JP2001158805A - Method of polymerization for methacrylic or acrylic ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain the anionic polymerization with high initiation efficiency and high living properties in a readily recoverable and recyclable solvent under the relaxed cooling conditions by using an organoalkali metal compound having excellent convenience over a wide range of methacrylic esters or acrylic esters. SOLUTION: Methacrylic esters or acrylic esters are anionically polymerized by using a specific polymerization initiator in the presence of a specific organoaluminum compound. The polymerization initiator is an addition reaction product between an organoalkali metal compound and a conjugated diene. The organoaluminum compound is a tertiary organoaluminum compound including the chemical structure represented by the formula: Al-O-(aromatic ring) in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an anion polymerization of a methacrylic acid ester or an acrylic acid ester using a specific polymerization initiator compound in the presence of a specific organoaluminum compound. The present invention relates to a polymerization method having excellent reaction results. The present invention also relates to a method for producing a polymer such as a block copolymer, which employs the polymerization method.

[0002]

2. Description of the Related Art In anionic polymerization, it is important not only to realize high living properties but also to increase initiation efficiency. A high initiation efficiency is particularly important not only in increasing the utilization efficiency of the polymerization initiator compound but also in synthesizing the block copolymer. For example, a living polymer is synthesized by polymerization of a certain monomer (hereinafter, referred to as a “first monomer”), and then the living polymer is used as a polymerization initiator compound to prepare another monomer. (Hereinafter, referred to as "second monomer"), a block copolymer having a polymer block composed of a first monomer and a polymer block composed of a second monomer. A method for synthesizing a polymer is envisaged, and the starting efficiency of the living polymer (in this case,
When the (block efficiency) is low, what is actually obtained is a mixture of the block copolymer and the polymer composed of the first monomer. Impurities formed by interruption of polymerization as described above often significantly reduce the performance of the block copolymer. For example, hard block-soft block-
It is known that a hard block type triblock copolymer has a function as a thermoplastic elastomer, but this type of triblock copolymer includes a hard block alone polymer or a hard block-soft block type. When the diblock copolymer is mixed, mechanical properties such as tensile strength are reduced. Also, the block copolymer may be used as a compatibilizer between different resins,
If the homopolymer is mixed in the block copolymer to be used, the function as a compatibilizer is reduced, and the advantages inherent in each resin in the obtained resin composition are not sufficiently exhibited.

In order to increase the initiation efficiency in the anionic polymerization of methacrylate or acrylate, for example, an organic alkali metal compound such as an alkyllithium such as butyllithium or a lithiated polymer such as polystyryllithium is used. By performing an addition reaction with 1,1-diphenylethylene or α-methylstyrene, a compound having a diphenylmethylene anion structure or a phenylmethylene anion structure at a terminal site is prepared, and the compound is used as a polymerization initiator compound to obtain methacrylic acid. A method comprising anionic polymerization of an ester in a solvent consisting of tetrahydrofuran alone or a mixture thereof with toluene at a low temperature such as -60 ° C or lower is known (Macromolecules, Vol. 23, Nos. 2618-262).
2 (1990)). A polar solvent such as tetrahydrofuran used in the method is easily mixed into wastewater during a water washing treatment after polymerization, and is not easy to separate and purify from wastewater, so that it is not suitable for industrial use. Therefore, in order to industrially carry out anionic polymerization in a solution of a methacrylic acid ester or an acrylic acid ester, it is desirable to use a non-polar solvent such as a hydrocarbon solvent as a solvent.

As a method for enabling anionic polymerization of a methacrylic acid ester or an acrylic acid ester in a hydrocarbon solvent, it has been proposed to include an organoaluminum compound in the polymerization system. In this case, the organoaluminum compound is considered to have a function of lowering and stabilizing the nucleophilicity of the growth terminal by coordinating as a Lewis acid to the growth terminal of the polymerization initiator compound or the living polymer during polymerization. I have. The following are examples of reports on such polymerization methods.

(1) Anionic polymerization of methacrylic acid ester using tert-butyllithium is carried out at -78 ° C. in toluene in the presence of an organoaluminum compound such as trialkylaluminum, dialkyl (diphenylamino) aluminum or the like. As a result, a methacrylate polymer having a narrow molecular weight distribution was obtained (JP-B 7-57).
766).

(2) An anionic polymerization of methacrylic acid ester using an organic lithium compound such as tert-butyllithium is carried out in a hydrocarbon solvent by using a specific organic aluminum compound having at least one bulky group (eg, triisobutyl). Aluminum, diisobutyl (2,6-di-tert
-Butyl-4-methylphenoxy) aluminum) at a temperature of about −10 ° C., which is a relatively moderate cooling condition (JP-A-5-5009).

(3) Anionic polymerization of methacrylic acid ester or acrylic acid ester using tert-butyllithium is carried out by adding methyl bis (2,6-di-t
tert-butylphenoxy) aluminum or ethyl bis (2,6-di-tert-butylphenoxy) aluminum at a temperature of -60 ° C. or -70 ° C. to obtain a homopolymer or block copolymer having a narrow molecular weight distribution. (Polymer Preprints,
Japan), Volume 46, Issue 7, Pages 1081 to 1082 (1997)
And Vol. 47, No. 2, p. 179 (1998)).

(4) tert-butyl lithium, sec
-Butyllithium, ethyl α-lithioisobutyrate, 1,1
-Organic lithium compounds such as diphenylhexyllithium are converted to methylbis (2,6-di-tert-butylphenoxy) aluminum, ethylbis (2,6-di-tert).
-Butylphenoxy) aluminum, tris (2,6-
After mixing with an organic aluminum compound such as di-tert-butylphenoxy) aluminum, anionic polymerization of methyl methacrylate in a non-polar organic solvent such as toluene at a temperature around room temperature through a procedure of contacting with methyl methacrylate. As a result, a starting efficiency of 0.05 to 0.63 was achieved (JP-A-7-330819).

(5) ethyl α-lithioisobutyrate, ter
An anionic polymerization of methacrylate or acrylate using an organolithium compound such as t-butyllithium is carried out in a hydrocarbon solvent such as toluene in an organic aluminum compound such as trialkylaluminum and an ester compound, an ether compound or an organic compound. By performing the reaction at a temperature of about -80 ° C to 0 ° C in the presence of a grade salt, a polymer having a narrow molecular weight distribution was obtained (Macromolecules, Vol. 31,
573-577 (1998) and International Application WO 98/23651).

(6) An organolithium compound such as n-butyllithium is subjected to an addition reaction with butadiene to prepare polybutadienyllithium.
By reacting with tert-butyl methacrylate at 50 ° C. in the presence of a trialkylaluminum such as triethylaluminum, a block copolymer was obtained (JP-A-7-70264).

[0011]

According to the above-mentioned methods (1) to (6), anionic polymerization of methacrylic acid ester or acrylic acid ester in a hydrocarbon solvent can be carried out. There are points to be further improved in adopting as follows.

In the specific polymerization examples in the above (1) to (3), the polymerization initiator compound used for the polymerization of the methacrylate or acrylate is terpolymer.
Limited to t-butyllithium. In these polymerization methods, it is presumed that the use of tert-butyllithium is desirable in order to achieve good polymerization results.
Since ert-butyllithium has a strong self-ignition property, there is a problem in safety and handling properties such as transportation and storage on the assumption of industrial use.

In the above methods (1) and (3), the polymerization temperature employed in the specific polymerization examples among them is extremely low, such as about -80 to -60 ° C. In these polymerization methods, it is presumed that it is desirable to employ such an extremely low temperature in order to achieve good polymerization results.However, since a large amount of utility is required for cooling, industrially, Disadvantageous.

In the above method (4), the initiation efficiency in the specific polymerization example of methyl methacrylate is almost the same even in the case of using tert-butyllithium as a polymerization initiator compound, which gives relatively good polymerization results. Is 0.5 or less, and the initiation efficiency is still insufficient, such as 0.17 in the case of using sec-butyl lithium, which is a polymerization initiator compound having relatively good handleability. .

The polymerization initiator compounds used in the specific polymerization examples in the above (5) are limited to tert-butyllithium and ethyl α-lithioisobutyrate. The use of these polymerization initiator compounds is presumed to be desirable in order to achieve good polymerization results, but as described above, tert-butyllithium has problems in industrial use in terms of safety and handling. It is. Also, α
-Ethyl lithioisobutyrate is still not suitable for industrial use because the synthesis operation for producing it and the subsequent purification operation are complicated.

The present inventors have tried to reproduce the above method (6) experimentally, but could not obtain a predetermined result. That is, based on the specific production example described in the above (6), a predetermined polybutadienyl lithium is prepared, and then tert-butyl methacrylate is added to the polybutadienyl lithium to form triethylaluminum. The reaction was carried out at a temperature of 50 ° C. in the presence of the polybutadienyl lithium in the present polymerization system. Was. Therefore, the above (6)
Is problematic to employ in industrial production where high reproducibility is required.

Further, the present inventors have established the above (1) to (6)
According to the results of an experimental study of the method, the esterification of primary alcohols such as methyl methacrylate and n-butyl acrylate with methacrylic acid or acrylic acid does not progress the polymerization, or in many cases, the polymerization reaction does not proceed. It has been found that even when the reaction proceeds, the reaction results such as the initiation efficiency and the living property are lower than those of esters of tertiary alcohols such as tert-butyl methacrylate and methacrylic acid.

In order to make the anionic polymerization of a methacrylic acid ester or an acrylic acid ester suitable for industrial practice, it is necessary to have a high living property at the time of polymerization and a starting efficiency (in the case of block copolymerization, a block efficiency). High, a hydrocarbon-based solvent can be used as a solvent for polymerization, a wide range of usable polymerization initiator compounds or precursor compounds thereof (organic alkali metal compounds), and cooling conditions during polymerization can be relaxed. is important. Furthermore, it is desired as an industrial production method that polymerization of an ester of a primary alcohol and methacrylic acid or acrylic acid can be performed while satisfying these requirements, from the viewpoint of high versatility.

Accordingly, an object of the present invention is to provide a methacrylic acid ester or an acrylic acid ester with a primary alcohol and methacrylic acid or acrylic acid, which generally tend to have low polymerization results as the methacrylic acid ester or the acrylic acid ester. Using an ester of a compound having relatively excellent safety and handling properties as a polymerization initiator compound or a precursor compound thereof, and using a hydrocarbon-based solvent which is easy to recover and reuse as a polymerization solvent, Even when a relatively high temperature condition (that is, a relatively weak cooling condition) is employed as the temperature, a high initiation efficiency (in the case of block copolymerization, a block efficiency) and a high living property are achieved, so that a narrow molecular weight distribution is obtained. Can be produced, and furthermore, the amount of impurities such as a homopolymer is small. Producing a lock copolymer also is to provide a polymerization process capable. Another object of the present invention is to provide an industrially advantageous method for producing a polymer using a polymerization method having such excellent advantages.

