JP2001316410A - Living radical polymerization initiator system and process for producing polymer by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a living radical polymerization initiator system which can be applied in a wide range in the kind of a monomer and in the combination of monomers where two or more monomers are used, so as to submit a radical polymerizable monomer to living radical polymerization while controlling the molecular weight and obtain a polymer of a narrow molecular weight distribution. SOLUTION: The living radical polymerization initiator system comprises the following components (A), (B) and (C): (A) a halogenopentamethylcyclopentadienylbis-(triarylphosphine)ruthenium; (B) an α-halogenocarbonyl compound or an α-halogeno-carboxylic acid ester; and (C) a Lewis acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a living radical polymerization initiator system and a method for producing a polymer using the same. More specifically, the present invention relates to a living radical polymerization initiator system applicable to a wide range of types and combinations of radical polymerizable monomers, and further uses the living radical polymerization initiator system to control the molecular weight. And a method for easily producing a polymer having a narrow molecular weight distribution.

[0002]

2. Description of the Related Art As a method for producing a polymer of a vinyl compound, a radical polymerization method is widely used industrially. This radical polymerization generally uses a radical generator as a polymerization initiator to initiate the chain of a vinyl compound, grows it, and polymerizes it.However, side reactions such as termination of polymerization at the growth end and chain transfer are caused. It is difficult to produce a polymer having a narrow molecular weight distribution while controlling the molecular weight because it is easily caused.

Therefore, as a method for producing a polymer having a narrow molecular weight distribution while controlling the molecular weight, a transition metal complex such as dichlorotris (triphenylphosphine) ruthenium, carbon tetrachloride, 1-phenylethyl chloride, 2-bromo A living radical polymerization method using a polymerization initiator system (living radical polymerization initiator system) comprising a halogen compound (polymerization initiator) such as ethyl-2-methylpropanoate and a Lewis acid such as an aluminum alkoxy compound has been proposed. (Macromolecules, vol. 28, 1721 (1995); J.
Am. Chem. Soc., 117, 5614 (1995);
No. 17, JP-A-9-208616).
For example, when methacrylic acid ester is subjected to living radical polymerization according to this living radical polymerization method, the molecular weight can be reduced by using dichlorotris (triphenylphosphine) ruthenium as the transition metal complex and carbon tetrachloride as the halogen compound. It is possible to produce a polymer having a controlled molecular weight distribution and a narrow molecular weight distribution.

[0004]

However, according to the knowledge obtained by the present inventors, when living radical polymerization of acrylate or styrene is carried out, it is favorable for the above-mentioned polymerization of methyl methacrylate. Even if the same polymerization initiator system as the living radical polymerization initiator system that gave the result was used, it also contained dichlorotris (triphenylphosphine) ruthenium as the transition metal complex and 2-bromo-2-methylpropane as the halogen compound. Even if a polymerization initiator system containing ethyl acid is used, there is a problem that the molecular weight distribution of the obtained polymer cannot be sufficiently narrowed.

As described above, in the living radical polymerization method using a polymerization initiator system containing a transition metal complex as described above, the molecular weight is controlled depending on the kind of the radical polymerizable monomer to be applied. However, it is difficult to produce a polymer having a narrow molecular weight distribution. In particular, when two or more types of radically polymerizable monomers are subjected to living radical copolymerization, it is often difficult to produce a copolymer having a narrow molecular weight distribution while controlling the molecular weight.

The present invention uses a monomer type and two or more types of monomers in order to obtain a polymer having a narrow molecular weight distribution by subjecting a radical polymerizable monomer to living radical polymerization while controlling the molecular weight. In this case, an object of the present invention is to provide a living radical polymerization initiator system applicable in a wide range in the combination. In addition, the present invention can be polymerized while controlling the molecular weight, in a wide range in the case of using two or more types of radically polymerizable monomers to be polymerized and two or more types of radically polymerizable monomers, and It is another object of the present invention to provide a method for producing a polymer (including a copolymer) capable of obtaining a polymer having a narrow molecular weight distribution.

[0007]

Means for Solving the Problems The present inventors have selected a specific ruthenium complex as a transition metal complex and combined the specific ruthenium complex with a specific halogen compound and a Lewis acid to form a living polymerization initiator system. The inventors have found that the above-mentioned problems can be solved by the formation, and have completed the present invention.

