JP2003268046A - Copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for much widely developing new materials and applied living radical polymerization by controlling polymerization of a radically polymerizable monomer in the presence of a nitroxide compound, wherein the polymerization of the radical-polymerizable monomer is hard to control molecular weight and the molecular-weight distribution. <P>SOLUTION: The copolymer having an alkoxyamine is produced by dividedly adding at least one styrene derivative or an acrylic acid ester to a polymerization system containing a methacrylic ester in the presence of one or more compound represented by the general formula (3) to (6) (refer to the specification) when polymerizing a copolymer having a unit of a methacrylic acid ester and a unit of a styrene derivative or an acrylic acid ester. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerization method for producing a copolymer containing two or more kinds of radically polymerizable monomers and having a controlled molecular weight and molecular weight distribution.

According to the polymerization method of the present invention, it becomes possible to control the polymerization of a copolymer containing a monomer species which is difficult to control the molecular weight and the molecular weight distribution as a constituent component. The copolymer obtained by the production method of the present invention can be used as a polymer radical polymerization initiator, and can be suitably used for various functional novel materials.

[0003]

2. Description of the Related Art Conventionally, it has been known that a polymer obtained by radical polymerization generally has a wide molecular weight distribution, and therefore it is difficult to produce a polymer having uniform physical properties by radical polymerization. Therefore, there has been a strong demand for a method of controlling the molecular weight and the molecular weight distribution in radical polymerization.

Recently, in the field of polymer polymerization, attention has been paid to polymerization utilizing a stable nitroxy radical (a kind of so-called "living radicals"). Polymerization utilizing such stable nitroxy radicals may allow precise control of the molecular structure of the polymer, including molecular weight, molecular weight distribution and morphology.

As a method for controlling the molecular weight and the molecular weight distribution in radical polymerization, a radical initiator such as benzoyl peroxide and a nitroxide compound such as 2.2.6.6-tetramethyl-1-piperidinitoxy (TEMPO) are used. A method for controlling the polymerization of styrene in the presence of a mixture is disclosed in JP-A-6-199916. The monomer whose polymerization is controlled in the presence of a nitroxide compound is mainly styrene or a styrene derivative, but it has been reported that the polymerization of acrylic acid esters can be controlled depending on the type of the nitroxide compound. There is. However, until now, there has been no success example in controlling the polymerization of methacrylic acid ester.

[0006] There are many reports of utilizing a polymerization method in the presence of this nitroxide compound, and among them, not only homopolymers but also copolymers using two or more kinds of radically polymerizable monomers are known. Many synthesized examples have been reported. Further, in such a report, there is JP-A-60-89.
No. 452, or J. Am. Chem. So
c. , 121 , 3904 (1999),
We reported a method of synthesizing a copolymer with a narrow molecular weight distribution by copolymerizing methyl methacrylate, which is difficult to control the molecular weight and molecular weight distribution in the presence of a nitroxide compound, with styrene, which can control the polymerization. Some have.

[0007]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The above-mentioned conventional methods (JP-A-60-89452 or J. Am. C.
hem. Soc. , 121 , 3904 (1999)) has a narrow molecular weight distribution, and at first glance, it seems that the same polymerization control as in styrene alone is performed. However, using the polymer thus obtained as a polymer radical polymerization initiator, even if the radical polymerizable monomer is subsequently polymerized, the polymer does not function as a polymer radical polymerization initiator, and There was a problem that polymerization did not occur at all. In other words, it was impossible to extend the scope of new material development by performing living radical polymerization using the copolymers obtained by these methods.

Therefore, it is an object of the present invention to provide a copolymer capable of solving the above-mentioned problems of the prior art and a method for producing the same.

Another object of the present invention is to control the polymerization of a radical-polymerizable monomer, which has been difficult to control the molecular weight and the molecular weight distribution in the presence of a nitroxide compound, and to utilize a novel material utilizing living radical polymerization. It is to significantly expand the scope of development.

[0010]

Means for Solving the Problems As a result of intensive studies on means for solving the problems, the present inventors have found that it is generally difficult to control polymerization in the presence of a nitroxide compound even when the nitroxide compound is used. It is possible to synthesize a random copolymer having an alkoxyamine group at the terminal by carrying out the polymerization while dividing and adding the controllable monomer into the system in which the monomer is polymerized. I found that.

Further, when the methacrylic acid ester and the acrylic ester are used as the monomer components in the presence of a nitroxide compound capable of controlling the polymerization of the acrylic ester, the present invention further polymerizes all the monomers. It was also found that a copolymer having an alkoxyamine group at the terminal can be synthesized even if charged at the start. in this way,
If an alkoxyamine group is present at the terminal of the polymer obtained by the present invention, it becomes possible to produce a block copolymer using the polymer as a polymer radical polymerization initiator, and the usefulness of the copolymer of the present invention is improved. Sex further increases.