[0020]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have conducted an anionic polymerization of methacrylic acid ester or acrylic acid ester by using a specific polymerization initiator compound. In the presence of an organoaluminum compound, the above-mentioned methacrylic acid ester or acrylic acid ester, the problem of the applicable range in the polymerization initiator compound (or its precursor compound) and the polymerization solvent, and the above polymerization conditions (temperature conditions) Of the present invention, and that the above-mentioned polymerization results (initiation efficiency and living property) are solved, and the present invention has been achieved.

That is, in the present invention, first, when an anionic polymerization of a methacrylate or an acrylate is carried out by using a polymerization initiator compound, a conjugated diene compound and an organic alkali metal compound are used as the polymerization initiator compound. Using the addition reaction product and in the polymerization system, the formula: Al
A polymerization method characterized by the presence of a tertiary organoaluminum compound having a chemical structure represented by —O—Ar (where Ar represents an aromatic ring) in a molecule.

The present invention also provides, secondly, a method for producing a polymer, which comprises polymerizing a methacrylic acid ester or an acrylic acid ester by the above polymerization method.

[0023]

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

A methacrylic acid ester or an acrylic acid ester which is a raw material in the polymerization method according to the present invention [hereinafter, referred to as
The methacrylic acid ester and the acrylic acid ester are sometimes collectively referred to as “(meth) acrylic acid ester”], and various types can be used. Specific examples of the methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, methacrylic acid 2
-Ethylhexyl, dodecyl methacrylate, lauryl methacrylate, methoxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, trimethoxysilylpropyl methacrylate, trifluoromethyl methacrylate, trifluoroethyl methacrylate, etc. Esters of primary alcohols with methacrylic acid; esters of secondary alcohols with methacrylic acid, such as isopropyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate; tertiary alcohols with methacrylic acid, such as tert-butyl methacrylate; And the like.
Specific examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and lauryl acrylate. Esters of primary alcohols and acrylic acid, such as methoxyethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, glycidyl acrylate, trimethoxysilylpropyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, etc. Esters of secondary alcohols with acrylic acid, such as isopropyl acrylate, cyclohexyl acrylate, isobornyl acrylate; tertiary alcohols, such as tert-butyl acrylate, with acrylic acid Ester and the like. When the ester of a primary alcohol and methacrylic acid or acrylic acid is used among the above (meth) acrylic esters, the effect of the present invention is particularly remarkably exhibited.

In the present invention, if necessary, other anionic polymerizable monomers can be used as raw materials in addition to the (meth) acrylic acid ester. Examples of the optionally usable anionic polymerizable monomer include, for example, trimethylsilyl methacrylate, N-isopropylmethacrylamide, N-tert-butylmethacrylamide, trimethylsilyl acrylate, N-isopropylacrylamide, N-tert-butylacrylamide, and the like. And methacrylic or acrylic monomers. Further, a polyfunctional anionic polymerizable monomer containing two or more methacrylic or acrylic structures such as a methacrylate structure and an acrylate structure in a molecule (for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate) 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, etc.) can also be used.

In the polymerization method according to the present invention,
Monomers such as (meth) acrylates may be used alone or in combination of two or more. When two or more monomers are used in combination, the combination of the monomers, the timing of adding the monomers to the polymerization system (for example, two or more monomers are added simultaneously, or By selecting conditions such as whether or not they are added separately, any copolymerization form such as random copolymerization, block copolymerization, and tapered block copolymerization can be obtained. Since the polymerization method of the present invention is a polymerization method excellent in initiation efficiency and living property, the effect is particularly remarkable in block copolymerization.

In the polymerization method according to the present invention, the polymerization of the (meth) acrylate

(A) In the presence of a tertiary organoaluminum compound having a chemical structure represented by the formula: Al—O—Ar (wherein Ar represents an aromatic ring) in the molecule,

(B) Using a polymerization initiator compound comprising an addition reaction product of a conjugated diene compound and an organic alkali metal compound,

It is important to do. When both of the above conditions (A) and (B) are satisfied, the application range of the (meth) acrylate, the organic alkali metal compound, and the solvent for polymerization is widened, and the cooling conditions during polymerization can be relaxed. Moreover, the polymerization results (initiation efficiency and living property) can be improved.

The polymerization initiator compound used in the present invention is a product obtained by subjecting a conjugated diene compound to an addition reaction with an organic alkali metal compound.

As the conjugated diene compound, 1,3-
Butadiene, isoprene, myrcene, 2-methyl-1,
Examples thereof include 3-pentadiene and cyclohexadiene. Among them, in terms of excellent starting efficiency,
1,3-butadiene or isoprene is preferred, and 1,3
-Butadiene is particularly preferred.

As the organic alkali metal compound, any alkali metal salt of an organic compound capable of nucleophilic addition to a conjugated diene compound can be used. As the alkali metal atom contained in the organic alkali metal compound, lithium, potassium, sodium or the like is preferable, and lithium is particularly preferable. Further, an organic group corresponding to a portion obtained by removing one or more alkali metal atoms contained therein from an organic alkali metal compound is n-butyl, sec-butyl,
monovalent or divalent or higher saturated hydrocarbon group such as tert-butyl; monovalent or divalent such as diphenylmethyl, 1,1-diphenyl-3-methylpentyl, 1,1-diphenylhexyl, triphenylmethyl, fluorenyl and the like The above aromatic hydrocarbon groups and the like can be mentioned. Note that the organic group may be a group in the form of a polymer (in the present specification, the term “polymer” includes the concept of “oligomer”), so that the molecular weight of the organic group is wide. , Generally, but not necessarily, 15 to 5,000
It is in the range of 0.000. Among the organic alkali metal compounds, typical examples of monofunctional organic alkali metal compounds include low molecular weight organic monolithium compounds having a primary carbon atom as an anion center such as n-butyllithium; sec-butyllithium, diphenylmethyllithium , Low molecular weight organic monolithium compounds having a secondary carbon atom as an anion center such as fluorenyllithium, tert-butyllithium, 1,1-diphenyl-3-methylpentyllithium, 1,1-diphenylhexyllithium, Low molecular weight organic monolithium compound having a tertiary carbon atom as an anion center such as phenylmethyllithium; chemistry in which lithium atom is bonded only to one molecular chain terminal such as polystyryllithium and poly-α-methylstyryllithium Monolithium salts of polymers having a structure Can. Representative examples of the polyfunctional organic alkali metal compound having two or more alkali metal atoms in the molecule among the organic alkali metal compounds include tetra-α-methylstyrenedilithium, 1,3-bis (1- Lithio-1,3
Organic dilithium compounds such as -dimethylpentyl) benzene, 1,3-bis (1-lithio-1-phenyl-3-methylpentyl) benzene, etc .; organic multilithium obtained by reacting a low molecular weight organic monolithium compound with divinylbenzene Two or more molecular chain terminal sites such as a compound (for example, a compound obtained by using sec-butyllithium as a low-molecular-weight organic monolithium compound and reacting divinylbenzene in an amount of 0.5 times or more with respect to this compound). A lithium salt of a polymer having a chemical structure in which a lithium atom is bonded to a polymer; a polymer having a plurality of double bonds in a molecule (for example, a conjugated diene polymer); and a low molecular weight organic monolithium compound (for example, sec. -Butyllithium) in a proportion of at least twice the mol of the polymer in a Lewis base (eg, N, N, N ′). , N'-tetramethylethylenediamine), one lithium atom is pendantly bonded to a plurality of sites in the polymer main chain, such as a multilithium salt of a polymer obtained by the reaction. A multilithium salt of a polymer having the following chemical structure.

Among the above-mentioned low molecular weight organic monolithium compounds, a secondary carbon atom or a primary carbon atom has an anion center in terms of safety, ease of handling, and high starting efficiency. Low molecular weight organic monolithium compounds are preferred, and sec-butyllithium and n-butyllithium are particularly preferred.

A monolithium salt of a polymer having a chemical structure in which a lithium atom is bonded only to one terminal of a molecular chain or a lithium of a polymer having a chemical structure in which a lithium atom is bonded to two or more molecular terminals. Like salt, 1
As a lithium salt of a polymer having a chemical structure in which a lithium atom is bonded to a terminal end of the molecular chain, a lithium salt formed by anionic polymerization of an anionic polymerizable monomer using a low molecular weight organic lithium compound as a polymerization initiator compound. Was
A so-called living polymer can be used. When the organolithium compound used as the polymerization initiator compound is monofunctional, the living polymer formed is basically a monolithium salt of a linear polymer. When the organolithium compound is bifunctional or more polyfunctional, the formed living polymer is basically a linear or star polymer dilithium salt or a multilithium salt thereof. Examples of the anionic polymerizable monomer used to form such a living polymer include:
Although not necessarily limited, non-polar or low-polar anionic polymerizable monomers such as aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene are preferred.

As a precursor compound (organic alkali metal compound) for preparing a polymerization initiator compound for (meth) acrylic acid ester polymerization, a chemical structure in which a lithium atom is bonded to one or more molecular chain terminal sites described above. When a lithium salt of a polymer having the following formula is used, the polymer obtained through the subsequent addition of the conjugated diene compound and the polymerization of the (meth) acrylate is a block copolymer. Also,
When a multi-lithium salt of a polymer having a chemical structure in which one lithium atom is pendantly bonded to each of a plurality of sites in the main chain of the polymer is used as the precursor compound, the subsequent addition of a conjugated diene compound And (meta)
The polymer obtained through the polymerization of the acrylate is a graft copolymer.

The polymerization initiator compound used in the polymerization of the (meth) acrylate according to the present invention is prepared by subjecting the conjugated diene compound to an addition reaction with the organic alkali metal compound. The anion center in the product of such an addition reaction is a carbon atom derived from the conjugated diene compound. In the present invention, as a polymerization initiator compound for the polymerization of (meth) acrylic acid ester,
The above-mentioned organic alkali metal compound is not used as it is, but is converted into an addition reaction product with a conjugated diene compound and used to obtain the compound represented by the formula: Al—O—Ar (where Ar
Represents an aromatic ring), and a tertiary organoaluminum compound having a chemical structure represented by the following formula in the molecule: , Expansion of polymerization conditions, relaxation of cooling conditions during polymerization, and improvement of polymerization results (starting efficiency and living property) can be achieved.

In the present invention, the reaction conditions for the addition reaction of the conjugated diene compound with the organic alkali metal compound are not necessarily limited. (Or an anion center) in an equimolar or more ratio. In order to complete the addition of the anion center of the organic alkali metal compound to the conjugated diene compound, the conjugated diene compound is converted to an alkali metal atom (or anion center) of the organic alkali metal compound.
It is preferably used in a proportion of at least twice the amount of The upper limit of the ratio of the conjugated diene compound to the organic alkali metal compound is not limited for the purpose of achieving the effects of the present invention. However, if the ratio of the conjugated diene compound to the organic alkali metal compound is increased, the chain of the polyconjugated diene compound becomes longer due to the anionic polymerization of the conjugated diene compound. It is preferable to set conditions appropriately. That is, when the purpose is to obtain a block copolymer or a graft copolymer containing a polymer fragment composed of a conjugated diene compound and a polymer fragment composed of a (meth) acrylate, the desired copolymer is obtained. Considering the degree of polymerization of the conjugated diene compound in the union,
It is preferable to set the use ratio of the conjugated diene compound to the organic alkali metal compound. If it is not desired to introduce a polymer fragment comprising a conjugated diene compound into the final target polymer, conditions that do not increase the ratio of the conjugated diene compound to the organic alkali metal compound so much (for example, organic alkali metal compound At a ratio of not more than 50 moles relative to the alkali metal atom (or the center of the anion)
It is good to adopt.

