JP2002145972A - Method for producing acrytic thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new acrylic thermoplastic elastomer capable of exhibiting sufficient elastomer performances by a living radical polymerization applicable to the exiting equipment. SOLUTION: (D) A methacrylic ester of a 1-3C alkanol is polymerized to >=90% conversion by using a living radical polymerization initiator system comprising a component (A): a transition metal complex, a component (B): an organic halide and a component (C): a Lewis acid or an amine and (E) an acrylic or a methacrylic ester of a 4-18C alkonol is then polymerized until the conversion reaches the range of 60-100%. Thereby, a block copolymer is formed and (F) a radically polymerizable compound having >=2 carbon-carbon double bonds is added and copolymerized therewith. As a result, a star-shaped copolymer in which >=50 wt.% of the block copolymer is bound to the periphery of the formed terpolymer is formed as a principal component of the acrylic thermoplastic elastomer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an acrylic thermoplastic elastomer composition by utilizing living radical polymerization. More specifically, the present invention uses a specific living radical polymerization initiator system to synthesize a block copolymer having a controlled molecular weight and molecular weight distribution,
Next, an acrylic thermoplastic elastomer composition in which a specific radical polymerizable compound having two or more carbon-carbon double bonds is further copolymerized to form a block copolymer of 50% by weight or more as a star copolymer The present invention relates to a method for manufacturing a product.

[0002]

2. Description of the Related Art Generally, a thermoplastic elastomer is a triblock copolymer having a hard segment serving as a pseudo-crosslinking point at both ends and a soft segment serving as a rubber component in the center, and the molecular weight of each segment is very uniform. Performance is exhibited by As a method of synthesizing a triblock copolymer satisfying the above, it is effective to sequentially polymerize by a living anion polymerization method.

However, in the production of acrylic thermoplastic elastomers, as can be seen in JP-A-11-335432, living anionic polymerization of (meth) acrylate is very difficult to suppress side reactions, It was indispensable to carry out the process, and industrialization was very difficult.

On the other hand, it has recently been found that living polymerization of (meth) acrylate is possible by a living radical polymerization method using an initiator system in which an organic halide and a transition metal complex are combined. This method is useful in that it can be applied to a wide range of monomers and that a polymerization temperature applicable to existing equipment can be adopted. Specifically, a transition metal complex such as dichlorotris (triphenylphosphine) ruthenium and an organic halide (polymerization initiator) such as carbon tetrachloride, 1-phenylethyl chloride or ethyl-2-bromoisobutyrate; Those using a polymerization initiator system comprising a Lewis acid such as an aluminum alkoxy compound have been proposed (Macromolecules, vol. 28, 172).
1 (1995); J. Am. Chem. Soc., 117, 5614 (1995); JP-A-8-41117; JP-A-9-208616 and the like).

[0005] As an example of the synthesis of an acrylic thermoplastic elastomer by living radical polymerization using a transition metal complex, for example, carbon-reactive carbon such as dibromobis (triphenylphosphine) nickel having nickel as a central metal is known.
Using an organic halide having two halogen bonds in the molecule, poly (butyl acrylate) (macro-initiator) having reactive carbon-halogen bonds at both ends is prepared, and then dibromobis (triphenylphosphine) nickel The polymerization of methyl methacrylate with an initiator system combining the above is synthesized into a triblock copolymer of methyl methacrylate-butyl acrylate-methyl methacrylate (Macromolecules, vol. 33, 470 (200
0)).

[0006]

However, in the triblock copolymer of methyl methacrylate-butyl acrylate-methyl methacrylate obtained by the above method, the molecular weight of the poly (methyl methacrylate) segment is not uniform, and the living anion polymerization method is not used. The performance as a thermoplastic elastomer was inferior to that obtained in 1.

The present invention is intended to solve the above-mentioned problems of the prior art, and provides a novel acrylic thermoplastic elastomer which exhibits sufficient elastomer performance by a living radical polymerization method applicable to existing equipment. It is intended to be able to be manufactured.

[0008]

The present inventors have conducted a living radical polymerization reaction using a living radical polymerization initiator system comprising a transition metal complex, an organic halide and a Lewis acid (or amine) to form a living radical polymerization reaction having 1 carbon atom. First step of polymerizing a monomer having a methacrylic acid ester of alkanol as a main component to a polymerization rate of 90% or more, and then having 4 to 1 carbon atoms
A second step of sequentially adding a monomer having a (meth) acrylic acid ester of alkanol as a main component and subjecting the copolymer to block copolymerization until a polymerization rate of 60 to 100% is reached; By dividing into a third step of copolymerizing a radical polymerizable compound having two or more carbon-carbon double bonds, the radical polymerizable compound is formed around the three-dimensional polymer formed by copolymerization of the radical polymerizable compound. The present inventors have found that a star copolymer having 50% by weight or more of a block copolymer bonded thereto can be obtained as a main component of an acrylic thermoplastic elastomer composition having excellent thermoplastic elastomer properties, and complete the present invention. Reached.

