JP2003252926A - Method for isolating polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for isolating an acrylic block copolymer resin which can remove a solvent from the solution in order to yield the resin in a solid state such as a pellet, while the resin is prevented from deteriorating and adhering to a vessel. <P>SOLUTION: The method comprises changing the acrylic block copolymer solution into the solid state by means of a twin-screw extruder having a twin- screw part preferably served with a heated liquid, under a condition that the twin-screw part has preferably a temperature of 150°C or more and 240°C or less and a vacuum degree of 10 Torr or more and 300 Torr or less; and an evaporation apparatus has an axial diameter (L) and a length (L) so that the ratio (L/D) is 5 or more and 20 or less. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for recovering a solid acrylic block copolymer from a resin solution containing an acrylic block copolymer and further removing volatile components from the solid polymer.

[0002]

2. Description of the Related Art It is known that an acrylic block having a hard segment such as methyl methacrylate and a soft segment such as butyl acrylate can be used as a thermoplastic elastomer. For example, Japanese Patent No. 2553134 discloses mechanical properties of an acrylic block body having a methacrylic block and an acrylic block manufactured by the iniferter method.

Acrylic block copolymers have weather resistance,
It is characterized by excellent heat resistance, durability, and oil resistance. Further, by appropriately selecting the components constituting the block body, an elastomer that is extremely softer than other thermoplastic elastomers such as styrene block bodies can be provided, and therefore a cross-linked rubber substitute is expected.

However, for the acrylic block copolymer, an advantageous method for obtaining a solid polymer having a small amount of volatile components from a polymer obtained in a liquid dispersion state or a solution state has not yet been known, and a resin There has been a strong demand for establishment of a method with good operability, which is capable of producing a resin in the form of pellets which can be easily handled while suppressing deterioration and adhesion in the apparatus.

As a method for removing an organic solvent from a resin solution composed of a polymer having an elasticity such as SEBS and SEPS and an organic solvent, heating is performed by using a multi-tube heat exchanger, and decompression is carried out through an atomizer or a spray nozzle. The method of removing the volatile components by flashing in the devolatilization tank is described in, for example, Japanese Patent Publication No.
It is generally used as shown in 8-29797. However, the acrylic block copolymer used in the present invention has a high resin tackiness and a low hardness, so that when the direct evaporation operation is performed using an atomizer or a spray nozzle in a flash evaporation tank that has been depressurized in advance. ,
Due to the adhesion of the concentrated resin in the vicinity of the nozzle, it is difficult to stably and continuously perform the evaporation operation.

[0006] Conventionally, as a method for producing a resin containing a small amount of volatile components by removing the organic solvent from a resin solution containing an acrylic block copolymer and an organic solvent, for example, Japanese Patent Laid-Open No.
In 000-198825, a method of contacting the block copolymer resin with a solvent that does not dissolve to reprecipitate is proposed, but in this method, the amount of the organic solvent used for the resin is increased, There are drawbacks such as difficulty in separating resin and solvent. In addition, it takes time and effort to filter and dry. In addition, in order to commercialize the dried product, there is the complexity of having to go through several steps such as melt extrusion to form a strand and then pelletizing. In addition, in Japanese Patent Laid-Open No. 6-93060,
There is an example in which the solvent of the block copolymer solution is distilled off using an evaporator, but this method is not suitable for large scale because there is no industrial scale evaporator, and the polymer after the solvent is distilled off. Is extremely difficult to recover. Further, the method of removing the solvent by devolatilizing the kettle after completion of the reaction has a drawback in that it becomes difficult to stir as the system thickens, and that after the completion of the reaction, payout is almost impossible.

Regarding the method of removing the organic solvent from the resin solution consisting of the thermoplastic polymer and the organic solvent, for example, as disclosed in JP-A-8-41123, a styrene-acrylic copolymer is used as a main component. In removing the volatile components from the resin composition described above, a method has been proposed in which the residual solvent is reduced to 1000 ppm or less without causing thermal / mechanical deterioration of the resin by using a uniaxial thin film evaporator. However, when this method is applied to the acrylic block copolymer used in the present invention, since the resin is brought into a molten state to evaporate the volatile components, problems such as coloring due to thermal and mechanical deterioration of the resin occur. The acrylic block copolymer used in the present invention is a thermoplastic elastomer having characteristics that resin has high tackiness and low hardness. Therefore, in the thin film evaporator, there are problems such as adhesion of resin on the can wall, deterioration of quality due to heat history during melting, and occurrence of blocking due to adhesiveness of resin.

Further, Japanese Patent Laid-Open No. 08-239420 discloses a method of directly pelletizing a reaction product containing a methacrylate polymer using a twin-screw extruder having a flash evaporation section. Since the twin-screw extruder is not originally given the performance as a desolvation machine, the desolvation efficiency of the resin is poor, and the economical efficiency for equipment installation is poor, and the twin-screw section has a feeding section and a kneading section. Since the resin, which is composed of, and has been concentrated, undergoes deaeration operation in a molten state, deterioration such as coloring due to heat history and deterioration of weather resistance occurs.

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to deteriorate a resin, to attach a resin in an apparatus, etc. when separating and taking out a solid polymer from a resin solution containing an acrylic block copolymer. It is an object of the present invention to provide a method for removing a solvent, which effectively reduces residual volatile components while preventing the above, and enables the production of a resin in pellet form or the like.

[0010]

[Means for Solving the Problems] The inventors of the present invention reduced the pressure when removing a solid acrylic block copolymer from a polymerization reaction liquid of an acrylic block copolymer or a solution of an acrylic block copolymer. It was found that a large amount of block copolymer can be obtained within a short time by using an extruder, and the present invention was completed.

According to the present invention, a vacuum extruder is used in the extraction of a solid acrylic block copolymer from a solution acrylic block copolymer (claim 1). ), The vacuum extruder is a twin screw extruder (claim 2), the block copolymer is 5 to 90% by weight of the methacrylic polymer block (A) and 95 to 10% by weight. % Of the acrylic polymer block (B) is a block copolymer, and the methacrylic polymer block (A) has methyl methacrylate as a main component. It is a block formed by polymerizing monomers, and the acrylic polymer block (B) is acrylic acid-n.
-Butyl or acrylate-n-butyl acrylate, ethyl acrylate and a block formed by polymerizing a monomer composed of a combination of ethyl acrylate and 2-methoxyethyl acrylate as a main component. 4), the block copolymer is produced by controlled radical polymerization, the extraction method according to claim 4 (claim 5), the block copolymer is an organic halide, or an initiator of a sulfonyl halide compound. And the Periodic Table No. 8
The extraction method according to claim 5 (claim 6), the shaft diameter of the reduced pressure extruder (claim 6), characterized in that the catalyst is produced by using a metal complex containing a group 9, 9, 10 or 11 element as a central metal. The ratio (L / D) of length (L) to D) is 5 to 20.
The extraction method according to claim 1 (claim 7), the heating medium is supplied to the twin screw portion (claim (), and the degree of pressure reduction of the reduced pressure extruder is The take-out method according to claim 8 (claim 9), which is 10 to 300 Torr, and the heating temperature of the reduced pressure extruder is 15.
The extraction method according to claim 9 (Claim 10), which is 0 to 240 ° C, and the extraction method according to claim 10, wherein the residual solvent amount in the extracted solid acrylic block copolymer is 10000 ppm or less (Claim 11). ) Concerning.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION <Acrylic Block Copolymer (a)> The acrylic block copolymer (a) used in the present invention is a polymer block (A) containing a methacrylic monomer as a main component. And a polymer block (B) containing an acrylic monomer as a main component, respectively. The block copolymer is at least one block copolymer selected from the group consisting of a linear block copolymer (a1) and a branched (star) block copolymer (a2).