The reaction between the conjugated diene compound and the organic alkali metal compound is not necessarily limited, but is preferably performed in an organic solvent. The organic solvent is not necessarily limited, but generally has a relatively high safety in handling chemicals, and can also serve as an organic solvent in the polymerization of the following (meth) acrylic acid ester. Aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene and xylene; saturated hydrocarbon solvents such as hexane, cyclohexane and methylcyclohexane; halogenated hydrocarbon solvents such as chloroform, methylene chloride and carbon tetrachloride; dimethyl phthalate And the like, such as ester solvents. These organic solvents may be used alone or in combination of two or more. When an organic solvent is used, the amount used can be appropriately adjusted according to the type of the organic alkali metal compound to be used, the molecular weight of the intended polymerization initiator compound, the type of the organic solvent, and the like, but the reaction proceeds smoothly. From the viewpoint of the above, it is generally preferable to use the organic solvent in a ratio of 200 to 3000 parts by weight based on 100 parts by weight of the total amount of the organic alkali metal compound and the conjugated diene compound.

In the reaction between the conjugated diene compound and the organic alkali metal compound according to the present invention, it is desirable to prevent water from entering the reaction system as much as possible. Therefore, it is preferable to use a chemical substance supplied to the system such as a conjugated diene compound or any other chemical substance (for example, an organic solvent) that does not contain as much moisture as possible. Can be preliminarily degassed and dehydrated. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon, and helium.

Further, it is preferable to carry out the addition reaction, for example, under sufficient stirring conditions so that the reaction conditions in the reaction system become uniform.

In the reaction between the organic alkali metal compound and the conjugated diene compound according to the present invention, the temperature of the reaction system is not particularly limited, and is suitably suitable depending on the type of the organic alkali metal compound, the type of the conjugated diene compound, and the like. The temperature condition may be selected and adopted.
It is preferable to employ a temperature in the range of 100C to 100C. The progress of the reaction is determined based on a change in color tone derived from anions in the reaction system, or a quantitative analysis by analysis means such as gas chromatography and nuclear magnetic resonance absorption spectrum (NMR) of a sample collected from the reaction system. While confirming, the reaction may be continued until the addition of the conjugated diene compound is completed, but the required time for the reaction is usually in the range of 1 minute to 24 hours.

In the polymerization method according to the present invention, in the step of polymerizing at least the (meth) acrylate, the chemical structure represented by the formula: Al—O—Ar (where Ar represents an aromatic ring) in the polymerization system. (Hereinafter, the tertiary organoaluminum compound may be referred to as “organoaluminum compound (I)”). In the present invention, by selecting and using the above-mentioned organoaluminum compound (I) as the organoaluminum compound to be present in the polymerization system of the (meth) acrylic acid ester, the addition of the above-mentioned organic alkali metal compound and the conjugated diene compound is achieved. Coupled with the use of a polymerization initiator compound composed of a reaction product, the range of application in (meth) acrylates, organic alkali metal compounds and polymerization solvents, expansion of cooling conditions during polymerization, and polymerization results (initiation efficiency and It is possible to achieve the effect of the present invention of improving the living property).

The above-mentioned organoaluminum compound (I) is an organoaluminum compound having a chemical structure in which one of the three bonds of an aluminum atom is bonded to an aromatic ring via an oxygen atom (hereinafter referred to as the organic aluminum compound (I)). The organoaluminum compound is sometimes referred to as “organoaluminum compound (I-1)”), a chemical structure in which two of the three bonds of an aluminum atom are bonded to an aromatic ring via an oxygen atom. (Hereinafter referred to as "organoaluminum compound (I)
-2)), and an organoaluminum compound having a chemical structure in which three of the three bonds of an aluminum atom are bonded to an aromatic ring via an oxygen atom (hereinafter, referred to as the organic aluminum compound). The organoaluminum compound is sometimes referred to as “organoaluminum compound (I-3)”).

A typical chemical structure of the organoaluminum compound (I-2) or (I-3) is represented by the following general formula (A):

[0046]

Embedded image AlR ¹ R ² R ³ (A)

(Wherein R ¹ is a monovalent saturated hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, or a group which has a substituent. A good alkoxy group, an aryloxy group which may have a substituent or an N, N-disubstituted amino group, and R ² and R ³ each independently represent an aryloxy group which may have a substituent Or an arylenedioxy group in which R ² and R ³ may combine to form a substituent.)

Is represented by A typical chemical structure of the organoaluminum compound (I-1) is represented by a general formula (B):

[0049]

Embedded image AlR ⁴ R ⁵ R ⁶ (B)

(Wherein, R ⁴ represents an aryloxy group which may have a substituent, and R ⁵ and R ⁶ each independently represent a monovalent saturated hydrocarbon group which may have a substituent; A monovalent aromatic hydrocarbon group which may have a substituent, an alkoxy group which may have a substituent, or an N, N-disubstituted amino group.)

Is represented by

As the organoaluminum compound (I),
Depending on the type of monomer such as (meth) acrylic acid ester to be used, a suitable one may be selected and used as appropriate. In terms of the height of the polymer, relaxation of cooling conditions during polymerization, etc.,
The above-mentioned organoaluminum compound (I-2) or (I-3)
Is more preferred.

In the general formulas (A) and (B), R ¹ , R ² , R ³ and R ⁴ each may have a substituent which may have a substituent. Methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,4-di-te
rt-butylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-di-tert-butyl-4
-Methylphenoxy group, 2,6-di-tert-butyl-4-ethylphenoxy group, 2,6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, 1-pyrenyloxy An aryloxy group having no substituent such as a group; and 7-methoxy-2
And an aryloxy group having a substituent such as a naphthoxy group. Among the aryloxy groups which may have a substituent, substituted phenoxy groups having an alkyl group bonded to each of the 2- and 6-positions (for example, 2,6-dimethylphenoxy group, 2,6-di-tert- A butylphenoxy group, a 2,6-di-tert-butyl-4-methylphenoxy group, a 2,6-di-tert-butyl-4-ethylphenoxy group, and the like, and a branched alkyl group at the 2- and 6-positions, respectively. Is bonded to a phenoxy group (a so-called hindered phenoxy group; for example, 2,6-di-
tert-butylphenoxy group, 2,6-di-tert
-Butyl-4-methylphenoxy group, 2,6-di-te
rt-butyl-4-ethylphenoxy group) is more preferred.

In the general formula (A), examples of the arylenedioxy group which may have a substituent, in which R ² and R ³ may be combined, include 2,2′-biphenol and
2,2′-methylenebisphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol),
(R)-(+)-1,1'-bi-2-naphthol, (S)-
(-)-1,1'-Bi-2-naphthol and the like in which hydrogen atoms in two phenolic hydroxyl groups have been removed can be mentioned.

The aryloxy group which may have a substituent and the arylenedioxy group which may have a substituent have one or more substituents.
Examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group and a tert-butoxy group; and a halogen atom such as chlorine and bromine.

In the above general formulas (A) and (B), R ¹ , R ⁵ and R ⁶ may each independently represent a monovalent saturated hydrocarbon group which may have a substituent, such as a methyl group, Ethyl group, n-propyl group, isopropyl group, n-
Butyl group, isobutyl group, sec-butyl group, tert
Alkyl groups such as -butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group and 2-ethylhexyl group; cycloalkyl groups such as cyclohexyl group; and R ¹ , R ⁵ and R ⁶ are each Examples of the monovalent aromatic hydrocarbon group which may have a substituent which may be independently represented include an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; and R ¹ , R ⁵ and R ⁶ Examples of the alkoxy group which may have a substituent which can be independently represented include a methoxy group, an ethoxy group, an isopropoxy group,
Examples of the N, N-disubstituted amino group which R ¹ , R ⁵ and R ⁶ can independently represent include tert-butoxy group and the like, and dialkylamino groups such as dimethylamino group, diethylamino group and diisopropylamino group. A bis (trimethylsilyl) amino group and the like; These monovalent saturated hydrocarbon groups, monovalent aromatic hydrocarbon groups,
Examples of the substituent which the alkoxy group and the N, N-disubstituted amino group may have include a methoxy group, an ethoxy group,
An alkoxy group such as an isopropoxy group and a tert-butoxy group; a halogen atom such as chlorine and bromine;

In the formula (A), R ¹ , R ² and R ³ may have the same chemical structure or different chemical structures within the range defined above. You may. Similarly, R ⁵ and R ⁶ in the general formula (B) may have the same chemical structure or different chemical structures within the range defined above.

As a typical example of the organoaluminum compound represented by the general formula (A), ethyl bis (2,6-
Di-tert-butyl-4-methylphenoxy) aluminum, ethyl bis (2,6-di-tert-butylphenoxy) aluminum, ethyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum , Isobutyl bis (2,6-di-t
tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, n-octylbis (2,6-di-
tert-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-di-tert-butylphenoxy) aluminum, n-octyl [2,2′-
Methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, methoxybis (2,6-di-
tert-butyl-4-methylphenoxy) aluminum, methoxybis (2,6-di-tert-butylphenoxy) aluminum, methoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, ethoxybis (2,6-di-te
rt-butyl-4-methylphenoxy) aluminum,
Ethoxybis (2,6-di-tert-butylphenoxy) aluminum, ethoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isopropoxybis (2,6-di-ter
t-butyl-4-methylphenoxy) aluminum, isopropoxybis (2,6-di-tert-butylphenoxy) aluminum, isopropoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] Aluminum, tert-butoxybis (2,
6-di-tert-butyl-4-methylphenoxy) aluminum, tert-butoxybis (2,6-di-t
tert-butylphenoxy) aluminum, tert-
Butoxy [2,2'-methylenebis (4-methyl-6-
tert-butylphenoxy)] aluminum, tris (2,6-di-tert-butyl-4-methylphenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum and the like. Among the organoaluminum compounds represented by the general formula (A), isobutyl bis (2,6-di-tert-butyl-
4-methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum and the like have an initiation efficiency. It is particularly preferable from the viewpoints of height, living property, availability, and ease of handling.

As a typical example of the organoaluminum compound represented by the general formula (B), diethyl (2,6
-Di-tert-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-tert-butylphenoxy) aluminum, diisobutyl (2,6-di-
tert-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-tert-butylphenoxy) aluminum, di-n-octyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, di -N-octyl (2,6-di-tert-butylphenoxy) aluminum and the like.

The method for producing the above-mentioned organoaluminum compound (I) is not particularly limited, and for example, it can be produced according to a known method.