That is, the present invention provides the following component (A):
(B) and (C): producing an acrylic thermoplastic elastomer composition using a living radical polymerization initiator system comprising: (A) a transition metal complex; (B) an organic halide; and (C) a Lewis acid or an amine. In the method, the following first step, second step and third step: (first step) a first monomer containing 50% by weight or more of a methacrylic acid ester (D) of an alkanol having 1 to 3 carbon atoms (Second stage) 50 wt. Of (C) alkanol (meth) acrylate (E) having 4 to 18 carbon atoms was added to the polymerization reaction mixture obtained in the first stage. % Of the second monomer composition containing the (meth) acrylic acid ester (E) at a polymerization rate of 60 to 100%.
And (iii) a carbon-carbon double bond is added to the polymerization reaction mixture containing the block copolymer obtained in the second step. By adding and polymerizing a radical polymerizable compound (F) having two or more, a star copolymer in which 50% by weight or more of the block copolymer is bonded to the periphery of the formed three-dimensional polymer is acrylic-based. The present invention provides a production method characterized by having a step of forming as a main component of a thermoplastic elastomer composition.

[0010]

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

In the method for producing an acrylic thermoplastic elastomer of the present invention, a transition metal complex (component (A)),
Living radical polymerization using a living radical polymerization initiator system comprising an organic halide (component (B)) as a polymerization initiator and a Lewis acid or amine (component (C)) as an activator is carried out in a first step, a first step, It is divided into two and three stages.

As the central metal constituting the transition metal complex of the component (A) constituting the living radical polymerization initiator system used in the present invention, iron, ruthenium, rhodium,
Preferable examples include elements of Groups 8 to 11 of the periodic table such as nickel and copper (according to the periodic table described in “Chemical Handbook Basic Edition I, Revised 4th Edition” (edited by The Chemical Society of Japan) (1993)). Among them, ruthenium is preferred. Specific examples of the transition metal complex having ruthenium as the central metal include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzeneruthenium, dichlorop-cymententhenium, Dichloro (norbornadiene) ruthenium, cis-dichlorobis (2,2′-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, chlorocyclopentadienylbis (triphenyl) Phosphine) ruthenium, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, chloroindenylbis (triphenylphosphine) ) Ruthenium and the like, especially dichlorotris (triphenylphosphine) ruthenium, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium or chloroindenylbis (triphenylphosphine)
Ruthenium is preferred.

The organic halogen compound (component (B)) constituting the living radical polymerization initiator system used in the present invention functions as a polymerization initiator. As such an organic halogen compound, an α-halogenocarbonyl compound or an α-halogenocarboxylic acid ester can be used, and among them, an α-halogenocarboxylic acid ester is preferable, and specific examples thereof include ethyl 2-bromo-2-methylpropanoate, Examples thereof include dimethyl 2-chloro-2,4,4-trimethylglutarate.

The Lewis acid or amine of the component (C) constituting the living radical polymerization initiator system used in the present invention functions as an activator. Examples of such Lewis acids include aluminum trialkoxides such as aluminum triisopropoxide and aluminum tri (t-butoxide); bis (2,6-di-t-butylphenoxy) methylaluminum; 6-Tri-
bis (substituted aryloxy) alkyl aluminum such as t-butylphenoxy) methyl aluminum; tris (substituted aryloxy) aluminum such as tris (2,6-diphenylphenoxy) aluminum; titanium tetraalkoxide such as titanium tetraisopropoxide; Preferred are aluminum trialkoxides, and particularly preferred is aluminum triisopropoxide. Examples of the amine include aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine and butylamine; aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine and dibutylamine; and trimethylamine. Aliphatic amines such as aliphatic tertiary amines such as triethylamine, tripropylamine, triisopropylamine and tributylamine; N, N,
N ′, N′-tetramethylethylenediamine, N, N,
Aliphatic polyamines such as N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine; aniline,
Examples thereof include aromatic primary amines such as toluidine, aromatic secondary amines such as diphenylamine, and aromatic amines such as aromatic tertiary amines such as triphenylamine. Among them, aliphatic amines are preferable, and butylamine, dibutylamine, tributylamine and the like are particularly preferable.

[0015] The content ratio of each component in the living radical polymerization initiator system used in the present invention is not necessarily limited, but if the ratio of component (A) to component (B) is too low, the polymerization will be slow. Conversely, if the molecular weight distribution is too high, the molecular weight distribution of the obtained polymer tends to widen. Therefore, the molar ratio of component (A): component (B) is in the range of 0.05: 1 to 1: 1. It is preferred that If the ratio of the component (C) to the component (B) is too low, the polymerization is slowed down. Conversely, if the ratio is too high, the molecular weight distribution of the obtained polymer tends to be widened. The molar ratio of C) is preferably in the range of 1: 1 to 1:10.