That is, the present invention provides the following component (A):
(B) and (C): (A) halogenopentamethylcyclopentadienyl bis (triarylphosphine) ruthenium; (B) α-halogenocarbonyl compound or α-halogenocarboxylic acid ester; and (C) Lewis acid A living radical polymerization initiator system is provided.

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

In this production method, when at least two kinds of radically polymerizable monomers are used as the radically polymerizable monomer, the obtained polymer is a copolymer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The living radical polymerization initiator system of the present invention uses halogenopentamethylcyclopentadienyl bis (triarylphosphine) ruthenium as a transition metal complex (component (A)) and uses a halogen compound (polymerization initiator (component An α-halogenocarbonyl compound or an α-halogenocarboxylic acid ester is used as (B)), and a Lewis acid (component (C)) is used as an activator.

In the present invention, halogenopentamethylcyclopentadienylbis (triarylphosphine) ruthenium is used as the transition metal complex of the component (A), and pentamethyl which is one of the ligands for the central metal ruthenium is used. If the cyclopentadienyl group is replaced with another coordinating group (for example, cyclopentadienyl group), the function and effect of the present invention will not be sufficiently achieved.
The reason is that, since the pentamethylcyclopentadienyl group is an appropriate electron-donating group, a transition metal complex having it as one of the ligands has an appropriate redox ability, and as a result, the polymerization initiator Not to efficiently activate the equilibrium reaction between the structure having a carbon-halogen bond at the growth terminal of the polymer and the structure of the carbon radical formed by radical dissociation of the structure by a transition metal complex It is estimated that.

Preferred specific examples of component (A) include chloropentamethylcyclopentadienyl bis (triarylphosphine) ruthenium such as chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium.

In the living radical polymerization initiator system of the present invention, an α-halogenocarbonyl compound or α-halogenocarboxylic acid ester of the component (B) is used as a polymerization initiator.

When the component (B) is an α-halogenocarbonyl compound, preferred specific examples thereof include 2,2-dichloroacetophenone. When the component (B) is an α-halogenocarboxylic acid ester, a preferred specific example thereof is 2-chloro-2,4,4.
-Dimethyl trimethylglutarate and the like.

In the living radical polymerization initiator system of the present invention, the halogen atom in the component (A) and the halogen atom in the component (B) are preferably the same type of halogen atom. As such a combination, for example, when chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium is used as the component (A), a halogen compound having the same kind of halogen atom (chlorine atom), , 2-dichloroacetophenone, 2
It is preferable to use dimethyl-chloro-2,4,4-trimethylglutarate.

As described above, by making the halogen atom in the component (A) and the halogen atom in the component (B) the same, in a living radical copolymerization using two or more radical polymerizable monomers. The molecular weight distribution of the resulting copolymer can be particularly narrowed. The reason is considered as follows.

In the living radical polymerization using the living radical polymerization initiator system of the present invention, a carbon atom at the growth terminal forms a carbon-halogen bond with a halogen atom derived from the polymerization initiator (halogen compound). And the structure of the carbon radical formed by the radical dissociation of this structure by the transition metal complex maintain the equilibrium state biased toward the former carbon-halogen bond structure. It is presumed that termination polymerization does not occur and living polymerization is achieved. Here, when the types of the halogen atoms of the polymerization initiator and the transition metal complex are different, halogen exchange occurs between the polymerization initiator (or the growth terminal) and the transition metal complex during the equilibrium reaction. ,
Two types of carbon-halogen bonds having different types of halogen atoms are formed at the growth terminals, but the two types of carbon-halogen bonds have different dissociation energies, resulting in a difference in the polymerization rate, and as a result, the respective heavy The growth rates of the coalesced molecules may not be uniform and the molecular weight distribution may be slightly wider. On the other hand, when the types of the halogen atoms of the polymerization initiator and the transition metal complex are the same, the type of the carbon-halogen bond at the growth terminal does not become non-uniform as described above. It is estimated that the uniformity of distribution is further improved.

In the living radical polymerization initiator system of the present invention, as a activating agent, a Lewis acid of component (C), for example, aluminum trialkoxide such as aluminum triisopropoxide or aluminum tri (t-butoxide); Bis (substituted aryloxy) alkyl aluminums such as 2,6-di-t-butylphenoxy) methyl aluminum and bis (2,4,6-tri-t-butylphenoxy) methyl aluminum; tris (2,6-diphenylphenoxy) Examples include tris (substituted aryloxy) aluminum such as aluminum; titanium tetraalkoxide such as titanium tetraisopropoxide; and the like, preferably aluminum trialkoxide, and particularly preferably aluminum triisopropoxide.