That is, in the first aspect, the present invention provides:
The present invention relates to a copolymer having an alkoxyamine group represented by the following general formula (1) or (2) at its terminal.

[0013]

[Chemical 5] (In the formula, R ¹ is a linear or branched alkyl group having a chain length that gives steric hindrance to the bond between the alkoxyamine group and the terminal of the copolymer and decreases the bond energy, or O═P (R ¹⁷ ) (R ¹⁸ ) group, R ² , R ^{5 to} R
⁸ , R ¹⁵ and R ¹⁶ represent the same or different linear or branched alkyl groups having a chain length that gives steric hindrance to the bond between the alkoxyamine group and the end of the copolymer and reduces the bond energy, R ³ , R ⁴ , R ⁹ , R
¹⁰ , R ¹³ and R ¹⁴ represent hydrogen or a linear or branched alkyl group, and may be the same or different from each other, and R ¹¹ and R ¹² are linear or branched alkyl groups, hydrogen, A hydroxyl group, an alkoxy group, an alkoxycarbonyl group and an acyloxy group are shown, and they may be the same or different, and R ¹⁷ and R ¹⁸ are an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aryl group and a perfluoro group. An alkyl group and a halogen group are shown, which may be the same or different. )

In a second aspect, the present invention relates to a method for simply producing the polymer radical polymerization initiator which is the above-mentioned first invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. In the following description, "part" and "%" representing the content are based on mass unless otherwise specified.

(Copolymer Having Alkoxyamine Group)
The copolymer of the present invention is a copolymer containing a styrene derivative unit or an acrylic acid ester unit and a methacrylic acid ester unit, and is represented by the general formula (1) or (2) at the terminal of the copolymer. Has an alkoxyamine group.

(Styrene derivative) In the present invention, the styrene derivative constituting the above copolymer is not particularly limited,
Known styrene derivatives can be used without particular limitation. Examples of the styrene derivative include styrene, p-methylstyrene, chloromethylstyrene, α-
Methylstyrene and the like can be preferably used.

(Acrylic acid ester) In the present invention,
The acrylic acid ester that constitutes the above-mentioned copolymer is not particularly limited, and a known acrylic acid ester can be used without particular limitation. Examples of the acrylic ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-acrylic acid acrylate. Hydroxypropyl, 3-hydroxypropyl acrylate, hydroxybutyl acrylate, acrylic acid 2
-Methoxyethyl, butoxyethyl acrylate, glycidyl acrylate, ethoxyethoxyethyl acrylate,
Methyl triglycol acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, cyclohexyl acrylate, cyanoethyl acrylate and the like can be preferably used.

(Methacrylic acid ester) In the present invention, the methacrylic acid ester is not particularly limited, and known methacrylic acid esters can be used without particular limitation. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, and methacrylic acid 2. -Ethylhexyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, butoxyethyl methacrylate, methacrylic acid Glycidyl, ethoxyethoxyethyl methacrylate,
Methyl triglycol methacrylate, tetrahydrofurfuryl methacrylate, cyanoethyl methacrylate, isodecyl methacrylate, tridecyl methacrylate, alkyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid Isobornyl, adamantyl methacrylate, polypropylene glycol methacrylate, allyl methacrylate, diaminoethyl methacrylate, ethyl phosphate methacrylate and the like can be preferably used.

(Content between Units) The content of the styrene derivative unit or the acrylate unit in the copolymer of the present invention is 0.1 to 49.9% by mass. The content of the styrene derivative unit or the acrylate unit is preferably in the range of 0.1 to 29.9% by mass. When the content of the styrene derivative unit or the acrylate unit is less than 0.1% by mass, the difficulty of controlling the molecular weight and molecular weight distribution of the copolymer tends to increase.

On the other hand, in the present invention, a copolymer having a methacrylic acid ester as a main component, which has been conventionally difficult to control the polymerization, is produced, and the range of material design using the polymer whose molecular weight and molecular weight distribution are controlled. It is possible to spread. In the copolymer of the present invention, if the styrene derivative unit or the acrylic acid ester unit exceeds 49.9% by mass, it becomes difficult to obtain a copolymer containing a methacrylic acid ester unit as a main component. Therefore, the content of the methacrylic acid ester unit in the present invention is 50.1 to 99.9.
It is at least mass%. The content of the methacrylic acid ester unit is preferably in the range of 70.1 to 99.9% by mass.

(Alkoxyamine group) Examples of the alkoxyamine group present at the terminal of the copolymer of the present invention include the structures represented by the above general formula (1) or (2).

In the above formula (1) or (2), R ¹ is a straight-chain type or branched type having a chain length that gives steric hindrance to the bond between the alkoxyamine group and the terminal of the copolymer and lowers the bond energy. It is an alkyl group. Here, the “chain length that causes steric hindrance to the bond with the terminal of the copolymer and lowers the bond energy” may be a group having 1 or more carbon atoms.

