KR20070030801A - Acrylic star polymer - Google Patents

Abstract

An object of the present invention is to provide an acrylic acid star polymer having a narrow molecular weight distribution and controlled acid decomposability. Its star polymer is formula (Ⅰ):

[Formula 1]

(In formula, R <_1> represents a hydrogen atom or a methyl group, R <_2> and R <_3> respectively independently represents the organic group couple | bonded with a carbon atom, C1 carbon interposes another part and a carbon atom A carbon chain having a repeating unit derived from a polyacrylate having at least two partial structures represented by the formula (II):

 [Formula 2]

(In formula, R <_4> represents a hydrogen atom or a methyl group, R <_5> represents an organic group.) It is a polymer chain which has a repeating unit derived from the (meth) acrylic acid ester represented by Formula (I). When R <_1> is a methyl group, let R <_5> make a polymer chain except the homopolymer chain which has a repeating unit derived from (meth) acrylic acid ester which is a C1-C4 alkyl group.

Description

Acrylic star polymer {ACRYLIC STAR POLYMER}

The present invention relates to an acrylic acid star polymer, and more particularly, to a star polymer having a repeating unit derived from polyacrylate as a core and a repeating unit derived from acrylate ester as an arm.

This application claims priority based on Japanese Patent Application No. 2004-162081 for which it applied on May 31, 2004, and Japanese Patent Application 2005-132073 for which it applied on April 28, 2005, and uses the content here. .

Methyl methacrylate, isobutyl methacrylate and t-butyl methacrylate are polymerized with diphenylhexyl lithium obtained by reacting 1,1-diphenylethylene with s-butyllithium as an initiator, followed by dicumyl alcohol. It is known that dimethacrylate or 2,5-dimethyl-2,5-hexanediol dimethacrylate is reacted to obtain a star polymer (see Non-Patent Document 1).

[Non-Patent Document 1] L. Kilian, et. Al., J. Polymer Science, Part A, 2003, 3083.

Disclosure of the Invention

Problems to be Solved by the Invention

However, the molecular weight distribution of the said compound is 1.5 or more mostly, and it cannot be said that molecular weight is controlled. Moreover, although the application was attempted as a resist material using the point which has acid decomposability, the characteristic which was not necessarily satisfactory was not obtained.

An object of the present invention is to provide an acrylic acid star polymer having a narrow molecular weight distribution and controlled acid decomposability.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the said subject can be solved by using the organic group which has a specific skeleton in the acrylate ester part which comprises an arm part, and also using the core part which has a tertiary carbon skeleton. It has been discovered that the present invention has been completed.

That is, the present invention,

(1) Formula (I):

[Formula 1]

(In formula, R <_1> represents a hydrogen atom or a methyl group, R <_2> and R <_3> respectively independently represents the organic group couple | bonded with a carbon atom, C1 carbon interposes another part and a carbon atom A polymer chain having a repeating unit derived from a polyacrylate having at least two or more partial structures represented by the formula (II):

[Formula 2]

(In formula, R <_4> represents a hydrogen atom or a methyl group, R <_5> represents an organic group.) It is a polymer chain which has a repeating unit derived from the (meth) acrylic acid ester represented by Formula (I). When R <_1> is a methyl group, R <_5> has a polymer chain as an arm part except the homopolymer chain which has a repeating unit derived from the (meth) acrylic acid ester which is a C1-C4 alkyl group. In that,

(2) The polyacrylate which has 2 or more of partial structures represented by Formula (I) is Formula (III):

[Formula 3]

(In formula, R <_11> and R <_21> represents a hydrogen atom or a methyl group each independently, and R <_12> , R <_13> , R <_22> and R <_23> represent each independently the organic group couple | bonded through a carbon atom. Display and R ₃₃ Is a diacrylate represented by a divalent linking group), wherein the star polymer according to (1),

(3) The star polymer according to (2), wherein R ₃₃ is an alkylene group which may have a substituent in formula (III),

(4) a star polymer having at least one repeating unit selected from the group consisting of a repeating unit having a lactone ring and a repeating unit having an alicyclic skeleton;

(5) the core part is represented by the formula (I)

[Formula 4]

(In formula, R <_1> represents a hydrogen atom or a methyl group, R <_2> and R <_3> respectively independently represents the organic group couple | bonded with a carbon atom, C1 carbon interposes another part and a carbon atom It has a repeating unit derived from the polyacrylate which has at least 2 or more partial structure represented by the carbon atom couple | bonded), and the star polymer as described in (4) characterized by the above-mentioned.

Effects of the Invention

As described above, since the star polymer of the present invention has a narrow molecular weight distribution and excellent acid decomposability, it is useful for resist materials and the like, and it can be said that the industrial use value is high.