In the present invention, the organoaluminum compound (I) may be used alone or in combination of two or more.

The amount of the organoaluminum compound (I) used in the present invention is suitably determined according to the type of the polymerization operation, the type of the solvent constituting the polymerization system when performing the solution polymerization, and various other polymerization conditions. Although the amount can be selected, it is generally preferable to use the organoaluminum compound (I) in a ratio of at least equimolar to the alkali metal atom (or anion center) of the polymerization initiator compound used. It is more preferable to use it at a ratio of 2 to 100 times mol. In addition, after preparing the polymerization initiator compound using the organic alkali metal compound and the conjugated diene compound, when substantially all of the polymerization initiator compound is used for the polymerization of the (meth) acrylate, Since the mole number of the alkali metal atom (or anion center) of the prepared organic alkali metal compound and the mole number of the alkali metal atom (or anion center) of the prepared polymerization initiator compound are substantially the same, the organic aluminum compound ( I) is preferably used in a proportion of at least equimolar to the alkali metal atom (or anion center) of the organic alkali metal compound used initially, and more preferably at a rate of 2 to 100 times mol. .

In the polymerization reaction according to the present invention, if desired, an ether compound; a tertiary polyamine compound; inorganic salts such as lithium chloride; Tetraethylammonium chloride;
Additives such as organic quaternary salts such as tetraethylphosphonium bromide may be present. In particular, when the ether compound or the tertiary polyamine compound is present,
In the polymerization of the (meth) acrylic acid ester, the initiation efficiency (or the block efficiency) and the polymerization rate can be further improved, and the living property can be further improved by suppressing the deactivation.

The above ether compound is appropriately selected from compounds having an ether bond (—O—) in the molecule and containing no metal component, as long as they do not adversely affect the polymerization reaction. Can be used but
A cyclic ether compound having two or more ether bonds in a molecule or a non-cyclic compound having one or more ether bonds in a molecule in terms of great effects such as high initiation efficiency and high living property during polymerization. Ether compounds are preferred.
Specific examples of the cyclic ether compound having two or more ether bonds in a molecule include 12-crown-4, 15-
And crown ethers such as crown-5 and 18-crown-6. Specific examples of the acyclic ether compound having one or more ether bonds in the molecule include acyclic monoether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole; 1,2-dimethoxyethane;
1,2-diethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1, 2-diisopropoxypropane, 1,2-dibutoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3 -Dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane, 1,4-diisopropoxybutane, 1,
Acyclic diether compounds such as 4-dibutoxybutane and 1,4-diphenoxybutane; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dibutylene glycol diethyl ether and the like; Acyclic triether compounds; triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, butylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, Tiger butylene glycol dimethyl ether, tetraethylene glycol diethyl ether,
Examples thereof include dialkyl ethers of polyalkylene glycol such as tetrapropylene glycol diethyl ether and tetrabutylene glycol diethyl ether.
Among the specific examples of the above ether compounds, there is little adverse effect on the organoaluminum compound (I), and the polymerization rate,
Acyclic ether compounds are preferred in terms of particularly remarkable effects such as living property and initiation efficiency (or block efficiency), and availability, and diethyl ether or 1,2-dimethoxyethane is particularly preferred. preferable.

When a cyclic ether compound having one ether bond in the molecule, such as an epoxy compound such as tetrahydrofuran or propylene oxide, is present in the polymerization system according to the present invention, the interaction with the organoaluminum compound (I) is too strong. Or a direct reaction with the polymerization initiator compound or the growing living polymer. In such a case, it is generally preferable to avoid the presence of the cyclic ether compound in the polymerization system at least in the polymerization step of the (meth) acrylate.

The above-mentioned tertiary polyamine compound can be appropriately selected from compounds having two or more tertiary amine structures in the molecule as long as they do not adversely affect the polymerization reaction. In the present invention, the “tertiary amine structure” means a partial chemical structure in which three carbon atoms are bonded to one nitrogen atom, and the nitrogen atom is bonded to three carbon atoms. As long as it is present, it may constitute a part of the aromatic ring. Preferred specific examples of the tertiary polyamine compound include N, N,
N ′, N′-tetramethylethylenediamine, N, N,
N ′, N′-tetraethylethylenediamine, N, N,
N ', N ", N" -pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, tris [2- (dimethylamino)
Linear polyamine compounds such as ethyl] amine;
5-trimethylhexahydro-1,3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4 2,7,10,13,16-hexaazacyclooctadecane and other non-aromatic heterocyclic compounds;
And aromatic heterocyclic compounds such as 2′-bipyridyl and 2,2 ′: 6 ′, 2 ″ -terpyridine. In a polymerization step of at least (meth) acrylic acid ester, triethylamine or the like is contained in a polymerization system. When the tertiary monoamine compound is present, the effect is hardly recognized or the effect is small.

Compounds having one or more ether bonds and one tertiary amine structure in the molecule can be regarded as the above ether compounds, and one or more ether bonds and two or more The compound having the above tertiary amine structure can be regarded as any one of the above ether compound and the above tertiary polyamine compound. Therefore, a compound having one or more ether bonds and one or more tertiary amine structures in the molecule can be used as the above ether compound or tertiary polyamine compound.

When the above ether compound or tertiary polyamine compound is used, the amount of the ether compound or tertiary polyamine compound is not necessarily limited. The ratio is such that the total number of moles of the polyamine compound is at least 0.1 times the number of moles of the alkali metal atom or the anion center of the polymerization initiator compound or the precursor compound (eg, organic alkali metal compound) used. Preferably,
The ratio is more preferably 0.3 times or more,
The ratio is more preferably 0.5 times or more.
Although the upper limit of the amount of the ether compound and the tertiary polyamine compound is not necessarily limited, the starting efficiency tends to decrease if the amount is too large.
In general, it is preferable to keep the total amount of the ether compound and the tertiary polyamine compound within a range of about 95% by weight or less based on the polymerization system so that the initiation efficiency is not significantly reduced.

In the polymerization reaction according to the present invention, a solution polymerization method,
Any polymerization form such as a bulk polymerization method and a precipitation polymerization method can be adopted. It is preferable to employ a solution polymerization method in an organic solvent. The organic solvent is not necessarily limited, but generally benzene, benzene, Aromatic hydrocarbon solvents such as toluene, ethylbenzene and xylene; hexane,
Saturated hydrocarbon solvents such as cyclohexane and methylcyclohexane; halogenated hydrocarbon solvents such as chloroform, methylene chloride and carbon tetrachloride; and ester solvents such as dimethyl phthalate are preferably used. These organic solvents may be used alone or in combination of two or more.

When an organic solvent is used, the amount used is
The degree of polymerization of the desired polymer, the type of monomer such as (meth) acrylic acid ester, the type of polymerization initiator compound, the type of organic aluminum compound (I), the type of organic solvent, etc. are appropriately adjusted. However, from the viewpoint of smooth progress of polymerization, ease of obtaining and obtaining the produced polymer, reduction of waste liquid treatment burden, etc., the organic solvent is generally used as the total amount of the polymerization initiator compound and the monomer. It is preferable to use it in a proportion within the range of 200 to 3000 parts by weight based on 100 parts by weight.

In the polymerization reaction according to the present invention, it is desirable to prevent water from entering the polymerization system as much as possible. Therefore, a monomer, an organoaluminum compound (I), any other chemical substance (for example, an organic solvent, an ether compound,
It is preferable to use a chemical substance supplied to the system such as a tertiary polyamine compound) that does not contain water as much as possible. For this purpose, if necessary, degassing and dewatering are performed in advance. be able to. Further, the polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon, and helium.

Further, it is preferable to carry out the polymerization under, for example, sufficient stirring conditions so that the reaction conditions in the polymerization reaction system become uniform.

The operation of the polymerization method of the present invention is generally carried out by preparing a polymerization initiator compound by subjecting a conjugated diene compound to an addition reaction with an organic alkali metal compound, and by using the polymerization initiator compound (meta- ) A polymerization operation of a (meth) acrylic ester, which comprises polymerizing the acrylic ester.

The polymerization reaction according to the present invention is not limited, but a conjugated diene compound is reacted with an organic alkali metal compound to prepare a polymerization initiator compound, and then (meth) acrylic acid is added to the system. It is convenient to do so by adding an ester. The timing of addition of the organoaluminum compound (I) at this time is not necessarily limited as long as the organoaluminum compound (I) can be present in the polymerization system of the (meth) acrylic acid ester. A method comprising, before the addition of the ester, adding the entire amount of the organoaluminum compound (I) to the system containing the polymerization initiator compound, wherein the total amount of the organoaluminum compound (I) is A method comprising adding the organoaluminum compound (I) together with the (meth) acrylic acid ester to a system containing a polymerization initiator compound by mixing, a method of converting a part of the organoaluminum compound (I) into (meth) ) Is mixed with an acrylate ester and the remainder of the organoaluminum compound (I) contains a polymerization initiator compound By adding a part of the organoaluminum compound (I) together with the (meth) acrylate to a system containing the polymerization initiator compound and the remainder of the organoaluminum compound (I). Various methods such as a method can be adopted. Among the above-mentioned methods for adding the organoaluminum compound (I), a method comprising mixing at least a part of the organoaluminum compound (I) with a (meth) acrylic acid ester and then adding the resulting mixture to the polymerization system is known as an organoaluminum compound. Suppression of side reactions due to coordination of compound (I) to (meth) acrylate,
It is preferable in that an effect such as suppression of deactivation of the polymerization initiator compound due to the reaction of the organoaluminum compound (I) with impurities in the (meth) acrylic acid ester is exhibited.

When the organoaluminum compound (I) is brought into contact with the polymerization initiator compound, the temperature of the reaction system may be controlled to 40 ° C. or lower from the viewpoint of increasing the initiation efficiency of the polymerization initiator compound. Preferably, 25 ° C
It is more preferable to control as follows.

When the polymerization reaction of the (meth) acrylic acid ester is carried out in the presence of an ether compound or a tertiary polyamine compound, the timing of addition of the ether compound or the tertiary polyamine compound is not necessarily limited, but the polymerization start time is not limited. It is preferable to employ a procedure that enables the contact with the organoaluminum compound (I) before the contact with the agent compound.

In the polymerization according to the present invention, the temperature of the reaction system is not particularly limited, and appropriate temperature conditions are appropriately selected according to the type of the monomer to be polymerized such as (meth) acrylate. It may be adopted, but in many cases, it is preferable to adopt a temperature in the range of −60 ° C. to + 100 ° C., and it is more preferable to adopt a temperature in the range of −50 ° C. to + 50 ° C. For example, when polymerizing a methacrylic acid ester, it is preferable to employ a temperature in the range of −40 ° C. to + 100 ° C., and −30 ° C. to + 5 ° C.
More preferably, a temperature in the range of 0 ° C. is employed. Further, when polymerizing the acrylate, -60
It is preferable to adopt a temperature in the range of -50 ° C to + 30 ° C, and it is more preferable to adopt a temperature in the range of -50 ° C to + 30 ° C. In addition, in the polymerization method according to the present invention, the cooling condition of the polymerization system can be eased as compared with the conventional anion polymerization method, and high living properties can be achieved even when the polymerization is performed at a temperature closer to room temperature.