The alkyl group that can be used in the present invention is not particularly limited as long as it has the above-mentioned "chain length that gives steric hindrance to the end of the copolymer and lowers the binding energy". Examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, or an O═P (R ¹⁷ ) (R ¹⁸ ) group, wherein R ¹⁷ and R ¹⁸ is an alkyl group such as a methyl group, an ethyl group or a propyl group; a cycloalkyl group such as a cyclohexyl group; an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group; a peroxy group such as an aryloxy group, an aryl group or a trifluoroethyl group Fluoroalkyl group; F, C
The halogen groups such as l and I are shown and may be the same or different.

In the above formula (1) or (2), R ² and R ⁵
To R ^8, R ¹⁵ and R ¹⁶ are the same or different straight-chain or branched alkyl group having a chain length gives a decrease in steric hindrance and binding energy coupling between the alkoxyamine group and a copolymer terminated Show. Such an alkyl group is also not particularly limited. For example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a t-butyl group and the like can be preferably used, and they may be the same or different.

In the above formula (1) or (2), R ³ ,
^{R 4, R 9, R 10} , R 13 and ^{R 1 4} represents hydrogen or straight-chain or branched alkyl group, and may be the same or different from each other. As such an alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a t-butyl group and the like can be preferably used.

In the above formula (1) or (2), R ¹¹ and R
¹² is a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a t-butyl group; an alkoxy group such as a hydrogen group, a hydroxyl group, a methoxy group, an ethoxy group or a butoxy group; An alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, and an acyloxy group such as an acetoxy group, an ethyloxy group and a benzoyloxy group are shown, and they may be the same or different.

The alkoxyamine group represented by the general formula (1) or (2) is not particularly limited. From the viewpoint of being a high-molecular radical polymerization initiator, for example, 2,6-
Diethyl-2,3,6-trimethyl-4-acetoxy-
1-piperidinyloxy, 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4
-Acetoxypiperidine, 2,6-diethyl-2,3
6-trimethyl-4-acetoxy-1-piperidinyloxy, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), 2,2,5,5-tetramethyl-1-pyrrolidinyloxy , Nt-butyl-N- (1
Examples include groups derived from -diethylphosphono-2,2-dimethylpropyl) nitroxide and the like. Among them, 2,6-diethyl-2,3,6-trimethyl-4-acetoxy-1-piperidinyloxy, 1- (1
-Phenylethoxy) -2,6-diethyl-2,3,6
-Trimethyl-4-acetoxypiperidine is preferred.

(Molecular weight)

The molecular weight of the alkoxyamine group-containing copolymer of the present invention can be appropriately determined depending on, for example, the desired physical properties when the copolymer is used as a polymer radical polymerization initiator. For example, when a block copolymer is prepared using a high molecular weight radical polymer and is used as a compatibilizer, the number average molecular weight of the copolymer having an alkoxyamine group is 5 x 10
^{2 to} 5 × 10 ^4, about 1 × 10 ³ to 10 × 10 ^4.
It is preferably about the same (number average molecular weight can be measured by GPC).

(Polymer radical polymerization initiator) The copolymer having an alkoxyamine group of the present invention can be used as a polymer radical polymerization initiator. The method of using this initiator is not particularly limited, but for example, the copolymer can be dissolved in a monomer and heated at 130 ° C. to generate radicals to start the polymerization of the monomer.

(Manufacturing method)

The method for producing the copolymer having an alkoxyamine group of the present invention is not particularly limited, but when the styrene derivative is used as a monomer component for polymerization, the styrene derivative is divided and added to the polymerization system. While carrying out the polymerization, it is preferable. On the other hand, when polymerizing acrylic acid ester as a monomer component in the presence of a nitroxide compound capable of controlling the polymerization of acrylic acid ester, when the acrylic acid ester is polymerized while being divided and added, Even when comparing the case where all the monomers are added at one time to carry out the polymerization, there is no remarkable difference in the produced copolymer, and the polymerization may be carried out by any method. It is possible to control the polymerization of acrylic acid ester means that the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the acrylic acid ester polymer obtained when only acrylic acid ester is polymerized is 1.70 or less, and When a polymer that can be used as a polymer radical polymerization initiator is obtained, it can be judged that "polymerization can be controlled".

(Nitroxide compound)

As the nitroxide compound used in the present invention, compounds represented by the following general formulas (3) to (6) can be used.