The content ratio of each component in the living radical polymerization initiator system of the present invention is not necessarily limited, but if the ratio of component (A) to component (B) is too low, the polymerization tends to be slow. On the contrary, if it is too high, the molecular weight distribution of the obtained polymer tends to be widened, so that the molar ratio of component (A): component (B) is 0.05: 1.
It is preferably within the range of 1: 1. If the ratio of the component (C) to the component (B) is too low, the polymerization tends to be slow. Conversely, if the ratio is too high, the molecular weight distribution of the obtained polymer tends to be wide. : The molar ratio of component (C) is preferably in the range of 1: 1 to 1:10.

In the living radical polymerization initiator system of the present invention, the transition metal complex of the component (A), the polymerization initiator of the component (B) and the activator of the component (C) are usually prepared by a conventional method immediately before use. It can be manufactured by mixing. Further, the transition metal complex of the component (A), the polymerization initiator of the component (B), and the activator of the component (C) are separately stored, and separately added to the polymerization reaction system. It may be mixed in the system to function as a living radical polymerization initiator system.

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

This production method basically involves living polymerization of a radically polymerizable monomer in a solvent such as toluene in the presence of the living radical polymerization initiator system of the present invention. Thereby, almost in proportion to the increase of the polymerization rate,
The number average molecular weight (Mn) of the obtained polymer can be increased, and the weight average molecular weight / number average molecular weight (Mw)
/ Mn) can be a value 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, even when two or more types of monomers are combined and random copolymerization is performed, the molecular weight can be controlled and the molecular weight distribution can be set to a value close to 1. In addition, as a first step, one kind of monomer or two or more kinds of monomer mixture is almost completed. By adding a mixture of monomers, the number average molecular weight can be increased while maintaining a molecular weight distribution close to 1, and a block copolymer can be produced. Thereafter, one kind of monomer or a mixture of two or more kinds of monomers are successively added in the same manner in the third or more steps to produce a triblock or more multiblock copolymer. can do.

The radically polymerizable monomers used in the living radical polymerization reaction according to the production method of the present invention include styrene-based monomers, methacrylic acid esters and acryl monomers in view of versatility and the remarkable effects of the present invention. At least one radical polymerizable monomer selected from the group consisting of acid esters is preferred. Styrene-based monomers include styrene, p-methylstyrene, p-methoxystyrene, p-
Examples thereof include t-butylstyrene, pn-butylstyrene, and p-chlorostyrene, and a particularly preferred example is styrene. Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like, and particularly preferred examples include methyl methacrylate and butyl methacrylate. Examples of the acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like, and particularly preferable examples include methyl acrylate and butyl acrylate.

In the living radical polymerization reaction according to the production method of the present invention, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid substituted amide, Radical polymerizable monomers such as acrylonitrile, methacrylonitrile, fumaric anhydride, methyl fumarate, and ethyl fumarate can be used. The “(meth) acrylic acid” is a general term for “methacrylic acid” and “acrylic acid”.

In the production method of the present invention, the initial concentration of the radically polymerizable monomer in the polymerization reaction system is not necessarily limited. Since the chain transfer reaction to the polymer tends to increase and the molecular weight distribution of the obtained polymer tends to be wide, it is preferably 0.5 to 8 mol (mol) / L (liter), and particularly preferably 1 to 4 mol / L. L. The concentration of each component in the polymerization system at that time is not necessarily limited, but the concentration of the polymerization initiator of the component (B) is preferably, although there is a difference depending on the concentration of the radical polymerizable monomer. 0.1 to 100 mmol (mmol) / L (liter), particularly preferably 0.5 to 50
mmol / L. The concentration of the transition metal complex of the component (A) is preferably from 0.1 to 50 mmol / L, particularly preferably from 0.5 to 10 mmol / L. The concentration of the Lewis acid of the component (C) is preferably 1 to 200 mm.
ol / L, particularly preferably 5 to 50 mmol / L.