In the (meth) acrylate polymerization reaction according to the present invention, a sample collected from the polymerization system is analyzed by gas chromatography, gel permeation chromatography (GPC), nuclear magnetic resonance absorption spectrum (NMR) or the like. The reaction may be continued as appropriate by performing a quantitative analysis and confirming the progress of the polymerization. Usually, the required time for the polymerization reaction is in the range of 1 minute to 24 hours.

When the (meth) acrylate polymerization reaction according to the present invention is carried out in the presence of the above ether compound or tertiary polyamine compound, the polymerization reaction rate can be further increased. That is, in the case of the polymerization of methacrylic acid ester, it is possible to complete the polymerization within several minutes, and in the case of the polymerization of acrylic acid ester, it is also possible to complete the polymerization within several tens of seconds. Therefore, when the polymerization reaction according to the present invention is performed in the presence of an ether compound or a tertiary polyamine compound, it is possible to employ a `` tubular continuous polymerization '' method having high productivity and good cooling efficiency. is there.

In the present invention, at the stage when the desired polymer chain is formed by the polymerization reaction, the polymerization reaction may be terminated by adding a polymerization terminator to the reaction mixture according to a known anionic polymerization method. it can. As the polymerization terminator, for example, a protic compound such as a methanol solution of methanol, acetic acid, or hydrochloric acid can be used. The amount of the polymerization terminator used is not particularly limited, but is generally preferably 1 to 100 times the mol of the alkali metal atom (or anion center) of the polymerization initiator compound.

In the present invention, the terminal functional group-providing agent (eg, aldehyde, lactone, carbon dioxide, etc.) is added to the reaction system after the completion of all the predetermined polymerizations and before the addition of the polymerization terminator. In such a case, a polymer having a functional group such as a hydroxyl group or a carboxyl group at the terminal of the molecular chain can be obtained. Further, at the stage after all the predetermined polymerization is completed and before adding the polymerization terminator,
A polyfunctional compound containing two or more functional groups such as a formyl group, a keto group, a chlorocarbonyl group, and a silyl halide group in a molecule may be added to the reaction system. A linear or star-shaped polymer formed by coupling (coupling) of two or more polymers around a residue derived from the compound can also be obtained.

If the polymerization initiator compound or the metal component derived from the organoaluminum compound (I) remains in the polymer separated and obtained from the reaction mixture after the termination of the polymerization, the polymer or the polymer was used. Depending on the intended use of the polymer, it is necessary to remove the polymerization initiator compound and the metal compound derived from the organoaluminum compound (I) after the completion of the polymerization, as this may cause deterioration in the physical properties of the material and poor transparency. Is preferred. As a method for removing the metal compound, it is effective to subject the polymer to a cleaning treatment such as a washing treatment using an acidic aqueous solution or an adsorption treatment using an adsorbent such as an ion exchange resin. Here, as the acidic aqueous solution, for example,
Hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution and the like can be used.

The method for separating and obtaining the polymer from the reaction mixture after the termination of the polymerization is not particularly limited, and any method according to a known method can be adopted. For example, a method in which the reaction mixture is poured into a poor solvent for the polymer to precipitate the polymer, a method in which the solvent is distilled off from the reaction mixture to obtain the polymer, and the like can be adopted.

Further, according to the present invention, a polymer having an arbitrary molecular weight can be produced. The molecular weights of the polymers that can be prepared vary widely, but generally the number average molecular weight is 10
It is preferable that it is in the range of 00 to 1,000,000 in view of handleability, fluidity, mechanical properties and the like of the obtained polymer. In addition, according to the present invention, a polymer having high molecular weight uniformity (ie, a narrow molecular weight distribution) is usually obtained,
It is possible to produce a polymer having a molecular weight distribution (Mw / Mn) of 1.5 or less. However, a polymer having a wide molecular weight distribution can be intentionally obtained by controlling the rate of addition of the monomer to the polymerization system, the rate of diffusion of the monomer in the polymerization system, and the like.

[0085]

EXAMPLES The present invention will be described below more specifically with reference to examples, but the present invention is not limited to the following examples.

In the following examples and the like, chemical substances which were dried and purified by a conventional method and degassed with nitrogen were used. The transfer and supply of the chemical substances were performed under a nitrogen atmosphere.

Example 1 (Styrene-methacrylic acid ter)
Example of Synthesis of t-Butyl Block Copolymer) In this example, a step of preparing polystyryllithium (organic alkali metal compound) by anionic polymerization of styrene, a step of preparing a polymerization initiator compound by addition reaction of butadiene, and diisobutyl ( 2,6-Di-tert-butyl-4-methylphenoxy) aluminum (organoaluminum compound) in the presence of tert-methacrylate
Styrene-methacrylic acid te comprising a butyl polymerization step
It is an example of manufacture of an rt-butyl block copolymer. In addition,
Styrene polymer has UV absorption but methacrylic acid ter
Taking advantage of the fact that the t-butyl polymer does not have UV absorption, the block efficiency in block copolymerization (initiation efficiency in the polymerization of tert-butyl methacrylate) was determined.

(1) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this was added 25 ml of cyclohexane and 1.0 ml of a cyclohexane solution containing 0.13 mmol of sec-butyllithium. In this solution,
2.0 g of styrene was added, and the mixture was stirred at 40 ° C. for 3 hours to prepare a polystyryllithium-containing solution.

(2) To the solution in the Schlenk tube obtained in the above (1) was added, at 40 ° C., 0.20 ml of a cyclohexane solution containing 0.30 mmol of butadiene. Faded. Stirring was continued at the same temperature for 10 minutes. About 0.5 ml of the obtained reaction mixture was sampled and analyzed by gas chromatography (hereinafter, referred to as "GC"). As a result, it was found that the conversion of butadiene and styrene was 99% or more. Further, as a result of analysis by GPC (in terms of polystyrene), the peak top molecular weight (Mt) of the obtained addition reaction product of polystyryllithium and butadiene was 171.
00, the number average molecular weight (Mn) was 16,400, and the ratio of the weight average molecular weight / number average molecular weight (Mw / M
n) was found to be 1.03.

(3) The solution in the Schlenk tube obtained in the above (2) was cooled to 15 ° C. and contained 0.65 mmol of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum. Toluene solution 0.8
1 ml was added and stirred for 10 minutes. The resulting solution was then stirred vigorously while adding tert-methacrylic acid
1.0 g of butyl was added. After polymerization was carried out at 15 ° C. for 5 hours with stirring, the polymerization was stopped by adding about 0.05 ml of methanol. A part of the obtained reaction mixture was sampled and analyzed by GC.
It was found that the conversion of tert-butyl was 100%. The polymer was obtained by removing the solvent in the obtained reaction mixture by a vacuum drying method. GPC-UV (25
4 nm) As a result of measurement (in terms of polystyrene), the polymer was found to be a block copolymer having Mt = 29100 and a polymer having Mt = 1.
A mixture with a polymer derived from a polymerization initiator compound of 8000 (polystyrene having a butadiene fragment at a terminal),
The weight ratio of the former to the latter was found to be 73:27. From this, it was found that the block efficiency in the block copolymerization was 73%.

Comparative Example 1 Diisobutyl (2,6-
Preparation of polystyryllithium by anionic polymerization of styrene in the same manner as in Example 1 except that di-tert-butyl-4-methylphenoxy) aluminum was replaced with the same molar number of triethylaluminum,
Preparation of polymerization initiator compound by addition reaction of butadiene,
And tert-butyl methacrylate in the presence of an organoaluminum compound were sequentially polymerized. GPC (polystyrene conversion) of the obtained polymerization initiator compound
As a result of analysis, Mt was 16900 and Mn was 1620.
0 and Mw / Mn was found to be 1.03. After the polymerization step of tert-butyl methacrylate, the obtained reaction mixture was analyzed by GC.
The polymerization rate of rt-butyl was found to be almost 100%. The polymer obtained after removing the solvent was GPC-UV
(254 nm) measurement (polystyrene conversion), Mt
= 34100 and Mn = 35700 high molecular weight components;
It is a mixture of a polymer (polystyrene having a butadiene fragment at a terminal) derived from a polymerization initiator compound having Mt = 17400 and Mn = 16600, and the weight ratio of the former to the latter is 63:
It turned out to be 37. The peak area ratio of the high molecular weight component is determined by the measurement result of GPC-UV detector and GPC-RI.
Since the measurement results obtained by the detector are almost the same and the Mt of the high molecular weight component is almost twice the Mt of the polymer derived from the polymerization initiator compound, the main component of the high molecular weight component is polymerized. It is presumed to be a dimer of the initiator compound (a coupling product obtained by nucleophilic addition of two polymerization initiator compound anions to the carbonyl group of one tert-butyl methacrylate). This proved that the main component of the obtained polymer was polystyrene containing butadiene fragments.

Comparative Example 2 Diisobutyl (2,6-
Preparation of polystyryllithium by anionic polymerization of styrene and butadiene in the same manner as in Example 1 except that triisobutylaluminum was used in the same molar number as that of di-tert-butyl-4-methylphenoxy) aluminum. Preparation of a polymerization initiator compound by an addition reaction and polymerization of tert-butyl methacrylate in the presence of an organoaluminum compound were sequentially performed. As a result of GPC (polystyrene conversion) analysis of the obtained polymerization initiator compound, Mt was 17,400 and Mn was 16
800 and Mw / Mn was found to be 1.03. After the polymerization step of tert-butyl methacrylate, the obtained reaction mixture was analyzed by GC.
The conversion of tert-butyl was found to be almost 100%. The polymer obtained after removing the solvent was GPC-U
As a result of V (254 nm) measurement (polystyrene conversion), M
It is a mixture of a high molecular weight component having t = 34800 and Mn = 37300 and a polymer (polystyrene having a butadiene fragment at a terminal) derived from a polymerization initiator compound having Mt = 18200 and Mn = 17500, and the weight ratio of the former to the latter is It turned out to be 51:49. The peak area ratio of the high molecular weight component is determined by the GPC-UV detector
-Since the Mt of the high molecular weight component is substantially the same as that of the polymer derived from the polymerization initiator compound, the main component of the high molecular weight component is Is a dimer of a polymerization initiator compound (a coupling product obtained by nucleophilic addition of two polymerization initiator compound anions to the carbonyl group of one tert-butyl methacrylate)
It is estimated that This proved that the main component of the obtained polymer was polystyrene containing butadiene fragments. Example 1 and Comparative Example 1
From the results of and 2, from the polymerization of methacrylic acid ester in the presence of an organic aluminum compound using a polymerization initiator compound consisting of an addition reaction product of an organic alkali metal compound and a conjugated diene compound, When a general trialkylaluminum is used (Comparative Examples 1 and 2), the above specific organoaluminum compound (I) is used as an organoaluminum compound even under polymerization conditions under which polymerization does not proceed. (Example 1) shows that polymerization can be performed with high initiation efficiency (block efficiency).