[0036]

[Chemical 6] (In the formula, X represents a group having at least one carbon atom.
However, the free radical X.
R is a group capable of polymerizing mer¹Is the alkoxyami
Steric hindrance and binding energy
Straight-chain or branched with chain length giving reduced ruggedness
Type alkyl group; or O = P (R^{1 7}) (R¹⁸)
The base is R^Two, R⁵~ R⁸, R¹⁵And R¹⁶Is the
There is steric hindrance to the bond between the lucoxyamine group and the end of the copolymer.
And having the same chain length to give a reduction in binding energy
Are different linear or branched alkyl groups, R^Three,
R ^Four, R⁹, R¹⁰, R^ThirteenAnd R¹⁴Is hydrogen, direct
Indicates a chain-type or branched-type alkyl group,
May be different, R¹¹, R¹²Is linear
Is a branched alkyl group, hydrogen, hydroxyl group, alkoxy group,
An alkoxycarbonyl group and an acyloxy group,
May be the same or different, and R¹⁷And R¹⁸Is
Alkyl group, cycloalkyl group, alkoxy group, aryl
Luoxy group, aryl group, perfluoroalkyl group, ha
Represents a rogen group, which may be the same or different from each other
Yes. )

In the above formula, X represents a group having at least one carbon atom such as, but not limited to, 1-phenylethoxy.

The compounds represented by the general formulas (3) to (6) are so-called "living" of living radical polymerization.
From the viewpoint of sex, for example, 2,6-diethyl-2,3,6-
Trimethyl-4-acetoxy-1-piperidinyloxy, 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine, 2,6-diethyl-2,3 , 6-trimethyl-4-
Acetoxy-1-piperidinyloxy, 2,2,6,6
-Tetramethyl-1-piperidinyloxy (TEMP
O), 2,2,5,5-tetramethyl-1-pyrrolidinyloxy, Nt-butyl-N- (1-diethylphosphono-2,2-dimethylpropyl) nitroxide and the like. Among them, especially 2,6-diethyl-
2,3,6-Trimethyl-4-acetoxy-1-piperidinyloxy, 1- (1-phenylethoxy) -2,6
-Diethyl-2,3,6-trimethyl-4-acetoxypiperidine is preferred.

In the present invention, these general formulas (3)
By using the compounds of (6) to (6), it is possible to control the polymerization of the styrene derivative. Furthermore, general formula (3)-
Depending on the structure of the compound (6), the use of these compounds also makes it possible to control the polymerization of acrylic acid ester. However, according to the findings of the present inventors, it is relatively difficult to control the polymerization of the methacrylic acid ester alone, even when the compounds of the general formulas (3) to (6) are used. Have been found.

(Compound (3) and / or (5))

General formulas (3) to (3) usable in the present invention
Among the compounds of (6), the compounds (3) and (5) generate “free radicals X.” capable of polymerizing an unsaturated monomer by radical polymerization when heated, and thus when no other radical initiator is present. Even in this case, the copolymer of the present invention can be obtained. In order to increase the polymerization rate, the compounds (3) and (5) and other radical initiator may be used, if necessary. In such an embodiment in which the initiator is used in combination, the molar ratio of the compound (3) or (5) to the other radical initiator is {compound (3) or (5)} / (other radical initiator) = 0. The range of 2/1 or less is preferable, and 0.
The range of 15/1 or less is more preferable. If the molar ratio of {compound (3) or (5)} / (other radical initiator) is too large, the molecular weight distribution of the obtained copolymer tends to be broad.

(Compound (4) and / or (6))

General formula (3) to be used in the present invention
When using the compound (4) or (6) among the compounds of (6), it is preferable to use a radical initiator together.
In such a combination mode, the molar ratio of the compound (4) or (6) to the radical initiator is {compound (4)
Or (6)} / (radical initiator) = 0.2 / 1-
The range of 2.5 / 1 is preferable, and the range of 1/1 to 1.5 / 1 is more preferable. If the molar ratio of this {compound (4) or (6)} / (radical initiator) is too small, the molecular weight distribution of the copolymer obtained will be wide, while if this molar ratio is too large, polymerization will occur. Speed tends to decrease significantly.

(Combination of Nitroxide Compounds) Compounds (3), which are typical examples of nitroxide compounds,
Regarding the combination of (6) and the monomer, when the above-mentioned monomer is a styrene derivative, compounds (3) to
Any of (6) can be used.

On the other hand, when the above-mentioned monomer is an acrylic ester, it is usually preferable to select a compound capable of controlling the polymerization of the acrylic ester alone. The compound capable of controlling the polymerization of such an acrylic ester alone is not particularly limited, but in view of the so-called "living" property of living radical polymerization, 2,6-diethyl-
2,3,6-Trimethyl-4-acetoxy-1-piperidinyloxy, 1- (1-phenylethoxy) -2,6
-Diethyl-2,3,6-trimethyl-4-acetoxypiperidine and the like can be preferably used.

(Monomers to be divided and added) As described above, the monomer to be divided and added in the method for producing the alkoxyamine group-containing copolymer of the present invention is a styrene derivative or an acrylic ester. is there. The styrene derivative and the acrylate ester are not particularly limited, but specific examples thereof include the compounds described above as the styrene derivative and the acrylate ester. These styrene derivatives or acrylic acid esters may be used alone or in combination of two or more as required.

When two or more kinds are used in combination, the combination may be a combination of styrene derivatives, a combination of acrylic acid esters, and / or a styrene derivative (two or more kinds as necessary) -acrylic acid ester (if necessary). And two or more).