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 transition metal are placed in a reaction vessel under an atmosphere of an inert gas such as nitrogen. It is preferable to prepare a mixture composed of the complex (component (A)) and add a polymerization initiator (component (B)) to the mixture. The mixture thus obtained is
For example, the polymerization can be started by heating to a temperature in the range of 60 to 120 ° C.

After the completion of the polymerization reaction, for example,
° C or lower, preferably about -78 ° C, to terminate the reaction, then extract the resulting polymer with an organic solvent such as toluene, remove the polymerization initiator system metal components and the like with dilute hydrochloric acid, and then remove the volatile components. Can be obtained by evaporating.

[0030]

The present invention will be described below in more detail with reference to examples.

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

The polymerization rate of the polymer was calculated based on the analytical value obtained by analyzing the concentration of the monomer in the reaction solution obtained using n-octane as an internal standard by gas chromatography. The values of the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution Mw / Mn of the obtained polymer were determined by gel permeation chromatography (GPC).
Is measured under the following conditions using polymethyl methacrylate, polymethyl methacrylate and methyl methacrylate-methyl acrylate copolymer, calculated in terms of polymethyl methacrylate, and polystyrene, styrene-acrylic. The butyl random copolymer and the block copolymer of the styrene-butyl acrylate random copolymer block and the polymethyl methacrylate block were calculated in terms of polystyrene.

GPC measurement conditions Column: Shodex K-805L (3 in series) Solvent: chloroform Temperature: 40 ° C Detector: RI and UV Flow rate: 1 ml / min Example 1 Methyl methacrylate 4.28 ml (40.1 mmol)
l), 1.17 ml of toluene and 0.85 of n-octane
6 ml was collected in a Schlenk reaction tube and mixed uniformly.
This mixed solution was mixed with 1 of aluminum triisopropoxide.
3.20 ml of a 25 mmol / L toluene solution (0.40
1 mmol), 31.9 mg (0.0401 mmol) of chloropentamethylcyclopentadienyl bis (triphenylphosphine) ruthenium are added at room temperature, stirred sufficiently, and finally, 2-chloro-2,4,4- 0.499 ml (0.401 mmol) of a 802 mmol / L toluene solution of dimethyl trimethylglutarate was added. The polymerization reaction was started by heating the obtained mixture to 80 ° C.

At the time when 30 hours had passed after the initiation of the polymerization reaction, the polymerization reaction was stopped by cooling the reaction solution to -78 ° C. The polymerization rate of methyl methacrylate is 26%
The number average molecular weight (Mn) of the polymethyl methacrylate present in the reaction solution is 2900, the polymerization average molecular weight (Mw) is 3200, and therefore, Mw / Mn is 1.1.
It was 0. Furthermore, the GPC curve was unimodal.

Example 2 A polymerization reaction was carried out in the same manner as in Example 1 except that the polymerization reaction was stopped 127 hours after the start of the polymerization reaction.
Analyzed similarly. As a result, the polymerization rate of methyl methacrylate was 94%, Mn of polymethyl methacrylate existing in the reaction system was 12,700, Mw was 14,400, and Mw / Mn
Was 1.13, and the GPC curve was unimodal.

As is clear from the comparison of Example 2 with Example 1, when the polymerization rate was increased, the Mn of the obtained polymer was increased almost in proportion thereto, and the value of Mw / Mn was close to 1. It can be seen that it is kept.

Comparative Example 1 4.28 ml of methyl methacrylate (40.1 mmol)
l), 1.28 ml of toluene and 0.85 of n-octane
6 ml was collected in a Schlenk reaction tube and mixed uniformly.
This mixed solution was mixed with 1 of aluminum triisopropoxide.
3.20 ml of a 25 mmol / L toluene solution (0.40
1 mmol), followed by 191.8 mg (0.2%) of dichlorotris (triphenylphosphine) ruthenium.
00 mmol) at room temperature and thoroughly stirred.
1030 mm of ethyl bromo-2-methylpropanoate
ol / L toluene solution 0.389 ml (0.401 mm
ol). The polymerization reaction was started by heating the obtained mixture to 80 ° C.

After a lapse of 57 hours from the start of the polymerization reaction, the reaction solution was cooled to -78 ° C to stop the polymerization reaction. The conversion of methyl methacrylate is 90%,
Further, the Mn of the polymethyl methacrylate present in the reaction solution was 21,300 and the Mw was 27,500.
Mn was 1.29.