To practice the invention  Best form for

The core part constituting the star polymer of the present invention is a repeating unit derived from a polyacrylate having at least two or more partial structures represented by the formula (I). In addition, when it describes as an acrylate, it shall contain both an acrylate ester and a methacrylate ester. In formula (I), R <_1> represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent an organic group bonded by a carbon atom. In this case, an organic group represents the general name of the functional group which has at least 1 carbon atom, and the organic group couple | bonded by a carbon bond means that the element of the (alpha) position of C1 carbon among organic groups is a carbon atom. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclohexyl group, benzyl group, phenethyl group, phenyl group, 1-naphthyl group, vinyl group , Allyl group, ethynyl group, propargyl group, chloromethyl group, 2-chloroethyl group, 1-chloroethyl group, 2-pyridyl group, 2-pyridylmethyl group and the like.

In addition to bonding with the oxygen atoms, R ₂ and R ₃ , the C 1 carbon further has another bond number, characterized in that the other side to be bonded is a carbon atom. That is, it means that it is not couple | bonded with atoms other than carbon atoms, such as an oxygen atom and a sulfur atom. As another part which makes a carbon atom the terminal, if it is a structure which can have at least 1 partial structure represented by Formula (I), it will not specifically limit. Specifically, the structure shown by following formula (5)-(7) can be illustrated. However, the partial structure represented by Formula (I) shall be omitted. In addition, the partial structure represented by two or more Formula (I) may be the same, and may differ.

[Formula 5]

[Formula 6]

[Formula 7]

In particular, the polyacrylate represented by Formula (III) can be illustrated preferably. In formula (III), R ₁₁ and R ₂₁ each independently represent a hydrogen atom or a methyl group, and R ₁₂ , R ₁₃ , R ₂₂ and R ₂₃ are each independently bonded via a carbon atom. An organic group is represented and the same specific example illustrated by R <_2> and R <_3> can be illustrated. R ₃₃ represents a divalent linking group in which both terminals are carbon atoms, and the divalent substituents in the substituents represented by the formulas (5) to (7) can be exemplified in the same manner. Among these, R ₃₃ is preferably an alkylene group which may have a substituent. As a polyacrylate which has at least 2 or more partial structure represented by Formula (I), the compound shown below can be illustrated concretely.

[Formula 8]

As for the polymer chain derived from the (meth) acrylic acid ester represented by Formula (II) used for this invention, when R <_1> in Formula (I) is a methyl group, R <_5> is (meth) acrylic acid which is a C1-C4 alkyl group. It is characterized by excluding homo polymer chains having repeating units derived from esters. In formula (II), R <_4> represents a hydrogen atom or a methyl group, and R <_5> represents an organic group. An organic group is a general term of the functional group containing at least 1 carbon atom, Specifically, the thing similar to the specific example illustrated by R <_2> and R <_3> can be illustrated, The organic group which has an alicyclic hydrocarbon skeleton, and has a lactone ring An organic group can be illustrated preferably.

As an organic group which has alicyclic hydrocarbon backbone, the organic group represented by following formula (V) can be illustrated concretely.

[Formula 9]

In formula, A represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or the bivalent group which combined these, and B represents any one of following formula (VI-1)-(VI-6) Display.

[Formula 10]

In the formulas (VI-1) to (VI-6), R ₁₁₁ represents a C1-C5 alkyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R ₁₁₂ to R ₁₁₆ each independently represent a C1 to C4 alkyl group or an alicyclic hydrocarbon group which may have a straight or branched chain in a hydrocarbon, and at least one of R ₁₁₂ to R ₁₁₄ , or R ₁₁₅ , R ₁₁₆ Any one of them represents an alicyclic hydrocarbon group. R ₁₁₇ to R ₁₂₁ each independently represent a hydrogen atom, a C1 to C4 alkyl group which may have a straight or branched chain, or an alicyclic hydrocarbon group, and at least one of R ₁₁₇ to R ₁₂₁ represents an alicyclic hydrocarbon group Any one of R ₁₁₉ and R ₁₂₁ represents a C1 to C4 alkyl group or an alicyclic hydrocarbon group having a straight or branched chain. R ₁₂₂ to R ₁₂₅ each independently represent a hydrogen atom, a C 1 to C 4 alkyl group which may have a straight chain or a branched chain, or an alicyclic hydrocarbon group, but R ₁₂₂ to R ₁₂₅ At least one of them represents an alicyclic hydrocarbon group. As an alicyclic hydrocarbon group, the skeleton shown by following formula can be illustrated concretely.

[Formula 11]

Among these, 1-adamantyl group and 2-adamantyl group are preferable, and the 2-substituted adamantyl group represented by a following formula (i) can be illustrated preferably.

[Formula 12]

In formula (iii), R ₁₃₀ represents an alkyl group which may have a substituent, and R ₁₃₁ to R ₁₃₂ each independently represent a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. P, q, r each independently represent an integer of 0 or 1 to 3, and when p, q or r is 2 or more, R ₁₃₁ , R ₁₃₂ and R ₁₃₃ are Each may be the same or different.

Moreover, as A, the bivalent group represented by a following formula can be illustrated concretely.

[Formula 13]

In said formula, Ra and Rb respectively independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, and an alkoxy group, Specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group Lower alkyl groups, such as these, can be illustrated preferably. As a substituent of a substituted alkyl group, a halogen atom and an alkoxy group are mentioned, As an alkoxy group, what is C1-C4, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated. r1 represents the integer of any one of 1-10, and m shows the integer of any one of 1-3.

In formula (II), the compound shown by following formula can be illustrated as (meth) acrylic acid ester which R <_5> represents an alicyclic hydrocarbon group. In addition, in formula, R <_6> and R <_7> respectively independently represents a linear or branched lower alkyl group.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

As (meth) acrylic acid ester which has an organic group which has a lactone ring, a butyrolactone acrylate, butyrolactone methacrylate, mevalonic lactone methacrylate, pantolactone methacrylate, etc. can be illustrated specifically ,. Although the organic group represented by a following formula (i) can be illustrated preferably.

[Formula 18]

In formula, A represents the same meaning as the said divalent group, and C shows any one of following formula (VII-1)-(VII-5).

[Formula 19]

In formulas (VII-1) to (VII-5), X represents an oxygen atom, a sulfur atom, or an alkylene group which may have a substituent, and R ₂₀₁ represents an alkyl group which may have a substituent, a cycloalkyl group, or Alkenyl group is represented. m1 represents the integer of any of 0 or 1-5, and when m1 is 2 or more, R < ₂₀₁ > may mutually be same or different, and may mutually combine and form a ring. As (meth) acrylic acid ester which has a lactone ring, the compound shown by following formula can be illustrated concretely.

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

The arm portion of the star polymer of the present invention has an arm having at least one repeating unit selected from the group consisting of at least one repeating unit derived from the (meth) acrylic acid ester or a repeating unit containing the following structure: Negative configuration is preferable.

Specifically as a repeating unit which comprises an arm part, the following repeating unit can be illustrated.

(a) a repeating unit having a lactone ring, and a repeating unit having an alicyclic skeleton,

(b) repeating units having a lactone ring, and repeating units having a tertiary carbon skeleton,

(c) repeating units having a lactone ring, and repeating units having an acid decomposition / leaving group,

(d) a repeating unit having an alicyclic skeleton, and a repeating unit having a tertiary carbon skeleton, and

(e) repeating units having an alicyclic skeleton, and repeating units having an acid decomposing / leaving group.

Arm units containing a repeating unit having a lactone ring, a repeating unit having an alicyclic skeleton, a repeating unit having a tertiary carbon skeleton, and a repeating unit having an acid decomposable / release group is a repeating unit derived from (meth) acrylic acid ester Is preferably.

Moreover, the arm part containing the repeating unit which has a lactone ring, the repeating unit which has an alicyclic skeleton, the repeating unit which has a tertiary carbon skeleton, and the repeating unit which has an acid-decomposable / release group is a lactone ring and an alicyclic type in an ester part. It is preferable that it is a repeating unit derived from a skeleton, a tertiary carbon skeleton, and (meth) acrylic acid ester which has an acid decomposable / release group.

Moreover, it is preferable that the arm part containing the repeating unit derived from the (meth) acrylic acid ester which has a tertiary carbon skeleton has a tertiary carbon skeleton in ester oxygen (alpha) position, and has a (meth) acrylic acid which has an alicyclic skeleton in an ester part. It is preferable that the carbon of the ester oxygen α position of the arm portion containing the repeating unit derived from the ester is tertiary carbon, and the arm portion containing the repeating unit having an alicyclic skeleton is (meth) acrylic acid-2-alkyl-2-a. It is preferable that it is a repeating unit derived from a mantyl or isoadamantyl (meth) acrylic acid.

Specific examples of the (meth) acrylic acid ester having a tertiary carbon skeleton in the ester moiety include t-butyl acrylate, t-butyl methacrylate, 1,1-dimethylpropyl acrylate and 1,1-dimethylpropyl methacryl. Rate and the like can be exemplified.

In addition to the repeating unit derived from the above-mentioned (meth) acrylic acid ester, the arm part of the star polymer of this invention can be made to contain the repeating unit derived from the (meth) acrylic acid ester shown below as needed.

Methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, t-octyl acrylate, chlorethyl acrylate, 2-ethoxyethyl acrylate, 2, 2-dimethyl-3-ethoxypropylacrylate, 5-ethoxypentylacrylate, 1-methoxyethylacrylate, 1-ethoxyethylacrylate, 1-methoxypropylacrylate, 1-methyl-1- Acrylate esters such as methoxyethyl acrylate, 1- (isopropoxy) ethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl Methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate Nitrate, benzyl methacrylate, chlorbenzyl methacrylate, octyl methacrylate, 2-ethoxyethyl methacrylate, 4-methoxybutyl methacrylate, 5-methoxypentyl methacrylate, 2,2-dimethyl 3-ethoxypropyl methacrylate, 1-methoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1-methoxypropyl methacrylate, 1-methyl-1-methoxyethyl methacrylate, Methacrylic acid esters such as 1- (isopropoxy) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate,

Methyl crotonate, ethyl crotonate, propyl crotonate, ammonium crotonate, cyclohexyl crotonate, ethyl hexyl crotonate, octyl crotonate, crotonic acid-t-octyl, chlorethyl crotonate, 2-ethoxyethyl croto Nate, 2,2-dimethyl-3-ethoxypropyl crotonate, 5-ethoxypentyl crotonate, 1-methoxyethyl crotonate, 1-ethoxyethyl crotonate, 1-methoxypropyl crotonate Tonate, 1-methyl-1-methoxyethylcrotonate, 1- (isopropoxy) ethylcrotonate, benzyl crotonate, methoxybenzyl crotonate, furfuryl crotonate, tetrahydrofurfuryl Crotonic acid esters such as crotonate, dimethyl itaconic acid, diethyl itaconate, dipropyl itaconate, diamyl itaconate, dicyclohexyl itaconate, bis (ethylhexyl itaconate), dioctyl itaconic acid, itaconic acid -Di-t-octyl, bis (chlorethyl) itaconate, bis (2-ethoxy Ethyl) Itaconate, Bis (2, 2-Dimethyl-3-ethoxypropyl) Itaconate, Bis (5-ethoxypentyl) Itaconate, Bis (1-methoxyethyl) Itaconate, Bis ( 1-ethoxyethyl) itaconate, bis (1-methoxypropyl) itaconate, bis (1-methyl-1-methoxyethyl) itaconate, bis (1- (isopropoxy) ethyl) ita Itaconic acid esters, such as a cornate, a dibenzyl itaconate, a bis (methoxybenzyl) itaconate, a difurfuryl itaconate, a ditetrahydrofurfuryl itaconate, etc .;

In the arm part of the star polymer of this invention, the ratio of each repeating unit can be arbitrarily selected according to the ratio of the monomer used for reaction. For example, content of the repeating unit which has a lactone ring is 30-70 mol% in all the arm part repeating units, Preferably it is 35-65 mol%, More preferably, it is 40-60 mol%. Content of the repeating unit which has an alicyclic skeleton is 20-75 mol% normally in all the arm part repeating units, Preferably it is 25-70 mol%, More preferably, it is 30-65 mol%. Content of the repeating unit which has structures other than a lactone ring and an alicyclic skeleton is 0 mol%-70 mol% normally in all the monomer repeating units, Preferably it is 2-40 mol%, More preferably, it is 5-30 mol. % to be.

The number average molecular weight (Mn) of the arm portion is, based on the gel permeation chromatography, a polystyrene standard, preferably 1,000 to 100,000, more preferably 1,500 to 500,000, still more preferably 2,000 to 200,000, particularly preferably 2,500 It is the range of-100,000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably in the range of 1.01 to 3.00, more preferably 1.01 to 2.00, and more preferably 1.01 to 1.50.

As a manufacturing method of the star polymer of this invention, (1) anionic polymerization of (meth) acrylic acid ester etc. which have an alicyclic skeleton, a lactone ring, etc. in presence of an anionic polymerization initiator, synthesize | combines an arm polymer, and then polyacryl The method of reacting a rate and (2) reacting a polyacrylate in the presence of an anionic polymerization initiator to form a polyfunctional core, followed by anionic polymerization of a (meth) acrylic acid ester having an alicyclic skeleton and a lactone ring or the like The method, (3) anionic polymerization of (meth) acrylic acid ester having an alicyclic skeleton, a lactone ring, etc. in the presence of an anionic polymerization initiator, and the like to synthesize an arm polymer, and then react the polyfunctional coupling agent, and further And the method of reacting the monomer which can be anion-polymerized etc. can be illustrated. The method of said (1), (3) is easy in the control of reaction, and is preferable in manufacturing the star polymer which controlled the structure.

An alkali metal or an organic alkali metal can be illustrated as an anionic polymerization initiator used for the said anion polymerization method. Examples of the alkali metals include lithium, sodium, potassium, cesium, and the like. As an organic alkali metal, the alkylate, allylide, arylide, etc. of the said alkali metal can be illustrated. Specifically, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, α-methylstyrene sodium dianion, 1,1 -Diphenylhexyl lithium, 1, 1- diphenyl-3- methyl pentyl lithium, etc. are mentioned.

As a polymerization reaction which synthesize | combines the arm polymer in the method of said (1) or (3), the monomer (mixing) liquid is added to the method of dripping an anionic polymerization initiator in the monomer (mixing) solution, or the solution containing an anionic polymerization initiator. Although it can carry out by any method of dripping, since the molecular weight and molecular weight distribution can be controlled, the method of dripping a monomer (mixing) liquid in the solution containing an anionic polymerization initiator is preferable. The synthesis reaction of this arm polymer is normally performed in the organic solvent in inert gas atmosphere, such as nitrogen and argon, in -100-50 degreeC, Preferably it is at the temperature of the range of -100-40 degreeC.

As an organic solvent used for the synthesis reaction of the said arm polymer, Aliphatic hydrocarbons, such as n-hexane and n-heptane, Alicyclic hydrocarbons, such as cyclohexane and cyclopentane, Aromatic hydrocarbons, such as benzene and toluene, Diethyl ether In addition to ethers, such as tetrahydrofuran (THF) and dioxane, the organic solvent normally used in anionic polymerization, such as anisole and hexamethylphosphoramide, is mentioned. These can be used as 1 type of single solvent or 2 or more types of mixed solvent. Among them, a mixed solvent of tetrahydrofuran and toluene, tetrahydrofuran and hexane, tetrahydrofuran and methylcyclohexane can be preferably exemplified from the viewpoint of polarity and solubility.

As a polymerization form of an arm polymer, the random copolymer, the partial block copolymer, and the full block copolymer in which each component is distributed statistically throughout the copolymer chain can be mentioned. These can be synthesize | combined respectively by selecting the addition method of the (meth) acrylic acid ester to be used.

The reaction which produces | generates the star polymer using the arm polymer obtained in this way as a branched polymer chain can be performed by adding the above-mentioned polyacrylate further to a reaction liquid after completion | finish of the synthesis reaction of an arm polymer. In general, the reaction is controlled by performing a polymerization reaction at a temperature of -100 ° C to 50 ° C, preferably -70 ° C to 40 ° C in an organic solvent under an inert gas atmosphere such as nitrogen or argon. The polymer with a narrow molecular weight distribution can be obtained. In addition, the formation reaction of such a star polymer can be performed not only continuously in the solvent used for forming an arm polymer, but can also be performed by adding a solvent, changing a composition, or substituting a solvent with another solvent. As such a solvent, the same solvent as that used for the synthesis reaction of an arm polymer can be used.

In the manufacturing method of the star polymer of this invention, superposition | polymerization, such as an alicyclic skeleton and (meth) acrylic acid ester which has a lactone ring by an anionic polymerization method which uses a polyacrylate (P) and an anionic polymerization initiator as a polymerization initiator It is preferable to make molar ratio [(P) / (D)] of the active terminal (D) of the made polymer chain into 0.1-10. The reaction between the arm polymer chain and the polyacrylate may be any of a method of adding a polyacrylate to an arm polymer chain having an active end, or a method of adding an arm polymer chain having an active end to a polyacrylate.

The number of arms of the star polymer is determined by the addition amount of the polyacrylate, the reaction temperature, and the reaction time, but is usually influenced by the reactivity difference between the living polymer terminal and vinyl groups such as polyacrylate, steric hindrance, and the like. A plurality of star block copolymers of different numbers are produced simultaneously. Moreover, it is preferable that ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the produced star polymer exists in the range of 1.00-1.50, and it is preferable that a number average molecular weight is 3,000-300,000. .

In the method of (3), a monomer capable of anionic polymerization is reacted with a central core (polyfunctional core) having an active terminal formed by reacting an arm polymer chain prepared in advance with a polyacrylate or the like to form a new arm polymer chain. It is possible to produce star polymers having different kinds of arm polymer chains. Although the monomer which can be directly polymerized can be made to react with the active terminal which exists in a center core, after reacting compounds, such as diphenylethylene and stilbene, and also adding the salt salt of alkali metals, such as lithium chloride, or alkaline-earth metals, When reacting a monomer later, when reacting a highly reactive monomer like an acrylic acid derivative, a polymerization reaction can be advanced slowly and it may be advantageous in controlling the structure of the whole star polymer produced | generated. In addition, the reaction may be carried out continuously in a solvent used to form a core having an active terminal, and may be carried out by adding a solvent to change the composition or by replacing the solvent with another solvent. As such a solvent, the solvent similar to the solvent used for the synthesis | combination of an arm polymer can be illustrated. Moreover, random copolymerization is carried out by mixing and reacting two kinds of monomers as the arm polymer chain newly introduced to the active terminal present in the core in the method (3) or the arm polymer chain in the method (2). It is also possible to set it as one polymer chain, and also to set it as a block polymer chain by adding two types of monomers sequentially. Moreover, it is also possible to introduce a functional group in the terminal by adding carbon dioxide, an epoxy, etc. after completion | finish of reaction.

Hereinafter, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited to an Example.

Example 1

Under a nitrogen atmosphere, 331 g of tetrahydrofuran (THF) containing 13 mmol of lithium chloride was kept at -40 ° C, and while stirring, 26 mmol of sec-butyllithium (SBL) was added to 2-methyl-2-adama 97 mmol of ylmethacrylate (2MAdMA) and (±) -octahydro-3-oxo-4,7-methanoisobenzofuran-5-ylmethacrylate and its positional isomers (±) -octahydro-1 88 g of a THF solution containing 78 mmol of a mixture of -oxo-4,7-methanoisobenzofuran-5-ylmethacrylate (TLMA) and 19 mmol of tert-butylmethacrylate (tBMA) was added dropwise, followed by 30 minutes. The reaction was continued. A small amount of the reaction solution was taken out from the reaction system, and gas chromatography (hereinafter abbreviated as GC) confirmed that the monomer was completely consumed.

Subsequently, 12 g of a THF solution containing 22 mmol of 2,5-dimethyl-2,5-hexanediol dimethacrylate (MDMA) was added dropwise, the reaction was continued for 30 minutes, and a small amount of the reaction solution was taken out of the reaction system. After confirming that the MDMA monomer was completely consumed by GC, the reaction was stopped by a THF solution containing hydrochloric acid. The reaction stopper was poured into a large amount of water to precipitate a polymer, filtered, washed and dried to obtain a white powdery polymer. The obtained polymer was redissolved in THF, then poured into a large amount of methanol to precipitate the polymer, filtered and washed, and dried under reduced pressure for 10 hours to obtain a white powdery star polymer. GPC analysis of the obtained polymer showed that Mw = 29400, Mw / Mn = 1.23, area = 67% in the star polymer part, Mw = 4800, Mw / Mn = 1.19, area = 33% in the arm polymer part, and 13C- From the NMR measurement, this polymer composition ratio was 2MAdMA: TLMA: tBMA: MDMA = 46: 31: 11: 12 (molar ratio).

Example 2

Under a nitrogen atmosphere, 233 g of THF containing 15 mmol of lithium chloride was kept at -40 ° C, and under stirring, 31 mmol of SBL was added to give 88 mmol of 2MAdMA and 5-methacrylic acid-5-oxo-4-oxatricyclo [4.2]. 1.0 g of a THF solution containing 88 mmol of .1.0 ^3,7 ] nonan- ² -yl (NLMA) and 19 mmol of tBMA was added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that GC completely consumed the monomer.

Subsequently, 12 g of a THF solution containing 22 mmol of MDMA was added dropwise, and the reaction was continued for another 30 minutes, and a small amount of the reaction solution was taken out from the reaction system, and after confirming that the MDMA monomer was completely consumed by GC, the solution contained hydrochloric acid. The reaction was stopped by THF solution. The reaction stopper was poured into a large amount of water to precipitate a polymer, filtered, washed and dried to obtain a white powdery polymer. The obtained polymer was redissolved in THF, then poured into a large amount of methanol to precipitate the polymer, filtered and washed, and dried under reduced pressure for 10 hours to obtain a white powdery star polymer. GPC analysis of the obtained polymer showed that Mw = 32700, Mw / Mn = 1.23, area = 52% in the star polymer portion, Mw = 5400, Mw / Mn = 1.20, area = 48% in the arm polymer portion, and 13C- From the NMR measurement, this polymer composition ratio was 2MAdMA: NLMA: tBMA: MDMA = 43: 37: 9: 11 (molar ratio).

Example 3

Under a nitrogen atmosphere, 341 g of THF containing 7 mmol of lithium chloride was kept at -40 ° C, and under stirring, 14 mmol of SBL was added, 10 g of a THF solution containing 22 mmol of 2MAdMA was added dropwise, and the reaction was continued for 30 minutes. . A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that 2MAdMA monomer was completely consumed by GC. Subsequently, 78 g of a THF solution containing 66 mmol of 2MAdMA, 88 mmol of TLMA, and 19 mmol of tBMA was added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that GC completely consumed the monomer.

Subsequently, 12 g of a THF solution containing 22 mmol of MDMA was added dropwise, and the reaction was continued for another 30 minutes, and a small amount of the reaction solution was taken out from the reaction system, and after confirming that the MDMA monomer was completely consumed by GC, the solution contained hydrochloric acid. The reaction was stopped by THF solution. The reaction stopper was poured into a large amount of water to precipitate a polymer, filtered, washed and dried to obtain a white powdery polymer. After dissolving the obtained polymer in THF, it was poured into a large amount of methanol to precipitate the polymer, filtered, washed, dried under reduced pressure for 10 hours, and a white powdery star polymer having 2MAdMA units disposed at the outermost part. Got it. GPC analysis of the obtained polymer showed that Mw = 21400, Mw / Mn = 1.23, area = 62% in the star polymer portion, Mw = 3800, Mw / Mn = 1.13, area = 38% in the arm polymer portion, and 13C- From the NMR measurement, this polymer composition ratio was 2MAdMA: TLMA: tBMA: MDMA = 43: 37: 10: 10 11 (molar ratio).

Example 4

Under nitrogen atmosphere, 343 g of THF containing 5 mmol of lithium chloride was kept at -40 ° C, and 11 mL of SBL was added while stirring, 10 g of THF solution containing 22 mmol of 2MAdMA was added dropwise, and the reaction was continued for 30 minutes. . A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that 2MAdMA monomer was completely consumed by GC. Subsequently, 78 g of a THF solution containing 79 mmol of 2MAdMA, 74 mmol of TLMA, and 19 mmol of tBMA was added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that GC completely consumed the monomer.

Subsequently, 12 g of a THF solution containing 22 mmol of MDMA was added dropwise, and the reaction was continued for another 30 minutes, and a small amount of the reaction solution was taken out from the reaction system, and after confirming that the MDMA monomer was completely consumed by GC, the solution contained hydrochloric acid. The reaction was stopped by THF solution. The reaction stopper was poured into a large amount of water to precipitate a polymer, filtered, washed and dried to obtain a white powdery polymer. The obtained polymer was redissolved in THF, then poured into a large amount of methanol to precipitate the polymer, filtered, washed, and dried under reduced pressure for 10 hours to obtain a white powdery star polymer in which 2MAdMA units were arranged at the outermost part. GPC analysis of the obtained polymer showed that Mw = 25400, Mw / Mn = 1.23, area = 62% in the star polymer portion, Mw = 4400, Mw / Mn = 1.15, area = 38% in the arm polymer portion, and 13C- From the NMR measurement, this polymer composition ratio was 2MAdMA: TLMA: tBMA: MDMA = 48: 32: 10: 11 (molar ratio).

Example 5

Under a nitrogen atmosphere, 256 g of THF containing 7 mmol of lithium chloride was kept at -40 ° C, and while stirring, 14 mmol of SBL was added to drop 10 g of a THF solution containing 22 mmol of 2MAdMA, and the reaction was continued for 30 minutes. . A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that 2MAdMA monomer was completely consumed by GC. Subsequently, 151 g of a THF solution containing 66 mmol of 2MAdMA, 88 mmol of NLMA and 19 mmol of tBMA was added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that GC completely consumed the monomer.

Subsequently, 12 g of a THF solution containing 22 mmol of MDMA was added dropwise, and the reaction was continued for another 30 minutes, and a small amount of the reaction solution was taken out from the reaction system, and after confirming that the MDMA monomer was completely consumed by GC, the solution contained hydrochloric acid. The reaction was stopped by THF solution. The reaction stopper was poured into a large amount of water to precipitate a polymer, filtered, washed and dried to obtain a white powdery polymer. The obtained polymer was redissolved in THF, then poured into a large amount of methanol to precipitate the polymer, filtered, washed, and dried under reduced pressure for 10 hours to obtain a white powdery star polymer in which 2MAdMA units were arranged at the outermost part. As a result of GPC analysis of the obtained polymer, Mw = 29900 and Mw / Mn = 1.26, and the polymer composition ratio was 2MAdMA: NLMA: tBMA: MDMA = 40: 42: 8: 10 (molar ratio) from 13C-NMR measurement.

Example 6

Under a nitrogen atmosphere, 315 g of THF containing 7 mmol of lithium chloride was kept at −40 ° C., and while stirring, 14 mmol of SBL was added to contain 22 mmol of 1-ethyl-1-cyclohexyl methacrylate (ECHMA). 9 g of THF solutions were added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and GC confirmed that the ECHMA monomer was completely consumed. Subsequently, 72 g of THF containing 66 mmol of ECHMA, 88 mmol of TLMA, and 19 mmol of tBMA were added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that GC completely consumed the monomer.

Subsequently, 12 g of a THF solution containing 22 mmol of MDMA was added dropwise, and the reaction was continued for another 30 minutes, and a small amount of the reaction solution was taken out from the reaction system, and after confirming that the MDMA monomer was completely consumed by GC, the solution contained hydrochloric acid. The reaction was stopped by THF solution. The reaction stopper was poured into a large amount of water to precipitate a polymer, filtered, washed and dried to obtain a white powdery polymer. The obtained polymer was redissolved in THF, then poured into a large amount of methanol to precipitate the polymer, filtered, washed, and dried under reduced pressure for 10 hours to obtain a white powdery star polymer in which the ECHMA unit was arranged at the outermost part. GPC analysis of the obtained polymer showed that Mw = 24100, Mw / Mn = 1.22, area = 64% in the star polymer portion, Mw = 3600, Mw / Mn = 1.19, area = 36% in the arm polymer portion, and 13C- From the NMR measurement, this polymer composition ratio was ECHMA: TLMA: tBMA: MDMA = 42: 37: 10: 10 11 (molar ratio).

Example 7

Under a nitrogen atmosphere, 315 g of THF containing 7 mmol of lithium chloride was kept at -40 ° C, and 15 mmol of SBL was added while stirring to thereby prepare 1- (1-methacryloyloxy-1-methylethyl) adamantane. (IAMA) 9g of THF solution containing 32 mmol was added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that GIA completely consumed the IAMA monomer. Then, 74 g of THF containing 53 mmol of IAMA, 85 mmol of TLMA, and 19 mmol of tBMA were added dropwise, and the reaction was continued for 30 minutes. A small amount of the reaction solution was taken out from the reaction system, and it was confirmed that GC completely consumed the monomer.

Subsequently, 13 g of a THF solution containing 24 mmol of MDMA was added dropwise, the reaction was continued for another 30 minutes, and a small amount of the reaction solution was taken out from the reaction system, and after confirming that the MDMA monomer was completely consumed by GC, the solution was further treated with hydrochloric acid. The reaction was stopped by THF solution. The reaction stopper was poured into a large amount of water to precipitate a polymer, filtered, washed and dried to obtain a white powdery polymer. The obtained polymer was redissolved in THF, then poured into a large amount of methanol to precipitate the polymer, filtered, washed, and dried under reduced pressure for 10 hours to obtain a white powdery star polymer in which an IAMA unit was arranged at the outermost part. GPC analysis of the obtained polymer showed that Mw = 30000, Mw / Mn = 1.27, area = 52% in the star polymer portion, Mw = 3400, Mw / Mn = 1.21, area = 48% in the arm polymer portion, and 13C- From the NMR measurement, this polymer composition ratio was IAMA: TLMA: tBMA: MDMA = 40: 40: 10: 11 (molar ratio).

Claims (5)

Formula (I) [Formula 1]

(In formula, R <_1> represents a hydrogen atom or a methyl group, R <_2> and R <_3> respectively independently represents the organic group couple | bonded with a carbon atom, C1 carbon interposes another part and a carbon atom A polymer chain having a repeating unit derived from a polyacrylate having at least two partial structures represented by the formula (II) [Formula 2]

(In formula, R <_4> represents a hydrogen atom or a methyl group, R <_5> represents an organic group.) It is a polymer chain which has a repeating unit derived from the (meth) acrylic acid ester represented by Formula (I) When R <_1> is a methyl group, R <_5> is a star polymer characterized by having a polymer chain except an homopolymer chain which has a repeating unit derived from the (meth) acrylic acid ester which is a C1-C4 alkyl group as an arm part. The method of claim 1, Polyacrylate which has two or more partial structures represented by Formula (I) is Formula (III) [Formula 3]

(In formula, R <_11> and R <_21> represents a hydrogen atom or a methyl group each independently, and R <_12> , R <_13> , R <_22> and R <_23> represent each independently the organic group couple | bonded through a carbon atom. Display and R ₃₃ Is a diacrylate represented by a divalent linking group). The method of claim 2, R <_33> is the alkylene group which may have a substituent in Formula (III), The star polymer characterized by the above-mentioned. A star polymer having at least one repeating unit selected from the group consisting of a repeating unit having a lactone ring and a repeating unit having an alicyclic skeleton. The method of claim 4, wherein The core part is of formula (I) [Formula 4]

(In formula, R <_1> represents a hydrogen atom or a methyl group, R <_2> and R <_3> respectively independently represents the organic group couple | bonded with a carbon atom, C1 carbon interposes another part and a carbon atom And a repeating unit derived from a polyacrylate having at least two or more partial structures represented by (a).