JPH10168101A - Method for recovering rubbery polymer - Google Patents

Abstract

(57) [Problem] To obtain a crumb of an appropriate size with equipment without a decontacting step, to reduce the amount of lithium metal that is a polymerization catalyst or a hydrogenation catalyst or the amount of metal remaining in a hydrogenation catalyst. To obtain a rubbery polymer having good transparency, resistance to devitrification, and resistance to moist heat. SOLUTION: (1) A solution or slurry of a rubber-like polymer is added to (a) phosphonic acid and / or phosphonate, (b) water, and (c) phosphate ester and / or
Or (d) adding a phosphate salt and then (2)
A stabilizer is added to the rubbery polymer solution or slurry, and then (3) optionally, the rubbery polymer solution or slurry is contacted with water, and (4) stripped to form a crumb-like solution. A slurry in which the polymer is dispersed in water is obtained, (5) the crumb of the rubbery polymer containing water is dehydrated to a water content of 3 to 30% by weight, and (6) the rubbery polymer obtained above. Is dried to a water content of less than 3% by weight, and a rubbery polymer from which metal components have been removed is recovered.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for recovering a rubber-like polymer by steam-stripping a solvent from a solution or slurry of the rubber-like polymer, and combining a specific treatment method with a polymerization catalyst or a hydrogenation catalyst. The present invention relates to a method for recovering a rubbery polymer having excellent transparency, devitrification resistance and wet heat resistance by reducing the amount of the catalyst residue.

[0002]

2. Description of the Related Art A rubbery polymer polymerized by a transition metal catalyst or an organolithium catalyst and then hydrogenated is
If there is no decontact step, the metal used for the polymerization catalyst or hydrogenation catalyst used at the time of polymerization or hydrogenation remains in the polymer, resulting in poor transparency, devitrification resistance, and wet heat resistance. Usually polymerized by a transition metal catalyst or an organolithium catalyst, and then
The production of a rubbery polymer hydrogenated by a hydrogenation catalyst is performed in a hydrocarbon solvent that is inert to the polymerization catalyst or the hydrogenation catalyst, and is uniformly dissolved in the produced polymer and the solvent. Therefore, a step of separating the solvent and the polymerization catalyst or the hydrogenation catalyst from the rubbery polymer and recovering the rubbery polymer is required.

In general, there are various methods for separating a rubbery polymer and a solvent. One of the methods is to inject a polymer solution into hot water, distill the solvent together with water vapor,
A steam stripping method for depositing a polymer in the form of a crumb is known. In such a method, it has been proposed to use an appropriate dispersing agent to improve the dispersion of the polymerization solution in hot water to prevent the polymer from agglomerating and to form a crumb having an appropriate size. For example, JP-A-50-89494
JP, JP-A-51-37987, JP-A-49-37987
No. 53991, JP-A-50-141693,
JP-A-50-90693, JP-A-47-2268
No. 7 publication. These proposals relate to a method of obtaining crumbs of an appropriate size, and no detailed proposal has been made on the removal of the used catalyst residue. JP-A-1-56712, JP-A-1-5671
No. 33 discloses a catalyst removal capability of lithium, but does not describe removal of the transition metal catalyst or the hydrogenation catalyst residue.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is intended for use in a polymerization catalyst or a hydrogenation catalyst for recovering an appropriate size of crumb using equipment without a decontacting step. It is an object of the present invention to obtain a rubber-like polymer having good transparency, devitrification resistance, and heat and humidity resistance by reducing the amount of lithium metal and metal remaining in the hydrogenation catalyst.

[0005]

SUMMARY OF THE INVENTION The present invention provides a method for recovering a rubbery polymer by steam stripping a solvent from a solution or slurry of the rubbery polymer in the following steps (1) to (6). An object of the present invention is to provide a method for recovering a rubbery polymer from which a metal component has been removed by a combination. (1) To a solution or slurry of a rubbery polymer, (a) phosphonic acid and / or a phosphonate, (b) water, and, if necessary, (c) a phosphoric acid ester and / or a phosphoric acid ester salt Step of adding (hereinafter also referred to as “first step”). (C) at least one phosphate ester selected from the group consisting of polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkenyl ether phosphates, polyoxyalkylene alkyl aryl ether phosphates and polyoxyalkylene alkenyl aryl ether phosphates . (D) at least one phosphate ester selected from the group consisting of polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkenyl ether phosphate, polyoxyalkylene alkyl aryl ether phosphate and polyoxyalkylene alkenyl aryl ether phosphate A phosphoric acid ester salt comprising an alkali metal salt and / or an ammonium salt.

(2) A step of adding a stabilizer to the rubbery polymer solution or slurry (hereinafter, also referred to as a “second step”). (3) A step of bringing 0 to 100 parts by weight of water into contact with 100 parts by weight of the solution or slurry of the rubbery polymer (hereinafter also referred to as “third step”). (4) a rubber-like polymer solution or slurry having a polymer concentration of 10 to 60% by weight at a boiling point of a solvent or at a temperature not lower than the azeotropic temperature and not higher than 120 ° C. when the solvent and water are azeotropic; Step of stripping to obtain a slurry in which a crumb-like polymer is dispersed in water (hereinafter, also referred to as “fourth step”). (5) A step of dehydrating the water-containing rubber-like polymer crumb obtained above to a water content of 3 to 30% by weight (hereinafter also referred to as “fifth step”). (6) A step of drying the rubber-like polymer obtained above to reduce the water content to less than 3% by weight (hereinafter also referred to as “sixth step”).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The rubbery polymer used in the steam stripping method of the present invention is a polymer obtained by polymerizing a conjugated diene compound as a main component in a hydrocarbon solvent with an organolithium compound as an initiator (hereinafter referred to as "(e )) By hydrogenation using a hydrogenation catalyst comprising dicyclopentadienyl titanium halide, nickel organic carboxylate, organic cobalt carboxylate and the like and an organometallic compound of Groups I to III of the periodic table. Hydrogenated, vanadium compounds, titanium compounds, nickel compounds, cobalt compounds,
An elastomer (hereinafter, also referred to as “component (f)”) obtained by polymerizing mainly a α-olefin or a conjugated diene compound using a polymerization catalyst comprising a transition metal compound such as a zirconium compound as an initiator.

The conjugated diene compound used in the component (e) used in the present invention includes 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,
One or more of 3-octadiene, chloroprene and the like can be mentioned, but in order to obtain a hydrogenated product which can be industrially used and has excellent physical properties, 1,3-butadiene, isoprene, 1,3-pentadiene And more preferably 1,3-butadiene and isoprene.

Other monomers that may be used as component (e) include styrene, t-butylstyrene,
Examples include α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1 diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine, and the like, with styrene and α-methylstyrene being particularly preferred. In the component (e), when the conjugated diene compound and another monomer are copolymerized, the distribution of the conjugated diene compound is block, random, tapered (the monomer component increases or decreases along the molecular chain), It may be partially block-shaped or any combination thereof. Further, the component (e) may be a star polymer by reacting a terminal living with a polyfunctional coupling agent.

Examples of the polyfunctional coupling agent include divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 3,
5,4-trivinylnaphthalene, 1,2-divinyl-
3,4-dimethylbenzene, 1,5,6-trivinyl-
Polyvinyl aromatic compounds such as 3,7-diethylnaphthalene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, 1,2,5,6,9,1
Polyepoxy compounds such as 0-triepoxydecane, benzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, triphenylmethanetriisocyanate, naphthalene-1,3,3 7
-Polyisocyanate compounds such as triisocyanate, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, itaconic acid, maleic acid, fumaric acid, glutaric acid, pimelic acid, sebacic acid, phthalic acid, terephthalic acid, Diphenic acid, isophthalic acid, naphthalic acid, 1,
3,5-benzenetricarboxylic acid, citric acid, trimellitic acid, polycarboxylic acids such as pyromellitic acid and methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
alcohols such as sec-butyl alcohol, t-butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, benzyl alcohol, or phenol, o-cresol, m-cresol, p-
Polycarboxylic acid ester compounds derived from phenols such as cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, and the above polycarboxylic acids Acid halide,
Carbonic ester compounds such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate, 1,3,6-hexanetrione,
Polyketone compounds such as 2,3-diacetonylcyclohexane, polyaldehyde compounds such as 1,4,7-naphthenetricarboxaldehyde, 1,7,9-anthracentricarboxaldehyde, chloroform, carbon tetrachloride, bromoform, tetraodor Carbonized, iodoform, tetraiodomethane, 1,1,2-trichloroethane, 1,
1,2,2-tetrachloroethane, 1,1,2,2-tetrabromoethane, hexachloroethane, 1,2,3-
Trichloropropane, 1,2,3-tribromopropane, 1,2,4-trichloropropane, 1,2,4,5
-Polyhalogenated hydrocarbons such as tetrachlorobenzene, 1,4-bis (trichloromethyl) benzene, trifluorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, tetrabutoxysilane, tetraiodo Silane, (dichloromethyl) trichlorosilane, (dichlorophenyl) trichlorosilane, 1,2-
Bis (trichlorosilyl) ethane, hexachlorodisilane, octachlorotrisiloxane, trichloromethyltrichlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, trimethoxymethylsilane, triethoxymethylsilane, triethoxychlorosilane, diethoxychloromethyl Silane compounds such as silane and methyltriacetoxysilane; tin compounds such as tetrachlorotin, methyltrichlorotin, butyltrichlorotin and tetramethoxytin; germanium compounds such as tetrachlorogermanium; and 2,4,6-tri (azilinyl)- 1,3,5-triazine, tri (1-
Polyaziridinyl compounds such as (aziridinyl) phosphine oxide and tri (2-methyl-1-aziridinyl) phosphine oxide;

Also, 1,3-dichloro-2-propanone, 2,4-dibromo-3-pentanone, 1,2,4,
5-diepoxy-3-pentanone, 1,2,11,12
Compounds having two or more functional groups capable of reacting with a living polymer in the molecule, such as -diepoxy-8-pentadecanone, can also be used as the coupling agent. Particularly preferred among these compounds are:
Divinylbenzene, 1,2,4-trivinylbenzene,
Epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene-1,2,4-triisocyanate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, Diethyl phthalate, diethyl terephthalate, pyromellitic dianhydride, diethyl carbonate,
1,1,2,2-tetrachloroethane, 1,4-bis (trichloromethyl) benzene, trichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, (dichloromethyl) trichlorosilane, hexachlorodisilane, tetraethoxysilane, Examples thereof include tetrachlorotin and 1,3-dichloro-2-propanone.

The component (e) may be a polymer in which a polar group-containing atomic group is bonded to a polymer chain terminal. The polar group-containing atomic group refers to an atomic group containing at least one atom selected from nitrogen, oxygen, silicon, phosphorus, sulfur, and tin. Specifically, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group,
Thioaldehyde group, carboxylic acid ester group, amide group,
Sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridine group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiothianate group And an atomic group containing at least one polar group selected from a silicon halide group, an alkoxysilicon group, a tin halide group, an alkyltin group, and a phenyltin group.

The total weight average molecular weight of the component (e) of the present invention is 50,000 to 700,000, preferably 70,000 to 650,000, and more preferably 100,000 to 650,000. If it is less than 50,000, it is not preferable because it is inferior in rubber-like properties. On the other hand, if it exceeds 700,000, the fluidity of the obtained hydrogenated product is reduced, and the processability and the appearance of the molded product are inferior.

The component (e) of the present invention may be prepared by any method. In general, when a living anion polymerization is carried out in an organic solvent using an organic alkali metal compound as an initiator and a coupling reaction is carried out, a polyfunctional coupling agent is added. And a coupling reaction.

As the organic solvent, a hydrocarbon solvent such as pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, xylene, and toluene is used. As the organic alkali metal compound as a polymerization initiator, an organic lithium compound is preferable.
As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyl lithium, n-propyl lithium, isopropyl lithium, n
-Butyllithium, sec-butyllithium, t-butyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isoprenyldilithium and the like.
Used in an amount of .about.0.4 parts by weight.

The vinyl bond content of the conjugated diene compound in the component (e) is adjusted by using a Lewis base such as an ether or an amine, specifically, diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ether, or ethylene. Ether derivatives of polyethylene glycol such as glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1-methoxy-2-ethoxyethane, 1,3-dimethoxypropane, 1-methoxy- Alkoxy compounds such as 3-ethoxypropane and amines include tertiary amines such as tetramethylethylenediamine, pyridine and tributylamine. It used with solvents.

Further, the polymerization reaction is usually carried out at a temperature of -30.degree.
Performed at 150 ° C. When a coupling reaction is performed, a polyfunctional coupling agent is added after the polymerization reaction.
The polymerization and the coupling may be performed by controlling the temperature, or may be performed at an elevated temperature in the adiabatic polymerization.
It is desirable to replace the atmosphere of the polymerization system with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited, as long as it is a pressure range sufficient to maintain the monomer and the solvent in the liquid phase within the above-mentioned polymerization temperature range.
Further, it is necessary to take care that impurities such as water, oxygen, carbon dioxide, etc., which inactivate the catalyst and the living polymer, do not enter the polymerization system.

The bonding content of the other monomer of component (e) is
It is regulated by the amount of monomer supplied during polymerization in each stage,
The vinyl bond content of the conjugated diene compound is adjusted by varying the components of the micromodulator. Further, the weight average molecular weight is adjusted by the addition amount of a polymerization initiator, for example, n-butyllithium.

By hydrogenating the component (e) polymerized as described above, the rubbery polymer of the present invention in which the double bond residue of the conjugated diene portion is hydrogenated can be obtained.
The rubbery polymer thus obtained is obtained by dissolving the component (e) in an inert solvent,
It is obtained by hydrogenation in the presence of a hydrogenation catalyst under pressurized hydrogen of g / cm ² G. Inert solvents used for hydrogenation include hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene and ethylbenzene, and polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether and tetrahydrofuran.

Examples of the hydrogenation catalyst include dicyclopentadienyl titanium halide, cyclopentadienyl titanium halide, dicyclopentadienyl titanium dialkyl-substituted phenyl, dicyclopentadienyl titanium dialkyl, dicyclopentadienyl titanium halide. Periodic rule with dialkyl-substituted phenol, diindenyl titanium halide, indenyl titanium halide, diindenyl titanium dialkyl-substituted phenyl, diindenyl titanium dialkyl, diindenyl titanium dialkyl-substituted phenol, nickel organic carboxylate, organic cobalt carboxylate, etc. Table I-III
Hydrogenation catalyst comprising an organometallic compound of group III, carbon,
Nickel, platinum supported on silica, diatomaceous earth, etc.
Metal catalysts such as palladium, ruthenium, rhenium and rhodium metal catalysts, cobalt, nickel, rhodium and ruthenium complexes can be mentioned. Also, hydrogenated compounds such as lithium aluminum hydride and p-toluenesulfonyl hydrazide, and further, Zr-Ti-Fe-VC
r alloy, Zr-Ti-Nb-Fe-V-Cr alloy, La
A hydrogenation reaction using a hydrogen storage alloy such as a Ni ₅ alloy is also included as a method for producing the hydrogenated component (e) of the present invention.

The hydrogenation rate of the conjugated diene portion is determined by the hydrogenation catalyst,
It is adjusted by changing the amount of the hydrogenated compound added, the hydrogen pressure during the hydrogenation reaction, and the reaction time.

On the other hand, the component (f) used in the present invention comprises:
Copolymers of α-olefins such as ethylene, propylene, 1-butene and 1-hexene, or copolymers thereof with non-conjugated dienes, homopolymers of higher α-olefins such as 1-hexene, butadiene And an isobutylene homopolymer, which is an elastomeric polymer. These components (f) include vanadium oxytrichloride, vanadium tetrachloride, their alcohols (1 to 12 carbons) modified products, vanadium compounds such as vanadium triacetyl acetylate, oxyvanadium diacetylacetonate, nickel naphthenate, etc. Nickel compounds, cobalt compounds such as cobalt bromide, zirconium compounds, titanium tetrachloride, titanium trichloride, or titanium compounds in which these are supported on a carrier such as silica, alumina, magnesium chloride, and the like. Polymerized with a polymerization catalyst comprising an organometallic compound. The weight average molecular weight of the component (f) of the present invention is 50,000 to 1,000,000, preferably 70,000 to 9
It is 50,000, more preferably 100,000 to 950,000. If it is less than 50,000, it is not preferable because it is inferior in rubber-like properties. on the other hand,
If it exceeds 1,000,000, the fluidity of the obtained elastomer will be reduced, and processability and molded appearance will be poor.

In the first step of the present invention, (a) a phosphonic acid and / or a phosphonate and (b) water and, if necessary, (c) a phosphoric acid ester are added to a solution or slurry of the rubbery polymer. And / or (d) a step of adding a phosphate salt. (A) phosphonic acid and / or phosphonate are used as a deactivator for removing metals used in a polymerization catalyst or a hydrogenation catalyst, and (b) water is used as a reaction terminator.
If necessary, (c) the phosphoric ester and / or (d) the phosphoric ester salt is added as a dispersant for a defatting agent or a reaction terminator. (A) When the phosphonic acid and / or phosphonate is not added, the amount of the catalyst residue in the finally obtained polymer is large, and a polymer excellent in transparency, devitrification resistance and wet heat resistance cannot be obtained. When (b) water and, if necessary, (c) the phosphate ester and / or (d) the phosphate salt are not added, the transparency of the finally obtained polymer is poor.

The (a) phosphonic acid and / or phosphonate used in the present invention includes aminotri (methylenephosphonic acid), aminotri (methylenephosphonic acid) 1Na salt,
Amino tri (methylene phosphonic acid) 2Na salt, amino tri (methylene phosphonic acid) 3Na salt, amino tri (methylene phosphonic acid) 4Na salt, amino tri (methylene phosphonic acid) 5Na salt, 1-hydroxyethylidene-1,1
-Diphosphonic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid 1Na salt, 1-hydroxyethylidene-
1,1-diphosphonic acid 2Na salt, 1-hydroxyethylidene-1,1-diphosphonic acid 3Na salt, 1-hydroxyethylidene-1,1-diphosphonic acid 4Na salt, ethylenediaminetetra (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) Acid) 1Na salt, ethylenediaminetetra (methylenephosphonic acid) 2Na salt, ethylenediaminetetra (methylenephosphonic acid) 3Na salt,
Ethylenediaminetetra (methylenephosphonic acid) 4Na
Salt, ethylenediaminetetra (methylenephosphonic acid) 5
Na salt, ethylenediaminetetra (methylenephosphonic acid) 6Na salt, ethylenediaminetetra (methylenephosphonic acid) 7Na salt, hexamethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid) 1Na salt, hexamethylenediaminetetra ( Methylenephosphonic acid) 2Na salt, hexamethylenediaminetetra (methylenephosphonic acid) 3Na
Salt, hexamethylenediaminetetra (methylenephosphonic acid) 4Na salt, hexamethylenediaminetetra (methylenephosphonic acid) 5Na salt, hexamethylenediaminetetra (methylenephosphonic acid) 6Na salt, hexamethylenediaminetetra (methylenephosphonic acid) 7Na salt, Diethylenetriaminepenta (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) 1Na
Salt, diethylene triamine penta (methylene phosphonic acid) 2Na salt, diethylene triamine penta (methylene phosphonic acid) 3Na salt, diethylene triamine penta (methylene phosphonic acid) 4Na salt, diethylene triamine penta (methylene phosphonic acid) 5Na salt, diethylene triamine penta (methylene phosphonic acid) 6Na Salt, diethylenetriaminepenta (methylenephosphonic acid) 7N
a salt, diethylenetriaminepenta (methylenephosphonic acid) 8Na salt, diethylenetriaminepenta (methylenephosphonic acid) 9Na salt and the like can be used.

(A) The addition amount of the phosphonic acid and / or phosphonate is determined by determining the lithium atom of the organolithium compound used as the initiator, the hydrogenation catalyst, the transition metal atom of the transition metal compound used as the hydrogenation co-catalyst, Periodic Table I-II
0.01 times mol to 10 times the total amount of group I metal atoms.
The molar amount is 0 times, preferably 0.02 times to 50 times, more preferably 0.05 times to 10 times.
(A) If the added amount of the phosphonic acid and / or phosphonate exceeds 100 moles, it remains during drying of the rubbery polymer and corrodes the equipment as a strong acid. On the other hand, if the molar ratio is less than 0.01 times, the detouching ability is not exhibited.

(B) The amount of water to be added depends on the lithium atoms of the organolithium compound used as the initiator, the hydrogenation catalyst, the transition metal atoms of the transition metal compound used as the hydrogenation co-catalyst,
0.01 to 100 moles, preferably 0.1 to 100 moles, based on the total amount of aluminum atoms in the organoaluminum compound.
The molar ratio is from 02 to 50 times, more preferably from 0.05 to 10 times. If it exceeds 100 moles, soft iron equipment will be corroded, while if it is less than 0.01 moles, the desorbing ability will decrease.

The amount of the above-mentioned (c) phosphate ester and / or (d) phosphate salt is 0.1% by weight or less, preferably 0.05% by weight, based on the amount of the rubbery polymer.
Or less, more preferably 0.03% by weight or less.
If the amount of the (c) phosphate ester and / or (d) phosphate ester salt exceeds 0.1% by weight, foaming during steam stripping becomes severe, making stripping practically impossible. .

Next, the second step of the present invention is a step of adding a stabilizer to the rubbery polymer solution or slurry. The addition of the stabilizer at this stage is effective in preventing the polymer from undergoing oxidative deterioration or thermal deterioration when the solvent is removed in the next step. The stabilizer may be added as it is to the polymer solution or slurry, or may be dissolved in the above-mentioned hydrocarbon solvent or slurry. As the stabilizer, any of conventionally known stabilizers may be used, and various known antioxidants such as phenol-based, organic phosphate-based, organic phosphite-based, amine-based, and sulfur-based are used. . The stabilizer is generally used in the range of 0.001 to 10 parts by weight based on 100 parts by weight of the rubbery polymer. If the amount exceeds 10 parts by weight, the stabilizer bleeds from the molded article using the rubbery polymer of the present invention, while if less than 0.001 part by weight, the ability of the rubbery polymer to prevent oxidative deterioration and thermal deterioration. Is low.

Next, in the third step of the present invention, 0 to 100 parts by weight, preferably 0 to 95 parts by weight, more preferably 0 to 100 parts by weight based on 100 parts by weight of the polymer solution or slurry.
This is a step of contacting 90 parts by weight of water. Here, the contact with water is performed by a mechanical mixer such as a line homomixer,
Mixing and stirring with a static mixer such as a static mixer. If the amount of water in contact with 100 parts by weight of the polymer solution or slurry exceeds 100 parts by weight, the crumb-like slurry obtained in the fourth step does not have a uniform crumb particle size. The temperature of the contacting water is not limited, but is preferably 10 to 120C, more preferably 20 to 110C.

Next, in the fourth step of the present invention, the polymer concentration of the polymer solution or slurry is adjusted to 10 to 60% by weight, preferably 15 to 50% by weight, more preferably 20 to 40% by weight. The rubbery polymer solution or slurry of the above, the boiling point of the solvent or, if the solvent and water azeotrope, the azeotropic temperature or more, the temperature range of 120 ℃ or less, preferably 10 ℃ from the boiling point or azeotropic temperature of the solvent Higher than 110
This is a step of obtaining a slurry in which a crumb-like polymer is dispersed in water by stripping in a temperature range of not more than ° C. When the concentration of the polymer is less than 10% by weight, the solvent removal efficiency is poor due to the large amount of the solvent with respect to the polymer. On the other hand, when the concentration exceeds 60% by weight, a small crumb particle size cannot be obtained. The amount of the polymer adhered to the vessel wall, stirring blades, etc. increases, which is not preferable. When the temperature at the time of steam stripping is lower than the boiling point of the solvent or lower than the azeotropic temperature of the solvent and water, the removal of the solvent is poor and the amount of the residual solvent in the crumb increases. In addition, the temperature at the time of steam stripping is 1
If the temperature exceeds 20 ° C., it is not preferable because a crumb having a small particle size cannot be obtained. In addition, pH in water at the time of solvent removal
Is carried out in 4 to 10, preferably 5 to 9. pH 4
If it is less than 10, or more than 10, corrosion of the solvent removing tank is severe, which is not preferable.

The polymer concentration of the polymer solution used in the fourth step of the present invention is adjusted particularly if the polymer concentration after the step of producing the polymer or after the second step is within the range specified in the present invention. unnecessary. However, when the concentration is less than 10% by weight, the polymer solution is introduced into a concentrator selected from a single or multi-stage type such as a flash tank type, a stirring tank, a thin film evaporator, a wet wall tower and the like to reduce the concentration. It is necessary to make it 10% by weight or more. Conversely, when the concentration exceeds 60% by weight,
It is necessary to dilute with a solvent to a concentration of 60% by weight or less. In the polymer solution used in the fourth step of the present invention, water is used in an amount of 30 to 3,000 parts by weight, preferably 50 parts by weight, based on 100 parts by weight of the polymer in order to obtain crumbs having good uniformity in particle size. 2,000 parts by weight, more preferably 100
After previously mixing up to 1,000 parts by weight, it can be introduced into a solvent removal tank. As the water to be mixed in advance, a part of the water at the time of stripping used in the fourth step may be circulated.

The concentration of the crumb-like polymer dispersed in water is generally 0.1 to 20% by weight, preferably 0.5 to 1% by weight.
The content is 5% by weight, more preferably 1 to 10% by weight (ratio to water at the time of stripping). Within this range, a crumb having a good particle size can be obtained without hindering operation. .

It is preferable that the processes of the first to fourth steps are performed in an inert atmosphere of nitrogen, argon, helium or the like. It is not preferable that the deoxidizing agent comes into contact with oxygen before coming into contact with the active polymerization catalyst or hydrogenation catalyst, because the desorbing ability of the deoxidizing agent is reduced.

Next, in the fifth step of the present invention, the water-containing rubbery polymer obtained above is dehydrated, and the water content is adjusted to 3 to 30.
%, Preferably 2 to 20% by weight, more preferably 2 to 10% by weight. Here, dewatering a crumb containing water means dewatering with a compressed water squeezing machine such as a roll, a Banbury type dewatering machine, or a screw extruder type squeezing dewatering machine. In the present invention, a single-screw or twin-screw multi-screw extruder-type squeezing dewatering machine is preferable in terms of dewatering efficiency and workability. In the fifth step, if the water content in the crumb is less than 3% by weight, the dehydration time becomes too long, or the polymer is decomposed or gelled by the shearing force of the water drawer, which is not preferable. On the other hand, when the water content exceeds 30% by weight, drying in the sixth step is insufficient, which is not preferable. In the present invention, the slurried crumb obtained in the fourth step is drained in advance to a water content of 35 to 60% by weight using a rotary screen, a vibrating screen, a centrifugal dehydrator or the like, and then introduced into a compressed water press. Is preferred.

Next, in a sixth step of the present invention, the rubbery polymer obtained above is dried to reduce the water content to less than 3% by weight, preferably 2% by weight or less, more preferably 1% by weight or less. This is the step of performing Here, drying means that the water content is reduced to less than 3% by weight by at least one of a screw extruder type, a kneader type dryer, an expander dryer and a hot air dryer. Particularly preferred dryers are single screw or twin screw multi-screw vented extruder type dryers having an L / D (screw length / diameter) of 10
~ 40 can be used. If the water content in the sixth step is 3% by weight or more, it is not preferable because foaming occurs during molding of the polymer and appearance defects such as silver occur. In the sixth step, a polymer can be obtained in the form of foamed crumb, granule, or powder,
It can also be obtained in the form of a strand or a pellet.

In the present invention, the fifth step and the sixth step are
The dehydrator and the dryer can be implemented by an integrated device. Suitable as such a device has at least one, preferably 2 to 4 slits for dewatering,
At least one vent for deaeration, preferably 2 to 4
And two or more vent extruders. As the vent extruder having such a structure, those having L / D = about 15 to 50 are preferable. The meshing structure of the screw can be either meshing or non-meshing, and the rotation direction is the same direction, different direction. Either may be used. The screw rotation speed, cylinder heating temperature, and vent pressure of such a vent extruder are selected in consideration of extrusion capability, polymer characteristics (viscosity and thermal stability), product quality, and the like. Screw rotation speed 20-500 rotations /
Min, preferably 30 to 400 revolutions / min, cylinder temperature 100 to 300 ° C, preferably 130 to 260 ° C, and the pellet pressure is selected from the range of atmospheric pressure to 10 mmHg absolute pressure, preferably 500 to 50 mmHg absolute pressure.

The polymer finally obtained through the above-mentioned first to sixth steps has a residual metal content of 500 p.
pm or less, preferably 300 ppm or less, more preferably 150 ppm or less. If the amount of the residual metal exceeds 500 ppm, the devitrification resistance and the moist heat resistance are inferior. Here, the amount of residual metal in the polymer is
It can be measured by atomic absorption spectroscopy using an atomic absorption spectrophotometer. In the present invention, a catalyst residue can be further removed by performing a decalcification treatment after the completion of the first step. Here, examples of the demineralization treatment include a phase transition method in which a catalyst residue remaining in a rubbery polymer solution or slurry is transferred to water by contact with a large amount of water, and only water is removed.

The rubbery polymer of the present invention may contain various additives depending on the purpose, for example, an antioxidant, a heat stabilizer, a UV absorber, a stabilizer such as a copper damage inhibitor, silica, talc, carbon, and carbonic acid. Calcium, magnesium carbonate, glass fiber,
Contains fillers such as carbon fibers, metal fibers, glass beads, mica, potassium titanate whiskers, aramid fibers, wood powder, cork powder, cellulose powder, rubber powder, plasticizers, oils, and softeners such as low molecular weight polymers. Can be used. These additives are the first
It can be added in any step after the step.

[0039]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, unless the gist of the present invention is exceeded, the present invention
It is not limited by such an embodiment. In the examples, parts and percentages are by weight unless otherwise specified. Each evaluation item in the examples was measured as follows.

Hydrogenation rate The hydrogenation rate of the hydrogenated rubbery polymer was calculated from ¹ H-NMR spectrum at 100 MHz using ethylene tetrachloride as a solvent. Weight average molecular weight The weight average molecular weight (hereinafter also referred to as “molecular weight”) was determined in terms of polystyrene using gel permeation chromatography (GPC). Melt flow rate (MFR ) Melt flow rate (MFR) is based on JIS K7210
It was measured according to. Mooney viscosity Mooney viscosity was measured according to JIS K6300.

The 1,2-vinyl bond content and cis-1,4 bond content of the microstructure conjugated diene of the polymer were calculated by the Hampton method using infrared analysis. Styrene content Styrene content is 100 MH
Calculated from z, ¹ H-NMR spectrum. Propylene content Propylene content is 400 M
Hz, calculated from the ¹³ C-NMR spectrum. Iodine value Measured according to JIS K0070.

Residual amount of catalytic metal The residual amount of catalytic metal was measured using the flame method of an atomic absorption spectrophotometer. The desorption rate is 100 times the value obtained by dividing the measured amount of residual catalyst metal by the amount of transition metal or organic metal used to obtain the rubbery polymer.

After the moisture-permeable , compression-molded plate having a thickness of 2 mm was left at 85 ° C. and 95% RH for 72 hours, the haze of each test piece was measured in accordance with JIS K6714, and the haze of the test piece before leaving was measured. The difference was determined and the devitrification resistance was determined. The larger the difference, the worse the devitrification resistance. Difference in Haze is less than 5 ◎ Difference in Haze is 5 to 15 ○ Difference in Haze exceeds 15 ×

Moisture / heat resistance A compression molding plate having a thickness of 2 mm was placed in a high-pressure steam at 120 ° C. for 72 hours.
After immersion for a period of time, the tensile breaking strength of each test piece was measured according to JIS K63.
01, and the rate of change from the tensile strength at break of the test piece before immersion was determined to determine the wet heat resistance. The higher the rate of change, the worse the wet heat resistance. Tensile rate of change is less than 10% of the intensity ◎ tensile rate of change in intensity is 10 to 30% ○ Tensile compression molded plate × color 1mm thick the rate of change of the breaking strength is more than 30% multi-light source spectrocolorimeter The yellowness (YI value) measured in was used as the color tone.

Various components used in the formulations shown in Examples and Comparative Examples are as follows. Dephosphorizer phosphon 1; 1-hydroxyethylidene-1,1-diphosphonic acid [manufactured by Nippon Monsanto Co., Ltd., Dequest 20
10] Phosphon 2; aminotri (methylene phosphonic acid) [manufactured by Nippon Monsanto Co., Ltd., Quest 2000] Phosphon 3; ethylenediaminetetra (methylene phosphonic acid) [manufactured by Nippon Monsanto Co., Ltd., Quest 204
1] Phosphon 4; 1-hydroxyethylidene-1,1-diphosphonic acid 3Na salt [manufactured by Nippon Monsanto Co., Ltd., Dequest 2015 DN] Phosphon 5; aminotri (methylene phosphonic acid) 5Na
Salt [manufactured by Nippon Monsanto Co., Ltd., Quest 2006] Dispersant Phosphate Ester; Polyoxyalkylene alkylphenyl ether phosphoric acid ester [Daiichi Kogyo Seiyaku Co., Ltd., Price Surf A-212E]

Hydrogenated rubbery polymer (A); internal volume 10
In a liter autoclave, 5 kg of degassed and dehydrated cyclohexane, 1,000 g of 1,3-butadiene and 8.5 g of tetrahydrofuran were charged, and the polymerization initiation temperature was set to 40.
C., 1.2 g of n-butyllithium was added, and the temperature was elevated. After the polymerization was completed, 0.64 g of tetrachlorosilane was added and the reaction was carried out for about 20 minutes. After the reaction was completed, the amount of living Li was measured and was 1.9 mmol. Into this system, 0.34 g of benzophenone was added to the autoclave and stirred for 10 minutes. From the change in the color of the polymer liquid, it was confirmed that there was no living lithium terminal lithium as a living anion. Next, 2
2. Benzophenone dissolved in 0 ml of cyclohexane.
A reaction product obtained by reacting 64 g and 1.28 g of n-butyllithium in advance in a nitrogen atmosphere for 10 minutes was charged, and further, 1.88 g of bis (cyclopentadienyl) titanium dichloride dissolved in 0.52 g and 10 ml of toluene was added. A component obtained by previously mixing diethylaluminum chloride in a nitrogen atmosphere was charged into an autoclave and stirred. Hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and a hydrogenation reaction was performed at 90 ° C. for 1.5 hours. The hydrogenated polymer thus obtained had a degree of hydrogenation of 98%, a weight average molecular weight of 251,000, and an MFR measured at 230 ° C and a load of 10 kg of 0.5 g / 10 minutes. The 1,2-vinyl bond content before hydrogenation was 40%. This hydrogenated rubbery polymer is designated as (A).

Hydrogenated rubbery polymer (B); internal volume 10
5 kg of degassed and dehydrated cyclohexane, 150 g of 1,3-butadiene, and 0.25 g of tetrahydrofuran were charged into a liter autoclave, and the polymerization initiation temperature was 70 ° C.
Then, 0.9 g of n-butyllithium was added, and the temperature was elevated by polymerization. After the polymerization conversion reached almost 100%, the reaction solution was cooled to 15 ° C., and 75 g of tetrahydrofuran was added.
500 g of 1,3-butadiene was added, and the temperature was elevated. After the polymerization conversion reached almost 100%, the reaction solution was cooled to 50 ° C., 150 g of styrene was added, and the temperature was increased by polymerization. After the polymerization was completed, the amount of living Li was measured and found to be 12 mmol. 2.15 g of benzophenone was added to the autoclave and stirred for 10 minutes. From the change in the color of the polymer liquid, it was confirmed that there was no living lithium terminal lithium as a living anion. Next, 1.90 g of benzophenone and 0.2 ml of n-butyllithium dissolved in 20 ml of cyclohexane.
A reaction product obtained by reacting 63 g in advance in a nitrogen atmosphere for 10 minutes was charged, and 0.52 g of bis (cyclopentadienyl) titanium dichloride and 1.88 g of diethylaluminum chloride dissolved in 10 ml of toluene were further charged in a nitrogen atmosphere. The components premixed below were charged into an autoclave and stirred. 8 hydrogen gas
kg / cm ² G at a pressure of 90 ° C. for 1.5 hours,
A hydrogenation reaction was performed. The hydrogenation rate of the obtained hydrogenated polymer was 98%, the weight average molecular weight was 15,000, 230 ° C,
The MFR measured under a load of 2.16 kg was 2.5 g / 10 minutes. Before the hydrogenation, the 1,2-vinyl bond content in the first-stage polymerization was 15%, the 1,2-vinyl bond content in the second-stage polymerization was 80%, and the styrene content was 14.9%.
This hydrogenated rubbery polymer is referred to as (B).

Hydrogenated rubbery polymer (C); internal volume 10
5 kg of degassed and dehydrated cyclohexane, 300 g of 1,3-butadiene and 0.25 g of tetrahydrofuran were charged into a liter autoclave, and the polymerization initiation temperature was set to 70 ° C.
And 1.00 g of n-butyllithium was added to carry out temperature-increasing polymerization. After the polymerization conversion reaches almost 100%,
The reaction solution was cooled to 15 ° C., 75 g of tetrahydrofuran,
700 g of 1,3-butadiene was added, and the temperature-raising polymerization was performed.
After the polymerization was completed, 0.53 g of tetrachlorosilane was added and the reaction was carried out for about 20 minutes. After the reaction was completed, the amount of living Li was measured and found to be 3.1 mmol.
Into this system, 0.56 g of benzophenone was added to the autoclave and stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living polymer terminal lithium as a living anion. Next, 3.51 g of benzophenone dissolved in 20 ml of cyclohexane and n-
A reaction product obtained by reacting 1.20 g of butyllithium in advance in a nitrogen atmosphere for 10 minutes was charged, and bis (cyclopentadienyl) titanium dichloride was added.
A component in which 52 g and 1.88 g of diethyl aluminum chloride dissolved in 10 ml of toluene were previously mixed in a nitrogen atmosphere was charged into an autoclave and stirred. Hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and 9
A hydrogenation reaction was performed at 0 ° C. for 1.5 hours. The hydrogenated polymer thus obtained had a degree of hydrogenation of 98% and a weight average molecular weight of 40.
MFR measured at 10,000, 230 ° C and 10 kg load is 10
g / 10 minutes. The 1,2-vinyl bond content of the first-stage polymerization before hydrogenation was 15%,
-The vinyl bond content was 80%. This hydrogenated rubbery polymer is designated as (C).

Hydrogenated rubbery polymer (D); internal volume 10
5 kg of degassed and dehydrated cyclohexane, 300 g of styrene and 75 g of tetrahydrofuran were charged into a liter autoclave, the polymerization initiation temperature was set to 50 ° C., and 1.60 g of n-butyllithium was added to carry out temperature-rise polymerization. After the polymerization conversion reached almost 100%, the reaction solution was cooled to 15 ° C.
, 700 g of 1,3-butadiene was added, and the temperature was raised. After the polymerization was completed, 0.85 g of tetrachlorosilane was added and the reaction was carried out for about 20 minutes. After the reaction was completed, the amount of living Li was measured and was found to be 2.5 mmol. In this system, 0.46 g of benzophenone was added to the autoclave and stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living polymer terminal lithium as a living anion. Next, 2
2. Benzophenone dissolved in 0 ml of cyclohexane.
A reaction product obtained by previously reacting 54 g with 1.24 g of n-butyllithium in a nitrogen atmosphere for 10 minutes was charged, and 0.52 g of bis (cyclopentadienyl) titanium dichloride and 1.88 g dissolved in 10 ml of toluene were further charged. A component obtained by previously mixing diethylaluminum chloride in a nitrogen atmosphere was charged into an autoclave and stirred. Hydrogen gas was supplied at a pressure of 8 kg / cm ² G, and a hydrogenation reaction was performed at 90 ° C. for 1.5 hours. The hydrogenation rate of the obtained hydrogenated polymer was 98%, the weight average molecular weight was 205,000, and the MFR measured at 230 ° C and 10 kg load was 10 g / 10 minutes. Before the hydrogenation, the 1,2-vinyl bond content was 80%, and the styrene content was 2%.
It was 9.5%. This hydrogenated rubbery polymer is (D)
And

Hydrogenated rubbery polymer (E): A block copolymer (Tuftec H1052) obtained by hydrogenating a polybutadiene portion of a polystyrene-polybutadiene-polystyrene copolymer manufactured by Asahi Kasei Corporation was dissolved in cyclohexane. This hydrogenated rubbery polymer is designated as (E).

Rubbery polymer (F): 5 kg of degassed and dehydrated normal hexane, 0.72 g of diethylaluminum chloride, were placed in an autoclave having an internal volume of 10 liters.
0.07 g of vanadium oxytrichloride was charged, the polymerization initiation temperature was set at 40 ° C., and ethylene, propylene, and 5-ethylidene-2-norbornene were continuously charged at a ratio of 5.5: 3.0: 1.5 to form a mixture. Polymerized. During the copolymerization, hydrogen was continuously charged as a molecular weight regulator. The obtained rubbery polymer had a propylene content of 30%, an iodine value of 15, and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 90. This rubbery polymer is designated as (F).

Rubbery polymer (G); Nippon Synthetic Rubber Co., Ltd.
Butadiene rubber (JSR BR11) was dissolved in cyclohexane. This rubbery polymer is designated as (G).

Rubbery polymer (H); Nippon Synthetic Rubber Co., Ltd.
Isoprene rubber (JSR IR2200) was dissolved in cyclohexane. This rubbery polymer is designated as (H).

Example 1 A solution of the hydrogenated rubbery polymer (A) in cyclohexane was
1-hydroxyethylidene-1,1-diphosphonic acid as a deactivator, water as a reaction terminator, 1.5-fold molar, 5.0-fold with respect to the metal amount of the catalyst used in the polymerization and hydrogenation reactions, respectively. As a dispersant, a polyoxyalkylene alkyl ether phosphate was added as a dispersant in an amount of 0.02% based on the amount of the rubbery polymer, and the mixture was sufficiently mixed to terminate the reaction (first step). Then, 0.5 part of pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as a stabilizer was added to 100 parts of the hydrogenated rubbery polymer (A). (2nd
Process). This polymer solution was subjected to steam stripping under the conditions shown in Table 1 (fourth step). The concentration of polymer crumb in the slurry in the solvent removal tank was 2%.

Next, the aqueous dispersion slurry of the crumb-like hydrogenated rubber-like polymer (A) obtained above was sent to a rotary screen to obtain a wet crumb having a water content of about 45%. The wet crumb was sent to a single screw extruder type water drawer to obtain a polymer having a moisture content shown in Table 1 (fifth step).
Thereafter, the polymer obtained above was supplied to an expander drier, and dried at a cylinder temperature of 150 ° C. to obtain crumb. Thereafter, the obtained crumb was supplied to a single-screw, single-stage vent extruder to obtain a cylinder temperature of 190. C., the screw rotation speed was about 70 rotations / minute, and the vent was extruded open (sixth step). The polymer obtained in the form of a strand from the tip of the extruder was formed into pellets using a pelletizer. Table 1 shows the water content, residual metal content, devitrification resistance, and moist heat resistance of the finally obtained polymer.
Shown in As shown in Table 1, the rubbery polymer obtained by the method of the present invention had a small amount of residual metal used for the polymerization catalyst and the hydrogenation catalyst, and was excellent in devitrification resistance and wet heat resistance. .

Examples 2 to 8 In the same manner as in Example 1, each of the hydrogenated rubbery polymer and the rubbery polymer obtained above was used to prepare the phosphonic acid or phosphonate described above. The conditions in the process were implemented within the scope of the present invention. As shown in Tables 1 and 2, the rubbery polymer obtained by the method of the present invention has a small amount of residual metal used for the polymerization catalyst and the hydrogenation catalyst, and has excellent devitrification resistance and wet heat resistance. there were.

Comparative Examples 1 to 5 In Comparative Examples 1 to 5 in Table 3, the conditions in each step were carried out outside the scope of the present invention. Comparative Examples 1 and 5 did not use a defatting agent, had a low defatting rate, and were inferior in devitrification resistance and wet heat resistance. Comparative Example 2 was an example in which no dispersant was used, and had a low defatting rate and was inferior in devitrification resistance. Comparative Example 3 is a case where the temperature of the solvent removal tank was set to 121 ° C.
The removal rate was low, and the devitrification resistance and wet heat resistance were poor. Comparative Example 4
Is the case where the temperature of the solvent removal tank is 90 ° C. or less,
The removal rate was low, and the devitrification resistance and wet heat resistance were poor. As described above, in Comparative Examples 1 to 5, any of the physical properties measured as compared with those in Examples were extremely poor.

Comparative Example 6 In the method of Example 1, a stabilizer was added before the addition of the reaction terminator. Table 4 shows the results. The residual amount of lithium in the obtained rubbery polymer was 90 ppm,
In addition to poor transparency, devitrification resistance, and wet heat resistance, the color tone (YI value) of Example 1 was excellent at 2.0, whereas
This comparative example was inferior to 22.3.

Comparative Example 7 The procedure of Example 1 was repeated, except that the solution obtained by flash-evaporating cyclohexane so that the concentration of the rubbery polymer solution was about 65% was used in the fourth step. Steam stripping was performed in the same manner as described above. Table 4 shows the results. As a result, crumbs having a particle size of more than 30 mm were generated, and at the same time, agglomeration between the crumbs was observed. In addition, the desorption rate was also low.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

(Note 1) The amounts of the deactivator and the reaction terminator are the number of moles relative to the metal atom used for the polymerization catalyst and the hydrogenation catalyst. (Note 2) The amount of the dispersant is% with respect to the amount of the rubbery polymer. (Note 3) Al = aluminum V = vanadium

[0065]

The present invention provides a method for efficiently removing catalyst residues when a rubbery polymer is obtained by a steam stripping method. The obtained polymer has transparency and devitrification resistance. Because of its excellent moisture and heat resistance, it is used as various molded products by injection molding, extrusion molding, vacuum molding, etc., taking advantage of its characteristics. By taking advantage of its excellent characteristics, it is used for sheets, films, automotive interior and exterior materials, electric and electronic materials. It can be used for various members, vulcanized rubber, toys, household goods, etc. In particular, since a rubber-like polymer having excellent devitrification resistance and moisture-heat resistance can be obtained, it can be used in a humid atmosphere or used in contact with water, such as food containers, food packaging materials, and food containers. Industrial sheets such as packaging materials, toys, waterproof sheets,
It can be used effectively for medical supplies.

Claims (1)

[Claims] 1. A rubber obtained by removing a metal component by a combination of the following steps (1) to (6) in recovering a rubbery polymer by steam stripping a solvent from a solution or slurry of the rubbery polymer. Of recovering a polymer in the form of a gel. (1) A solution or slurry of a rubbery polymer is added to (a) phosphonic acid and / or phosphonate, (b) water and, if necessary, the following (c) phosphoric acid ester and / or (d) phosphoric acid A step of adding an ester salt. (C) at least one phosphate ester selected from the group consisting of polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkenyl ether phosphate, polyoxyalkylene alkyl aryl ether phosphate and polyoxyalkylene alkenyl aryl ether phosphate . (D) at least one phosphate ester selected from the group consisting of polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkenyl ether phosphates, polyoxyalkylene alkyl aryl ether ether phosphates and polyoxyalkylene alkenyl aryl ether phosphates A phosphoric acid ester salt comprising an alkali metal salt and / or an ammonium salt. (2) A step of adding a stabilizer to the solution or slurry of the rubbery polymer. (3) A step of bringing 0 to 100 parts by weight of water into contact with 100 parts by weight of the rubbery polymer solution or slurry. (4) a rubber-like polymer solution or slurry having a polymer concentration of 10 to 60% by weight at a boiling point of a solvent or at a temperature not lower than the azeotropic temperature and not higher than 120 ° C. when the solvent and water are azeotropic; A step of stripping to obtain a slurry in which a crumb-like polymer is dispersed in water. (5) A step of dehydrating the water-containing rubber-like polymer crumb obtained above to a water content of 3 to 30% by weight. (6) A step of drying the rubber-like polymer obtained above to make the water content less than 3% by weight.