Example 2 (Synthesis Example of Styrene-Methyl Methacrylate Block Copolymer) In this example, a process of preparing polystyryllithium (organic alkali metal compound) by anionic polymerization of styrene and the initiation of polymerization by butadiene addition reaction A styrene-methyl methacrylate block comprising a step of preparing a chemical compound and a step of polymerizing methyl methacrylate in the presence of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum (organoaluminum compound) It is an example of manufacture of union.

(1) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. 25 ml of toluene and 0.15
0.12 ml of a cyclohexane solution containing mmol of sec-butyllithium was added. 0.75 g of styrene was added to this solution, and the mixture was stirred at 23 ° C. for 1.5 hours to prepare a polystyryllithium-containing solution.

(2) 0.40 ml of a cyclohexane solution containing 0.60 mmol of butadiene was added at 23 ° C. to the solution in the Schlenk tube obtained in the above (1), and immediately, the solution turned orange to colorless. Faded. Stirring was continued at the same temperature for 10 minutes. As a result of sampling and GC analysis of a part of the obtained reaction mixture, it was found that the conversion of butadiene and styrene was 99% or more. Further, as a result of analysis by GPC (in terms of polystyrene), it was found that Mn of the obtained addition reaction product of polystyryllithium and butadiene was 5,700, and Mw / Mn was 1.03.

(3) The solution in the Schlenk tube obtained in the above (2) was cooled to −30 ° C., and 0.80 mmol of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum was added. Toluene solution containing
0 ml was added and stirred for 10 minutes. Then, while stirring the obtained solution vigorously, 2.25 g of methyl methacrylate was added thereto. After the polymerization was performed at −30 ° C. for 2 hours with stirring, the polymerization was stopped by adding about 0.05 ml of methanol. The obtained reaction mixture is mixed with 300
The polymer was obtained by reprecipitation in ml of methanol. The yield of the obtained polymer was almost 100%. As a result of GPC-UV (254 nm) measurement (in terms of polystyrene), the polymer was found to have Mn = 23300 and Mw / M
It is a mixture of a block copolymer of n = 1.05 and a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at a terminal), and the weight ratio of the former to the latter is 96:
It turned out to be 4. From this, it was found that the block efficiency in the block copolymerization was 96%.
The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Example 3 (Synthesis example of styrene-methyl methacrylate block copolymer) Addition temperature of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, addition temperature of methyl methacrylate and polymerization Preparation of polystyryllithium by anionic polymerization of styrene, butadiene, in the same manner as in Example 2 except that the temperature was changed from -30 ° C to 0 ° C, and the polymerization time of methyl methacrylate was changed from 2 hours to 1 hour. , And polymerization of methyl methacrylate in the presence of an organoaluminum compound was sequentially performed. GPC (polystyrene conversion) analysis of the obtained polymerization initiator compound revealed that Mn was 5,200 and Mw / Mn was 1.03. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. In addition, GPC-UV (254n
m) As a result of measurement (in terms of polystyrene), the polymer
a block copolymer having n = 23600 and Mw / Mn = 1.06, and a dimer of a polymerization initiator compound (the two polymerization initiator compound anions are obtained by nucleophilic addition to the carbonyl group of one methyl methacrylate) And a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at the end), and the weight ratio thereof was found to be 85: 6: 9. did. From this, it was found that the block efficiency in the block copolymerization was 85%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Example 4 (Synthesis Example of Styrene-Methyl Methacrylate Block Copolymer) In the same manner as in Example 2 except that butadiene was used in place of butadiene as a conjugated diene compound, the anion of styrene was anionic. Preparation of polystyryllithium by polymerization, preparation of a polymerization initiator compound by addition reaction of isoprene, and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. GPC (polystyrene equivalent) analysis of the obtained polymerization initiator compound revealed that Mn was 5,300 and Mw / Mn was 1.04. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. GPC-UV
As a result of (254 nm) measurement (in terms of polystyrene), the polymer was found to have a block copolymer of Mn = 24500 and Mw / Mn = 1.07 and a dimer of a polymerization initiator compound (two polymerization initiator compound anions). Is a mixture of a compound presumed to be a coupling product obtained by nucleophilic addition to the carbonyl group of one methyl methacrylate) and a polymer derived from a polymerization initiator compound (polystyrene having an isoprene fragment at a terminal). , Their weight ratio was found to be 80: 8: 12. From this, it was found that the block efficiency in the block copolymerization was 80%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Example 5 (Synthesis example of styrene-methyl methacrylate block copolymer) 0.80 mmol of diisobutyl (2,6-di-ter
Instead of 1.0 ml of a toluene solution containing t-butyl-4-methylphenoxy) aluminum, 0.80 m
except that a solution prepared by mixing 1.0 ml of a toluene solution containing 0.2 mol of isobutyl bis (2,6-di-tert-butyl-4-methylphenoxy) aluminum and 0.22 g of 1,2-dimethoxyethane was used. In the same manner as in Example 3, preparation of polystyryllithium by anionic polymerization of styrene, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. As a result of GPC (polystyrene conversion) analysis of the obtained polymerization initiator compound, Mn was 5,500,
Mw / Mn was found to be 1.03. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. G
As a result of PC-UV (254 nm) measurement (in terms of polystyrene), the polymer was found to have Mn = 23800 and Mw / Mn =
It is a mixture of a block copolymer of 1.06 and a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at a terminal), and the weight ratio of the former to the latter is 93: 7.
Turned out to be. From this, it was found that the block efficiency in the block copolymerization was 93%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Comparative Example 3 Diisobutyl (2,6-
Same as Example 2 except that instead of di-tert-butyl-4-methylphenoxy) aluminum, the same molar number of triethylaluminum was used and the polymerization time of methyl methacrylate was extended from 2 hours to 24 hours. Then, preparation of polystyryllithium by anionic polymerization of styrene, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. GPC (polystyrene equivalent) analysis of the obtained polymerization initiator compound revealed that Mn was 5,600 and Mw / Mn was 1.03. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. GPC-UV
As a result of (254 nm) measurement (in terms of polystyrene), the polymer was found to have a block copolymer of Mn = 49800 and Mw / Mn = 1.14, and a dimer of a polymerization initiator compound (two polymerization initiator compound anions). Is a mixture of a compound presumed to be a coupling product obtained by nucleophilic addition to the carbonyl group of one methyl methacrylate) and a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at a terminal). , Their weight ratio was found to be 37:42:21. From this, it was found that the block efficiency in the block copolymerization was 37%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Comparative Example 4 Preparation of polystyryl lithium by anionic polymerization of styrene, butadiene Preparation of a polymerization initiator compound by an addition reaction and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. As a result of GPC (polystyrene conversion) analysis of the obtained polymerization initiator compound,
Mn was 5100 and Mw / Mn was found to be 1.04. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. The yield of the obtained polymer is about 10
It was 0%. As a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to have Mn = 41.
900, a block copolymer of Mw / Mn = 1.12,
Dimer of polymerization initiator compound (compound presumed to be a coupling product obtained by nucleophilic addition of two polymerization initiator compound anions to the carbonyl group of one methyl methacrylate)
And a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at a terminal), and the weight ratio thereof was found to be 41:35:24. From this, the block efficiency in block copolymerization is 4
It turned out to be 1%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Comparative Example 5 Polystyryl lithium was used as a polymerization initiator compound for methyl methacrylate without being subjected to an addition reaction using butadiene, and the polymerization time of methyl methacrylate was extended from 2 hours to 3 hours. Preparation of polystyryllithium by anionic polymerization of styrene and polymerization of methyl methacrylate in the presence of an organoaluminum compound were performed sequentially in the same manner as in Example 2 except for the above. The solution containing polystyryllithium prepared by anionic polymerization of styrene was added with diisobutyl (2,6-di-
At the time when tert-butyl-4-methylphenoxy) aluminum was added, the color of the solution became colorless because the orange color derived from the growth terminal anion of polystyrene disappeared. This color change suggests that the added organoaluminum compound formed an art complex with the growing terminal anion of polystyrene. As a result of GPC (polystyrene conversion) analysis of the obtained polymerization initiator compound (polystyryllithium), Mn was 5,100, and Mw / Mn was obtained.
Was found to be 1.04. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. ¹ H-NMR
As a result of the analysis, the polymerization rate of methyl methacrylate was found to be about 6%, indicating that almost no polymerization occurred. G
As a result of PC-UV (254 nm) measurement (in terms of polystyrene), the polymer was found to be a polymer (polystyrene) derived from a polymerization initiator compound. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Comparative Example 6 The step of preparing a polymerization initiator compound by the addition reaction of butadiene was performed by adding 0.60 mmol of 1,0 mmol to a polystyryllithium-containing solution prepared by anionic polymerization of styrene.
0.60 ml of a cyclohexane solution containing 1-diphenylethylene was added and the reaction was changed to a polymerization initiator compound preparation step of reacting at 50 ° C. for 6 hours, and the polymerization time of methyl methacrylate was extended from 2 hours to 3 hours Preparation of polystyryllithium by anionic polymerization of styrene, preparation of polymerization initiator compound by addition reaction of 1,1-diphenylethylene, in the same manner as in Example 2, except that
And the polymerization of methyl methacrylate in the presence of an organoaluminum compound. The color of the polystyryllithium-containing solution changed from orange to deep red after the addition of 1,1-diphenylethylene. This phenomenon suggests that 1,1-diphenylethylene was capped at the end of polystyrene and the terminal anion was changed to 1,1-diphenylmethylene anion. The color of the polymerization initiator compound-containing solution is such that after addition of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, the deep red color derived from 1,1-diphenylmethylene anion becomes orange. changed. This phenomenon suggests that the added organoaluminum compound formed an ate complex with the 1,1-diphenylmethylene anion. GPC for the obtained polymerization initiator compound
As a result of (polystyrene conversion) analysis, it was found that Mn was 5,600 and Mw / Mn was 1.03. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. As a result of GPC-UV (254 nm) measurement (in terms of polystyrene), the polymer was found to have Mn = 38800 and Mw / M
a block copolymer of n = 1.07 and a dimer of a polymerization initiator compound (estimated as a coupling product obtained by nucleophilic addition of two polymerization initiator compound anions to the carbonyl group of one methyl methacrylate) ) And a polymer derived from a polymerization initiator compound (polystyrene having a 1,1-diphenylethylene fragment at the end), and the weight ratio thereof was found to be 54: 9: 33. . From this, the block efficiency in block copolymerization is 54
%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 1 below.