(Addition rate) When the monomer of the present invention (styrene derivative or acrylic acid ester) is divided and added to produce a copolymer, 30% of the monomer (styrene derivative or acrylic acid ester) is added. It is preferable to mix not more than 70% by mass with a methacrylic acid ester to initiate polymerization, and to add more than 70% by mass dividedly to the polymerization system. The addition rate of the monomer (styrene derivative or acrylic ester) to the polymerization system can be determined in consideration of the monomer reactivity ratio of the monomers constituting the copolymer to be produced. . In this case, it is preferable to add the methacrylic acid ester so that only the methacrylic acid ester does not remain in the latter stage of the polymerization. Examples include a method of dropping from the start of polymerization over 50% to 98% of the total polymerization time. The addition to the polymerization system may be performed using only the monomer, or may be performed using a mixed solution with a solvent that dissolves the monomer. The addition to the polymerization system is not limited to styrene derivatives or acrylic acid esters,
If necessary, the methacrylic acid ester can be dividedly added at the same time (or in combination).

(Polymerization method)

The copolymerization (for example, random copolymerization) for obtaining the alkoxyamine group-containing copolymer of the present invention is not particularly limited, and known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Can be done at. In this polymerization, an appropriate polymerization method can be selected depending on the kind of the monomer, the polymerization temperature and the like. When using an initiator for the polymerization, an appropriate radical initiator may be selected and used in consideration of the polymerization temperature, the polymerization solvent and the like.

(Initiator)

Examples of the initiator usable in the above bulk polymerization, solution polymerization and suspension polymerization include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2-methylbutyronitrile). ), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbo) Azo initiators such as nitrile); benzoyl peroxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, etc. Agents.

(Emulsion polymerization)

When the above emulsion polymerization is carried out, for example, benzoyl peroxide, dicumyl peroxide,
Water-soluble radical initiators such as ethyl 3,3-di (t-amylperoxy) butyrate, 2,2′-azobis (2-amidinopropane) dihydrochloride, potassium sulfate and ammonium persulfate can be used.

When emulsion polymerization is carried out, it is generally necessary to allow an emulsifier to be present in the polymerization system. As the emulsifier in such an embodiment, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, anionic surfactant such as sodium lauryl sulfate, sorbitan polyethylene glycol monolaurate ester, monopalmitate ester, monooleate ester, stearate ester, Polyethylene glycol stearyl ester,
A nonionic surfactant such as polyethylene glycol stearyl ether can be used.

(Solution polymerization)

When carrying out the above solution polymerization, the solubility of the monomer, the nitroxide compound and the radical initiator,
It is possible to select an appropriate solvent in consideration of the polymerization temperature and the like and carry out the polymerization in the solvent. As this solvent,
Examples thereof include benzene, toluene, ethylbenzene, xylene, chlorobenzene, methyl ethyl ketone, ethyl lactate and isopropyl alcohol.

(Polymerization temperature)

The polymerization temperature is not particularly limited, but is usually 0.
The temperature is preferably in the range of 0 ° C to 180 ° C, more preferably 70 ° C to 150 ° C. When the polymerization temperature is lower than 0 ° C, the polymerization rate is remarkably reduced, and as a result, the polymerization time tends to be long. On the other hand, when the polymerization temperature is higher than 180 ° C., not only is it difficult to control the polymerization rate, but there is a high possibility that thermal polymerization will occur.

The optimum polymerization time can be determined by the polymerization initiator selected, the type and amount of the nitroxide compound, and the polymerization temperature.

(Copolymer)

According to the present invention, for example, a copolymer in which the polymerization is controlled until the end of the polymerization (for example, by carrying out the polymerization while adding a small amount of the controllable monomer in a divided manner to the polymerization system) (for example, A random copolymer) can be synthesized. Since the terminal of the alkoxyamine group-containing copolymer obtained by this method has living activity, this copolymer also functions as a polymer radical polymerization initiator, and other components (for example, other It can be preferably used for the synthesis of block copolymers and the like using a (monomer).

The thus-obtained copolymer or polymer radical polymerization initiator of the present invention is an elastomer, a compatibilizer, a surfactant, or a paint, taking advantage of the fact that the polymerization is controlled. It can also be used for various purposes such as the synthesis of adhesives and the like.

[0064]

EXAMPLES Examples of the present invention (experimental results are shown in Tables 1 and 2) are shown below. However, the present invention is not limited to these.

The evaluations in the examples were carried out according to the following methods.