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

The process for producing the acrylic thermoplastic elastomer composition of the present invention is basically carried out by subjecting a radical polymerizable monomer to a living radical polymerization solvent in a solvent such as toluene in the presence of the aforementioned living radical polymerization initiator system. It is to be polymerized. As a result, the number average molecular weight (Mn) of the obtained polymer is increased almost in proportion to the increase in the degree of polymerization, and the molecular weight distribution expressed by weight average molecular weight / number average molecular weight (Mw / Mn) is close to 1. It is possible to suppress the generation of a polymer due to chain termination or transfer reaction during the progress of polymerization, and to allow living polymerization to proceed (first stage). Furthermore, if another monomer is newly added, the number average molecular weight can be increased while maintaining the molecular weight distribution close to 1, and a block copolymer can be produced (second step). Furthermore, a so-called star copolymer can be obtained by copolymerizing a radical polymerizable compound having two or more carbon-carbon double bonds (third stage).

Hereinafter, the first, second, and third steps of the living radical polymerization will be described in more detail.

(First Step) A first monomer composition containing 50% by weight or more of a methacrylic acid ester (D) of an alkanol having 1 to 3 carbon atoms is polymerized to a polymerization rate of 90% or more. If the monomer in the next stage is added at a polymerization rate of less than 90%, the glass transition temperature of the rubber-like segment of the obtained elastomer is increased, and the performance as an elastomer is undesirably lowered.

As the methacrylic acid ester (D) of an alkanol having 1 to 3 carbon atoms, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate or the like may be used alone or in combination of two or more. it can. Among these, methyl methacrylate can be preferably used.

Assuming that the content of the methacrylate (D) is at least 50% by weight in the first monomer composition, the first monomer composition can be subjected to living radical polymerization with the methacrylate (D) if necessary. Other monomers may be blended. Examples of such other monomers include radical polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid. Isobutyl acrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, -n-methacrylic acid
Heptyl, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate,
Isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate , Γ-
(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, 2-trifluoromethylethyl methacrylate, 2-methacrylic acid
Perfluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethylmethyl methacrylate,
Methacrylic esters such as 2-perfluoromethyl-2-perfluoroethylmethyl methacrylate, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate; acrylic acid Methyl, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid
n-pentyl, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate,
Nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyacrylate Ethyl, acrylic acid-
2-hydroxypropyl, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, γ-
(Acryloyloxypropyl) trimethoxysilane,
γ- (acryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroacrylate Ethyl-2-
Perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate Acrylates such as 2-perfluorodecylethyl acrylate and 2-perfluorohexadecylethyl acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene and p-methoxystyrene; acrylonitrile; Vinyl cyanide compounds such as methacrylonitrile;
Conjugated diene compounds such as butadiene and isoprene; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane Compounds; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, fumaric acid, unsaturated dicarboxylic acid compounds such as monoalkyl esters and dialkyl esters of fumaric acid; vinyl acetate, vinyl propionate, vinyl pivalate; Vinyl ester compounds such as vinyl benzoate and vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimi , Stearyl maleimide, phenyl maleimide, the various vinyl monomers of the maleimide-based compounds such as cyclohexyl maleimide.

In the first step, the initial concentration of the methacrylic acid ester (D) of an alkanol having 1 to 3 carbon atoms is as follows:
Although not necessarily limited, if the reaction rate is too low, the reaction rate is too slow, and if it is too high, the chain transfer reaction of the generated radicals to the monomer increases, and the molecular weight distribution of the obtained polymer tends to be broadened. Preferably 0.5 to 8 mol (mol) / L (liter), particularly preferably 1 to 4 mol
/ L. At this time, the concentration of each component in the polymerization system is not necessarily limited. However, although there is a difference depending on the concentration of the monomer having methacrylic acid ester (D) as a main component, the concentration of component (B) The concentration of the polymerization initiator is preferably 0.1 to 100 mmol (mmol) /
L (liter), particularly preferably 0.5 to 50 mmol
/ L. The concentration of the transition metal complex of the component (A) is preferably 0.1 to 50 mmol / L, particularly preferably 0.1 to 50 mmol / L.
It is 1 to 10 mmol / L. Further, the concentration of the Lewis acid or amine of the component (C) is preferably 1 to 200 mmol.
1 / L, particularly preferably 1 to 50 mmol / L.

(Second Step) The polymerization reaction mixture obtained in the first step contains at least 50% by weight of (meth) acrylic acid ester (E) of an alkanol having 4 to 18 carbon atoms.
Are successively added, and the polymerization rate of the second monomer composition containing the (meth) acrylate (E) is 6
Polymerize to reach a range of 0-100% to form a block copolymer. When a radically polymerizable compound (F) having a polymerization rate of less than 60% and having two or more carbon-carbon double bonds in the next stage is added, a star-shaped polymer is not formed and the entire polymerization system gels. Not preferred.