As is apparent from a comparison between Example 1 and Example 2 and Comparative Example 1, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium was used as the transition metal complex, and the same kind of halogen atom was used. When dimethyl 2-chloro-2,4,4-trimethylglutarate is used, dichlorotris (triphenylphosphine) ruthenium, which is outside the scope of the present invention, is used as the transition metal complex, and the compound having a halogen atom of a different kind is used. -Bromo-
It can be seen that the molecular weight distribution is narrower than when ethyl 2-methylpropanoate is used.

Example 3 5.04 ml (44.0 mmol) of styrene, 0.882 ml of toluene and 1.01 ml of n-octane were collected in a Schlenk reaction tube and mixed uniformly. 125 mmol / l of aluminum triisopropoxide was added to this mixed solution.
3.52 ml (0.440 mmol) of L toluene solution was added, followed by 35.0 m of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium.
g (0.0440 mmol) at room temperature and sufficiently stirred. Finally, a 0.5% 802 mmol / L toluene solution of dimethyl 2-chloro-2,4,4-trimethylglutarate was added.
49 ml (0.440 mmol) were added. The polymerization reaction was started by heating the obtained mixture to 100 ° C.

At the time when 20 hours had passed since the start of the polymerization reaction, the reaction solution was cooled to -78 ° C to stop the polymerization reaction. The polymerization rate of styrene is 32%, and the Mn of polystyrene present in the reaction solution is 380
0, Mw was 4100, and therefore Mw / Mn was 1.08. Furthermore, the GPC curve was unimodal.

Example 4 A polymerization reaction was carried out in the same manner as in Example 3 except that the polymerization reaction was started and stopped 129 hours later.
Analyzed similarly. As a result, the conversion of styrene was 89
%, Mn of polystyrene present in the reaction system is 1090
0, Mw is 11,900, Mw / Mn is 1.09,
The GPC curve was unimodal.

As is apparent from comparison of Example 4 with Example 3, when the polymerization rate was increased, the Mn of the obtained polymer was increased almost in proportion thereto, and the value of Mw / Mn was close to 1. It can be seen that it is kept.

Comparative Example 2 2.52 ml (22.0 mmol) of styrene, 4.24 ml of toluene and 0.504 ml of n-octane were collected in a Schlenk reaction tube and mixed uniformly. 125 mmol / l of aluminum triisopropoxide was added to this mixed solution.
3.52 ml (0.440 mmol) of L toluene solution was added, and then 105.5 mg (0.110 mmol) of dichlorotris (triphenylphosphine) ruthenium.
At room temperature and stirred well, and finally 2-bromo-2-
0.214 ml (0.220 mmol) of a 1030 mmol / L toluene solution of ethyl methyl propanoate was added. The polymerization reaction was started by heating the obtained mixture to 100 ° C.

After 50 hours from the start of the polymerization reaction, the reaction solution was cooled to -78 ° C to stop the polymerization reaction. The polymerization rate of styrene is 90%, and the Mn of polystyrene present in the reaction solution is 950.
0, Mw is 16,800, so Mw / Mn is 1.77
Met.

As is clear from a comparison between Examples 3 and 4 and Comparative Example 2, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium was used as the transition metal complex, and the same kind of halogen atom was used. When dimethyl 2-chloro-2,4,4-trimethylglutarate is used, dichlorotris (triphenylphosphine) ruthenium, which is outside the scope of the present invention, is used as the transition metal complex, and the compound having a halogen atom of a different kind is used. -Bromo-
It can be seen that the molecular weight distribution is narrower than when ethyl 2-methylpropanoate is used. This difference is more remarkable in the case where styrene is used as the radical polymerizable monomer as in Examples 3 and 4 than in the case where methyl methacrylate is used as in Examples 1 and 2. It turns out that it becomes.

Example 5 3.42 ml (38.0 mmol) of methyl acrylate,
1.88 ml of toluene and 0.684 ml of n-octane
Was collected in a Schlenk reaction tube and mixed uniformly. 125 m of aluminum triisopropoxide was added to this mixed solution.
3.04 ml of a mol / L toluene solution (0.380 mm
ol), followed by chloropentamethylcyclopentadienyl bis (triphenylphosphine) ruthenium 3
0.3 mg (0.0381 mmol) was added at room temperature and the mixture was sufficiently stirred. Finally, 0.474 ml (0.380 mmol) of a 802 mmol / L toluene solution of dimethyl 2-chloro-2,4,4-trimethylglutarate was added. Was. The polymerization reaction was started by heating the obtained mixture to 80 ° C.