(1) Number average molecular weight and molecular weight distribution Gel permeation chromatography (Waters)
HPLC pump 510, differential refractometer R401,
Data processing Millennium 2010 Chromatography Manager) Column: Shodex K-805L (inner diameter 8 mm, length 300 mm) Column tank temperature: 35 ° C. Mobile phase: chloroform, flow rate 1.0 ml / min Standard sample: PMMA (Mn: 330000, 880)
00, 34500, 10300, 2990) Sample: concentration 2 mg / ml, chloroform solution sample injection amount: 100 μl)

(2) Copolymer composition ¹ H-NMR (EX270 manufactured by JEOL) Temperature: 30 ° C. Solvent: Deuterated chloroform Sample concentration: 5 mass / volume%, sample amount 0.5 ml

Example 1

Solution A was prepared by mixing the following components. 100m capacity equipped with stirrer, cooling tube, nitrogen introduction tube
This solution A was placed in a 3-necked flask with a volume of 10 ml / mi.
After bubbling nitrogen for 60 minutes at a flow rate of n, 90 ° C
The temperature was raised to and polymerization was started. The dropping of the solution B was started immediately after the start of the polymerization, and the dropping was performed for 8 hours, and then, 1 hour later, the solution B was taken out from the oil bath to stop the polymerization. The obtained polymerization solution was slowly poured into 800 ml of hexane under stirring to reprecipitate, and the polymer was taken out. The pressure was reduced to 1.3 kPa by a vacuum dryer, and the polymer was dried at 60 ° C. for 24 hours. The physical properties of the obtained polymer are shown in Table 1.

Solution A Methyl methacrylate 16 g Styrene 0.33 g 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine 0.70 g Toluene 40 g

Solution B (for dropping) Styrene 3.7 g Toluene 20 g

Example 2

A styrene solution C of the polymethylmethacrylate / polystyrene copolymer synthesized in Example 1 was prepared. Solution C was poured into a glass ampoule having a volume of 5 ml, the lid was closed with a two-way cock, the vacuum line was connected, and the liquid C was frozen with liquid nitrogen. After confirming that the solution C had frozen, the solution was deaerated with a vacuum pump, and the two-way cock was closed to remove it from the vacuum line. The frozen glass ampoule with a two-way cock was thawed with running water at room temperature and freeze-deaerated. The operation from freezing to thawing was performed three times, and the third time was not thawed, the tube was sealed below the two-way cock using a gas burner, and then polymerization was performed at 130 ° C. for 6 hours. After the completion of the polymerization, the pressure of the polymerization solution was reduced to 1.3 kPa by a vacuum dryer, and the polymer was dried at 70 ° C. for 24 hours to obtain a polymer. The physical properties of the obtained polymer are shown in Table 1.

Solution C Polymethylmethacrylate / Polystyrene Copolymer 0.1 g Styrene 0.6 g

Example 3

Solution D was prepared by mixing the following components.
Solution E (for dropping) was prepared, and polymerization was carried out in the same manner as in Example 1. The physical properties of the obtained polymer are shown in Table 1.

Solution D Methyl methacrylate 18 g Styrene 0.37 g 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine 0.70 g Toluene 40 g

Solution E (for dropping) Styrene 1.63 g Toluene 20 g

Example 4

The following components were mixed to prepare a styrene solution F of the poly (methyl methacrylate) / polystyrene copolymer synthesized in Example 3. Polymerization was carried out in the same manner as in Example 2 using this solution F. The physical properties of the obtained polymer are shown in Table 1.

Solution F Polymethylmethacrylate / Polystyrene Copolymer 0.1 g Styrene
0.6 g

Example 5

The following components were respectively mixed to prepare the following solution G and solution H (for dropping). These solutions G
Polymerization was performed in the same manner as in Example 1 using Solution H (for dropping). The physical properties of the obtained polymer are shown in Table 1.

Solution G Methyl methacrylate 17.5 g n-Butyl acrylate 0.45 g 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine 0.70 g

[0085]   40 g of toluene

Solution H (for dropping) n-butyl acrylate 2.05 g Toluene 20 g

Example 6

The following components were mixed to prepare a styrene solution I of the polymethyl methacrylate / n-butyl acrylate copolymer synthesized in Example 5. A polymer was obtained from this solution I under the same conditions as in Example 2. The physical properties of the obtained polymer are shown in Table 1.

Solution I Poly (methyl methacrylate) / poly (n-butyl acrylate) copolymer 0.5 g Styrene 1.5 g

Example 7

The following solutions J and K (for dropping) were prepared. Polymerization was performed in the same manner as in Example 1 using this solution. The physical properties of the obtained polymer are shown in Table 1.

Solution J Methyl methacrylate 18.8 g n-butyl acrylate 0.40 g 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine 0.70 g toluene 40 g

Solution K (for dropping) n-butyl acrylate 0.8 g Toluene 20 g

Example 8

The following components were mixed to prepare a styrene solution L of the poly (methyl methacrylate) / poly (n-butyl acrylate) copolymer synthesized in Example 7. Using this solution L, a polymer was obtained under the same conditions as in Example 2. The physical properties of the obtained polymer are shown in Table 1.