(Meth) of alkanol having 4 to 18 carbon atoms
As the acrylate (E), butyl methacrylate, t-butyl methacrylate, pentyl methacrylate,
Methacrylates such as hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate, butyl acrylate, t-butyl acrylate, acrylic Acrylic esters such as pentyl acid, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, alone or in combination of two or more Can be mixed and used.
Among these, 2-ethylhexyl methacrylate or dodecyl methacrylate can be preferably used.

In the second monomer composition, the (meth) acrylic acid ester (E) may be added if necessary, provided that the content of the (meth) acrylic acid ester (E) is 50% by weight or more. ) And other monomers capable of living radical polymerization. As such another monomer, the same monomer as the other monomer capable of being subjected to living radical polymerization with methacrylate (D), which is blended as required in the first step, is appropriately selected and used. be able to.

The above-mentioned first monomer composition containing a alkanol methacrylate ester having 1 to 3 carbon atoms (D) as a main component, and a (meth) acrylate ester of an alkanol having 4 to 18 carbon atoms. The proportion of the second monomer composition containing (E) as a main component is such that the first monomer composition containing methacrylate (D) as a main component is 10 to 10% of the total amount of both. It is preferable that the content of the monomer containing 40% by weight of the (meth) acrylate (E) as a main component is 90 to 60% by weight.

To the polymerization reaction mixture obtained in the first step, a second monomer composition containing 50% by weight or more of (meth) acrylic acid ester (E) of an alkanol having 4 to 18 carbon atoms is sequentially added. As a method for carrying out the reaction, it may be added to the polymerization system alone, but it is preferable to newly add the components (A) and (C) and a mixture with a solvent such as toluene. In this case, the concentration of the mixture is 1 to 4 mol / L for the second monomer composition, and 0.1 to 10 m for the component (A).
mol / L, component (C) is 1 to 50 mmol / L.

(Third step) To the polymerization reaction mixture containing the block copolymer obtained in the second step, a radical polymerizable compound (F) having two or more carbon-carbon double bonds is added to form a copolymer. By polymerizing, a star copolymer in which 50% by weight or more of the block copolymer is bonded around the formed three-dimensional polymer is formed as a main component of the acrylic thermoplastic elastomer composition.

Although not particularly limited, the molecular weight of the polymer segment formed from the first monomer composition containing methacrylate (D) as a main component in the above-mentioned block copolymer is as follows: Preferably 5000
-200,000, more preferably 10,000-5000
0, and the molecular weight of the polymer segment formed from the second monomer composition containing (meth) acrylate (E) as a main component is preferably 20,000 to 10,000.
00, more preferably 30,000 to 100,000.

The radical polymerizable compound (F) having two or more carbon-carbon double bonds used in the present invention includes ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth) acrylate. ) Poly (meth) acrylates such as acrylate and trimethylopropane tri (meth) acrylate; polyvinyl aromatic compounds such as divinylbenzene and diisopropenylbenzene can be used alone or in combination of two or more. Among these, compounds having two or more methacryloyl groups can be preferably used.

In the present invention, the amount of the radical polymerizable compound (F) having two or more carbon-carbon double bonds is as follows:
Preferably from 2 to 100 molar equivalents, more preferably from 5 to 100 mole equivalents relative to the block copolymer (or to component (B)).
５０50 molar equivalents.

In the third step of the present invention, the radical polymerizable compound (F) having two or more carbon-carbon double bonds may be added directly to the polymerization system. Preferably, it can be added by diluting it in a solvent or the like, or can be newly added by mixing components (A) and (C) with a solvent such as toluene. In this case, the concentration of the mixture was 0.1 to 4 mol / mol of the compound (F).
L, component (A) is 0.1 to 10 mmol / L, and component (C) is 1 to 50 mmol / L.

In the production method of the present invention, when the living radical polymerization reaction is started, a monomer, a solvent, a Lewis acid or an amine (component (C)) and Transition metal complex (component (A))
It is preferred to prepare a mixture consisting of: and adding a polymerization initiator (component (B)) thereto. Polymerization can be started by heating the mixture thus obtained to a temperature in the range of, for example, 60 to 120 ° C.

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

[0035]

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

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

The polymerization rate of the polymer is determined by measuring the concentration of the monomer in the reaction mixture by gas chromatography (internal standard: n-
(Octane or 1,2,3,4-tetrahydronaphthalene) and calculated based on the analysis value.

Number average molecular weight (Mn) of the obtained polymer,
Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Was measured under the following conditions using gel permeation chromatography (GPC) and calculated in terms of polymethyl methacrylate.