When 49 hours had passed since the start of the polymerization reaction, the reaction solution was cooled to -78 ° C. to stop the polymerization reaction. The polymerization rate of methyl acrylate is 27%, and Mn of polymethyl acrylate present in the reaction solution is 3000 and Mw is 3500, so that Mw /
Mn was 1.17. Furthermore, the GPC curve was unimodal.

Example 6 A polymerization reaction was carried out in the same manner as in Example 5 except that the polymerization reaction was stopped 159 hours after the start of the polymerization reaction.
Analyzed similarly. As a result, the polymerization rate of methyl acrylate was 91%, Mn of polymethyl acrylate present in the reaction system was 10,000, Mw was 11,900, Mw / Mn was 1.19, and the GPC curve was unimodal. Was.

As is apparent from comparison of Example 6 with Example 5, when the polymerization rate was increased, the Mn of the obtained polymer was increased almost in proportion thereto, and the value of Mw / Mn was close to 1. It can be seen that it is kept.

Comparative Example 3 1.71 ml (19.0 mmol) of methyl acrylate,
4.22 ml of toluene and 0.342 ml of n-octane
Was collected in a Schlenk reaction tube and mixed uniformly. 125 m of aluminum triisopropoxide was added to this mixed solution.
3.04 ml of a mol / L toluene solution (0.380 mm
ol), and then 91.1 mg (0.0950 mm) of dichlorotris (triphenylphosphine) ruthenium.
ol) at room temperature and stirred well, and finally 1030 mmol / L of ethyl 2-bromo-2-methylpropanoate
0.185 ml (0.190 mmol) of a toluene solution was added. The polymerization reaction was started by heating the obtained mixture to 80 ° C.

When 145 hours had elapsed after the initiation of the polymerization reaction, the polymerization reaction was stopped by cooling the reaction solution to -78 ° C. The polymerization rate of methyl acrylate is 95%, and the polymethyl acrylate present in the reaction solution has Mn of 6,800 and Mw of 10,900.
/ Mn was 1.60.

As is clear from the comparison between Examples 5 and 6 and Comparative Example 3, chloropentamethylcyclopentadienyl bis (triphenylphosphine) ruthenium was used as the transition metal complex, and the same kind of halogen atom was used. When dimethyl 2-chloro-2,4,4-trimethylglutarate is used, dichlorotris (triphenylphosphine) ruthenium, which is outside the scope of the present invention, is used as the transition metal complex, and the compound having a halogen atom of a different kind is used. -Bromo-
It can be seen that the molecular weight distribution is narrower than when ethyl 2-methylpropanoate is used. This difference is more pronounced in the case where methyl acrylate as in Examples 5 and 6 is used as the radical polymerizable monomer than in the case where methyl methacrylate as in Examples 1 and 2 is used. It turns out that it becomes remarkable.

Example 7 3.21 ml of methyl methacrylate (30.0 mmol)
l), 2.70 ml of methyl acrylate (30.0 mmol
l), 2.36 ml of toluene and 1.18 of n-octane
ml was collected in a Schlenk reaction tube and mixed uniformly. To this mixed solution was added 12 parts of aluminum triisopropoxide.
4.80 ml of a 5 mmol / L toluene solution (0.600
mmol), 47.8 mg (0.0600 mmol) of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium were added at room temperature, and the mixture was sufficiently stirred. Finally, 2-chloro-2,4,4- 0.748 ml (0.600 mmol) of a 802 mmol / L toluene solution of dimethyl trimethylglutarate was added. The polymerization reaction was started by heating the obtained mixture to 80 ° C.

After 98 hours from the start of the polymerization reaction, the reaction solution was cooled to -78 ° C. to stop the polymerization reaction. The polymerization rates of methyl methacrylate and methyl acrylate are 92% and 65%, respectively, and the Mn of the methyl methacrylate-methyl acrylate random copolymer present in the reaction solution is 7,900, and Mw is 9,400.
Therefore, Mw / Mn was 1.19.

Comparative Example 4 2.14 ml of methyl methacrylate (20.0 mmol)
l), 1.80 ml of methyl acrylate (20.0 mmol
l), 1.68 ml of toluene and 0.78 of n-octane
8 ml was collected in a Schlenk reaction tube and mixed uniformly.
This mixed solution was mixed with 1 of aluminum triisopropoxide.
3.20 ml of a 25 mmol / L toluene solution (0.40
0 mmol), followed by 191.78 mg of dichlorotris (triphenylphosphine) ruthenium (0.1 mmol).
200 mmol) at room temperature and thoroughly stirred. Finally, a 0.30 mmol / L toluene solution of carbon tetrachloride 0.3
89 ml (0.400 mmol) were added. The polymerization reaction was started by heating the obtained mixture to 80 ° C.

After a lapse of 57 hours from the start of the polymerization reaction, the reaction solution was cooled to -78 ° C to stop the polymerization reaction. The polymerization rates of methyl methacrylate and methyl acrylate are 93% and 75%, respectively, and the Mn of the methyl methacrylate-methyl acrylate random copolymer present in the reaction solution is 6,000 and Mw is 8,000.
Therefore, Mw / Mn was 1.33.

As is apparent from a comparison between Example 7 and Comparative Example 4, 2-chlorochloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium was used as the transition metal complex and had the same halogen atom. −
When dimethyl 2,4,4-trimethylglutarate is used, dichlorotris (triphenylphosphine) ruthenium outside the scope of the present invention is used as the transition metal complex, and carbon tetrachloride having the same kind of halogen atom is used. It can be seen that the molecular weight distribution of the random copolymer using two types of monomer mixtures is narrower than that of the above.

Example 8 3.44 ml (30.0 mmol) of styrene, 4.30 ml (30.0 mmol) of butyl acrylate, 0.166 ml of toluene and 1.55 ml of n-octane were collected in a Schlenk reaction tube and mixed uniformly. did. 125 mmol / l of aluminum triisopropoxide was added to this mixed solution.
4.80 ml (0.600 mmol) of L toluene solution were added, and then chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium 47.8 m
g (0.0600 mmol) at room temperature and thoroughly stirred. Finally, a 802 mmol / L toluene solution of dimethyl 2-chloro-2,4,4-trimethylglutarate in 0.7
48 ml (0.600 mmol) were added. The polymerization reaction was started by heating the obtained mixture to 80 ° C.

When 213 hours had elapsed after the initiation of the polymerization reaction, a part (2.50 ml) of the reaction solution was withdrawn and cooled to −78 ° C. to stop the polymerization reaction, which was used for analysis. The polymerization rates of styrene and butyl acrylate are 60% and 45%, respectively, and the Mn of the styrene-butyl acrylate random copolymer present in the reaction solution is 3900, Mw is 4300, and therefore M
w / Mn was 1.10. Furthermore, the GPC curve was unimodal.

Example 9 The polymerization reaction of the remainder of Example 8 after extraction was continued. After 430 hours from the start of the polymerization reaction, 2.50 ml of the reaction solution was withdrawn from the polymerization reaction system and cooled to -78 ° C to stop the polymerization reaction. The polymerization rates of styrene and butyl acrylate in the extraction liquid were 93% and 76%, respectively.
Mn of the styrene-butyl acrylate random copolymer present therein was 9,300, Mw was 10,000, and therefore Mw / Mn was 1.08. Furthermore, the GPC
The curves were unimodal.

As a second step, 4.28 ml (40.0 mmol) of methyl methacrylate and 1.17 ml of toluene were added to 10.0 ml of the remaining reaction solution in the reaction tube after the extraction.
ml, 125 mm of aluminum triisopropoxide
ol / L toluene solution 3.20 ml (0.400 mmol
l) and 31.9 mg of chloropentamethylcyclopentadienyl bis (triphenylphosphine) ruthenium
(0.0401 mmol), and the mixture was sufficiently stirred, and the resulting mixture was heated to 80 ° C. to continuously carry out a polymerization reaction.

After a lapse of 23 hours from the start of the second stage polymerization reaction, the polymerization reaction was stopped by cooling the reaction solution to -78 ° C. The polymerization rates of styrene, butyl acrylate and methyl methacrylate are 96%, 95% and 86%, respectively, and the styrene-butyl acrylate random copolymer block and polymethyl methacrylate block present in the reaction solution are Mn of the block copolymer
Is 19800 and Mw is 23100, thus Mw /
Mn was 1.17. Furthermore, the GPC curve was unimodal.