Solution L Poly (methyl methacrylate) / poly (n-butyl acrylate) copolymer 0.5 g Styrene 1.1 g

Example 9

Solution M was prepared by mixing the following components. Polymerization was carried out under the same conditions as in Example 2 except that the solution M was used for a polymerization time of 3 hours to obtain a polymerization solution. The polymerization solution was taken out and dried in a vacuum dryer at 60 ° C. for 24 hours. The physical properties of the obtained polymer are shown in Table 1.

Solution M Methyl methacrylate 2.27 g Methyl acrylate 0.23 g 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine 0.089 g

Example 10

The following components were mixed to prepare a styrene solution N of the poly (methyl methacrylate) / poly (methyl acrylate) copolymer synthesized in Example 9. Stirrer, cooling pipe,
Put this solution N in a three-necked flask equipped with a nitrogen introduction tube,
Polymerization was carried out at 90 ° C. for 6 hours. Then, it was reprecipitated with hexane to obtain a polymer. The physical properties of the obtained polymer are shown in Table 1.

Solution N Poly (methyl methacrylate) / Poly (methyl acrylate) Copolymer 0.3 g Styrene 2 g

Comparative Example 1

The following components were mixed to prepare a monomer solution O
Was prepared and polymerized under the same conditions as in Example 1 to obtain a polymer. The physical properties of the obtained polymer are shown in Table 2.

Solution O Methyl methacrylate 16 g Styrene 4 g 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine 0.70 g Toluene 40 g

Comparative Example 2

The following components were mixed to prepare a styrene solution P of the polymethylmethacrylate / polystyrene copolymer synthesized in Comparative Example 1, and a polymer was obtained under the same conditions as in Example 2. The results are shown in Table 2.

Solution P Polymethylmethacrylate / Polystyrene Copolymer 0.1 g Styrene 0.6 g

Comparative Example 3

The following components were mixed to prepare a monomer solution Q
Was prepared and a polymer was obtained under the same conditions as in Example 1. The physical properties of the obtained polymer are shown in Table 2.

Solution Q Methyl methacrylate 19.99 g Styrene 0.002 g 1- (1-phenylethoxy) -2,6-diethyl-2,3,6-trimethyl-4-acetoxypiperidine 0.70 g Toluene 40 g

Solution R Styrene 0.008 g Toluene 20 g

Comparative Example 4

The following components were mixed to prepare a styrene solution S of the polymethylmethacrylate / polystyrene copolymer synthesized in Comparative Example 3 and a polymer was obtained under the same conditions as in Example 2. The results are shown in Table 2.

Solution S Polymethylmethacrylate / Polystyrene Copolymer 0.1 g Styrene 0.6 g

The results obtained in the above Examples and Comparative Examples are summarized in Tables 1 and 2 below.

[0117]

[Table 1]

[0118]

[Table 2]

[0119]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, there is provided a copolymer having an alkoxyamine group, the terminal of which has living activity and thus functions as a polymer radical polymerization initiator. Such a polymer radical polymerization initiator can be suitably used for synthesis of a block copolymer or the like, for example.

Further, in the present invention, when a monomer which is difficult to control in the presence of a nitroxide compound used for controlling the molecular weight and the molecular weight distribution in radical polymerization is polymerized, a small amount of the monomer is added to the polymerization system. By carrying out the polymerization while dividing and adding the polymerization-controllable monomer, it becomes possible to synthesize the above-mentioned copolymer (for example, a random copolymer) in which the polymerization is controlled until the end of the polymerization.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takayuki Makino             20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayo             Central Technology Research Institute F-term (reference) 4J011 BB01 BB03 BB05 BB06 BB09                       BB12 NA02 NB04 NB05                 4J015 EA04 EA07                 4J100 AB02Q AB03Q AB04Q AB08Q                       AL03P AL03Q AL04P AL04Q                       AL05P AL05Q AL08P AL08Q                       AL09P AL09Q AL10P AL10Q                       AL74P BA03P BA06P BA06Q                       BA29P BA40P BA40Q BA65P                       BC04P BC04Q BC08P BC09P                       BC43Q BC53P CA03 CA04                       CA27 FA03 FA04 FA06 FA34                       FA37 JA15

Claims (4)