The linear block copolymer (a1) is AB
Type diblock copolymer, ABA type triblock copolymer, BAB type triblock copolymer, (-
AB-) n-type multi-block copolymer. The branched (star) block copolymer (a2) is a branched (star) block copolymer having the above linear block copolymer (a1) as a basic structure. Among these, from the viewpoint of the physical properties of the composition, an ABA type triblock copolymer, an AB type diblock copolymer, or a mixture thereof is preferable.

The number average molecular weight of the block copolymer (a) is not particularly limited, but preferably 30,000 to 5,000.
00, more preferably 50,000 to 400,000. When the number average molecular weight is small, the viscosity is low, and when the number average molecular weight is large, the viscosity tends to be high, and therefore the viscosity is set according to the required processing characteristics.

The weight average molecular weight of the block copolymer measured by gel permeation chromatography (M
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is not particularly limited, but is preferably 1.8 or less, more preferably 1.5 or less. When Mw / Mn exceeds 1.8, the uniformity of the block copolymer tends to decrease.

The composition ratio of the methacrylic polymer block (A) and the acrylic polymer block (B) of the block copolymer (a) is such that the block (A) is 5 to 90% by weight,
Block (B) is 95 to 10% by weight. From the viewpoint of maintaining the shape during molding and elasticity as an elastomer,
A more preferable range of the composition ratio is 10 to 80% by weight of (A), 90 to 20% by weight of (B), and more preferably 20 to 50% by weight of (A) and 80 to 10% by weight of (B). It is 50% by weight. If the proportion of (A) is less than 5% by weight, the shape tends to be difficult to retain during molding, and if the proportion of (B) is less than 10% by weight, the elasticity as an elastomer tends to decrease.

From the viewpoint of hardness of the elastomer composition,
When the proportion of (A) is small, the hardness becomes low, and (A)
When the ratio is large, the hardness tends to be high, and therefore the hardness can be set according to the required hardness of the elastomer composition. From the viewpoint of processing, when the proportion of (A) is low, the viscosity tends to be low, and when the proportion of (A) is high, the viscosity tends to be high, so that it should be set according to the required processing characteristics. it can.

The methacrylic polymer block (A) is
It is a block formed by polymerizing a monomer whose main component is methacrylic acid ester,
It is preferably composed of 100% by weight and 0 to 50% by weight of a vinyl-based monomer copolymerizable therewith.

Examples of the methacrylic acid ester constituting (A) include methacrylic acid, methyl methacrylate, ethyl methacrylate, and methacrylic acid-n-.
Propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate,
-N-hexyl methacrylate, cyclohexyl methacrylate, -n-heptyl methacrylate, -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-hydroxymethacrylate. Ethyl, methacrylic acid-
2-hydroxypropyl, stearyl methacrylate,
Glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl)
Dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylic acid, 2-trifluoromethylethyl methacrylic acid, 2-perfluoroethylethyl methacrylic acid,
Methacrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-per Fluoromethyl-2-perfluoroethylmethyl, methacrylic acid-2-perfluorohexylethyl, methacrylic acid-2-perfluorodecylethyl,
Examples thereof include 2-perfluorohexadecylethyl methacrylate.

These may be used alone or in combination of two or more. Among these, methyl methacrylate is preferable in terms of processability, cost and availability. Further, the glass transition point can be increased by copolymerizing isobornyl methacrylate and cyclohexyl methacrylate.

Examples of the vinyl monomer copolymerizable with the methacrylic acid ester constituting (A) include acrylic acid esters, aromatic alkenyl compounds, conjugated diene compounds, halogen-containing unsaturated compounds, silicon-containing compounds. Examples thereof include unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds and maleimide compounds.

As the acrylic ester, for example,
Methyl acrylate, ethyl acrylate, acrylic acid-n
-Propyl, isopropyl acrylate, acrylic acid-n
-Butyl, isobutyl acrylate, -t-butyl acrylate, -n-pentyl acrylate, -n-hexyl acrylate, cyclohexyl acrylate, acrylate -n-
Heptyl, acrylic acid-n-octyl, acrylic acid-2
-Ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, acrylic acid- 2-hydroxyethyl, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-acrylic acid
Aminoethyl, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl acrylate Ethyl, acrylic acid 2-
Perfluoroethyl, perfluoromethyl acrylate,
Diperfluoromethyl methyl acrylate, acrylic acid-
2-perfluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, acrylic acid-
2-perfluorohexadecylethyl etc. can be mentioned.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

As the conjugated diene compound, for example,
Examples thereof include butadiene and isoprene.

Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like.

Examples of the silicon-containing unsaturated compound include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of unsaturated dicarboxylic acid compounds include maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, and the like.

Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like.

Examples of the maleimide compound include:
Maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like can be mentioned.

These can be used alone or in combination of two or more. These vinyl monomers are
From the viewpoint of adjusting the glass transition temperature required for the block (A), compatibility with the acrylic polymer block (B), and the like, preferable ones can be selected.

The glass transition temperature of (A) is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher from the viewpoint of thermal deformation of the elastomer composition. If the glass transition temperature of (A) is lower than the temperature of the environment in which the elastomer composition is used, the cohesive force tends to be low, so that thermal deformation tends to occur easily.

The acrylic polymer block (B) is a block obtained by polymerizing a monomer containing an acrylic ester as a main component, and the acrylic ester is 50 to 100% by weight.
And 0 to 50% by weight of a vinyl monomer copolymerizable therewith.

Examples of the acrylate ester constituting (B) include methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate,
Acrylic acid-t-butyl, acrylic acid-n-pentyl,
Acrylic acid-n-hexyl, acrylic acid cyclohexyl, acrylic acid-n-heptyl, acrylic acid-n-octyl, acrylic acid-2-ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, acrylic acid Toluyl, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-Aminoethyl acrylate, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perful acrylate Roechiru -2 perfluorobutyl ethyl, 2 perfluoroethyl acrylate, perfluoromethyl, acrylate di perfluoro methyl, acrylate-2-perfluoromethyl -
Examples thereof include 2-perfluoroethylmethyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, and 2-perfluorohexadecylethyl acrylate.

These may be used alone or in combination of two or more thereof. Among these, -n-butyl acrylate is preferable in terms of the balance of rubber elasticity, low temperature characteristics and cost. If further low temperature characteristics are required, 2-ethylhexyl acrylate may be copolymerized. Ethyl acrylate is preferred when oil resistance is required. When a balance between oil resistance and low temperature properties is required, a combination of ethyl acrylate, -n-butyl acrylate and 2-methoxyethyl acrylate is preferable.

Examples of the vinyl monomer copolymerizable with the acrylic ester which constitutes the block (B) include, for example, methacrylic ester, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, halogen-containing compounds. Examples thereof include unsaturated compounds, silicon-containing unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds and maleimide compounds.

Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methacrylic acid. Acid-t-butyl, methacrylic acid-n-pentyl, methacrylic acid-n-hexyl, cyclohexyl methacrylic acid, n-heptyl methacrylic acid, -n-octyl methacrylic acid, 2-ethylhexyl methacrylic acid , Nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, -3 methacrylate -Methoxybutyl, 2-hydroxyethyl acrylate, 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-perfluoroethylethyl methacrylate, methacrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-perfluoro Chill 2-perfluoroethyl methyl, it can be mentioned methacrylic acid-2-perfluorohexylethyl, methacrylic acid-2-perfluorodecyl ethyl, meth-2-perfluoroalkyl-hexadecyl acrylate and the like.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

As the conjugated diene compound, for example,
Examples thereof include butadiene and isoprene.

Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like.

Examples of the silicon-containing unsaturated compound include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of unsaturated dicarboxylic acid compounds include maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, and the like.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like.

Examples of the maleimide compound include:
Maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like can be mentioned.

These may be used alone or in combination of two or more. These vinyl monomers are
From the viewpoint of the balance of the glass transition temperature and oil resistance required for the block (B), the compatibility with the methacrylic polymer block (A), and the like, preferable ones can be selected.

The glass transition temperature of (B) is preferably 25 ° C. or lower from the viewpoint of rubber elasticity of the elastomer composition.
It is more preferably 0 ° C or lower, and even more preferably -20 ° C or lower. If the glass transition temperature of (B) is higher than the temperature of the environment in which the elastomer composition is used, rubber elasticity is difficult to develop, which is disadvantageous.

<Method for Producing Block Copolymer (a)> The method for producing the block copolymer (a) is not particularly limited, but controlled polymerization is preferably used. Controlled polymerization includes living anionic polymerization, radical polymerization using a chain transfer agent, and living radical polymerization recently developed. Living radical polymerization is preferable from the viewpoint of controlling the molecular weight and structure of the block copolymer and copolymerizing a monomer having a crosslinkable functional group.

Living radical polymerization is radical polymerization in which the activity at the polymerization end is maintained without loss. Living polymerization, in a narrow sense, refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the activated one is in an equilibrium state. Be done. The definition in the present invention is also the latter. Living radical polymerization has been actively studied in various groups in recent years.

Examples thereof include those using a chain transfer agent such as polysulfide, cobalt porphyrin complex (Journal of American Chemical Society (J. Am. C
hem.Soc.), 1994, 116, 7943) and nitroxide compounds and other radical scavengers (Macromolecules, 1994, 27, 7228), transition metal complexes initiated with organic halides, etc. Atom Transfer Radical Polymerization
on): ATRP) and the like. In the present invention, which of these methods is used is not particularly limited, but atom transfer radical polymerization is preferable from the viewpoint of easy control.

Atom transfer radical polymerization is carried out by using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having an element of Group 8, 9, 10 or 11 of the periodic table as a central metal as a catalyst. To be done. For example,
Matyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem.
Soc.), 1995, 117, 5614, Macromolecules (Ma
cromolecules), 1995, 28, 7901, Science (Scienc
e), 1996, 272, 866, or Sawamoto
Et al., Macromolecules, 1995,
28, 1721.

According to these methods, the polymerization rate is generally very high, and although the termination reaction such as the coupling reaction between radicals is likely to occur, the polymerization proceeds in a living manner and has a narrow molecular weight distribution Mw / Mn = 1.
A polymer of about 1 to 1.5 is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In the atom transfer radical polymerization method, as the organic halide or the sulfonyl halide compound used as an initiator, a monofunctional, difunctional or polyfunctional compound can be used. These can be used properly according to the purpose. Monofunctional compounds are preferred for the production of diblock copolymers. A-B-A
It is preferable to use a bifunctional compound in the case of producing a triblock copolymer of the type and a BAB type triblock copolymer. In the case of producing a branched block copolymer, it is preferable to use a polyfunctional compound.

Examples of monofunctional compounds include compounds represented by the following chemical formulas. _{C 6 H 5 -CH 2 X C} 6 H 5 -CHX-CH 3 C 6 H 5 -C (CH3) 2 X R 1 -CHX-COOR 2 R 1 -C (CH 3) X-COOR 2 R 1 - ^{CHX-CO-R 2 R 1} -C (CH 3) X-CO-R 2 R 1 -C 6 H 4 -SO 2 X in formula, C ₆ H ₄ represents a phenylene group. The phenylene group may be ortho-substituted, meta-substituted or para-substituted. R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 2 carbon atoms.
Represents an aralkyl group of 0. X represents chlorine, bromine or iodine. R ² represents a monovalent organic group having 1 to 20 carbon atoms.

Examples of the bifunctional compound include compounds represented by the following chemical formulas. _{X-CH 2 -C 6 H 4} -CH 2 -X X-CH (CH 3) -C 6 H 4 -CH (CH 3) -X X-C (CH 3) 2 -C 6 H 4 -C ( _{CH 3) 2 -X X-CH} (COOR 3) - (CH 2) n -CH (COO
^{R 3) -X X-C (} CH 3) (COOR 3) - (CH 2) n -C (CH
^{_{3) (COOR 3) -X X}} -CH (COR 3) - (CH 2) n -CH (COR 3) -
_{X X-C (CH 3)} (COR 3) - (CH 2) n -C (C
^{_{H 3) (COR 3) -X}} X-CH 2 -CO-CH 2 -X X-CH (CH 3) -CO-CH (CH 3) -X X-C (CH 3) 2 -CO-C ( _{CH 3) 2 -X X-CH} (C 6 H 5) -CO-CH (C 6 H 5) -X X-CH 2 -COO- (CH 2) n -OCO-CH 2 -X X-CH ( _{CH 3) -COO- (CH 2)} n -OCO-C
_{H (CH 3) -X X-} C (CH 3) 2 -COO- (CH 2) n -OCO-C
_{(CH 3) 2 -X X-} CH 2 -CO-CO-CH 2 -X X-CH (CH 3) -CO-CO-CH (CH 3) -X X-C (CH 3) 2 -CO- _{CO-C (CH 3) 2} -X X-CH 2 -COO-C 6 H 4 -OCO-CH 2 -X X-CH (CH 3) -COO-C 6 H 4 -OCO-CH
_{(CH 3) -X X-C} (CH 3) 2 -COO-C 6 H 4 -OCO-C (CH
₃ ) ₂₋ X X—SO ₂ —C ₆ H ₄ —SO ₂ —X In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms and 6 to 6 carbon atoms.
20 represents an aryl group or a C7-20 aralkyl group. C ₆ H ₄ represents a phenylene group. The phenylene group may be ortho-substituted, meta-substituted or para-substituted. C ₆ H ₅ represents a phenyl group. n represents an integer of 0 to 20. X represents chlorine, bromine or iodine.

Examples of polyfunctional compounds include compounds represented by the following chemical formulas. _{C 6 H 3 (CH 2 -X} ) 3 C 6 H 3 (CH (CH 3) -X) 3 C 6 H 3 (C (CH 3) 2 -X) 3 C 6 H 3 (OCO-CH 2 - _{X) 3 C 6 H 3 (} OCO-CH (CH 3) -X) 3 C 6 H 3 (OCO-C (CH 3) in _{2 -X) 3 C 6 H 3} (SO 2 -X) 3 formula, C ₆ H ₃ represents a trisubstituted phenyl group. In the tri-substituted phenyl group, the position of the substituent may be any of 1-position to 6-position. X represents chlorine, bromine or iodine.

The organic halide or sulfonyl halide compound which can be used as these initiators has a carbon to which a halogen is bonded bonded to a carbonyl group, a phenyl group or the like, and the carbon-halogen bond is activated. Polymerization begins. The amount of the initiator used may be determined from the ratio with the monomer in accordance with the required molecular weight of the block copolymer. That is, the molecular weight of the block copolymer can be controlled depending on the number of molecules of the monomer used per one molecule of the initiator.

The transition metal complex used as a catalyst for the atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zerovalent copper, divalent ruthenium, divalent iron and divalent nickel. The complex of can be mentioned. Among these, a copper complex is preferable in terms of cost and reaction control.

Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide,
Examples thereof include cuprous oxide and cuprous perchlorate. When using a copper compound, in order to enhance the catalytic activity,
Add 2,2'-bipyridyl and its derivative, 1,10-phenanthroline and its derivative, polyamine such as tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine, hexamethyl (2-aminoethyl) amine as a ligand. You can also A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst.

When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator. Further, divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistriphenylphosphine complex (NiCl
₂ (PPh ₃ ) ₂ ) and a bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ )
Preferred as a catalyst. The amounts of the catalyst, ligand and activator used are not particularly limited, but can be appropriately determined based on the relationship between the amounts of the initiator, monomer and solvent used and the required reaction rate.

The atom transfer radical polymerization can be carried out without solvent (bulk polymerization) or in various solvents. Examples of the solvent include hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, alcohol solvents,
Examples thereof include nitrile solvents, ester solvents, carbonate solvents and the like.

Examples of the hydrocarbon solvent include benzene and toluene. Examples of ether solvents include diethyl ether and tetrahydrofuran. As the halogenated hydrocarbon solvent,
Examples thereof include methylene chloride and chloroform. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.

As the alcohol solvent, methanol,
Examples thereof include ethanol, propanol, isopropanol, n-butanol, t-butanol and the like.
Examples of the nitrile solvent include acetonitrile, propionitrile, benzonitrile and the like. Examples of ester solvents include ethyl acetate and butyl acetate. Examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate. These may be used alone or in admixture of two or more.

When the reaction is carried out without a solvent, bulk polymerization results.
On the other hand, when a solvent is used, the amount used can be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency, that is, the reaction rate.

The atom transfer radical polymerization is preferably room temperature to 200 ° C., more preferably 50 to 150 ° C.
It can be done in the range of.

As the method for producing the block copolymer by the atom transfer radical polymerization, a method of sequentially adding monomers, a method of polymerizing the next block by using a previously synthesized polymer as a polymer initiator, separately Examples of the method include a method in which a polymer polymerized in the above is bonded by a reaction. These methods can be used properly according to the purpose. From the viewpoint of simplicity of the production process, the method of sequentially adding the monomers is preferable.

The reaction liquid obtained by the polymerization contains a mixture of the polymer and the metal complex, and the metal complex can be removed by adding an organic acid, for example. Subsequently, the impurities are removed by an adsorption treatment to obtain an acrylic block copolymer resin solution containing the acrylic block copolymer.

The organic acid that can be used is not particularly limited, but is preferably an organic substance containing a carboxylic acid group or a sulfonic acid group.

The organic carboxylic acid which can be used, that is, the organic substance containing a carboxylic acid group, is not particularly limited, but for example, formic acid, acetic acid, propionic acid,
Butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, 4
-Saturated aliphatic monofunctional carboxylic acids such as methylvaleric acid, heptanoic acid, undecanoic acid, and icosanoic acid, and saturated aliphatic monofunctional carboxylic acids containing halogens such as monochloroacetic acid, dichloroacetic acid and trichloroacetic acid. , Acetoxysuccinic acid, acetoacetic acid, ethoxyacetic acid, 4-oxovaleric acid, glycolic acid, glycidic acid, glyceric acid, 2
-Saturated aliphatic monofunctional carboxylic acid containing a substituent such as oxobutyric acid and glutaric acid, propiolic acid, acrylic acid, crotonic acid, 4-pentenoic acid, allylmalonic acid,
Aliphatic unsaturated monofunctional carboxylic acids such as itaconic acid and oxaloacetic acid, benzoic acid, acetylbenzoic acid, acetylsalicylic acid, atropic acid, anisic acid, cinnamic acid, salicylic acid and other aromatic rings or unsaturated bond α Monofunctional carboxylic acid in which carbon of carboxylic acid is bonded to position, oxalic acid, malonic acid, succinic acid, adipic acid, 3-oxoglutaric acid, azelaic acid, ethylmalonic acid, 4-oxoheptane diacid, 3-oxoglutaric acid Saturated aliphatic difunctional carboxylic acid such as acid, unsaturated aliphatic difunctional carboxylic acid such as acetylenedicarboxylic acid, aromatic difunctional carboxylic acid such as isophthalic acid, anicot acid, isocamphoronic acid Examples thereof include tricarboxylic acids, aminobutyric acid, amino acids such as alanine, and the like. These two
You may use together the above. Among these, oxalic acid is preferable because it is easily dispersed in an organic solvent, the properties of the product of the reaction between the acid and the metal complex, and the availability.

The organic sulfonic acid that can be used, that is, the organic substance containing a sulfonic acid group is not particularly limited, but for example, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, etc. Saturated aliphatic monofunctional sulfonic acid, 1,2-ethanesulfonic acid, 1,3-propanesulfonic acid, 1,4-butanesulfonic acid, 1,5-pentanesulfonic acid, etc. Functional sulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m
-Aromatic monofunctional sulfonic acids such as toluenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, naphthylaminesulfonic acid, and aminophenolsulfonic acid. Two or more of these may be used in combination. Among these, benzenesulfonic acid or a derivative thereof is preferable because of its ease of dispersion in an organic solvent, properties of the product of the reaction between an acid and a metal complex, and availability, among which p-toluene is preferred. Sulfonic acid is more preferred.

In selecting an organic acid that can be preferably used,
The conditions will be described in detail. First, the organic acid forms a metal salt with the copper-centered metal complex to be removed. Second, the metal salt formed can be separated from the polymer solution or melt. Third, the organic acid does not have a fatal effect on the polymer. The organic acid itself may be a liquid or a solid, but it does not matter if it satisfies the above conditions.

These conditions will be described in more detail. First, in order for the organic acid to form the metal complex centering on the copper to be removed and the metal salt, the organic acid needs to have an acidity above a certain level. When the dissociation constant of an organic compound in an aqueous solution is used as an index of acidity, the logarithmic value (pKa) of the reciprocal of the acid dissociation constant of the first dissociation stage is preferably 6.0 or less, and 5.5 or less. Is more preferable, and 5.0 or less is further preferable. For this dissociation constant, see, for example, the Handbook of Chemistry
Reference can be made to Table 10.11 on page II-339 of the Basic Edition, edited by The Chemical Society of Japan, 1984). For example,
The pKa of acetic acid is 4.56 and the pKa of benzoic acid is 4.2.
0, the pKa of oxalic acid is 1.04 (1st stage), 3.82
(Second stage). Benzenesulfonic acid, p-
Although the value of toluenesulfonic acid is not described, all are soluble in water, and the pKa of benzenesulfonic acid is-.
2.7 (organic compound dictionary page 942, edited by The Society of Synthetic Organic Chemistry, 1985), and p-toluenesulfonic acid is a strong acid similar to hydrochloric acid and sulfuric acid (organic compound dictionary page 645, Organic Synthetic Chemistry Association,
1985) Its pKa can be at most about 2. In the case of an organic acid which is insoluble in water, its derivative can be analogized from the water-soluble organic acid and its strength relationship with other acids.

Secondly, in order that the produced metal salt can be separated from the solution or melt of the polymer, the solubility of the produced metal salt in the solvent is preferably small, and it is more difficult to dissolve. Most preferably, it is insoluble. Although it is difficult to predict the solubility of the metal salt in advance, the solubility of the metal complex in the solvent and the solubility of the organic acid used in the solvent can be referred to.

Thirdly, in order that the organic acid does not have a fatal effect on the polymer, the main chain and side chains of the polymer have a structure which is not decomposed by the acid, and the polymer reacts with the acid. It is preferably free of functional groups. If the preferred case does not apply, it is necessary to adjust the amount and concentration of the organic acid to be reacted, the reaction temperature, the reaction time, the solvent and the like. However, it excludes the case where the functional group of the polymer is converted into a desired functional group by reacting with an acid, or the case where the functional group can be returned to its original state by a chemical means even when reacted with an acid.

Assuming that the metal complex is partially decomposed by the action of the organic acid, it is preferable that the liberated ligand can also be removed. That is, it is preferable that the liberated ligand is insoluble in the solvent, or the reaction between the ligand and the organic acid produces an organic salt insoluble in the solvent. Although it is difficult to predict the solubility of this salt in advance, it is possible to refer to the solubility of the ligand in the solvent and the solubility of the organic acid used in the solvent.

There is no particular restriction as to whether the organic acid is used as it is, as an aqueous solution or as a solution of an organic solvent, but any one may be used as long as the above conditions are satisfied.

The metal complex to be removed in the present invention is not particularly limited, but it may be a metal complex formed by the reaction of a copper halide and a nitrogen-containing ligand. Further, the nitrogen-containing ligand mentioned here may be a chelate ligand having two or more coordination sites. This is because the metal complex preferably used as the catalyst for the atom transfer radical polymerization is a metal complex having monovalent copper as a central metal, and examples of the monovalent copper compound include cuprous chloride and first bromide. Examples thereof include copper halides such as copper, and further nitrogen-containing ligands such as 2,2′-bipyridyl and its derivatives (eg, 4,4′-dinolyl-2, to enhance catalytic activity).
2'-bipyridyl, 4,4'-di (5-nolyl) -2,
2,2′-bipyridyl compounds such as 2′-bipyridyl, etc., 1,10-phenanthroline, and derivatives thereof (eg 4,7-dinolyl-1,10-phenanthroline, 5,6-dinolyl-1,10-phenanthroline) Etc.), polymethylamine such as tetramethyldiethylenetriamine (TMEDA), pentamethyldiethylenetriamine, hexamethyl (2-aminoethyl) amine, and the like, and chelate ligands having two or more coordination sites. This is because it may be added. Of course, the metal complex that can be removed by the present invention is not limited to the atom transfer radical polymerization catalyst, and may be a metal complex having no catalytic function.

The amount of the organic acid used is preferably 1 mol or more of the organic acid based on 1 mol of copper contained in the metal complex containing copper. The amount of the organic acid is preferably 0.5 mol, and more preferably 1.0 mol or more per 1 mol of the ligand coordination site. Although the reaction time is shortened if the amount of the organic acid is increased, it is desirable to suppress the reaction time to a necessary amount considering the reaction time, from the viewpoint of cost and the necessity of removing the surplus organic acid.

The reaction of adding an organic acid of the present invention can be carried out without solvent (polymer melt) or in various solvents.

Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; methylene chloride,
Halogenated hydrocarbon solvents such as chloroform; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol; acetonitrile, propionitrile, Examples thereof include nitrile solvents such as benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more. When a solvent is used, the amount to be used may be appropriately determined from the relationship between the viscosity of the entire system, the required stirring efficiency, and the reaction rate. The reaction can be carried out in the range of 0 ° C to 200 ° C, preferably room temperature to 150 ° C.

The method of removing the metal salt produced as a result of the reaction is not particularly limited, but known methods such as filtration using a filter press, decantation and centrifugal sedimentation can be used if necessary. Further, if necessary, it may be possible to proceed to the next neutralization step without removing the metal salt. However, even in this case, the metal salt must be removed after the completion of the neutralization step. If the metal salt remains in the solid acrylic block copolymer, the polymer may deteriorate during the removal of volatile components by a reduced pressure extruder, or the physical properties of the molded product may be adversely affected.

After removing the metal complex by adding an organic acid to a mixture containing a polymer and a metal complex having copper as a central metal, the system sometimes approaches the acidic side, which is a problem. There are cases. Therefore, a step of neutralizing the system may be required. As a method for neutralizing the system, a known method can be used, and there is no particular limitation, and examples thereof include a method using a basic solid. Examples of basic solids include basic activated alumina, basic adsorbents, solid inorganic acids, anion exchange resins, and cellulose anion exchangers. Examples of the basic adsorbent include Kyoward 500SH (manufactured by Kyowa Kagaku) and the like. As the solid inorganic acid, Na
₂ O, K ₂ O, MgO, CaO and the like can be mentioned. Examples of the anion exchange resin include a styrene-based strongly basic anion exchange resin, a styrene-based weakly basic anion exchange resin, and an acrylic-based weakly basic anion exchange resin.

The method of removing the adsorbent added during the neutralization step is not particularly limited, but known methods such as filtration using a filter press, decantation, and centrifugal sedimentation can be used as necessary.

The solution type acrylic block copolymer in the present invention is not particularly limited as long as it contains a solution in which the acrylic block copolymer is dissolved in an organic solvent.
In addition to the polymer solution synthesized by the known solution polymerization method or the above various controlled polymerization methods, a solid polymer may be partially precipitated during the polymerization, or a solution in which the polymerization is completed The polymer may be precipitated by adding a precipitant. Among them, those obtained by treating the reaction solution after polymerization are preferable, and in this case, the organic solvent in which the acrylic block copolymer is dissolved is the reaction solvent used in the polymerization reaction and the polymerization reaction. Of unreacted residual monomers in.

<Low Pressure Extruder> When the solid polymer is taken out from the acrylic block copolymer solution in the present invention to remove volatile components, the low pressure extruder used in the present invention is an evaporator having a low pressure extrusion mechanism. Yes, preferably a heating extruder having a twin-screw section, and it is sufficient to use one that supplies a heating medium to the screw section, and various specific methods without particular limitation in an industrially feasible range. Can be used.

In the case of a normal twin-screw extruder, the heating medium is not supplied to the twin-screw part, the barrel temperature is controlled to evaporate and concentrate in the vent part, and the screw is composed of the feeding part and the kneading part. ing. As the concentration proceeds, the resin is sent to the die while being degassed in the molten state in the kneading section,
Extruded and pelletized. Therefore, in this case, since the resin stays in the molten state for a long time, the resin deteriorates. Further, even when only the thin film evaporator is used, the evaporation operation is similarly carried out in a molten state, so that the thermal deterioration of the resin also occurs in this case. On the other hand, in the method of the present invention, since the heating medium is supplied to the twin screw portion, the evaporation efficiency is high, and the temperature is relatively low, for example, 150 to
The thermal deterioration of the resin can be suppressed by the fact that the evaporation operation can be performed at 240 ° C., the evaporation operation can be performed in a state where the molten state is not reached in the evaporation device, and the like.

The reduced-pressure extruder in the present invention may be either a single-screw extruder or a twin-screw extruder, but the twin-screw extrusion is advantageous in that the sample solution can be smoothly introduced and the devolatilization ability is excellent. A machine is preferred.

For example, as an evaporator capable of supplying a heating medium to such a twin-screw part, there are an SC processor manufactured by Kurimoto Iron Works and an SCR manufactured by Mitsubishi Heavy Industries, which have both self-cleaning property and degassing ability. It is not particularly limited. These devices may be used alone or in combination.

The ratio (L / D) of the length (L) to the shaft diameter (D) of the evaporator having such a function is not particularly limited, but is preferably 5 to 20.
When L / D is less than 5, it is not desirable because sufficient evaporation ability cannot be obtained. If the L / D exceeds 20, the device becomes large in scale, which is not preferable.

Further, in order to prevent resin accumulation in the upper space existing inside the evaporator, it is desirable to attach a filling component to the upper space.

As the material of these evaporators, stainless steel, iron or the like can be used, or a corrosion resistant material can be used.

As the heating medium supplied to the screw portion, steam such as heating oil or steam can be generally applied, but it is preferable to use the heating oil in consideration of stress deformation due to heating of the screw portion. Examples of the heat transfer oil include aromatic hydrocarbon series, aliphatic hydrocarbon series, diphenyl series, dichlorobenzene series, alkylbenzene series, alkylnaphthalene series, and the like. For example, Nippon Steel Chemical's Therm S 300, Therm S 600, Therm S 700 , Therms 800, Therms 900 and Soken Chemical SK-O
IL series etc. can be used conveniently.

The temperature condition of the screw part in the evaporator is preferably 150 to 240 ° C. 240 ° C
Higher levels lead to thermal decomposition of the polymer backbone, significantly reducing the quality of the resin. On the other hand, when the temperature is lower than 150 ° C, the resin viscosity increases and the evaporation efficiency decreases. It is preferable that not only the screw portion but also the jacket portion satisfy the same temperature condition.

The degree of reduced pressure applicable in the present invention is preferably 10 to 300 Torr. The degree of pressure reduction here is defined by the display of a vacuum gauge attached near the degassing port of the pressure reducing extruder. The lower the degree of pressure reduction of the low pressure extruder is, the more the amount of residual solvent in the resin after evaporation and separation can be reduced, which is preferable. When the degree of pressure reduction is 300 Torr or more, the devolatilization time becomes long and the quality of the resin deteriorates, which is not preferable. In addition, if the pressure is less than 10 Torr, a large-scale pressure reducing device is required, which is not preferable. Furthermore, if the degree of pressure reduction is extremely increased when the solvent content of the resin solution is high, the solvent vapor from the resin solution flashes near the supply port, and the resin entrains with the solvent vapor in the degassing port due to the splash of resin. It is not preferable because it is attached or adheres.

The residual solvent amount in the resin is 10,000
It is desirable that the content is ppm or less. Residual solvent amount is 100
If the amount exceeds 00 ppm, the working environment is deteriorated due to the problem of the odor of the solvent and the load on the environment is applied, which is not desirable.

The form of the resin discharged from the reduced pressure extruder is not particularly limited, but it is preferable that the resin is discharged in a strand form in order to improve the handling of the resin.
Further, by connecting a discharge machine, preferably a discharge machine having a single-screw or twin-screw extrusion function, to the reduced pressure extruder, a strand-shaped resin can be obtained from the discharge machine outlet. The resin discharged in the form of a strand is not particularly limited as long as it can be used as a pellet in general, but it is preferable to discharge it in a columnar shape having an inner diameter of 1 to 20 mm. The obtained strand is generally cut into a cylindrical or spherical / hemispherical pellet having an arbitrary length by using a cutter or the like to be manufactured as a product. As a cutting method, in addition to the strand cutting method of pelletizing the strands as described above,
There are a hot cut method and an underwater cut method, in which the cutting is performed in the vicinity of the outlet of the ejector, but the cutting method is not particularly limited. Further, the resin can be pulverized into a powder product by using a reduced pressure extruder in combination with a pulverizer or a crusher.

The presence of an antioxidant during the devolatilization operation from the resin solution can further suppress the quality deterioration due to the thermal decomposition of the polymer. These antioxidants may be dissolved in the resin solution stage. The above antioxidant preferably has a function as a radical chain inhibitor. Such a substance is not particularly limited, and examples thereof include a phenol-based antioxidant and an amine-based antioxidant.

Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,6-
Di-t-butylphenol, 2,4-dimethyl-6-t
-Butylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,
4'thiobis (3-methyl-6-t-butylphenol), tetrakis [methylene-3- (3,5-di-t-)
Butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl) -5-methyl-4
-Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4
-Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate] and the like.

Examples of amine antioxidants include phenyl-β-naphthylamine, α-naphthylamine,
N, N'-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N'-diphenyl-p-phenylenediamine and the like can be mentioned. The addition amount of the antioxidant is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the acrylic block copolymer.
If it is less than 0.001 part by weight, the effect of the antioxidant may be reduced, and if it exceeds 10 parts by weight, the product quality may be adversely affected.

The solid acrylic block copolymer obtained in the present invention can be used as a thermoplastic elastomer composition by appropriately mixing known fillers, plasticizers, antioxidants and the like.

[0101]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

The molecular weights shown in this Example are the GPC values shown below.
The measurement was performed with an analyzer, and the molecular weight in terms of polystyrene was determined using chloroform as the mobile phase. As a system, using a Waters GPC system,
Shodex K-80 manufactured by Showa Denko K.K.
4 (polystyrene gel) was used.

The organic solvent content in the resin shown in this example was measured by the following analyzer. Equipment used: Shimadzu Corporation gas chromatography GC-14B Separation column: J & W SCIENTIFIC INC
Manufactured by Capillary Column Supelcowax-10,
0.35mmφ x 30m Sample preparation: Resin 0.5g, Diluting solvent Methylene chloride 7
g, standard sample butyl acetate about 0.005 g (Production Example 1) Synthesis of MMA-BA-MMA type block copolymer (composition ratio MMA / BA = 6/4) 113.70 g of cuprous bromide in 50 L reactor Was charged, and the inside of the reactor was replaced with nitrogen. Acetonitrile 376.45 g
Then, a solution in which 1341.0 g of butyl acrylate was mixed in advance was charged while the pressure inside the reactor was reduced to 6
It heated up at 5 degreeC and stirred for 30 minutes. Then, a solution of 57.08 g of diethyl 2,5-dibromoadipate dissolved in 3129.0 g of butyl acrylate and 88.20 g of butyl acetate, and 800 g of acetonitrile were charged, and the mixture was further stirred for 30 minutes while raising the temperature to 85 ° C. went.
Add 17 ml of pentamethyldiethylenetriamine,
Polymerization of butyl acrylate, which is the first block, was started. When the conversion rate reached 95%, toluene 11
815 g, cuprous chloride 78.47 g, and methyl methacrylate 13332 g were charged, and 17 ml of pentamethyldiethylenetriamine was added to start polymerization of methyl methacrylate as the second block. When the conversion reached 51%, 11815 g of toluene was added to dilute the reaction solution and the reactor was cooled to terminate the polymerization. GPC analysis of the obtained block copolymer revealed that
Number average molecular weight Mn is 108100, molecular weight distribution Mw / M
n was 1.60. Moreover, the compositional analysis by NMR revealed that MMA / BA was 64/36 (% by weight). Toluene was added to the obtained block copolymer solution to adjust the polymer concentration to 12 wt%, and 32 g of p-toluenesulfonic acid was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours. The reaction solution was sampled, and the reaction was stopped after confirming that the solution was colorless and transparent. Then, the solution was discharged, and the solid content was removed using a separation plate type centrifugal settler. 50L of this block copolymer solution
On the other hand, 150 g of Kyoward 500SH was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours. The reaction solution was sampled, and the reaction was stopped after confirming that the solution was neutral. After that, the solution was discharged and solid-liquid separation was performed to remove the adsorbent.

(Production Example 2) Synthesis of MMA-BA-MMA type block copolymer (composition ratio MMA / BA = 3/7) 112.56 g of cuprous bromide was charged into a 50 L reactor, and nitrogen was fed in the reactor. Replaced. Acetonitrile 627.44 g
And 1072.8 g of butyl acrylate were mixed in advance, and the solution was charged in a state where the inside of the reactor was under reduced pressure.
It heated up at 5 degreeC and stirred for 30 minutes. Then, a solution of 56.50 g of diethyl 2,5-dibromoadipate dissolved in 6973.2 g of butyl acrylate and 158.76 g of butyl acetate, and 784.30 g of acetonitrile
Was charged, and the mixture was stirred for 30 minutes while raising the temperature to 85 ° C. 16 ml of pentamethyldiethylenetriamine was added to initiate the polymerization of butyl acrylate as the first block. When the conversion reached 95%, 14228.8 g of toluene, 77.68 g of cuprous chloride and 5182.5 g of methyl methacrylate were charged, and 16 ml of pentamethyldiethylenetriamine was added to polymerize methyl methacrylate to be the second block. Started. Conversion rate is 56
When the amount reached%, 8660 g of toluene was added to dilute the reaction solution and the reactor was cooled to terminate the polymerization. GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn107,000 and the molecular weight distribution Mw / Mn were 1.46. Moreover, the compositional analysis by NMR revealed that MMA / BA was 29/71 (% by weight). Toluene was added to the obtained block copolymer solution so that the polymer concentration was 14.6 wt%, and 32 g of p-toluenesulfonic acid was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours. The reaction solution was sampled, and the reaction was stopped after confirming that the solution was colorless and transparent. Then, the solution was discharged, and the solid content was removed using a separation plate type centrifugal settler. To 50 L of this block copolymer solution, 150 g of KYOWARD 500SH was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours.
The reaction solution was sampled, and the reaction was stopped after confirming that the solution was neutral. Then dispense the solution,
Solid-liquid separation was performed to remove the adsorbent.

Example 1 Extraction of MMA-BA-MMA type block copolymer (composition ratio MMA / BA = 6/4) A device diagram used in Example 1 is shown in FIG. As the evaporator, SCP100 (L / D = 9) manufactured by Kurimoto Iron Works was used. The temperature of the jacket part and the twin screw part of the evaporator 3 is set to 20
At 0 ° C., the degree of vacuum was set to 70 Torr, and the resin solution obtained in Production Example 1 was pumped from the pump 2 at 18 kg / hour to the evaporator 3
Supplied to. Moreover, the temperature of the discharger connected to the evaporator 3 was set to 180 ° C., and the resin was continuously discharged as a strand. The strand was cooled with a water bath and then formed into pellets with a cutter. The residual solvent content in the resin is shown in Table 1.

[0106]

[Table 1] (Example 2) The same operation as in Example 1 was performed except that the supply condition to the evaporator 3 was 24 kg / hour. The obtained results are also shown in Table 1.

Comparative Example 1 The resin solution obtained in Production Example 1 was used, and a universal mixing stirrer 25 AMV manufactured by Dalton Co., Ltd. was used.
An attempt was made to take out the block copolymer using the -rr type. Vacuum pump is a water-sealed SB-50 type (displacement 850L
/ Min), and ODC-370M as a solvent recovery device
CJ-II was used. The degree of vacuum was set to 675 Torr and the jacket temperature was set to 170 ° C. to start evaporation. The processing time is 1 hour and 45 minutes, and the solvent content is 85% to 1
It decreased to 4%. However, the polymer after the treatment remained and adhered in the apparatus, and it was very difficult to pay it out.

Example 3 Extraction of MMA-BA-MMA Type Block Copolymer (Composition Ratio MMA / BA = 3/7) The resin solution obtained in Production Example 2 was supplied to the evaporator shown in FIG. . The same operation as in Example 1 was performed except that the supply conditions to the evaporator 3 were 24 kg / hour and the degree of vacuum was 80 to 90 Torr. Table 2 shows the residual solvent content in the resin.

[0109]

[Table 2] (Example 4) The same operation as in Example 3 was performed except that the supply amount of the resin solution was 30 kg / hour. The obtained results are also shown in Table 2.

(Example 5) The supply amount of the resin solution was 36 kg.
The same operation as in Example 3 was performed except that / hour was set. The obtained results are also shown in Table 2.

(Example 6) The supply condition of the resin solution was set to 42 k.
Example 3 except that the degree of vacuum was set to 120 Torr.
The same operation was performed. The obtained results are also shown in Table 2.

(Example 7) The supply amount of the resin solution was 48 kg.
The same operation as in Example 6 was performed except that / hour was set. The obtained results are also shown in Table 2.

(Embodiment 8) Same as Embodiment 1 except that the temperature of the jacket portion and the twin screw portion of the evaporator 3 is 180 ° C., the supply condition to the evaporator 3 is 24 kg / hour, and the degree of vacuum is 100 Torr. The operation was performed. The residual solvent content in the resin is shown in Table 3.

[0114]

[Table 3] (Example 9) The same operation as in Example 8 was performed except that the supply amount of the resin solution was 36 kg / hour and the degree of vacuum was 120 Torr. The results obtained are also shown in Table 3.

(Embodiment 10) Same as Embodiment 1 except that the temperature of the jacket portion and the twin screw portion of the evaporator 3 is 220 ° C., the supply condition to the evaporator 3 is 36 kg / hour, and the degree of vacuum is 120 Torr. The operation was performed. The residual solvent content in the resin is shown in Table 4.

[0116]

[Table 4] (Example 11) The same operation as in Example 10 was performed except that the supply amount of the resin solution was 48 kg / hour and the degree of vacuum was 130 Torr. The results obtained are also shown in Table 4.

(Example 12) The supply amount of the resin solution was 60 k
Example 1 except that the degree of vacuum was set to 170 Torr.
The same operation as 0 was performed. The results obtained are also shown in Table 4.

Comparative Example 2 The same operation as in Comparative Example 1 was performed except that the resin solution obtained in Production Example 2 was used as the resin solution. It takes 1 hour and 34 minutes to process, and the solvent content is 88.
% To 45%. The polymer after the treatment remained and adhered inside the apparatus, and it was very difficult to dispense it. From the above results, Table 5 shows the results of taking out the polymer by the vacuum extruder used in the present invention and the results of taking out the polymer by other methods.

[0119]

[Table 5]

[0120]

The resin extraction method of the present invention effectively removes volatile components by supplying a resin solution containing an acrylic block copolymer to a reduced pressure extruder capable of introducing a heating medium into the screw section. Thus, it is possible to mass-produce a high-quality polymer in a short time without causing deterioration such as coloring.

[Brief description of drawings]

FIG. 1 is a schematic flow sheet for obtaining a pellet resin from a resin solution, which is equipped with a twin screw extrusion mechanism in which a heating medium is supplied to a twin screw portion used in the present invention.

[Explanation of Codes] 1: Raw material tank 2: Supply pump 3: Evaporator having a twin screw extrusion mechanism in which a heating medium is supplied to a twin screw portion 4: Ejector 5: Cooling tank 6: Cutter 7: Storage tank 8: Condenser 9: Vacuum pump 10: Recovery tank 11: Heat medium

Continued front page    F-term (reference) 4F201 AA21F AM28 AR06 AR20                       BA01 BC01 BK02 BK13 BK26                       BK36 BK40 BN39                 4J100 GA08 GA11 GB02 GB05 GB07                       GC02 GC07 GC26 GC37 GD02                       GD19

Claims (11)

[Claims] 1. A method for extracting a solid acrylic block copolymer from a solution type acrylic block copolymer, which comprises using a reduced pressure extruder for extracting the solid acrylic block copolymer. 2. The reduced pressure extruder is a twin-screw extruder.
How to take out described. 3. The block copolymer is a block copolymer comprising 5 to 90% by weight of a methacrylic polymer block (A) and 95 to 10% by weight of an acrylic polymer block (B). The removal method described in 1. 4. The methacrylic polymer block (A) is a block obtained by polymerizing a monomer containing methyl methacrylate as a main component, and the acrylic polymer block (B).
4. The block according to claim 3, wherein is a block formed by polymerizing a monomer composed of -n-butyl acrylate or a combination of -n-butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate as a main component. How to take out. 5. The extraction method according to claim 4, wherein the block copolymer is produced by controlled radical polymerization. 6. The block copolymer is an organic halide,
Alternatively, it is produced by using a sulfonyl halide compound as an initiator and a metal complex having a central metal of a group 8, 9, 10 or 11 element of the periodic table as a catalyst. How to take out. 7. The extraction method according to claim 1, wherein the ratio (L / D) of the length (L) to the shaft diameter (D) of the reduced pressure extruder is 5 to 20. 8. The take-out method according to claim 7, wherein the heating medium is supplied to the twin screw portion. 9. The reduced pressure degree of the reduced pressure extruder is 10 to 300 To.
The extraction method according to claim 8, which is rr. 10. The heating temperature of the reduced pressure extruder is 150 to 24.
The extraction method according to claim 9, which is 0 ° C. 11. The extraction method according to claim 10, wherein the amount of residual solvent in the extracted solid acrylic block copolymer is 10,000 ppm or less.