned.

In the formula (B2), examples of the halogen atom for X include iodine, bromine and chlorine. Examples of the alkyl group for R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. , An ether group, a thioester group, a thioether group, a sulfonyl halide group, an imino group, an amide group, a halogen atom, or the like. Examples of the aryl group include a phenyl group, a naphthyl group, a pyranyl group, a furanyl group, a pyridyl group, and the like. May be substituted with a sulfonyl chloride group, an imino group, an amide group, a halogen atom, or the like.

Specific examples of the compound of the above formula (B2) include trichloromethanesulfonyl chloride, trichloromethanesulfonyl bromide, trichloromethanesulfonyl iodide, dichloromethanesulfonyl chloride, dichloromethanesulfonyl bromide, dichloromethanesulfonyl iodide,
Chloromethanesulfonyl chloride, chloromethanesulfonyl bromide, chloromethanesulfonyl iodide, methanesulfonyl chloride, methanesulfonyl bromide, methanesulfonyl iodide, dibromomethanesulfonyl chloride, dibromomethanesulfonyl bromide, dibromomethanesulfonyl iodide, bromochloride Methanesulfonyl, bromomethanesulfonyl bromide, bromomethanesulfonyl iodide, diiodomethanesulfonyl chloride, diiodomethanesulfonyl bromide, diiodomethanesulfonyl iodide, iodomethanesulfonyl chloride, iodomethanesulfonyl bromide, iodomethane iodide Sulfonyl, chloromethanesulfonyl chloride, chloromethanesulfonyl bromide, chloromethanesulfonyl iodide, tribromomethanesulfonyl chloride, tribromomethanesulfonyl bromide, iodide Libromomethanesulfonyl, triiodomethanesulfonyl chloride, triiodomethanesulfonyl bromide, triiodomethanesulfonyl iodide, benzenesulfonyl chloride, parachlorobenzenesulfonyl chloride, paramethylbenzenesulfonyl chloride, paranitrobenzenesulfonyl chloride, paranitrobenzenesulfonyl chloride, benzenesulfonyl bromide, Parachlorobenzenesulfonyl bromide, paramethylbenzenesulfonyl bromide, paranitrobenzenesulfonyl bromide, 1,4-disulfonylbenzene dichloride, 1,4-disulfonylbenzene dibromide, 1,4-disulfonylbenzene diiodide 2,6-disulfonylnaphthalene dichloride, 2,6-disulfonylnaphthalene dibromide, 2,6-diiodide
Disulfonylnaphthalene and the like can be mentioned.

In the present invention, the Lewis acid of the component (C) is used as an activator for promoting the progress of living radical polymerization in cooperation with the metal complex of the component (A). C1) or (C2)

[0026]

Embedded image AlY ¹ Y ² Y ³ (C1) MZ ¹ Z ² Z ³ Z ⁴ (C2) (in the formula (C1) or (C2), Y ¹ , Y ² , Y ³ , Z ¹ , Z
² , Z ³ and Z ⁴ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group or an optionally substituted aryloxy group. , M is Ti (IV) or Sn
(IV). )).

In the formula (C1) or (C2),
The halogen atom of Y ¹ , Y ² , Y ³ , Z ¹ , Z ² , Z ³ or Z ⁴ is chlorine, bromine or iodine. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

As the aryl group, a phenyl group,
Examples include a naphthyl group. These may also be substituted with one or more alkyl groups having 1 to 5 carbon atoms, preferably a methylphenyl group, an ethylphenyl group,
And a methylnaphthyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group and a t-butoxy group.

Examples of the aryloxy group include a phenoxy group and a naphthoxy group. These may be substituted on the aromatic ring with one or more alkyl groups having 1 to 5 carbon atoms, and preferably, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, or a 2-methylphenoxy group. Ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,6-dimethylphenoxy group, 2,6-diethylphenoxy group, 2,6-di-
Examples thereof include an n-butylphenoxy group and a 2,6-di-t-butylphenoxy group.

Preferred specific examples of the above-mentioned Lewis acid of the formula (C1) include trialkoxyaluminum, and particularly preferred is triisopropoxyaluminum.

Preferred examples of the Lewis acid of the formula (C2) include titanium halides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide, titanium tetraethoxide and titanium tetra-n-butoxide. Examples thereof include tin halides such as titanium tetraalkoxide, tin tetrachloride, tin tetrabromide, and tin tetraiodide.