[Claims] 1. A copolymer comprising 0.1 to 49.9% by mass of a styrene derivative unit or an acrylic acid ester unit and 50.1 to 99.9% by mass of a methacrylic acid ester unit, the copolymer comprising: A copolymer having an alkoxyamine group represented by the following general formula (1) or (2) at the terminal. [Chemical 1] (In the formula, R ¹ is a linear or branched alkyl group having a chain length that gives steric hindrance to the bond between the alkoxyamine group and the terminal of the copolymer and decreases the bond energy, or O═P (R ¹⁷ ) (R ¹⁸ ) group, R ² , R ^{5 to} R
⁸ , R ¹⁵ and R ¹⁶ represent the same or different linear or branched alkyl groups having a chain length that gives steric hindrance to the bond between the alkoxyamine group and the end of the copolymer and reduces the bond energy, R ³ , R ⁴ , R ⁹ , R
¹⁰ , R ¹³ and R ¹⁴ represent hydrogen or a linear or branched alkyl group, and may be the same or different from each other, and R ¹¹ and R ¹² are linear or branched alkyl groups, hydrogen, A hydroxyl group, an alkoxy group, an alkoxycarbonyl group and an acyloxy group are shown, and they may be the same or different, and R ¹⁷ and R ¹⁸ are an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aryl group and a perfluoro group. An alkyl group and a halogen group are shown, which may be the same or different. ) 2. A polymer radical polymerization initiator comprising the copolymer according to claim 1. 3. A methacrylic acid ester unit and styrene
Copolymer containing derivative unit or acrylic acid ester unit
When polymerizing the coalescence, the following general formulas (3) to (6) are shown.
Methacrylic acid in the presence of at least one compound
At least one or more for the polymerization system containing acid ester
Of styrene derivative or acrylic ester of
The copolymer according to claim 1, which is added.
Build method. [Chemical 2] (In the formula, X represents a group having at least one carbon atom.
However, the free radical X.
R is a group capable of polymerizing mer¹Is the alkoxyami
Steric hindrance and binding energy
Straight-chain or branched with chain length giving reduced ruggedness
Type alkyl group; or O = P (R^{1 7}) (R¹⁸)
The base is R^Two, R⁵~ R⁸, R¹⁵And R¹⁶Is the
There is steric hindrance to the bond between the lucoxyamine group and the end of the copolymer.
And having the same chain length to give a reduction in binding energy
Are different linear or branched alkyl groups, R^Three,
R ^Four, R⁹, R¹⁰, R^ThirteenAnd R¹⁴Is hydrogen, direct
Indicates a chain-type or branched-type alkyl group,
May be different, R¹¹, R¹²Is linear
Is a branched alkyl group, hydrogen, hydroxyl group, alkoxy group,
An alkoxycarbonyl group and an acyloxy group,
May be the same or different, and R¹⁷And R¹⁸Is
Alkyl group, cycloalkyl group, alkoxy group, aryl
Luoxy group, aryl group, perfluoroalkyl group, ha
Represents a rogen group, which may be the same or different from each other
Yes. ) 4. A compound represented by the following general formulas (3) to (6):
In the presence of at least one compound selected from the compounds
And acrylic acid ester derivative unit 0.1 to 49.9 quality
% And methacrylic acid ester unit 50.1 to 99.9 quality
Characterized in that it polymerizes a monomer containing
An alkoxy represented by the following general formula (1) or (2)
A method for producing a copolymer having an amine group. [Chemical 3] (In the formula, R¹Is the alkoxyamine group and the end of the copolymer
Gives steric hindrance and lowers binding energy
A linear or branched alkyl group having a chain length,
I O = P (R¹⁷) (R¹⁸) Group, R^Two, R⁵~ R
⁸, R¹⁵And R¹⁶Together with the alkoxyamine group
Steric hindrance and binding energy of the bond with the polymer end
Same or different straight chain type with chain length giving reduction
Represents a branched alkyl group, R^Three, R^Four, R⁹, R
¹⁰, R^ThirteenAnd R¹⁴Is hydrogen, linear or
Indicates a branched alkyl group, which may be the same or different
Well, R¹¹, R¹²Is a linear or branched al
Kill group, hydrogen, hydroxyl group, alkoxy group, alkoxycal
Indicates a carbonyl group or an acyloxy group, which may be the same or different.
And R¹⁷And R¹⁸Is an alkyl group,
Chloroalkyl group, alkoxy group, aryloxy group,
Reel group, perfluoroalkyl group, halogen group
However, they may be the same or different from each other. ) [Chemical 4] (In the formula, X represents a group having at least one carbon atom.
However, the free radical X.
R is a group capable of polymerizing mer¹Is the alkoxyami
Steric hindrance and binding energy
Straight-chain or branched with chain length giving reduced ruggedness
Type alkyl group; or O = P (R^{1 7}) (R¹⁸)
The base is R^Two, R⁵~ R⁸, R¹⁵And R¹⁶Is the
There is steric hindrance to the bond between the lucoxyamine group and the end of the copolymer.
And having the same chain length to give a reduction in binding energy
Are different linear or branched alkyl groups, R^Three,
R ^Four, R⁹, R¹⁰, R^ThirteenAnd R¹⁴Is hydrogen, direct
Indicates a chain-type or branched-type alkyl group,
May be different, R¹¹, R¹²Is linear
Is a branched alkyl group, hydrogen, hydroxyl group, alkoxy group,
An alkoxycarbonyl group and an acyloxy group,
May be the same or different, and R¹⁷And R¹⁸Is
Alkyl group, cycloalkyl group, alkoxy group, aryl
Luoxy group, aryl group, perfluoroalkyl group, ha
Represents a rogen group, which may be the same or different from each other
Yes. )