Comparative Example 7 The process of preparing a polymerization initiator compound by the addition reaction of butadiene was performed by adding 1.8 mmol of α-methylstyrene to a polystyryllithium-containing solution prepared by anionic polymerization of styrene and reacting at 50 ° C. for 3 hours. In the same manner as in Example 2 except that the polymerization step was changed to a step of preparing a polymerization initiator compound, and the polymerization time of methyl methacrylate was extended from 2 hours to 3 hours. Preparation, preparation of a polymerization initiator compound by addition reaction of α-methylstyrene, and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. The color of the polystyryllithium-containing solution changed from orange to deep red after the addition of α-methylstyrene. This phenomenon suggests that α-methylstyrene was capped at the end of polystyrene and the terminal anion was changed to α-methylstyryl anion. In addition, the color of the solution containing the polymerization initiator compound was such that, after addition of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, the deep red color derived from α-methylstyryl anion changed to orange. .
This phenomenon suggests that the added organoaluminum compound formed an ate complex with the α-methylstyryl anion. GPC for the obtained polymerization initiator compound
As a result of (polystyrene conversion) analysis, it was found that Mn was 6,100 and Mw / Mn was 1.04. After the methyl methacrylate polymerization step, a polymer was obtained by reprecipitation. As a result of ¹ H-NMR analysis, the polymerization rate of methyl methacrylate was found to be about 3%, indicating that the polymer was hardly polymerized. GPC-UV (254 nm) measurement (in terms of polystyrene) showed that the polymer was a polymer (polystyrene) derived from a polymerization initiator compound. The chemicals used, the polymerization conditions used and the results obtained are
It is shown in Table 1 below.

[0105]

[Table 1]

In the above Table 1, "organoaluminum compound"
And the symbol in the column of "additives" means the following compounds.

IB ₂ Al (BHT): diisobutyl (2,6-di-t-butyl-4-methylphenoxy) aluminum iBAl (BHT) ₂ : isobutyl bis (2,6-di-t-butyl-4-methyl) phenoxy) aluminum Et ₃ Al: triethylaluminum iB ₃ Al: triisobutylaluminum DME: 1,2-dimethoxyethane

From the results of Examples 2 to 5 shown in Table 1, when methacrylic acid ester was polymerized in the presence of an organoaluminum compound using an anionic polymerization initiator compound, When an addition reaction product of an organic alkali metal compound such as polystyryllithium and a conjugated diene compound is used, and the above-mentioned specific organoaluminum compound (I) is used as the organoaluminum compound, high initiation efficiency is obtained. (Block efficiency) can be achieved. In contrast, Table 1
From the results of Comparative Examples 3 to 7 described in (3), when a trialkylaluminum which is a general organic aluminum compound is used as the organic aluminum compound (Comparative Example 3)
And 4), the initiation efficiency (block efficiency) is low, and an organic alkali metal compound such as polystyryllithium is used as an anionic polymerization initiator compound in its original form or in an addition reaction with an unsaturated compound other than a conjugated diene compound. When used in the form of a product (Comparative Examples 5 to 7), it can be seen that the conversion is extremely low or the initiation efficiency (block efficiency) is low.

Example 6 (Synthesis example of styrene-n-butyl acrylate block copolymer) In this example, a process for preparing polystyryllithium (organic alkali metal compound) by anionic polymerization of styrene and an addition reaction of butadiene were used. Styrene-acryl comprising a step of preparing a polymerization initiator compound and a step of polymerizing n-butyl acrylate in the presence of isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum (organoaluminum compound) It is an example of manufacture of an acid n-butyl block copolymer. The block efficiency in block copolymerization (initiation efficiency in polymerization of n-butyl acrylate) is calculated based on the number average molecular weight in terms of polystyrene determined by GPC measurement of the block copolymer, and the amount used and the yield. From the molecular weight of the obtained block copolymer.

Isobutyl bis (2,6-di-tert-
The addition temperature of a solution prepared by mixing a toluene solution containing (butyl-4-methylphenoxy) aluminum and 1,2-dimethoxyethane was changed from 0 ° C. to −30 ° C., and 2.25 g of methyl methacrylate was added to 0%. Styrene in the same manner as in Example 5 except that 2.25 g of n-butyl acrylate was added at -30 ° C and polymerized at -30 ° C for 5 minutes instead of adding at 0 ° C and polymerizing at 0 ° C for 1 hour. Of polystyryllithium by anionic polymerization of butadiene, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of n-butyl acrylate in the presence of an organoaluminum compound. GPC (polystyrene equivalent) analysis of the obtained polymerization initiator compound revealed that Mn was 5000 and Mw / Mn was 1.04. After the polymerization step of n-butyl acrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer is almost 100%.
Met. As a result of GPC-UV (254 nm) measurement (in terms of polystyrene), the polymer was found to have Mn = 2150
0, a mixture of a block copolymer having Mw / Mn = 1.09 and a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at a terminal), and the weight ratio of the former to the latter is 96: 4. It turned out to be. Based on the molecular weight of the polymerization initiator polymer, the molecular weight of the block copolymer and the yield, the block efficiency was estimated to be 91%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 2 below.

Example 7 (Synthesis example of styrene-n-butyl acrylate block copolymer) 0.80 mmol of isobutyl bis (2,6-di-te
Instead of adding a solution prepared by mixing 1.0 ml of a toluene solution containing rt-butyl-4-methylphenoxy) aluminum and 0.22 g of 1,2-dimethoxyethane, 0.40 mmol of isobutylbis (2,2 6
Instead of adding only 0.50 ml of a toluene solution containing -di-tert-butyl-4-methylphenoxy) aluminum and adding n-butyl acrylate alone,
0.40 mmo of the same weight of n-butyl acrylate
l of isobutyl bis (2,6-di-tert-butyl-
A solution prepared by mixing with 0.50 ml of a toluene solution containing 4-methylphenoxy) aluminum was added,
And the polymerization time of n-butyl acrylate is 5 minutes to 30 minutes.
Minutes in the same manner as in Example 6, except that the polystyrene is prepared by anionic polymerization of styrene, a polymerization initiator compound is prepared by an addition reaction of butadiene, and n-butyl acrylate is used in the presence of an organoaluminum compound. Was sequentially performed. GPC (polystyrene conversion) analysis of the obtained polymerization initiator compound revealed that Mn was 5,100 and Mw / Mn was 1.02. After the polymerization step of n-butyl acrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. In addition, GPC-UV (254n
m) As a result of measurement (in terms of polystyrene), the polymer
It is a mixture of a block copolymer having n = 24000 and Mw / Mn = 1.12 and a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at a terminal), and the weight ratio of the former to the latter is 93: It turned out to be 7. Based on the molecular weight of the polymerization initiator polymer, the molecular weight of the block copolymer and the yield, the block efficiency was estimated to be 81%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 2 below.

Comparative Example 8 Isobutyl bis (2,6-di-tert-butyl-4-
Methylphenoxy) aluminum was replaced by the same molar number of triisobutylaluminum, and the polymerization time of n-butyl acrylate was changed from 5 minutes to 6 hours. Preparation of polystyryllithium by polymerization, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of n-butyl acrylate in the presence of an organoaluminum compound were sequentially performed. As a result of GPC (polystyrene conversion) analysis of the obtained polymerization initiator compound, Mn was 5
800 and Mw / Mn was found to be 1.04. After the polymerization step of n-butyl acrylate, a polymer was obtained by reprecipitation. ¹ H-NMR of the obtained polymer
As a result of the analysis, it was found that n-butyl acrylate was not polymerized at all. GPC-UV (254 nm)
As a result of measurement (in terms of polystyrene), it was found that the polymer was a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at a terminal). The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 2 below.

[0113]

[Table 2]

In the above Table 2, "organoaluminum compound"
And the symbol in the column of "additive" has the following meaning. IBAL _{(BHT) 2:} isobutylbis (2,6-di -t- butyl-4-methylphenoxy) aluminum iB ₃ Al: triisobutylaluminum DME: 1,2-dimethoxyethane a): acrylic acid n- butyl Added in the form of a mixture

From the results shown in Table 2, the acrylic acid ester is polymerized in the presence of an organic aluminum compound using a polymerization initiator compound comprising an addition reaction product of an organic alkali metal compound and a conjugated diene compound. On the occasion,
When the above-mentioned specific organoaluminum compound (I) is used as the organoaluminum compound (Examples 6 and 7), a high initiation efficiency (block efficiency) can be achieved. It can be seen that when alkyl aluminum was used (Comparative Example 8), the polymerization reaction did not proceed.

Example 8 (Synthesis example of methyl methacrylate polymer) In this example, oligobutadienyllithium (polymerization initiator compound ) And diisobutyl (2,6-di-tert-
It is a production example of a methyl methacrylate polymer comprising a polymerization step of methyl methacrylate in the presence of (butyl-4-methylphenoxy) aluminum (organoaluminum compound). The initiation efficiency of the methyl methacrylate polymer is calculated based on the number average molecular weight in terms of polystyrene determined by GPC measurement of the methyl methacrylate polymer, and the molecular weight of the methyl methacrylate polymer calculated based on the amount used and the yield. From the ratio.

(1) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this, 18.5 ml of a cyclohexane solution containing 1.2 g of butadiene was added and cooled to 0 ° C. To this solution, 1.6 ml of a 1.3 M solution of sec-butyllithium in cyclohexane was added.
The reaction was carried out with stirring for 4 hours. As a result of GPC measurement of the obtained reaction mixture, the number average molecular weight (Mn) in terms of polystyrene was 1200, and the molecular weight distribution (Mw / M
It was found that oligobutadienyl lithium having n) of 1.18 was produced.

(2) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this, 15 ml of toluene and 1.5 ml of the 0.1M oligobutadienyllithium cyclohexane solution prepared in the above (1) were added. The solution was cooled to −30 ° C., and 1.0 ml of a toluene solution containing 0.80 mmol of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum was added, followed by stirring for 10 minutes. Then, while stirring the obtained solution vigorously, 1.50 g of methyl methacrylate was added thereto. After the polymerization was performed at −30 ° C. for 2 hours with stirring, the polymerization was stopped by adding about 0.05 ml of methanol. The obtained reaction mixture is mixed with 30
The polymer was obtained by reprecipitation in 0 ml of methanol. The yield of the obtained polymer was almost 100%. As a result of GPC measurement (in terms of polystyrene), Mn = 1900 and Mw / Mn = 1.07 for the polymer.
Turned out to be. From these, it was found that the initiation efficiency in the polymerization of methyl methacrylate was 93%. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 3 below.

Comparative Example 9 A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. 15 ml of toluene was added thereto, and the mixture was cooled to −30 ° C., and 0.95 ml of a 1.6 M solution of tert-butyllithium in cyclohexane was added. The solution is kept at -30 ° C and 0.80 mmol of diisobutyl (2,6-di-t
1.0 ml of a toluene solution containing tert-butyl-4-methylphenoxy) aluminum was added, and the mixture was stirred for 10 minutes. Then, while vigorously stirring the resulting solution,
To this, 1.50 g of methyl methacrylate was added. -3
After polymerization was carried out at 0 ° C. for 2 hours with stirring, the polymerization was stopped by adding about 0.05 ml of methanol.
The polymer was obtained by reprecipitating the obtained reaction mixture in 300 ml of methanol. The yield of the obtained polymer was almost 100%. As a result of GPC measurement (in terms of polystyrene), Mn = 13000 for the polymer.
And Mw / Mn = 1.11. From these, it was found that the initiation efficiency in the polymerization of methyl methacrylate was 77%. Chemicals used,
The polymerization conditions employed and the results obtained are shown in Table 3 below.