In the living radical polymerization initiator system of the present invention, the molar ratio of the metal complex of the component (A) to the compound of the component (B) is such that if the latter is too small, the polymerization rate is reduced, and if the latter is too large, the molecular weight distribution is reduced. (A) /
(B) is preferably in the range of 0.1 to 100, more preferably 0.5 to 10. If the compound molar ratio of the compound of the component (B) and the Lewis acid of the component (C) is too small, the polymerization rate becomes slow, and if it is too large, the treatment after the polymerization reaction becomes complicated. / (C) is preferably in the range of 0.05 to 5, more preferably 0.2 to 2.

The living radical polymerization initiator system of the present invention can be usually produced by mixing components (A), (B) and (C) by a conventional method immediately before use.
Further, the components (A), (B) and (C) are separately stored, separately added to the polymerization reaction system, and mixed in the polymerization reaction system to form a living radical polymerization initiator system. It may be made to function as.

Next, a method for producing a polymer using the living radical polymerization initiator system of the present invention will be described.

In this production method, a radical polymerizable monomer is basically subjected to living polymerization in an organic solvent in the presence of the living radical polymerization initiator system of the present invention. As a result, the number average molecular weight (Mn) of the obtained polymer can be increased almost in proportion to the increase in the polymerization rate, and further represented by the ratio of weight average molecular weight / number average molecular weight (Mw / Mn). The molecular weight distribution can be close to 1. Therefore, during the progress of the polymerization, living polymerization can proceed without generating a polymer due to chain termination or transfer reaction. Furthermore, if a new monomer is added to the polymerization reaction system in which polymerization has been almost completed, the number average molecular weight can be increased while maintaining the molecular weight distribution (Mw / Mn) close to 1. Therefore, according to the present invention, even after the completion of the polymerization reaction, the terminating end of the radical does not cause a termination reaction, and the living state can be maintained.

As the organic solvent used in the production method of the present invention, for example, an unsubstituted or one or more alkyl group-substituted aromatic hydrocarbon such as benzene, toluene, isopropylbenzene and xylene is preferably used. it can. The amount of the solvent used can be appropriately determined according to the type of the solvent, the type of the radical polymerizable monomer, and the like.

The radical polymerizable monomer to be polymerized is not particularly limited as long as it is capable of undergoing radical polymerization, and may be a (meth) acrylate monomer, a vinyl ester monomer, or a styrene monomer. , Halogen-based unsaturated monomers, olefin-based monomers, diene-based monomers, unsaturated carboxylic acid monomers and the like. These can be used in combination of two or more.

Here, the (meth) acrylate monomer includes a monomer unit having an alkyl group having 1 to 12 carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate,
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, (meth)
Dimethylaminoethyl acrylate and quaternary compounds thereof, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylamido-2-methylpropylsulfonic acid or its sodium salt, hydroxyethyl (meth) acrylate , Caprolactone-modified (meth) acrylate, N-methylol (meth)
Preferred examples include N-alkylolamides of α, β-ethylenically unsaturated carboxylic acids such as acrylamide, ethylene glycol (meth) acrylate, and the like. In this specification, “(meth) acrylic acid”
Is a generic term for “acrylic acid” and “methacrylic acid”, and similarly, “(meth) acrylamide” is a generic term for “acrylamide” and “methacrylamide”, and “(meth) acrylate” is “acrylate”. "And" methacrylate ".

Preferred examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate and vinyl pivalate.

As the styrene monomer, styrene, α
Preferred examples include -methylstyrene, o-methylstyrene, p-methylstyrene, p-styrenesulfonic acid, and alkali metal salts thereof (sodium salt, potassium salt, and the like).

Preferred examples of the halogenated unsaturated monomer include vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and vinylidene bromide.

As the olefin-based monomer, ethylene,
Preferred are propylene and isobutylene.

Preferred examples of the diene-based monomer include butadiene, isoprene, chlorobrene, and neobrene.

Preferred examples of the unsaturated carboxylic acid monomer include (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid and salts thereof.

In the production method of the present invention, if the initial concentration of the radically polymerizable monomer in the polymerization reaction system is too low, the reaction rate is too slow, and if it is too high, the chain transfer reaction of the generated radical to the monomer will not occur. Increases, and the molecular weight distribution of the obtained polymer is widened, so that it is preferably 0.01 to 5 M (mol) / L.
(Liter), more preferably in the range of 0.05 to 3 M / L. At this time, the concentration of the compound of the component (B) is preferably from 1 to 1 in accordance with the concentration of the radical polymerizable monomer.
The range is 100 mM (mmol) / L (liter), preferably 10 to 50 mM / L. The concentration of the metal complex of component (A) is in the range of 0.1 to 100 mM / L, preferably 1 to 100 mM / L. The concentration of the component (C) Lewis acid is 1 to 200 mM / L, preferably 10 to 200 mM / L.
The range is 100 mM / L.

The preferred compounding molar ratio of the metal complex of the component (A) and the compound of the component (B) in the polymerization reaction system, and the preferable mixing of the compound of the component (B) and the Lewis acid of the component (C) The molar ratios are the same as those preferred molar ratios in the living radical polymerization initiator system of the present invention.

In the production method of the present invention, when starting the living radical polymerization reaction, a monomer, a solvent, a Lewis acid (component (C)) and a metal complex are placed in a reaction vessel under an atmosphere of an inert gas such as argon. It is preferable to prepare a mixture consisting of (component (A)) and to add an initiator (component (B)) thereto. The polymerization is initiated by heating the mixture thus obtained.

The polymerization temperature is not particularly limited, but is usually in the range of 25 to 100 ° C. A polymerization time of about several hours to several tens hours is generally sufficient, and the polymerization rate of the monomer can be increased to about 70 to 90% or more.

After the completion of the polymerization reaction, the polymerization reaction system
Preferably, the reaction is stopped by cooling to about -78 ° C,
Next, the polymer can be obtained by extracting the produced polymer with an organic solvent such as toluene, removing the polymerization initiator-based metal component and the like with a dilute mineral acid aqueous solution, and evaporating volatile components.

[0051]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

In the following Examples and Comparative Examples, unless otherwise specified, all operations were performed in a dry argon gas atmosphere, and reagents were collected from the container by a syringe and added to the reaction system. Further, the solvent and the monomer were purified by distillation, and used after blowing dry argon gas into this.

Example 1 2.56 mL (24 mmol) of methyl methacrylate and 2 mL of n-octane were collected in a Schlenk reaction tube and mixed uniformly. 7.68 mL of a 125 mM / L toluene solution of triisopropoxy aluminum is added to this mixed solution.
(0.96 mmol) and then 25 mM / L of dicarbonylbis (triphenylphosphine) nickel
19.2 mL (0.48 mmol) of the toluene solution was
The mixture was added at 78 ° C and stirred well. Finally, 0.48 mL of a 1 M / L toluene solution of bromotrichloromethane (0.48 mL) was added.
Mmol). The polymerization reaction was started by heating the obtained mixture to 80 ° C.

When one hour has elapsed after the initiation of the polymerization reaction,
The polymerization reaction was stopped by cooling the polymerization reaction system to -78 ° C. Using n-octane as an internal standard, the concentration of methyl methacrylate in the obtained reaction solution was analyzed by gas chromatography. As a result, the polymerization rate of methyl methacrylate was 47%.

The polymethyl methacrylate present in the reaction solution had a number average molecular weight (Mn) of 2100 and a weight average molecular weight (Mw) of 2810, and therefore Mw / Mw
Mn was 1.34.

Here, the values of Mn and Mw are values obtained as a result of measurement under the following conditions using gel permeation chromatography (GPC). In addition, the GPC curve of the obtained poly (methyl methacrylate) was monomodal.

Column: Shodex K-805L (3 in series) Solvent: chloroform Temperature: 40 ° C. Detector: RI Flow rate: 1 mL / min

Example 2 A polymerization reaction was carried out in the same manner as in Example 1 except that the polymerization reaction was stopped 25 hours after the initiation of the polymerization reaction, and the same analysis was conducted. As a result, the polymerization rate of methyl methacrylate was 95%, the number average molecular weight was 4100, the weight average molecular weight was 5850, Mw / Mn was 1.43, and G
The PC curve was unimodal.

Example 3 A polymerization reaction was started in the same manner as in Example 1 except that the polymerization temperature was changed to 30 ° C. Ten hours after the start of the polymerization reaction, the polymerization reaction system was cooled to stop the polymerization reaction, and the result of the polymerization reaction was examined in the same manner as in Example 1. As a result, the polymerization rate of methyl methacrylate was 35
%, Number average molecular weight is 2600, and weight average molecular weight is 315
0, Mw / Mn was 1.21, and the GPC curve was monomodal.

Example 4 The procedure of Example 3 was repeated, except that the polymerization reaction was stopped 48 hours after the start of the polymerization reaction. The conversion of methyl methacrylate is 73
%, Number average molecular weight is 4600, and weight average molecular weight is 590
0, Mw / Mn was 1.28, and the GPC curve was unimodal.

Example 5 A polymerization reaction was started in the same manner as in Example 1 except that the polymerization temperature was changed to 10 ° C. Twenty-one hours after the start of the polymerization reaction, the polymerization reaction system was cooled to stop the polymerization reaction, and the result of the polymerization reaction was examined in the same manner as in Example 1. As a result, the polymerization rate of methyl methacrylate was 24
%, Number average molecular weight is 1200, and weight average molecular weight is 151
0, Mw / Mn was 1.26, and the GPC curve was unimodal.

Example 6 The procedure of Example 5 was repeated, except that the polymerization reaction was stopped 72 hours after the start of the polymerization reaction, and the results of the polymerization reaction were examined. The polymerization rate of methyl methacrylate was 47%, the number average molecular weight was 2,300, the weight average molecular weight was 2,670, Mw / Mn was 1.16, and the GPC curve was unimodal.

As can be seen by comparing Example 2 with Example 1, Example 4 with Example 3, and Example 6 with Example 5, increasing the degree of polymerization: It can be seen that the number average molecular weight (Mn) of the obtained polymer increases almost in proportion thereto, and the value of Mw / Mn is kept close to 1.

Example 7 6.42 mL (60 mmol) of methyl methacrylate and 0.88 mL of n-octane were collected in a Schlenk reaction tube and uniformly mixed. 9.6 m of a 125 mM / L toluene solution of triisopropoxy aluminum was added to this mixed solution.
L (1.2 mmol) was added, followed by 25 mM / L of dicarbonylbis (triphenylphosphine) nickel.
12 mL (0.30 mmol) of a toluene solution was added at -78 ° C.
And stirred well, and finally, 0.60 mL (0.60 mmol) of a 1 M / L toluene solution of bromotrichloromethane was added. This was heated to 80 ° C. to start a polymerization reaction.

Thirty minutes after the start of the polymerization reaction, the same treatment as in Example 1 was conducted, except that the polymerization reaction was stopped by cooling the polymerization reaction system, and the result of the polymerization reaction was examined. As a result, the polymerization rate of methyl methacrylate was 35%, the number average molecular weight was 5200, the weight average molecular weight was 7750, and Mw / M
n was 1.49 and the GPC curve was unimodal.

Example 8 The procedure of Example 7 was repeated, except that the polymerization reaction was stopped 24 hours after the start of the polymerization reaction, and the results of the polymerization reaction were examined in the same manner as in Example 7. The polymerization rate of methyl methacrylate was 89%, the number average molecular weight was 11,200, the weight average molecular weight was 16,350, Mw / Mn was 1.46, and the GPC curve was unimodal.

Comparative Example 1 Example 7 was repeated except that dichlorotris (triphenylphosphine) ruthenium was used instead of dicarbonylbis (triphenylphosphine) nickel.
The polymerization reaction was started in the same manner as described above. 23 hours after the start of the polymerization reaction, except that the polymerization reaction was stopped by cooling the polymerization reaction system, the result of the polymerization reaction was examined in the same manner as in Example 1, and the polymerization rate of methyl methacrylate was determined. Was 75%, the number average molecular weight was 10,300, the weight average molecular weight was 13,300, and Mw / Mn was 1.29.

As is clear from comparison between Example 8 and Comparative Example 1, when dicarbonylbis (triphenylphosphine) nickel is used as the metal complex, dichlorotris (triphenylphosphine) ruthenium is used as the metal complex. It can be seen that the polymerization is completed relatively quickly as compared with the case in which

Comparative Example 2 A polymerization reaction was started in the same manner as in Example 7, except that triisobroboxy aluminum was not used. Except that the polymerization reaction was stopped by cooling the polymerization reaction system 22 hours after the initiation of the polymerization reaction, the same procedure as in Example 1 was carried out to examine the result of the polymerization reaction. The polymerization rate of methyl methacrylate was determined. Is 65%, the number average molecular weight is 8,500, the weight average molecular weight is 13,700, and Mw is
/ Mn was 1.61.

As is clear from a comparison between Example 8 and Comparative Example 2, when triisopropoxyaluminum was used, a relatively short time was obtained as compared with the case where triisopropoxyaluminum was not used.
It can be seen that a polymer having a narrow molecular weight distribution can be obtained.

Comparative Example 3 A polymerization reaction was started in the same manner as in Example 7 except that dibromobis (triphenylphosphine) nickel was used instead of dicarbonylbis (triphenylphosphine) nickel. . Except for stopping the polymerization reaction by cooling the polymerization reaction system 30 minutes after the start of the polymerization reaction, the same treatment as in Example 1 was carried out to examine the result of the polymerization reaction. The polymerization rate of methyl methacrylate was determined. Is 13%, the number average molecular weight is 1700, and the weight average molecular weight is 2
Mw / Mn was 1.47.

Comparative Example 4 A polymerization reaction was started in the same manner as in Example 7, except that tetrakis (triphenylphosphine) nickel was used instead of dicarbonylbis (triphenylphosphine) nickel. 30 minutes after starting the polymerization reaction
After a minute, the polymerization reaction was stopped by cooling the polymerization reaction system, and the result of the polymerization reaction was examined in the same manner as in Example 1. The polymerization rate of methyl methacrylate was 1
5%, number average molecular weight 2500, weight average molecular weight 36
00, Mw / Mn was 1.44.

As is apparent from a comparison between Example 7 and Comparative Example 3 and a comparison between Example 7 and Comparative Example 4, when dicarbonylbis (triphenylphosphine) nickel was used, dibromobis (triphenylphosphine) was used. It can be seen that the polymerization proceeds relatively faster than when phenylphosphine) nickel or tetrakis (triphenylphosphine) nickel is used as the metal complex.

Example 9 6.42 mL (60 mmol) of methyl methacrylate and 0.20 mL of n-octane were collected in a Schlenk reaction tube and mixed uniformly. 9.6 m of a 125 mM / L toluene solution of triisopropoxyaluminum was added to this mixed solution.
L (1.2 mmol) was added, followed by 384 mg of dicarbonylbis (triphenylphosphine) nickel
(0.6 mmol), 13.2 mL of toluene at -78 ° C
And stirred well, and finally, 0.60 mL (0.60 mmol) of a 1 M / L toluene solution of bromotrichloromethane was added. This was heated to 80 ° C. to start a polymerization reaction.

Eight hours after the initiation of the polymerization reaction, the polymerization reaction system was cooled and the polymerization reaction was terminated, except that the polymerization reaction was stopped, and the results of the polymerization reaction were examined. As a result, the conversion of methyl methacrylate was 95%, and the number average molecular weight was 8%.
The weight average molecular weight was 700, Mw / Mn was 1.67, and the GPC curve was unimodal.

Example 10 Polymerization was carried out in the same manner as in Example 7 except that 6.87 mL (60 mmol) of styrene was used instead of methyl methacrylate and tetralin was used instead of n-octane. The reaction was started. 2 after starting the polymerization reaction
Except that the polymerization reaction was stopped by cooling the polymerization reaction system after 0 hour, the same treatment as in Example 1 was performed to examine the result of the polymerization reaction. The polymerization rate of styrene was 53%, and the number average molecular weight was 6800, weight average molecular weight 9450, M
w / Mn was 1.39 and the GPC curve was unimodal.

Example 11 The procedure of Example 10 was repeated, except that the polymerization reaction was stopped 50 hours after the start of the polymerization reaction, and the result of the polymerization reaction was examined. Styrene conversion is 74
%, Number average molecular weight is 6300, and weight average molecular weight is 950
0, Mw / Mn was 1.51, and the GPC curve was unimodal.

As is evident from the comparison of Example 10 with Example 11, increasing the polymerization rate increases the number average molecular weight (Mn) of the polymer obtained in proportion to the polymerization rate. It can be seen that the value is kept close to 1.

Comparative Example 5 A polymerization reaction was started in the same manner as in Example 10 except that dichlorotris (triphenylphosphine) ruthenium was used instead of dicarbonylbis (triphenylphosphine) nickel. . Except that the polymerization reaction was stopped by cooling the polymerization reaction system 22 hours after the start of the polymerization reaction, the same treatment as in Example 1 was performed and the result of the polymerization reaction was examined. 17%, the number average molecular weight was 3,800, the weight average molecular weight was 11,150, and Mw / Mn was 2.93.

As is apparent from a comparison between Example 10 and Comparative Example 5, when dicarbonylbis (triphenylphosphine) nickel was used as the metal complex, and when dichlorotris (triphenylphosphine) ruthenium was used as the metal complex. In comparison, a polymer having a narrow molecular weight distribution can be obtained in a relatively short time.

Example 12 25 hours after the start of the polymerization reaction in Example 2, 2.16 mL (24 mmol) of methyl acrylate was added.
After another 6 hours, the polymerization reaction was stopped by cooling the polymerization reaction system. When the result of the polymerization reaction was examined in the same manner as in Example 1, the polymerization rate of methyl acrylate was found to be 22.
%, The number average molecular weight of the methyl methacrylate-methyl acrylate copolymer is 5800, the weight average molecular weight is 9000,
Mw / Mn was 1.55, and the GPC curve was unimodal.

From this example, it is understood that the radical active species is present in the polymerization system in a living state until the polymerization reaction is stopped, and that a block copolymer can be easily obtained.

[0083]

According to the living radical polymerization initiator system of the present invention, when a radical polymerizable monomer is subjected to living radical polymerization, a polymer having a narrow molecular weight distribution can be compared with a polymer having a controlled molecular weight while suppressing a side reaction. It can be generated in a very short time.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshio Okamoto 2-66 Yadacho, Higashi-ku, Nagoya-shi, Aichi 222 Oyada-cho lodgings (72) Inventor Yoshimichi Okano 1239 Shinzaike, Aboshi-ku, Himeji-shi, Hyogo Daicel Chemical Industry Co., Ltd. Inside the laboratory (72) Inventor Masamichi Nishimura 1239 Shinzai, Aboshi-ku, Himeji-shi, Hyogo Prefecture Inside Dai-ichi Kagaku Kogyo Co., Ltd. (72) Inventor Tetsuya Asahi 1-8 Kasumi, Yokkaichi-shi, Mie Tosoh Co., Ltd. (72) Invention 1) Kazuno Oki 1-8 Kasumi, Yokkaichi-shi, Mie Tosoh Corporation Yokkaichi Laboratory (72) Inventor Hiroshi Nakajima 23 Uji Kozakura, Uji-city, Kyoto Prefecture Unitika Corporation Central Research Laboratory (72) Kazunobu Yamada Uji Kyoto-fu 23 Uji Kozakura, Unitichi Unitika Corporation Central Research Laboratory

Claims (8)

[Claims] 1. The following components (A), (B) and (C): (A) carbon monoxide and a phosphorus compound as ligands are added to a central metal selected from Group 10 elements of the periodic table. (B) a compound having at least one of a halogenated sulfonyl group and a halogen atom bonded to a carbon atom having no unsaturated bond; and (C) a Lewis acid. Living radical polymerization initiator system. 2. The phosphorous compound of the ligand of the metal complex of the component (A) is a trialkylphosphine, a triarylphosphine, a trialkylphosphite, a triarylphosphite, a bis (dialkylphosphino) alkane, a bis (diaryl). The living radical polymerization initiator system according to claim 1, which is a phosphino) alkane or a phosphaalkene. 3. The living radical polymerization initiator system according to claim 1, wherein the metal complex of the component (A) is dicarbonylbis (triphenylphosphine) nickel. 4. The compound of the component (B) is represented by the formula (B1) or (B2): CX ¹ X ² X ³ X ⁴ (B1) RSO ₂ X (B2) (wherein (B1) or (B1) In B2), X and X ¹ each represent a halogen atom, and X ² , X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group and The living radical according to claim 1, wherein the living radical is a compound selected from the group consisting of a hetero atom-containing organic group, and R is an optionally substituted alkyl group or an optionally substituted aryl group. Polymerization initiator system. 5. The Lewis acid of the component (C) is represented by the formula (C1) or (C2): AlY ¹ Y ² Y ³ (C1) MZ ¹ Z ² Z ³ Z ⁴ (C2) (Formula (C1) ) Or (C2), Y ¹ , Y ² , Y ³ , Z ¹ , Z
² , Z ³ and Z ⁴ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group or an optionally substituted aryloxy group. , M is Ti (IV) or Sn (IV)
It is. The living radical polymerization initiator system according to claim 1, which is a compound represented by the formula: 6. The living radical polymerization initiator system according to claim 5, wherein the Lewis acid of component (C) is trialkoxyaluminum. 7. The molar ratio of component (A) / component (B) is 0.
The living radical polymerization initiator system according to any one of claims 1 to 6, wherein the molar ratio of the component (B) / the component (C) is 0.05 to 5. 8. A method for producing a polymer, comprising subjecting a radically polymerizable monomer to living polymerization in the presence of the living radical polymerization initiator system according to claim 1.