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

Example 1 As a first step, 12.4 m of chloroindenylbis (triphenylphosphine) ruthenium was placed in a Schlenk reaction tube.
g (0.0160 mmol) was collected, and 0.856 ml (8.00 mmol) of methyl methacrylate, 2.79 ml of toluene, and 0.0860 ml of n-octane were added and uniformly mixed. 0.160 ml of a 500 mmol / L toluene solution of dibutylamine (0.
0800 mmol) and finally 2-chloro-2,
751 mmol of dimethyl 4,4-trimethylglutarate
0.107 ml of 1 / L toluene solution (0.0800 mm
ol). The polymerization reaction was started by heating the obtained mixture to 80 ° C.

After 28 hours from the start of the polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn and cooled to -78 ° C to stop the polymerization reaction.
It was subjected to analysis. The polymerization rate of methyl methacrylate is 92%, and the number average molecular weight (Mn) of polymethyl methacrylate present in the reaction mixture is 9400, the weight average molecular weight (Mw) is 10300, and therefore Mw / Mn is 1.
It was 10. Furthermore, the GPC curve was unimodal.

In the second step, 3.52 ml (12.0 mmol) of dodecyl methacrylate and 3.8 parts of toluene were added to 2.00 ml of the remaining reaction solution in the reaction tube after the extraction.
1 ml, 1,52,3,4-tetrahydronaphthalene 0.352 ml, 500 mmol / L of dibutylamine
0.320 ml (0.160 mmol) of a toluene solution and 24.8 mg (0.0320 mmol) of chloroindenylbis (triphenylphosphine) ruthenium were added, stirred sufficiently, and the resulting mixture was heated to 80 ° C. Subsequently, a polymerization reaction was performed.

When 47 hours had elapsed since the start of the second-stage polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn and cooled to -78 ° C. to stop the polymerization reaction. Was served. The polymerization rate of methyl methacrylate is 99%, the polymerization rate of dodecyl methacrylate is 70%, and the number average molecular weight (Mn) of the methyl methacrylate-dodecyl methacrylate block copolymer present in the reaction mixture is 76800, weight average molecular weight (Mw) is 8
6300 and therefore Mw / Mn was 1.12. Furthermore, the GPC curve was unimodal.

As a third step, 0.300 ml (1.60 mmol) of ethylene glycol dimethacrylate was added to 8.00 ml of the remaining reaction solution in the reaction tube after the extraction.
And 3.70 ml of toluene were added, and the mixture was sufficiently stirred, and the resulting mixture was heated to 80 ° C. to continuously carry out a polymerization reaction.

After 48 hours from the start of the third-stage polymerization reaction, the reaction solution was cooled to -78 ° C. to stop the polymerization reaction, and subjected to analysis. The conversion of methyl methacrylate was 100%, the conversion of dodecyl methacrylate was 94%, and the conversion of ethylene glycol dimethacrylate was 86%. Also, where GPC measurement was performed,
A star-shaped copolymer peak other than the peak of the methyl methacrylate-dodecyl methacrylate block copolymer newly appeared. The block copolymer has a number average molecular weight (Mn) of 7
7600, the weight average molecular weight (Mw) is 93900, and therefore Mw / Mn is 1.21. The star copolymer has a number average molecular weight (Mn) of 453000 and a weight average molecular weight (Mw) of 666000, and thus Mw / Mn. Was 1.47. From the area ratio of the two peaks, it was found that the star copolymer was obtained from the block copolymer in a yield of 65% by weight.

When a sheet was prepared from the obtained polymer by hot press molding, it was found that the sheet was transparent and had a rubbery feel.

Example 2 As a first step, 12.4 m of chloroindenylbis (triphenylphosphine) ruthenium was placed in a Schlenk reaction tube.
g (0.0160 mmol) was collected, and 0.856 ml (8.00 mmol) of methyl methacrylate, 2.79 ml of toluene, and 0.0860 ml of n-octane were added and uniformly mixed. 0.160 ml of a 500 mmol / L toluene solution of dibutylamine (0.
0800 mmol) and finally 2-chloro-2,
751 mmol of dimethyl 4,4-trimethylglutarate
0.107 ml / l / L toluene solution (0.0800 mm
ol). The polymerization reaction was started by heating the obtained mixture to 80 ° C.

When 27 hours had elapsed after the initiation of the polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn and the polymerization reaction was stopped by cooling it to -78 ° C.
It was subjected to analysis. The polymerization rate of methyl methacrylate is 93%, and the number average molecular weight (Mn) of polymethyl methacrylate present in the reaction mixture is 10800, the weight average molecular weight (Mw) is 11800, and therefore Mw / Mn is It was 1.09. Furthermore, the GPC curve was unimodal.

As a second step, 3.17 ml of dodecyl methacrylate (10.8 mmol), benzyl methacrylate (1.20 mmol), 3.81 mol of toluene were added to 2.00 ml of the remaining reaction solution in the reaction tube after the extraction.
1,1,2,3,4-tetrahydronaphthalene 0.3
52 mol, 0.320 ml (0.160 mmol) of a 500 mmol / L toluene solution of dibutylamine and 24.8 mg (0.0320 mmol) of chloroindenylbis (triphenylphosphine) ruthenium were added, and the mixture was sufficiently stirred. The polymerization reaction was continued by heating to 80 ° C.

At the time when 29 hours had passed since the start of the second stage polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn, and the polymerization reaction was stopped by cooling it to -78 ° C. Was served. The polymerization rate of methyl methacrylate is 98%, the polymerization rate of dodecyl methacrylate is 65%, the polymerization rate of benzyl methacrylate is 72%, and methyl methacrylate and dodecyl methacrylate-methacrylic acid present in the reaction mixture are present. Number average molecular weight (Mn) of the block copolymer with the benzyl acid random copolymer is 6770
0, the weight average molecular weight (Mw) is 77900,
w / Mn was 1.15. Furthermore, the GPC curve was unimodal.

As a third step, 0.180 ml (0.960 mmol) of ethylene glycol dimethacrylate was added to 8.00 ml of the remaining reaction solution in the reaction tube after the extraction.
1) and 2.22 ml of toluene were added, and the mixture was sufficiently stirred, and the resulting mixture was heated to 80 ° C. to continuously carry out a polymerization reaction.

At the point of time 60 hours after the start of the third stage polymerization reaction, the reaction solution was cooled to −78 ° C. to stop the polymerization reaction, which was subjected to analysis. The conversion of methyl methacrylate was 100%, the conversion of dodecyl methacrylate was 92%, the conversion of benzyl methacrylate was 94%, and the conversion of ethylene glycol dimethacrylate was 98%.
When GPC measurement was performed, a new peak of the star copolymer other than the peak of the block copolymer appeared. The block copolymer has a number average molecular weight (Mn) of 63,800,
The weight average molecular weight (Mw) is 75300 and therefore Mw /
Mn is 1.18, and the star copolymer has a number average molecular weight (M
n) is 441300, and the weight average molecular weight (Mw) is 569.
200 and therefore Mw / Mn was 1.29. From the area ratio of the two peaks, it was found that the star copolymer was obtained from the block copolymer in a yield of 64% by weight.

When a sheet was formed from the obtained polymer by hot press molding, it was found that the sheet was transparent and had a rubbery feel.

Example 3 As a first step, 12.4 m of chloroindenylbis (triphenylphosphine) ruthenium was placed in a Schlenk reaction tube.
g (0.0160 mmol) was collected, and 0.856 ml (8.00 mmol) of methyl methacrylate, 2.79 ml of toluene, and 0.0860 ml of n-octane were added and uniformly mixed. 0.160 ml of a 500 mmol / L toluene solution of dibutylamine (0.
0800 mmol) and finally 2-chloro-2,
751 mmol of dimethyl 4,4-trimethylglutarate
0.107 ml of 1 / L toluene solution (0.0800 mm
ol). The polymerization reaction was started by heating the obtained mixture to 80 ° C.

After 28 hours from the start of the polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn, and the polymerization reaction was stopped by cooling it to -78 ° C.
It was subjected to analysis. The polymerization rate of methyl methacrylate is 94%, and the number average molecular weight (Mn) of polymethyl methacrylate present in the reaction mixture is 10800, the weight average molecular weight (Mw) is 12000, and therefore Mw / Mn is ,
1.11. Furthermore, the GPC curve was unimodal.

As the second step, 3.52 ml (12.0 mmol) of dodecyl methacrylate and 3.8 parts of toluene were added to 2.00 ml of the remaining reaction solution in the reaction tube after the extraction.
1 ml, 1,52,3,4-tetrahydronaphthalene 0.352 ml, 500 mmol / L of dibutylamine
0.320 ml (0.160 mmol) of a toluene solution and 24.8 mg (0.0320 mmol) of chloroindenylbis (triphenylphosphine) ruthenium were added, stirred sufficiently, and the resulting mixture was heated to 80 ° C. Subsequently, a polymerization reaction was performed.

At the time point 58 hours after the initiation of the second stage polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn, and the polymerization reaction was stopped by cooling it to -78 ° C. Was served. The conversion of methyl methacrylate is 99%, the conversion of dodecyl methacrylate is 78%, and the number average molecular weight (Mn) of the methyl methacrylate-dodecyl methacrylate block copolymer present in the reaction mixture is 75000, weight average molecular weight (Mw) is 8
7000 and therefore Mw / Mn was 1.16. Furthermore, the GPC curve was unimodal.

As a third step, 0.204 ml (0.640 m) of trimethylolpropane trimethacrylate was added to 8.00 ml of the remaining reaction solution in the reaction tube after the extraction.
mol) and 1.40 ml of toluene, and the mixture was sufficiently stirred, and the resulting mixture was heated to 80 ° C. to continuously carry out a polymerization reaction.

At the time when 20 hours had passed since the start of the third stage polymerization reaction, the reaction solution was cooled to -78 ° C. to stop the polymerization reaction, and subjected to analysis. The conversion of methyl methacrylate was 100%, the conversion of dodecyl methacrylate was 89%, and the conversion of trimethylolpropane trimethacrylate was 80%. GPC measurement revealed that a star-shaped copolymer peak other than the methyl methacrylate-dodecyl methacrylate block copolymer peak appeared. Number average molecular weight of the block copolymer (M
n) is 66600, and the weight average molecular weight (Mw) is 8130.
0, therefore Mw / Mn is 1.22, the number average molecular weight (Mn) of the star copolymer is 1071,700, and the weight average molecular weight (Mw) is 2,182,900.
04. From the area ratio of the two peaks, it was found that the star copolymer was obtained from the block copolymer in a yield of 73% by weight.

When a sheet was prepared from the obtained polymer by hot press molding, it was found that the sheet was transparent and had a rubbery feel.

Comparative Example 1 As a first step, 12.4 m of chloroindenylbis (triphenylphosphine) ruthenium was placed in a Schlenk reaction tube.
g (0.0160 mmol) was collected, and 0.856 ml (8.00 mmol) of methyl methacrylate, 2.79 ml of toluene, and 0.0860 ml of n-octane were added and uniformly mixed. 0.160 ml of a 500 mmol / L toluene solution of dibutylamine (0.
0800 mmol) and finally 2-chloro-2,
751 mmol of dimethyl 4,4-trimethylglutarate
0.107 mmol of 1 / L toluene solution (0.0800
mmol). The polymerization reaction was started by heating the obtained mixture to 80 ° C.

After 28 hours from the start of the polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn and the polymerization reaction was stopped by cooling it to −78 ° C.
It was subjected to analysis. The polymerization rate of methyl methacrylate is 91%, and the number average molecular weight (Mn) of polymethyl methacrylate present in the reaction mixture is 9900, the weight average molecular weight (Mw) is 10900, and therefore Mw / Mn is 1.
It was 10. Furthermore, the GPC curve was unimodal.

As a second step, 3.52 ml (12.0 mmol) of dodecyl methacrylate and 3.8 parts of toluene were added to 2.00 ml of the remaining reaction solution in the reaction tube after the extraction.
1 ml, 1,52,3,4-tetrahydronaphthalene 0.852 ml, 500 mmol / L of dibutylamine
0.320 ml (0.160 mmol) of toluene solution and chloroindenyl bis (triphenylphenylphosphine)
Ruthenium (24.8 mg, 0.0320 mmol) was added, and the mixture was sufficiently stirred, and the obtained mixture was heated to 80 ° C. to continuously perform a polymerization reaction.

At the time when 20 hours have passed since the start of the second stage polymerization reaction, a part (2.00 ml) of the reaction solution was withdrawn and cooled to −78 ° C. to stop the polymerization reaction. Was served. The conversion of methyl methacrylate is 97%, the conversion of dodecyl methacrylate is 32%, and the number average molecular weight (Mn) of the methyl methacrylate-dodecyl methacrylate block copolymer present in the reaction mixture is 41300, weight average molecular weight (Mw) is 4
6700 and therefore Mw / Mn was 1.13. Furthermore, the GPC curve was unimodal.

As the third step, 0.300 ml (1.60 mmol) of ethylene glycol dimethacrylate was added to 8.00 ml of the remaining reaction solution in the reaction tube after the extraction.
And 3.70 ml of toluene were added, and the mixture was sufficiently stirred, and the resulting mixture was heated to 80 ° C. to continuously carry out a polymerization reaction.

30 hours after the start of the third stage polymerization reaction, the polymer became insoluble in toluene. Attempted molding by hot pressing, but not thermoplastic.

Comparative Example 2 As a first step, 58.2 mg of chloroindenibis (triphenylphosphine) ruthenium was added to a Schlenk reaction tube.
(0.0750 mmol), 6.60 ml (22.5 mmol) of dodecyl methacrylate, and 7.7 ml of toluene.
09 ml and 0.659 ml of 1,2,3,4-tetrahydronaphthalene were added and mixed uniformly. To this mixed solution, 0.600 ml (0.300 mmol) of a 500 mmol / L toluene solution of dibutylamine was added, and finally, a solution of 1,2-bis (bromopropionyloxy) ethane in 7
0.0610 ml of a 40 mmol / L toluene solution (0.0
450 mmol) was added. The polymerization reaction was started by heating the obtained mixture to 80 ° C.

After 30 hours from the start of the polymerization reaction, a part (5.00 ml) of the reaction solution was withdrawn and the polymerization reaction was stopped by cooling it to -78 ° C.
It was subjected to analysis. The conversion of dodecyl methacrylate is 90%
And the number average molecular weight (Mn) of polydecyl methacrylate present in the reaction mixture is 76800, and the weight average molecular weight (Mw) is 95200, and therefore Mw / Mn
Was 1.24. Furthermore, the GPC curve was unimodal.

As a second step, 1.60 ml (15.0 mmol) of methyl methacrylate and 3.40 of toluene were added to 10.0 ml of the remaining reaction solution in the reaction tube after the extraction.
Then, 0.160 ml of n-octane and 0.160 ml of n-octane were added, and the mixture was sufficiently stirred, and the obtained mixture was heated to 80 ° C. to continuously carry out a polymerization reaction.

When 47 hours had elapsed since the start of the second-stage polymerization reaction, the reaction solution was cooled to −78 ° C. to stop the polymerization reaction, and then subjected to analysis. The polymerization rate of dodecyl methacrylate is 96%, the polymerization rate of methyl methacrylate is 84%, and the number average of methyl methacrylate-dodecyl methacrylate-methyl methacrylate triblock copolymer present in the reaction mixture. The molecular weight (Mn) is 1
01000, weight average molecular weight (Mw) is 139400
Therefore, Mw / Mn was 1.38. The GPC curve was bimodal.

When a sheet was prepared from the obtained polymer by hot press molding, the sheet was opaque and had no rubber-like elasticity.

In Examples 1, 2 and 3, the thermoplastic elastomer composition obtained by the production method of the present invention was:
Although rubber-like elasticity was good, in Comparative Example 1, a thermoplastic elastomer composition could not be obtained because the polymerization rate of dodecyl methacrylate in the second stage was very low at 32%. In Comparative Example 2, the production of the present invention was carried out using a bifunctional initiator (1,2-bis (bromopropionyloxy) ethane) without using the living radical polymerization initiator system used in Example 1. Unlike the method, the first step and the second step are interchanged, and the polymerization is sequentially performed from dodecyl methacrylate to methyl methacrylate (that is, by performing the polymerization by exchanging the first step and the second step). ) A triblock copolymer was obtained, but was not a thermoplastic elastomer showing rubber elasticity.

[0073]

According to the production method of the present invention, a novel acrylic thermoplastic elastomer exhibiting sufficient elastomer performance can be produced by a living radical polymerization method applicable to existing equipment.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaki Uegaki outside 11-50 Fragrance Hi-view B Bldg. Address F-term in Kuraray Tsukuba Research Laboratories Co., Ltd. F-term (reference) 4J026 HA11 HA27 HA39 HB11 HC07 HC11 HC27 HE05 4J028 AA01A AB00A AB01A AC07A AC45A AC46A AC48A BA00A BA01B BB00A BB00B BB01B CB45C CB58A01 CB62C01B AC45 AC46 AC48 BA00A BA01B BB00A BB00B BB01B CB45C CB58C CB62C CB63C CB64C EB25 EC01 ED06 EE06 GA01 GA26

Claims (8)

[Claims] 1. A living radical polymerization initiator system comprising the following components (A), (B) and (C): (A) a transition metal complex; (B) an organic halide; and (C) a Lewis acid or amine. In the method for producing an acrylic thermoplastic elastomer composition by using the following, a first step, a second step and a third step: (first step) a methacrylic acid ester (D) of an alkanol having 1 to 3 carbon atoms Polymerizing a first monomer composition containing 50% by weight or more to a polymerization rate of 90% or more; (second step) adding a alkanol having 4 to 18 carbon atoms to the polymerization reaction mixture obtained in the first step. A second monomer composition containing (meth) acrylic ester (E) in an amount of 50% by weight or more is sequentially added, and the second monomer composition containing (meth) acrylic ester (E) is added. Polymerization rate is 60-100%
And (iii) a carbon-carbon double bond is added to the polymerization reaction mixture containing the block copolymer obtained in the second step. By adding and polymerizing a radical polymerizable compound (F) having two or more, a star copolymer in which 50% by weight or more of the block copolymer is bonded to the periphery of the formed three-dimensional polymer is acrylic-based. A production method, comprising the step of forming as a main component of a thermoplastic elastomer composition. 2. The method according to claim 1, wherein the component (A) is a transition metal complex having ruthenium as a central metal. 3. The composition of claim 1, wherein component (A) is dichlorotris (triphenylphosphine) ruthenium, chloroindenylbis (triphenylphosphine) ruthenium or chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium. 2. The production method according to 2. 4. The method according to claim 1, wherein the component (B) is an α-halogenocarboxylic acid ester. 5. The method according to claim 1, wherein the Lewis acid of the component (C) is an aluminum trialkoxide. 6. The method according to claim 1, wherein the amine of the component (C) is an aliphatic amine. 7. The alkanol methacrylate (C) having 1 to 3 carbon atoms is methyl methacrylate, and the (meth) acrylate (E) of alkanol having 4 to 18 carbon atoms is dodecyl methacrylate. Item 7. The production method according to any one of Items 1 to 6. 8. The production method according to claim 1, wherein the radical polymerizable compound (F) having two or more carbon-carbon double bonds is a compound having two or more methacryloyl groups.