Comparative Example 10 Instead of 0.95 ml of a 1.6 M tert-butyllithium cyclohexane solution, a 1.3 M sec was used.
Of methyl methacrylate in the presence of an organoaluminum compound in the same manner as in Comparative Example 9 except that 1.15 ml of -butyllithium cyclohexane solution was used and the polymerization time of methyl methacrylate was extended from 2 hours to 6 hours. The polymerization was attempted. However, it was found that methyl methacrylate was not polymerized. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 3 below.

Comparative Example 11 Instead of 0.95 ml of a 1.6 M solution of tert-butyllithium in cyclohexane, 1.0 ml of a 1.5 M solution of n-butyllithium in cyclohexane was used, and the polymerization time of methyl methacrylate was changed. From 2 hours to 6
Polymerization of methyl methacrylate in the presence of an organoaluminum compound was attempted in the same manner as in Comparative Example 9 except that the time was extended. However, it was found that methyl methacrylate was not polymerized. The chemicals used, the polymerization conditions employed and the results obtained are shown in Table 3 below.

[0122]

[Table 3]

In the above Table 3, "organoaluminum compound"
The symbols in the column mean the following compounds.

IB ₂ Al (BHT): diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum

From the results of Example 8 shown in Table 3 above,
The presence of an organoaluminum compound having a chemical structure in which one of three bonds of an aluminum atom is bonded to an aromatic ring via an oxygen atom by using a methacrylate ester as an anionic polymerization initiator compound Upon polymerization below, when the addition reaction product of an organic alkali metal compound such as a low molecular weight alkyl lithium and a conjugated diene compound is used as the anionic polymerization initiator compound, it can be seen that high initiation efficiency can be achieved. . On the other hand, from the results of Comparative Examples 9 to 11 shown in Table 3, when a general polymerization initiator compound such as a low molecular weight alkyl lithium was used as it was as the anionic polymerization initiator compound, Is very low or the initiation efficiency is low.

Example 9 (Synthesis example of butadiene-methyl methacrylate diblock copolymer) In this example, a large amount of butadiene was added to sec-butyllithium (organic alkali metal compound) (polymerization).
For preparing a living anion of polybutadiene (polybutadienyl lithium; polymerization initiator compound) by using the method described above, and isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum (organoaluminum compound)
1 is a production example of a butadiene-methyl methacrylate diblock copolymer comprising a polymerization step of methyl methacrylate in the presence of (1) The inside of a 1 liter autoclave apparatus was purged with nitrogen, and 520 g of toluene and 1.3 M of se
2.5 ml of a cyclohexane solution of c-butyllithium was added. To the resulting solution was added 65 g of butadiene at 18 ° C., and the mixture was polymerized for 5 hours to obtain a living anion of polybutadiene. A sample was collected from the obtained reaction mixture and measured by GPC. As a result, the polybutadiene formed was found to have a polystyrene-equivalent number average molecular weight (Mn).
Was 29,400, and the molecular weight distribution (Mw / Mn) was found to be 1.01. (2) The reaction mixture obtained in the above (1) was cooled to −3 ° C., and 0.8M isobutyl bis (2,6
A mixed solution prepared from 20 ml of a toluene solution of -di-t-butyl-4-methylphenoxy) aluminum and 6 ml of 1,2-dimethoxyethane was added, and the mixture was stirred for 10 minutes. Further, to this solution, a mixed solution prepared from 65 g of methyl methacrylate and 3 ml of a 0.8 M isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum toluene solution was added, and the mixture was heated to 0 ° C. For 2 hours. A sample is taken from the obtained reaction mixture and GP
As a result of the measurement at C, the resulting polymer had a polystyrene reduced number average molecular weight (Mn) of 49,300,
The molecular weight distribution (Mw / Mn) was found to be 1.03. Further, no peak derived from the polybutadiene (homopolymer) obtained in the above (1) was observed, and the produced polymer was only the butadiene-methyl methacrylate diblock copolymer (PBd-b-PMMA). I understood. Further, as a result of ¹ H-MNR analysis of the sample, the weight ratio of polybutadiene block / polymethyl methacrylate block in the obtained polymer was 47/53,
It was found that the ratio (molar ratio) of 1,4 bonds / 1,2 bonds in the polybutadiene block was 10/90.

Reference Example 1 In this reference example, a block copolymer obtained by converting the polybutadiene block into a substantial ethylene-butylene copolymer block by hydrogenating the block copolymer obtained in Example 9 was used. This is an example of the production of Nickel / aluminum hydrogenation catalyst (nickel content: 1 mmol;
(Aluminum content: 3 mmol), which was added to the reaction mixture finally obtained in Example 9.
The obtained mixture was heated to 80 ° C. while stirring under a hydrogen pressurized (1 MPa) atmosphere, and reacted at this temperature for 3 hours. During this time, the hydrogen pressure was increased to 1M by supplying hydrogen.
Pa was maintained. As a result of ¹ H-MNR analysis of the obtained reaction mixture, 98% of the double bonds of the polybutadiene block were lost in the produced polymer, and a dimer having a hydrogenated polybutadiene block and a polymethyl methacrylate block was obtained. Block copolymer (hydrogenated PBd-b-PMM
It was found that A) was obtained.

Example 10 (isoprene-acrylic acid n-
Example of Synthesis of Butyl Diblock Copolymer) In this example, a large amount of isoprene was added to sec-butyllithium (organic alkali metal compound) for addition reaction (polymerization).
For preparing a living anion (polyisoprenyllithium; polymerization initiator compound) of polyisoprene, and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum (organoaluminum compound)
1 is a production example of an isoprene-n-butyl acrylate diblock copolymer comprising a step of polymerizing n-butyl acrylate in the presence of a. (1) The inside of a 1 liter autoclave apparatus was purged with nitrogen, and 440 g of toluene and 1.3 M of se
2.8 ml of a cyclohexane solution of c-butyllithium was added. 55 g of isoprene was added to the obtained solution at 23 ° C., and polymerization was performed for 4 hours to obtain a living anion of polyisoprene. A sample was collected from the obtained reaction mixture and measured by GPC. As a result, the resulting polyisoprene was found to have a polystyrene reduced number average molecular weight (Mn).
Was 11,000, and the molecular weight distribution (Mw / Mn) was found to be 1.02. (2) The reaction mixture obtained in the above (1) was cooled to −31 ° C., and 0.8M isobutyl bis (2,2
A mixed solution prepared from 40 ml of a toluene solution of 6-di-t-butyl-4-methylphenoxy) aluminum and 7 ml of 1,2-dimethoxyethane was added, and the mixture was stirred for 10 minutes. Further, n-butyl acrylate 55 was added to this solution.
g of isobutyl bis (2,6-di-t-
A mixed solution prepared from 5 ml of a toluene solution of butyl-4-methylphenoxy) aluminum was added, and polymerized at -27 ° C for 2 hours. As a result of sampling from the obtained reaction mixture and measuring it by GPC, the resulting polymer had a polystyrene reduced number average molecular weight (Mn) of 37,8.
00, and the molecular weight distribution (Mw / Mn) was found to be 1.03. Further, no peak derived from the polyisoprene (homopolymer) obtained in the above (1) was observed, and the produced polymer was only an isoprene-n-butyl acrylate diblock copolymer (PIp-b-PnBA). Turned out to be. Further, the ¹ H-MNR of the sample
As a result of the analysis, the weight ratio of polyisoprene block / poly (n-butyl acrylate) in the obtained polymer was 49/51, and the ratio (molar ratio) of 1,4 bonds / 3,4 bonds in the polyisoprene block was obtained. Was found to be 7/93. The obtained isoprene-acrylic acid n
The GPC chart of the -butyl diblock copolymer and the polyisoprene obtained in the above (1) are shown in FIG. In FIG. 1, curves A and B show an isoprene-n-butyl acrylate diblock copolymer and polyisoprene, respectively.

According to Examples 9 and 10, according to the production method of the present invention, a block copolymer having a diene polymer block and a (meth) acrylic acid ester polymer block was obtained with a narrow molecular weight distribution and a very low molecular weight distribution. It can be seen that it can be manufactured with high block efficiency.

[0130]

According to the present invention, methyl methacrylate,
For a wide range of (meth) acrylates such as tert-butyl methacrylate and n-butyl acrylate,
Using a relatively convenient organic alkali metal compound such as ec-butyllithium, and in a solvent such as a hydrocarbon-based solvent which is easy to collect and reuse, for example, -30 ° C to 15 ° C
Under moderate cooling conditions such as ° C, anion polymerization can be performed with high initiation efficiency and high living properties. Therefore, according to the present invention, a (meth) acrylate-based polymer such as a block copolymer can be industrially advantageously produced.

[Brief description of the drawings]

FIG. 1 is a GPC chart (A) of an isoprene-n-butyl acrylate diblock copolymer finally obtained in Example 10 according to the present invention and a graph for producing the diblock copolymer. 5 is a GPC chart (B) of the polyisoprene prepared in the first step. The horizontal axis represents the outflow time.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Sachie Yaginuma 41st Miyukigaoka, Tsukuba, Ibaraki Pref. Reference) 4J015 DA02 DA05

Claims (10)

[Claims] When anionic polymerization of a methacrylic acid ester or an acrylic acid ester is carried out using a polymerization initiator compound, an addition reaction product of a conjugated diene compound and an organic alkali metal compound is used as the polymerization initiator compound,
And a tertiary organoaluminum compound having a chemical structure represented by the formula: Al-O-Ar (where Ar represents an aromatic ring) in the molecule, in a polymerization system. 2. The polymerization method according to claim 1, wherein the methacrylic acid ester or the acrylic acid ester is an ester of a primary alcohol and methacrylic acid or acrylic acid. 3. The polymerization method according to claim 1, wherein the conjugated diene compound is 1,3-butadiene. 4. The polymerization method according to claim 1, wherein the organic alkali metal compound is a low molecular weight organic monolithium compound having a secondary carbon atom or a primary carbon atom as an anion center. 5. The method according to claim 1, wherein the organic alkali metal compound is at least one.
The polymerization method according to any one of claims 1 to 3, which is a lithium salt of a polymer having a chemical structure in which a lithium atom is bonded to two molecular chain terminal portions. 6. The tertiary organoaluminum compound according to claim 1, wherein at least two of the three bonds of the aluminum atom are bonded to the aromatic ring via an oxygen atom. The polymerization method according to any one of the preceding claims. 7. The polymerization method according to claim 1, wherein at least a part of the tertiary organoaluminum compound is mixed with a methacrylate or an acrylate and then added to the polymerization system. 8. The polymerization method according to claim 1, wherein an ether compound or a tertiary polyamine compound is further present in the polymerization system. 9. A method for producing a polymer, comprising polymerizing a methacrylic acid ester or an acrylic acid ester by the polymerization method according to any one of claims 1 to 8. 10. A method for producing a block copolymer, comprising polymerizing a methacrylic acid ester or an acrylic acid ester by the polymerization method according to claim 5. Description: