JPH09235316A - Production of polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymer excellent in color, clearance and anti-whitening in warm water and enabling a recovered solvent to be reused. SOLUTION: A conjugated diene and/or an aromatic vinyl are polymerized in a hydrocarbon-based solvent by using an organic active metal as an initiator, and 0.01-50mol water per 1mol organic active metal and 0.01-10 pts.wt. nonion surfactant per 100 pts.wt. of the obtained polymer are added to the obtained solution containing the active living polymer. A stabilizer is added to the solution after the addition of the water and the nonion surfactant, and further the polymer is separated from the polymer solution by a steam stripping or a direct drying.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a polymer which has excellent properties such as color tone, transparency and resistance to warm water whitening and which can be repeatedly used with a solvent.

[0002]

2. Description of the Related Art Polymers composed of conjugated dienes and / or aromatic vinyls having an organic active metal as an initiator are used in a wide variety of applications by taking advantage of various properties. For example, a block copolymer composed of a conjugated diene and an aromatic vinyl is used for various purposes by changing the content of the aromatic vinyl. For example, a block copolymer having a low aromatic vinyl content has mechanical properties and elasticity similar to those of vulcanized rubber at room temperature and has processability similar to that of thermoplastic resin at high temperature. It is used in the fields of resin modification, asphalt modification, footwear and adhesive bonding. On the other hand, block copolymers with high aromatic vinyl content are widely used for resin modification applications such as transparent containers and heat-shrinkable films, because they give transparent resins with excellent mechanical properties such as impact resistance. ing.

By the way, in the case of an active living polymer having an organic active metal as an initiator, a polymer having good transparency cannot be obtained unless an appropriate termination prescription is taken after completion of the polymerization.
There is a problem that the final product is colored yellow, and various solutions have been proposed. For example, in Japanese Examined Patent Publication No. 54-2679, water, carbon dioxide gas, and then a phenolic antioxidant are added to a polymerization solution containing a living polymer containing an active metal in the order of 150 to 200. A method of removing the solvent by treating with warm water in the range of ℃ is disclosed in Japanese Patent Laid-Open No.
No. 2,232,402 discloses a method of removing a solvent from a polymer solution after adding an organic acid, a stabilizer or a stabilizer and a terminating agent such as water to a polymer solution containing an active living polymer. Japanese Patent Publication No. 3-60844 discloses that a solution of an active living polymer is added with water, alcohol, an inorganic acid or an organic acid as a reaction terminator to stop the reaction, and then a stabilizer and a nonionic surfactant are used. A method of adding agents in order and steam stripping is disclosed.

However, the polymers obtained by these methods are improved in color tone such as transparency and coloring resistance, but they are not yet at a satisfactory level and there is a problem that hot water whitening resistance is lowered. , Further improvement is desired.

Therefore, in recent years, the present inventors have added a stabilizer to a polymer solution of an active living polymer, after adding an alcohol and a nonionic surfactant, and then removing the solvent by steam stripping. A method of doing so has been reported (JP-A-7-70265). However, in this method, the transparency, color tone and warm water whitening resistance of the obtained polymer are sufficiently improved, but it is difficult to reuse because the recovered polymerization solvent contains an alcohol serving as a reaction terminator. There is a problem.

[0006]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive studies made by the present inventors to solve the problems of the prior art,
Stable after adding water and a nonionic surfactant to a polymerization solution containing an active living polymer obtained by polymerizing a conjugated diene and / or an aromatic vinyl with an organic active metal as an initiator in a hydrocarbon solvent. A block copolymer having excellent color tone, transparency and hot water whitening resistance can be produced by adding an agent and then separating the polymer and the hydrocarbon solvent by a method such as direct heating or steam stripping. Moreover, they have found that the hydrocarbon solvent recovered can be reused by performing a simple dehydration operation, and have completed the present invention.

[0007]

Thus, according to the present invention, (1) an active living polymer obtained by polymerizing a conjugated diene and / or an aromatic vinyl with an organic active metal as an initiator in a hydrocarbon solvent. (2) 0.01 to 50 mol of water per mol of organic active metal and 0.01 to 10 parts by weight of nonionic surfactant per 100 parts by weight of polymer are added to the polymerization solution containing (3) A method for producing a polymer is provided, which comprises adding the stabilizer and then (4) separating the polymer from the polymerization solution.

According to the present invention, (1) a conjugated diene and / or an organic active metal is used as an initiator in a hydrocarbon solvent.
Alternatively, in a polymerization solution containing an active living polymer obtained by polymerizing an aromatic vinyl, (2) 0.01 to 50 mol of water per 1 mol of an organic active metal and 0.
01 to 10 parts by weight of a nonionic surfactant are added,
Next, (3) after adding the stabilizer, (4) the hydrocarbon solvent and the polymer are separated from the polymerization solution, (5) the recovered hydrocarbon solvent is dehydrated, and at least a part of The method for producing a polymer is provided, which is used in the polymerization reaction).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Polymerization Step of Polymer As the conjugated diene used in the present invention, for example, 1,
3-butadiene, isoprene, 2,3-dimethyl-1,
Examples include 3-butadiene and 1,3-pentadiene. Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is particularly preferable.
These conjugated dienes are used alone or in combination of two or more.

Examples of the aromatic vinyl used in the present invention include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, and the like. Of these, styrene is preferable. These aromatic vinyls are used alone or in combination of two or more.

The proportions of the conjugated diene and the aromatic vinyl in the monomer are appropriately selected according to the type of polymer required and are not particularly limited.

As the organic active metal used as the initiator, those generally used in anionic polymerization are used, and examples thereof include organic alkali metals, organic alkaline earth metals, and organic acid lanthanoid series rare earth metals. Of these, organic alkali metals are particularly preferred.

Examples of the organic alkali metal include n-
Organic monolithium compounds such as butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3 And multifunctional organolithium compounds such as 1,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like.
Among these, an organic lithium compound is preferable, and an organic monolithium compound is particularly preferable.

As the organic alkaline earth metal, for example,
n-butylmagnesium, n-hexylmagnesium,
Ethoxy calcium, calcium stearate, t-butoxystrontium, ethoxy barium, isopropoxy barium, ethyl mercapto barium, t-butoxy barium, phenoxy barium, diethylamino barium, barium stearate, ethyl barium and the like.

Examples of the lanthanoid organic acid rare earth metal include a composite catalyst composed of neodymium versatic acid / triethylaluminum / ethylaluminum sesquichloride as described in JP-B-63-64444.

These organic active metals can be used alone or in combination of two or more. The amount of the organic active metal used is appropriately selected according to the required molecular weight of the polymer, and is usually 0.01 to 10 mmol, preferably 0.05 to 5 mmol, and more preferably 0.1 to 100 g of the monomer. It is in the range of 2 mmol.

The polymerization reaction using the above organic active metal as an initiator is carried out in a hydrocarbon solvent which does not destroy the initiator. Suitable hydrocarbon solvents are not particularly limited as long as they are used for ordinary solution polymerization.
aliphatic hydrocarbon solvents such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane and iso-octane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbon solvents such as benzene and toluene; and n-hexane, cyclohexane, toluene and the like are preferable. Also, if necessary, 1-butene,
An unsaturated hydrocarbon solvent having low polymerizability such as cis-2-butene and 2-hexene may be used. These hydrocarbon solvents are used alone or in combination of two or more, and usually have a monomer concentration of 1 to 50% by weight, preferably 5 to 40% by weight, preferably 10 to 30% by weight.
It is used in the quantity ratio.

In the present invention, a Lewis basic compound or the like is added in order to adjust the randomness of the aromatic vinyl, the microstructure of the conjugated diene part, the initiation reaction rate and the polymerization reaction rate. You can Examples of Lewis basic compounds and the like include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and diethylene glycol dimethyl ether; amines such as triethylamine, tetramethylethylenediamine and hexamethylenetetramine; phosphines such as triphenylphosphine; hexamethylphosphonate Amides such as luamide; potassium-t-amyl oxide, potassium-
Alkali metal alkoxides such as t-butyl oxide; thioethers; and the like. These Lewis basic compounds may be used alone or in combination of two or more.

The polymerization reaction is appropriately selected depending on the purpose of use of the polymer. For example, the polymerization temperature is usually −20 ° C. to +
It is in the range of 150 ° C, preferably 30 ° C to 120 ° C, and the polymerization time varies depending on the conditions such as the polymerization temperature,
It is usually within 24 hours, preferably in the range of 1 to 10 hours. The pressure is selected from the range in which the solvent and the monomer are maintained in the liquid phase within the above-mentioned polymerization temperature range, and is not particularly limited.

By the above-mentioned polymerization reaction, an active living polymer having an active metal bonded to the polymer chain is produced. The resulting polymer is selected from a conjugated diene polymer, an aromatic vinyl polymer, a random copolymer composed of a conjugated diene and an aromatic vinyl, and a block copolymer composed of a conjugated diene and an aromatic vinyl. Any of the polymers described above may be used, but the effect of the present invention when the block copolymer is a block copolymer composed of a conjugated diene and an aromatic vinyl (hereinafter abbreviated as block copolymer) , The color tone and resistance to warm water whitening are remarkable, which is preferable.

The block copolymer is not particularly limited, but for example, at least one polymer block (A) mainly containing an aromatic vinyl and a polymer block (B) mainly containing a conjugated diene. And a block copolymer having at least one. The polymer block (A) mainly composed of aromatic vinyl refers to a polymer block containing 50 parts of aromatic vinyl.
% By weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, even more preferably 80 to 1% by weight.
The polymer block is contained in an amount of 00% by weight and is a homopolymer of aromatic vinyl or a polymer block composed of aromatic vinyl and a conjugated diene. The distribution of the conjugated diene in the polymer block (A) may be random, tapered, partially block-shaped, or a combination thereof. The polymer block (B) containing a conjugated diene as a main component means that the conjugated diene exceeds 50% by weight, preferably 60 to 100% by weight, more preferably 70 to 100%.
The polymer block is contained in an amount of 80% by weight, more preferably 80 to 100% by weight, and is a homopolymer of a conjugated diene or a polymer block composed of a conjugated diene and an aromatic vinyl. The distribution of the aromatic vinyl in the polymer block (B) may be random, tapered, partially block-shaped, or a combination thereof.

The polymer structure of the block copolymer may be either a linear structure or a branched structure, for example, one having a structure represented by the following general formulas (A) to (G). (A) (AB) _n (b) (AB) _n -A (c) (BA) _n -B (d) [(AB) _n ] _p -X (e) [( BA) _n ] _p -X (f) [(AB) _n -A] _p -X (g) [(BA) _n -B] _p -X In these general formulas, A is A is a polymer block mainly composed of aromatic vinyl (A), B is a polymer block mainly composed of conjugated diene (B), and X is a residue of a polyfunctional initiator or a polyfunctional coupling. The residue of the agent. n is an integer of 1 to 10 and p is an integer of 2 to 6.

The content ratio of the aromatic vinyl and the conjugated diene in the block copolymer may be appropriately selected according to the purpose of use, and for example, the weight ratio is usually 5:95 to 9 respectively.
The range is 5: 5, preferably 10:90 to 90:10, and more preferably 20:80 to 80:20.

The molecular weight of the polymer (preferably block copolymer) is determined by gel permeation chromatography (GPC) in terms of polystyrene equivalent weight average molecular weight (Mw).
And usually in the range of 10,000 to 3,000,000, preferably 30,000 to 1,000,000, and more preferably 50,000 to 500,000.

The polymer of the present invention may be subjected to a treatment such as a terminal modifier, a coupling agent or hydrogenation after the above polymerization reaction. The treatment with a terminal modifier is described in, for example, JP-A-58-162604 and JP-A-60-13793.
No. 3, JP-A-62-86074, JP-A-62.
The method can be performed according to a method disclosed in, for example, JP-A-119257. The treatment with a coupling agent is described, for example, in JP-A-56-143209 and JP-A-56-143209.
17362, JP-A-57-55912, JP-A-58-162605, JP-A-64-8184
The method can be carried out according to the method disclosed in Japanese Patent Publication No. 4 (JP-A) No. 4 and the like. The hydrogenation treatment is performed, for example, in Japanese Patent Publication No.
8704, JP-B-43-6636, JP-A-59-133203, JP-A-60-220147
Can be carried out according to the method disclosed in Japanese Patent Application Publication No.

Examples of the terminal modifier include a compound having at least one functional group selected from a carbonyl group, a thiocarbonyl group, an amino group, an aziridine group, and an epoxy group in the molecule, or a carbonyl group in the molecule, Thiocarbonyl group, amino group, aziridine group, epoxy group,
Examples thereof include a compound having a halogen atom and at least one functional group selected from carbon-carbon unsaturated groups such as a vinyl group and a tertiary amino group.

Specific examples of the terminal modifier having at least one functional group selected from carbonyl group, thiocarbonyl group, amino group, aziridine group, and epoxy group in the molecule include, for example, acetone, benzophenone, acetylacetone and the like. Ketones; aldehydes such as benzaldehyde; ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-i
so-butane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxydecane
-Epoxy hexadecane, 1,2-epoxy octadecane, 1,2-epoxy eicosane, 1,2-epoxy-
2-pentylpropane, 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, 1,2-epoxycyclopentane,
1,2-epoxycyclohexane, 1,2-epoxycyclododecane, 1,2-epoxyethylbenzene, 1,
2-epoxy-1-methoxy-2-methylpropane, glycidyl methyl ether, glycidyl ethyl ether,
Glycidyl isopropyl ether, glycidyl allyl ether, glycidyl phenyl ether, glycidyl butyl ether, epichlorohydrin, epibromohydrin, epiiodohydrin, 2,3-epoxy-1,1,
1-trifluoropropane, 1,2-epoxy-1H,
Epoxy compounds such as 1H, 2H, 3H, 3H, -heptadecafluoroundecane; dimethylcarbodiimide, diethylcarbodiimide, dipropylcarbodiimide, dibutylcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, methylpropylcarbodiimide, butylcyclohexyl Carbodiimides such as carbodiimide, ethylbenzylcarbodiimide, propylphenylcarbodiimide, phenylbenzylcarbodiimide; N-ethylethylideneimine, N-methylbenzylideneimine, N-hexylcinnamylideneimine, N-decyl-2-ethyl-1,2- Diphenylbutylidene imine, N-phenylbenzylidene imine, N-
Dodecylcyclohexaneimine, N-propyl-2,5
-Schiff bases such as cyclohexadieneimine and N-methyl-1-naphthaleneimine; N-unsubstituted aziridine compounds such as ethyleneimine and propyleneimine and N-unsubstituted aziridine compounds such as trimethyleneimine and the like having 2 carbon atoms ~ 3 cyclic imine compound; and the like.

Specific examples of the terminal modifying agent having a carbon-carbon unsaturated bond and a tertiary amino group include, for example, N, N.
-Dimethylaminomethyl (meth) acrylate, N, N
-Dimethylaminoethyl (meth) acrylate, N, N
-Dimethylaminopropyl (meth) acrylate, N,
N-dimethylaminobutyl (meth) acrylate, N,
N-diethylaminoethyl (meth) acrylate, N,
N-diethylaminopropyl (meth) acrylate,
N, N-diethylaminobutyl (meth) acrylate,
N-methyl-N-ethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate , N, N-dibutylaminobutyl (meth) acrylate, N, N-dihexylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth)
N, N such as acrylate and acryloylmorpholine
-Disubstituted aminoalkyl acrylate, N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N
-Dimethylaminobutyl (meth) acrylamide, N,
N-diethylaminoethyl (meth) acrylamide,
N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N-methyl-N-ethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N , N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dibutylaminobutyl (meth) acrylamide, N, N-dihexylaminoethyl (meth) acrylamide, N, N -N, N-disubstituted aminoalkyl acrylamides such as dihexylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide, N, N
-N, N-disubstituted amino aromatic vinyl compounds such as dimethylaminoethylstyrene, N, N-diethylaminoethylstyrene, N, N-dipropylaminoethylstyrene, N, N-dioctylaminoethylstyrene, 2-vinylpyridine , 4-vinylpyridine, 5-methyl-2-
Compounds having a vinyl group and a tertiary amino group in the molecule, such as vinyl compounds having a pyridyl group such as vinyl pyridine and 5-ethyl-2-vinyl pyridine;

Specific examples of the terminal modifying agent having a carbonyl group and a tertiary amino group include, for example, N-methyl-β.
-Propiolactam, N-phenyl-β-propiolactam, N-methyl-2-pyrrolidone, N-vinyl-2-
Pyrrolidone, N-phenyl-2-pyrrolidone, Nt-
Butyl-2-pyrrolidone, N-methyl-5-methyl-2
-Pyrrolidone, N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2-piperidone,
N-methyl-ε-caprolactam, N-phenyl-ε-
Caprolactam, N-methyl-ω-laurylolactam,
N-Substituted amides such as N-vinyl-ω-laurylolactam, 1,3-dimethylethylene urea, 1,3-divinylethylene urea, 1,3-diethyl-2-imidazolidinone, 1-methyl-3 -N-substituted ureas such as ethyl-2-imidazolidinone, 4-N, N-dimethylaminoacetophenone, 4-N, N-diethylaminoacetophenone, 1,3-bis (diphenylamino) -2-propanone, 1 , 7-bis (methylethylamino) -4-heptanone, 4-N, N-dimethylaminobenzophenone,
4-N, N-di-t-butylaminobenzophenone, 4
-N, N-diphenylaminobenzophenone, 4,4 '
-Bis (dimethylamino) benzophenone, 4,4'-
N-substituted aminoketones such as bis (diethylamino) benzophenone and 4,4′-bis (diphenylamino) benzophenone, 4-N, N-dimethylaminobenzaldehyde, 4-N. N-diphenylaminobenzaldehyde, 4-N, N-divinylaminobenzaldehyde and other N-substituted aminoaldehydes, N-substituted isocyanuric acid and other compounds having a carbonyl group and a tertiary amino group in the molecule; .

Specific examples of the polyfunctional coupling agent include:
For example, tin dichloride, tin tetrachloride, tin tetrabromide, monomethyltrichlorotin, monoethyltrichlorotin, monobutyltrichlorotin, monohexyltrichlorotin,
Tin-based coupling agents such as dimethyldichlorotin, diethyldichlorotin, dibutyldichlorotin, dibutyldibromotin, tetramethoxytin, tetraethoxytin, tetrabutoxytin, bistrichlorostannylethane; silicon dichloride, silicon dibromide , Silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, monomethyltrichlorosilicon, monoethyltrichlorosilicon, monobutyltrichlorosilicon, monohexyltrichlorosilicon, monomethyltribromosilicon, dimethyldichlorosilicon, diethyldichlorosilicon, butyltrichlorosilicon , Dibutyldichlorosilicon, dihexyldichlorosilicon, dimethyldibromosilicon, tetramethoxysilicon, tetraethoxysilicon, tetrabutoxysilicon, diphenyldimethoxysilicon, dipheni Jietokishikei arsenide, monochloro trimethoxy silicon, monobromo trimethoxy silicon, dichloro-dimethoxy silicon, dibromo-dimethoxy silicon, trichloromethoxy silicon, tribromometoxy silicon,
Silicon-based coupling agents such as alkyltriphenoxy silicon and bistrichlorosilylethane; Metal halide coupling agents such as lead dichloride and germanium tetrachloride; Unsaturated nitrile coupling agents such as ethylacrylonitrile; Dichloromethane, Dibromomethane , Dichloroethane, dibromoethane, dichloropropane, dibromopropane, dibromobenzene, dichlorobenzene,
Chloroform, tribromomethane, trichloroethane,
Halogenated hydrocarbon coupling agents such as trichloropropane, tribromopropane, carbon tetrachloride, tetrachloroethane; methyl formate, ethyl formate, methyl acetate,
Ethyl acetate, propyl acetate, isopropyl acetate, amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl trimethyl acetate, methyl caproate, ethyl caproate, methyl benzoate, ethyl benzoate, dimethyl adipate, adipine Ester-based coupling agents such as diethyl acid, ethyl benzoate, dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, dimethyl isophthalate; halide-based cups such as terephthalic acid dichloride, phthalic acid dichloride, isophthalic acid dichloride, and adipic acid dichloride. Examples thereof include ring agents; phosphorus-based coupling agents such as trisnonylphenyl phosphite, trimethyl phosphite, and triethyl phosphite. Among these, tin coupling agents, silicon coupling agents,
Ester-based coupling agents, halogenated hydrocarbon-based coupling agents and the like are preferable, and tin-based coupling agents and silicon-based coupling agents are particularly preferable.

(2) Water and a nonionic surface active agent are added to the polymer solution.
The next step is added and sexual agent, a polymerization solution containing the active living polymer obtained above adding water and nonionic surfactant. Water and the nonionic surfactant may be added at the same time or before or after both. Examples of the method of adding water and the nonionic surfactant include a method of preparing a mixed solution of both and then adding, a method of simultaneously adding from different lines, etc., but not limited to these. It is not something that will be done. If the addition of either water or a nonionic surfactant comes after the stabilizer addition described below, the transparency,
Color tone and warm water whitening resistance are not sufficient, which is not preferable. Further, if alcohol is used instead of water, separation of alcohol is difficult when the recovered hydrocarbon solvent is reused, which is not preferable.

The amount of water used is in the range of 0.01 to 50 mol, preferably 0.1 to 40 mol, and more preferably 1 to 20 mol, per mol of the organic active metal. If the amount of water used is too small, the color tone and resistance to warm water whitening will be poor, and if it is too large, the transparency will be poor.

Examples of the nonionic surfactant include, for example,
Block condensation polymers of two or more alkylene oxides such as oxyethylene oxypropylene block polymers;
Higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, octylphenol, isooctylphenol, alkylphenols such as nonylphenol and butylnaphthol, polyoxyethylene lauryl ether obtained by polymerizing addition of alkylene oxide to alkylnaphthol such as octylnaphthol, Polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene higher alcohol (C ₁₂ -C ₁₄ ) ether, etc. Alkylene ether compounds; lauric acid, palmitic acid, stearic acid, oleic acid, etc. Higher fatty acid was polymerized addition is not an alkylene oxide to polyoxyethylene glycol monolaurate, polyoxyethylene glycol monopalmitate, polyethylene glycol monostearate,
Polyoxyalkylene glycol fatty acid ester compounds such as polyethylene glycol distearate, polyethylene glycol monooleate; glycerin, pentaerythritol, sorbitan, mannitane, hexitane, and polycondensates thereof having 3 or more hydroxyl groups in the molecule Glyceryl monostearate, glyceryl monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, which are ester compounds of polyhydric alcohols and higher fatty acids.
Sorbitan monooleate, sorbitan dioleate,
Mannitan monolaurate, Mannitan monostearate, Mannitan distearate, Mannitan monooleate, Hexitan monolaurate, Hexitan monopalmitate, Hexitan monostearate, Hexitan distearate, Hexitant Polyhydric alcohol fatty acid ester compounds such as listearate, hexitane monooleate, hexitane dioleate; polyoxyethylene sorbitan monolaurate, polyoxy obtained by polymerizing addition of alkylene oxide to the polyhydric alcohol fatty acid ester compound Ethylene sorbitan monostearate,
Polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan monooleate, polyoxyethylene mannitane monopalmitate, polyoxyethylene mannitane monostearate, polyoxyethylene mannitane monooleate, polyoxyethylene hexitane monolaurate Examples thereof include polyoxyalkylene polyhydric alcohol fatty acid ester compounds such as rate and polyoxyethylene hexitane monostearate; polyoxyalkylene alkylamine compounds such as polyoxyethylene alkylamine; alkylalkanolamide compounds; and the like. Among these, block condensation polymers of two or more kinds of alkylene oxides, polyoxyalkylene ether compounds, polyoxyalkylene glycol fatty acid ester compounds, polyoxyalkylene polyhydric alcohol fatty acid ester compounds, polyoxyalkylene alkylamine compounds, etc. The polyoxyalkylene-based compound which is the alkylene oxide polymerization adduct of is preferable, and the polyoxyalkylene ether-based compound, the polyoxyalkylene glycol fatty acid ester-based compound, and the polyoxyalkylene polyhydric alcohol-based fatty acid ester compound are particularly preferable.

These nonionic surfactants may be used alone or in combination of two or more. The amount of the nonionic surfactant used is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the produced polymer. It is a range. If the amount of the nonionic surfactant used is too small, the properties of color tone, transparency and resistance to whitening with warm water will be poor, and if it is too large, it will remain in the polymer, both of which are not preferred.

(3) Step of Adding Stabilizer Next, a stabilizer is added to the polymerization solution after the water and the nonionic surfactant are added.

The stabilizer to be added is not particularly limited as long as it is a compound usually used for (co) polymers of conjugated dienes and / or aromatic vinyl, but it is usually phenol-based,
At least one stabilizer selected from phosphorus, sulfur, amine and benzotriazole is used. Among these, phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers and the like are particularly preferable.

As the phenolic stabilizer, conventionally known ones can be used, for example, 2-t-butyl-6- (3-
t-butyl-2-hydroxy-5-methylbenzyl)-
4-methylphenyl acrylate, 2,4-di-t-
Amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and the like are disclosed in JP-A-63-179953 and JP-A-1-16.
Acrylate compounds described in Japanese Patent No. 8643;
2,6-di-t-butyl-4-methylphenol, 2,
6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6 t-butylphenol), 4,4 '
-Butylidene-bis (6-t-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane , 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5) -T-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-T-butyl-4-hydroxybenzyl)
Benzene, tetrakis (methylene-3- (3 ′, 5′-
Di-t-butyl-4'-hydroxyphenyl) propionate) methane, triethylene glycol bis (3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate), alkyl-substituted phenolic compounds such as tocopherol; 6- (4-hydroxy-3,
5-di-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3,5-dimethylanilino) -2,4-bis-octylthio-1 , 3,5-Triazine, 6- (4-hydroxy-3-methyl-5-t-butylanilino) -2,4
-Bis-octylthio-1,3,5-triazine, 2-
Triazine-based compounds such as octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine; and the like.

As the phosphorus-based stabilizer, for example, triphe
Nylphosphite, diphenylisodecylphosphite
, Phenyldiisodecyl phosphite, tris (noni
Luphenyl) phosphite, tris (dinonylpheni)
) Phosphite, tris (2,4-di-t-butylphen)
Phenyl) phosphite, tris (2-t-butyl-4-)
Methylphenyl) phosphite, tris (cyclohexyl)
Ruphenyl) phosphite, 2,2-methylenebis
(4,6-di-t-butylphenyl) octylphospha
Ito, 9,10-dihydro-9-oxa-10-phosph
Aphenanthrene-10-oxide, 10- (3,5
-Di-t-butyl-4-hydroxybenzyl) -9,1
0-dihydro-9-oxa-10-phosphaphenant
Len-10-oxide, 10-decyloxy-9,10
-Dihydro-9-oxa-10-phosphaphenanthre
Monophosphite-based stabilizers such as amines; 4,4'-butyri
Den-bis (3-methyl-6-t-butylphenyl-di
-Tridecyl phosphite), 4,4'-isopropylidene
Den-bis (phenyl-di-alkyl (C₁₂~ C_Fifteen)
Sphite), 4,4'-isopropylidene-bis (di)
Phenyl monoalkyl (C₁₂ ~ C_Fifteen) Phosphite),
1,1,3-tris (2-methyl-4-di-tridecyl)
Phosphite-5-t-butylphenyl) butane, tet
Lakis (2,4-di-t-butylphenyl) -4,4 '
-Biphenylenediphosphite, cyclic neopen
Tantetrayl bis (octadecyl phosphite),
Iclick neopentane tetraylbis (isodecylpho
(Sfight), cyclic neopentane tetrairubi
Su (nonyl phenyl phosphite), cyclic neo
Pentanetetraylbis (2,4-di-t-butylphene
Nylphosphite), cyclic neopentane tetra
Irbis (2,4-dimethylphenylphosphite),
Cyclic neopentane tetraylbis (2,6-di
-T-butylphenyl phosphite)
Ito-based stabilizers and the like.

Examples of sulfur stabilizers include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl.
3,3′-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl)-
2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

As the amine-based stabilizer, for example, 2,
2,6,6-Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) -2- (3,5-di-t
-Butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionyloxy) -1-
(2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2
Examples thereof include hindered amine-based stabilizers such as 6,6-tetramethylpiperidine.

Examples of the benzotriazole-based stabilizer include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chloro. Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Examples thereof include benzotriazole.

These stabilizers can be used alone or in combination of two or more kinds. The amount of the stabilizer used is usually in the range of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the produced polymer.
The antioxidant is usually added as a solution of a hydrocarbon solvent, but it may be added as it is to the polymer solution.

In the present invention, various additives may be added to the polymer after adding water and the nonionic surfactant depending on the purpose. The addition of other additives may be performed simultaneously with or before or after the stabilizer. Specific examples of other additives include, for example, softening agents such as oils;
Reinforcing agents such as silica and carbon black; dimethyl phthalate, diethyl phthalate, dihexyl phthalate,
Butyl lauryl phthalate, di (2-ethylhexyl)
Phthalate, dilauryl phthalate, di-2-octyl phthalate, di-n-butyl adipate, diisooctyl adipate, octyl decyl adipate, di-2-ethylhexyl-4-thioazelate, diethyl sebacate, di-n-butyl malate, diethyl Plasticizers such as malate; titanium oxide, zinc white, lead white, red lead, cuprous oxide,
Iron black, cadmium yellow, molybdenum red, silver vermilion,
Colorants such as inorganic pigments and organic pigments such as yellow lead, chromium oxide, navy blue, barium sulfate, alumina white and white carbon; conductivity imparting agents such as ferrite; calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, water Magnesium oxide, aluminum hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, calcium sulfite, mica, dolomite, clay, talc, zinc oxide,
Various additives such as inorganic fillers such as glass fibers; conductivity imparting agents such as ferrite; antistatic agents; nucleating agents; flame retardants; These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately determined within a range that does not impair the effects of the present invention.

(4) Polymerization from a polymerization solution with a hydrocarbon solvent
Step of separating body The desired polymer can be separated by removing the solvent from the polymer solution that has undergone the above steps. The method of separating the polymer and the hydrocarbon solvent is not particularly limited and may be carried out by a conventional method, and examples thereof include methods such as steam stripping and direct drying.

The steam stripping method is carried out, for example, by adding a solution of a hydrocarbon solvent whose polymer concentration is adjusted to 10 to 50% by weight by any means to a temperature not lower than the boiling point of the hydrocarbon solvent or the azeotropic temperature of water with it. Carried out at a temperature of. The polymer is separated as an aqueous slurry crumb by steam stripping, and the water content of the water content crumb is first adjusted to about 30 to 60% by weight with a vibrating screen, a centrifugal dehydrator or the like, and further dehydrated with a screw type extrusion dehydrator or the like. Dehydrate with a machine to a water content of about 1 to 20% by weight.
The dehydrated crumbs have a water content of less than 1% by weight by a dryer such as a hot air dryer, an extrusion dryer, and an expansion dryer.

The direct drying method is carried out by dropping a hydrocarbon-based solution having a predetermined concentration on a roll heated to a temperature not lower than the boiling point of the hydrocarbon-based solvent and evaporating the solvent, or by using a vented solvent. The solvent is removed using a shaft extrusion dryer or the like to obtain a desolvated polymer.

Since the obtained polymer is sufficiently excellent in color tone, transparency and hot water whitening resistance, it can be widely used in various applications.

On the other hand, the hydrocarbon solvent is usually vaporized and separated from the polymer, so that the gasified hydrocarbon solvent can be cooled and recovered by a conventional method.

(5) Dehydrate the recovered hydrocarbon solvent
The hydrocarbon solvent separated from the polymer in the step (4) can be reused only by performing dehydration operation.

The water content of the hydrocarbon solvent after dehydration is appropriately selected depending on the amount of the organic active metal used in the next polymerization step and the like, but is usually 50 ppm or less, preferably 20 p.
It is set to pm or less, more preferably 10 ppm or less.

The dehydration method may be carried out according to a conventional method, for example, distillation using an apparatus equipped with a distillation column such as azeotropic distillation or dehydration column; contact with a dehydrating agent such as silica gel, activated alumina or molecular sieve. The method of doing is mentioned.

An example of the method of contacting with a dehydrating agent is as follows:
For example, a dehydrating agent is usually added to the hydrocarbon solvent in an amount of 1 to 7
0% by weight, preferably 5 to 50% by weight, more preferably 10 to 30% by weight, and usually at room temperature for 0.1 to 48 hours, preferably 1 to 24 hours, more preferably 6 to 12 hours.
After standing for a time, the supernatant can be collected and used.

[0053]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Parts and percentages in these examples are on a weight basis unless otherwise specified. Various physical properties were measured according to the following methods. (1) The amount of bound styrene in the polymer is 500 MHz ¹ H
-Measured by NMR. (2) The weight average molecular weight (Mw) of the polymer was measured by GPC, and the weight average molecular weight and number average molecular weight in terms of standard polystyrene were determined. (3) The water content of the hydrocarbon-based solvent was measured by a water content measuring device by the Karl Fischer volumetric titration method. (4) The color tone was measured by measuring the yellow index [YI] of the compression-molded sample plate having a thickness of 2 mm with a color computer of Suga Test Machine. (5) Transparency (Haze) is compression molded thickness 2mm
The haze value of the sample plate was measured according to JIS K7105. (6) Warm water whitening resistance is an evaluation of devitrification in which transparency is impaired by moisture absorption and the like.
The mm sample plate was immersed in warm water at 60 ° C., and the time until the Haze increased by 20% was determined.

Production Example 1 [Polymerization of Active Living Polymer (I)] Styrene 20 was placed in a polymerization reaction vessel sufficiently replaced with nitrogen gas.
Parts by weight and 1,3-butadiene 2 parts by weight, tetramethylethylenediamine 0.0078 parts by weight, cyclohexane 3
00 parts by weight were mixed and kept at 60 ° C. Next, 0.091 parts by weight of n-butyllithium was added, polymerization was started while raising the temperature by about 0.5 ° C. per minute, and when the temperature reached 75 ° C., the temperature was maintained and after polymerization for 30 minutes, 1, 3-butadiene 5
8 parts by weight was added and polymerization was carried out at 75 ° C. for 60 minutes. Further, 20 parts by weight of styrene was added and polymerization was carried out at 75 ° C. for 60 minutes. The obtained active living polymer (I) was a block copolymer having an ABA structure, and the concentration of the polymer solution was 25% by weight.
Met. Further, when a part of the active living polymer (I) was separated and the molecular weight and the styrene content were measured, the weight average molecular weight was 115,000 and the styrene content was 40% by weight.

Production Example 2 [Polymerization of Active Living Polymer (II)] Styrene 35 was placed in a polymerization reaction vessel sufficiently replaced with nitrogen gas.
Parts by weight, 1,3-butadiene 2 parts by weight, temeramethylethylenediamine 0.0097 parts by weight, cyclohexane 4
00 parts by weight were mixed and kept at 50 ° C. Next, 0.059 parts by weight of n-butyllithium was added, and the polymerization was started while raising the temperature by about 1.0 ° C./min. -Butadiene 28
1 part by weight and 7 parts by weight of styrene were added and polymerization was carried out at 75 ° C. for 60 minutes. Add 28 parts by weight of styrene to 60 at 75 ° C.
Polymerized for minutes. The obtained active living polymer (II) was a block copolymer having an ABA structure, and the concentration of the polymer solution was 20% by weight. Moreover, when a part of the active living polymer (II) was separated and the molecular weight and the styrene content were measured, the weight average molecular weight was 155,000 and the styrene content was 70% by weight.

Production Example 3 [Active living polymer (III)]
Polymerization] In a polymerization reaction vessel sufficiently replaced with nitrogen gas, styrene 15
By weight, 0.0061 parts by weight of tetramethylethylenediamine and 300 parts by weight of cyclohexane were mixed and kept at 60 ° C. Next, 0.071 parts by weight of n-butyllithium is added, and the polymerization is started at a temperature of about 1 ° C per minute to start polymerization at 80 ° C.
When the temperature reached, the temperature was maintained and the polymerization was continued for 10 minutes.
Then, 70 parts by weight of 1,3-butadiene were continuously added over 60 minutes, followed by polymerization for 30 minutes.
After 10 parts by weight was continuously added over 20 minutes, polymerization was carried out for another 10 minutes. The obtained active living polymer (III) was a block copolymer having an ABA structure, and the concentration of the polymer solution was 25% by weight. Moreover, when a part of the active living polymer (I) was separated and the molecular weight and the styrene content were measured, the weight average molecular weight was 154,000 and the styrene content was 30% by weight.

Example 1 In a solution of the active living polymer (I), 0.5 part by weight of water relative to n-butyllithium and 0.1 part by weight of 100 parts by weight of the active living polymer (I). The reaction mixture was stopped by adding a mixed solution of ADECATOL LO7 (polyoxyalkylene ether type; manufactured by Asahi Denka Co., Ltd.). Next, as a stabilizer, 0.4 part by weight of 2,6-di-t-butyl-4-methylphenol and 0.5 part by weight of tris (nonylphenyl) phosphite are used with respect to 100 parts by weight of the polymer (I). Two
-T-pentyl-6- (3-t-pentyl-5-t-pentyl-2-hydroxyphenyl-ethylidene) -4-
After adding 0.2 part by weight of t-pentylphenyl acrylate, the solution was steam stripped at a bath temperature of 90 to 98 ° C. to obtain a polymer crumb having a water content of about 55%.
The crumb is vacuum dried to obtain a polymer (I having a water content of 0.1%).
-1) was obtained. The color tone, transparency and warm water whitening resistance of the obtained polymer (I-1) were evaluated, and the results are shown in Table 1.

Example 2 Polymer (I-2) was prepared in the same manner as in Example 1 except that water was added and then ADECATOL LO7 was added.
I got The color tone, transparency and hot water whitening resistance of the obtained polymer (I-2) were evaluated, and the results are shown in Table 1.

Comparative Example 1 A polymer (I-3) was obtained by the same method as in Example 2, except that the stabilizer was added before the addition of ADECATOL LO7. Color tone of the obtained polymer (I-3),
The transparency and warm water whitening resistance were evaluated, and the results are shown in Table 1.

Comparative Example 2 A polymer (I-4) was obtained in the same manner as in the method of Example 1, except that ADECATOL LO7 was not added at all. The color tone, transparency and hot water whitening resistance of the obtained polymer (I-4) were evaluated, and the results are shown in Table 1.

[0061]

[Table 1]

It can be seen from Table 1 that the polymers obtained according to the method of the present invention (Examples 1 and 2) are sufficiently excellent in all of the characteristics such as color tone, transparency and warm water whitening resistance. On the other hand, when the stabilizer is added before the addition of the nonionic surfactant, all the properties such as color tone, transparency and hot water whitening resistance are inferior (Comparative Example 1). It can be seen that, when no C. is added, none of the properties of color tone, transparency and warm water whitening resistance is sufficient (Comparative Example 2).

Examples 3 to 5 and Comparative Examples 3 to 4 Polymer (II) solutions were mixed with water in the amounts shown in Table 2 and Emulgen 108 (polyoxyalkylene ether type; manufactured by Kao Corporation) as a nonionic surfactant. The reaction solution was stopped by adding the mixed solution of 1). Next, as a stabilizer, the polymer (II) 10
2,6-di-tert-butyl-4-based on 0 parts by weight
0.4 parts by weight of methylphenol, 0.5 parts by weight of tris (nonylphenyl) phosphite, 2,4-bis- (n-
Octylthio) -6- (4-hydroxy-3,5-di-
t-Butylanilino) -1,3,5-triazine 0.0
After adding 25 parts by weight, the solution was steam stripped at a bath temperature of 105 ° C. to obtain crumbs having a water content of about 50%. The obtained crumbs were passed through a uniaxial extrusion type squeezer to obtain a polymer having a water content of about 15%, and then dried with a uniaxial extrusion type expansion dryer to obtain a polymer having a water content of 0.2% (II-1 to 5). ) Got. Obtained polymer (II
-1 to 5) to evaluate the color tone, transparency and warm water whitening resistance,
The results are shown in Table 2.

Comparative Example 5 A polymer (II-6) was obtained in the same manner as in Example 3, except that water was not added at all. The color tone, transparency and warm water whitening resistance of the obtained polymer (II-6) were evaluated, and the results are shown in Table 2.

[0065]

[Table 2]

(* 1) Molar ratio to n-butyllithium (* 2) Parts by weight relative to 100 parts by weight of the polymer (II)

From the results shown in Table 2, the polymers (Examples 3 to 5) obtained according to the method of the present invention are excellent in all of the characteristics such as color tone, transparency and hot water whitening resistance, and the addition of water. It can be seen that when used in an amount of 1 to 20 times the molar amount of the initiator (Examples 4 to 5), the properties of color tone, transparency, and hot water whitening resistance are highly balanced. On the other hand, when the amount of the nonionic surfactant used is excessively low, the properties such as color tone, transparency and warm water whitening resistance are inferior (Comparative Example 3), and when the amount of water used is excessive, the transparency is low. It was found that the properties were poor (Comparative Example 4), and conversely, when no water was used at all, the properties such as color tone, transparency and warm water whitening resistance were inferior (Comparative Example 5).

Example 6 Styrene 14 was placed in a polymerization reaction vessel sufficiently replaced with nitrogen gas.
Parts by weight and 350 parts by weight of cyclohexane were mixed and kept at 60 ° C. Next, 0.085 parts by weight of n-butyllithium was added and polymerized at 60 ° C. for 60 minutes, followed by isoprene 86.
A part by weight was added and polymerization was performed at 60 ° C. for 180 minutes. Subsequently, 0.38 mol of dibromobenzene was added to 1 mol of n-butyllithium as a coupling agent to carry out a coupling reaction. The obtained polymer was a polymer having an (AB) 2-X structure, and the concentration of the polymer solution was 25% by weight.

2,4-bis (n-octylthio) -6- (4-hydroxy-di-t-butylanilino) -1,3,5 as an antioxidant was added to the above polymer solution per 100 parts by weight of the polymer. -A dried polymer was obtained in the same manner as in Example 3 except that 0.05 part by weight of triazine and 0.5 part by weight of tris (nonyl) phosphite were used. Color,
The transparency and warm water whitening resistance were evaluated, and the same results as in Example 3 were obtained.

Example 7 In a solution of the active living polymer (III), 5 times mol of water and active living polymer (I) were added to n-butyllithium.
II) The reaction was stopped by adding a mixed solution of 0.1 part by weight of ADECATOL LO7 to 100 parts by weight. next,
After adding 0.7 parts by weight of 2,6-di-t-butyl-4-methylphenol to 100 parts by weight of the active living polymer (III) as a stabilizer, the solution was heated to a bath temperature of 90 to 98 ° C. I did steam stripping. The gas flowing out from the tank was cooled to recover the polymerization solvent, 20% by weight of Molecular Sieve 3A-1.6 was added, and the mixture was stirred for 10 minutes and allowed to stand overnight, and the supernatant was recovered and used as the recovered polymerization solvent. The water content of the recovered polymerization solvent was 10 ppm or less.
Polymerization reaction was performed in the same manner as in Production Example 3 except that a recovered polymerization solvent was used instead of cyclohexane to obtain a polymer (IV). The weight average molecular weight of the polymer (IV) is 156,000.
It was 0, which was almost the same as the weight average molecular weight of the polymer (III).

Comparative Example 6 Example 7 except that isopropanol was used instead of water.
Polymer (V) was obtained in the same manner as above. The weight average molecular weight of the polymer (V) is 253,000, and the polymer (II
I) could not be reproduced.

The preferred embodiments of the present invention will be described below. (1) (1) In a polymerization solution containing an active living polymer obtained by polymerizing a conjugated diene and / or an aromatic vinyl with an organic active metal as an initiator in a hydrocarbon solvent, (2)
After adding 0.01 to 50 mol of water per mol of the organic active metal and 0.01 to 10 parts by weight of nonionic surfactant per 100 parts by weight of polymer, and then adding (3) stabilizer. (4) A method for producing a polymer, which comprises separating the polymer from the polymerization solution. (2) (1) A polymerization solution containing an active living polymer obtained by polymerizing a conjugated diene and / or an aromatic vinyl with an organic active metal as an initiator in a hydrocarbon solvent, (2)
After adding 0.01 to 50 mol of water per mol of the organic active metal and 0.01 to 10 parts by weight of nonionic surfactant per 100 parts by weight of polymer, and then adding (3) stabilizer. , (4) separating the hydrocarbon solvent and the polymer from the polymerization solution, (5) dehydrating the recovered hydrocarbon solvent, and then using at least a part thereof in the polymerization reaction of (1). And a method for producing the polymer.

(3) The polymer is a conjugated diene polymer, an aromatic vinyl polymer, a conjugated diene-aromatic vinyl random copolymer, or a conjugated diene-aromatic vinyl block copolymer, preferably Conjugated diene-aromatic vinyl block copolymer (hereinafter abbreviated as block copolymer)
The production method according to (1) or (2). (4) The block copolymer has the following general formulas (A) to (G) (A) (A-B) _n (B) (A-B) _n- A (C) (BA) _n- B. (D) [(A-B) _n ] _p- X (e) [(B-A) _n ] _p- X (f) [(A-B) _n- A] _p- X (to) [(B -A) _n -B] _p -X (In the formula, A is a polymer block mainly containing aromatic vinyl (A), B is a polymer block mainly containing a conjugated diene (B), and X is a polyfunctional initiation. The residue of the agent or the residue of the polyfunctional coupling agent, n is an integer of 1 to 10, and p is an integer of 2 to 6). Production method. (5) The production method according to (3) or (4), wherein the content ratio of the aromatic vinyl and the conjugated diene in the block copolymer is in the range of 5:95 to 95: 5 by weight.

(6) The molecular weight of the polymer is 10,000 in terms of polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).
The manufacturing method in any one of (1)-(5) which is the range of -3,000,000. (7) The production method according to any one of (1) to (6), wherein the amount of the organic active metal used is in the range of 0.01 to 10 mmol per 100 g of the monomer. (8) The production method according to any one of (1) to (7), wherein the organic active metal is anionically polymerizable. (9) The production according to (8), wherein the anionically polymerizable organic active metal is at least one selected from organic alkali metals, organic alkaline earth metals and organic acid lanthanoid series rare earth metals, and preferably organic alkali metals. Method. (10) The production method according to (9), wherein the organic alkali metal is an organic monolithium compound.

(11) The hydrocarbon solvent is used in an amount ratio such that the monomer concentration becomes 1 to 50% by weight (1) to (1)
The production method according to any one of 0).

(12) The nonionic surfactant is a compound obtained by polymerizing addition of alkylene oxide (1) to (1)
The manufacturing method according to any one of 1). (13) The nonionic surfactant having an alkylene oxide polymerized and added is a block condensation polymer of two or more kinds of alkylene oxides, a polyoxyalkylene ether compound,
At least one selected from polyoxyalkylene glycol fatty acid ester compounds, polyoxyalkylene polyhydric alcohol fatty acid ester compounds, and polyoxyalkylene alkylamine compounds, and preferably polyoxyalkylene ether compounds and polyoxyalkylene glycol fatty acid esters. The production method according to (12), which is a system compound or a polyoxyalkylene polyhydric alcohol fatty acid ester compound.

(14) The amount of the stabilizer used is 100
It is in the range of 0.001 to 10 parts by weight per 1 part by weight (1)
~ The manufacturing method according to any one of (13). (15) The stabilizer is at least one stabilizer selected from a phenol-based stabilizer, a phosphorus-based stabilizer, a sulfur-based stabilizer, an amine-based stabilizer, and a benzotriazole-based stabilizer, preferably a phenol-based stabilizer. The production method according to any one of (1) to (14), which is a phosphorus-based stabilizer or a sulfur-based stabilizer.

(16) The production method according to any one of (1) to (15), wherein the method of separating the hydrocarbon solvent and the polymer is steam stripping or direct drying. (17) The water content of the hydrocarbon solvent after dehydration is 50 pp.
The production method according to any one of (2) to (16), which is m or less. (18) The production method according to any one of (2) to (17), wherein the dehydration method is a distillation method or a method using a dehydrating agent.

(19) The method according to any one of (1) to (18), wherein the conjugated diene is 1,3-butadiene or isoprene. (20) Aromatic vinyl is styrene (1) to (1
The production method according to any one of 9).

[0080]

By carrying out the method of the present invention, the polymer obtained is excellent in color tone, transparency and hot water whitening resistance,
In addition, since the solvent to be recovered is easily reused, a practically excellent method for recovering the polymer is provided. Further, since the obtained polymer has the above-mentioned properties, it can be used as a material for various uses such as resin modifiers, asphalt modifiers, adhesives, footwear, etc. by utilizing the characteristics. In addition, various moldings such as extrusion molded products such as films and sheets, injection molded products, hollow molded products are possible, and it can be used for various containers, packaging materials, home appliances, home appliances, toys, medical supplies, industrial parts, etc. .

Claims (2)

[Claims] 1. A polymerization solution containing an active living polymer obtained by polymerizing a conjugated diene and / or an aromatic vinyl by using (1) an organic active metal as an initiator in a hydrocarbon solvent, and (2) an organic activity. After adding 0.01 to 50 mol of water per mol of metal and 0.01 to 10 parts by weight of nonionic surfactant per 100 parts by weight of polymer, and then adding (3) stabilizer, ( 4) A method for producing a polymer, which comprises separating the polymer from the polymerization solution. 2. A polymerization solution containing (1) an active living polymer obtained by polymerizing a conjugated diene and / or an aromatic vinyl with an organic active metal as an initiator in a hydrocarbon solvent, and (2) an organic activity. After adding 0.01 to 50 mol of water per mol of metal and 0.01 to 10 parts by weight of nonionic surfactant per 100 parts by weight of polymer, and then adding (3) stabilizer, ( 4) It is characterized in that the hydrocarbon solvent and the polymer are separated from the polymerization solution, (5) the recovered hydrocarbon solvent is dehydrated, and at least a part thereof is used in the polymerization reaction of (1). Method for producing polymer.