As is clear from the comparison of Example 8 with Example 9, even in the random copolymerization using two kinds of monomer mixtures, when the polymerization rate is increased, the weight obtained almost in proportion thereto is increased. The combined Mn is increased and the value of Mw / Mn is 1
It can be seen that the value is kept close to. Further, Example 9
From, when a monomer different from the first-stage monomer mixture is added following the polymerization reaction of the first-stage monomer mixture, the second-stage polymerization reaction is continued, and the value of Mw / Mn becomes close to 1. It can be seen that the retained block copolymer is easily produced.

[0065]

According to the living radical polymerization initiator system of the present invention, a wide variety of radically polymerizable monomers can be polymerized while controlling the molecular weight, and a polymer having a narrow molecular weight distribution can be produced. It is possible to do.
And when the living radical polymerization initiator system is applied to the copolymerization of two or more types of radically polymerizable monomers, it is possible to copolymerize a wide combination of various monomers while controlling the molecular weight. Further, it is possible to produce a copolymer having a narrow molecular weight distribution.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsuyoshi Ando 26 eight-star apartment 31, No. 26 Rengezo-cho, Shogo-in, Sakyo-ku, Kyoto, Kyoto (72) Inventor Koyomi Abe 2-902-566 (72) Inventor Yasuhiro Watanabe 191 Horikawa Nishiiri Nishimaruta-cho 406, Kamigyo-ku, Kyoto-shi, Kyoto Joyful Nijo Castle Room 406 (72) Inventor Kazutoshi Terada 41 Miyukigaoka, Tsukuba, Ibaraki Pref.Kuraray Tsukuba Research Institute Co., Ltd. Akira 41 Miyukigaoka, Tsukuba City, Ibaraki Prefecture Kuraray Tsukuba Research Institute Co., Ltd. (72) Inventor Yoshimichi Okano 1239 Shinzai, Aboshi-ku, Himeji City, Hyogo Prefecture Daicel Chemical Industry Co., Ltd. (72) Inventor Masamichi Nishimura Himeji City, Hyogo Prefecture 1239 Shinzai, Aboshi-ku Daicel Chemical Industries, Ltd. (72) Inventor Junichi Kanasaka 1-8 Kasumi, Yokkaichi-shi, Mie Tosoh Co., Ltd. Yokkaichi Research Laboratories (72) Inventor Shoka Oki 1-8 Kasumi, Yokkaichi-shi, Mie, Yokkaichi Laboratories Tosoh Corporation (72) Inventor Naohiko Nagata 23 Uji Kozakura, Uji-shi, Kyoto Address Unitika Central Research Laboratories (72) Inventor Yoshitaka Nagara 23 Uji Kozakura, Uji-shi, Kyoto Prefecture Unitika Central Research Laboratories F-term (reference) 4J015 CA04 CA15

Claims (9)

[Claims] 1. The following components (A), (B) and (C): (A) halogenopentamethylcyclopentadienylbis (triarylphosphine) ruthenium; (B) α-halogenocarbonyl compound or α-halogeno A living radical polymerization initiator system, comprising: a carboxylic acid ester; and (C) a Lewis acid. 2. The living radical polymerization initiator system according to claim 1, wherein the halogen atom in component (A) and the halogen atom in component (B) are the same type of halogen atom. 3. A living radical polymerization initiator system according to claim 1, wherein component (A) is chloropentamethylcyclopentadienyl bis (triarylphosphine) ruthenium. 4. Component (B) is 2-chloro-2,4,4-
The living radical polymerization initiator system according to any one of claims 1 to 3, which is dimethyl trimethylglutarate. 5. The living radical polymerization initiator system according to claim 1, wherein the component (C) is an aluminum trialkoxide. 6. Production of a polymer, characterized in that at least one radical polymerizable monomer is subjected to living radical polymerization in the presence of the living radical polymerization initiator system according to claim 1. Method. 7. The method according to claim 6, wherein the radically polymerizable monomer is at least one radically polymerizable monomer selected from the group consisting of a styrene monomer, a methacrylic ester and an acrylate ester. 8. The production method according to claim 6, wherein the copolymerization is carried out using at least two kinds of radically polymerizable monomers. 9. The method according to claim 8, wherein at least two radical polymerizable monomers selected from the group consisting of styrene monomers, methacrylic esters and acrylic esters are used.