JPS61151217A - Production of polymer particle - Google Patents

Abstract

PURPOSE:To obtain easily in high yield polymer particles each of which contains both of a crystalline conjugated diene polymer and another copolymer, by mixing a first catalyst component with an aqueous dispersion of polymer seed particles containing a conjugated diene monomer, adding a second catalyst component to the reaction mixture and polymerizing the resulting mixture. CONSTITUTION:In stem 1, an aqueous dispersion (i) of a polymer seed particles containing a conjugated diene monomer is mixed with an aqueous dispersion (ii) of a first catalyst component solution containing a cobalt compound (A), at least one (B) selected from among alkali metal, organometallic compounds containing a Group I-III metal of the periodic table and metal hydride compounds containing Group I-III metal of the periodic table, and a conjugated diene compound (C) in an amount corresponding to 1-1,000mol per mol of said cobalt compound (A). In step 2, a second catalyst comprising at least one compound selected from among carbon disulfide, phenyl isotyiocynate and xanthogenic compounds are added to the reaction mixture and the resulting mixture is polymerized.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention is directed to the production of conjugated diene monocapsules,
The present invention relates to a method for producing polymer particles in which a crystalline polymer containing a high proportion of unsaturated hydrocarbon groups in its side chains and another polymer coexist within the same particle. [Prior Art] 1,2-polybutadiene, which is a crystalline polymer having a high proportion of vinyl groups in its side chains, has features such as a high melting point, excellent mechanical properties, and solvent resistance, and is used in adhesives, for example. (JP-A-56-79169) Coating agents (JP-A-56-98160), asphalt m-acid (JP-A-50-135114), thermal adhesives (JP-A-50-135114),
-13674 Publication, JP-A-56-89934 Publication]
No. Publication Photosensitive resin for printing plates (Japanese Patent Application Laid-open No. 52-12004
(Japanese Patent Application Laid-Open No. 52-54301), backing agents for carpets (Japanese Patent Application Laid-Open No. 51-72683), foams (Japanese Patent Application Laid-Open No. 55-73071, Japanese Patent Application Laid-Open No. 52-4)
It is widely used in fields such as 3873 Publication). However, since the synthesis of such crystalline polymers generally requires the use of organometallic compounds as catalysts, it is difficult to polymerize them in an aqueous system, and therefore it is generally said that they must be produced by solution polymerization. but,
This causes various problems as described below. (1) The viscosity of the reaction solution increases as the polymerization reaction progresses, making it difficult to stir the solution and control the 7M degree, making it difficult to obtain a crystalline polymer with the desired properties. be. (2) Since the obtained crystalline polymer is in a solution state, it is difficult to separate it (in addition, it is necessary to recover the solvent, so handling is complicated and the work efficiency is poor. (3) Obtained When using crystalline polymers in solution state, it is not only necessary to ensure safety against the odor, toxicity, or flammability of organic solvents, but also to ultimately remove and recover the organic solvents. However, there are limitations in terms of applications. For these reasons, there is a desire to develop a method for producing crystalline polymers in an aqueous system. [Problems to be Solved by the Invention] The present invention , which was developed against the above background, solved the problem of deactivation of organometallic compound catalysts in aqueous systems, and created an unsaturated hydrocarbon group in the side chain, which is useful for various applications. An object of the present invention is to provide a production method that can efficiently and easily produce polymer particles in an aqueous dispersion in which a high proportion of a crystalline polymer and another polymer coexist in the same grain preform. [Means for Solving the Problems] A particularly characteristic feature of the production method of the present invention is that the catalyst used is composed of a first catalyst component solution and a second catalyst component solution, which will be described in detail later. It is a specific catalyst that exhibits catalytic action only when both catalyst components are combined, and each of these catalyst components is gradually added to the reaction system dispersion in steps (I) and (B) below. Step (1): An aqueous dispersion obtained by dispersing polymer seed particles containing a conjugated diene monomer in water and a first catalyst component solution are added to water. The first catalyst component solution is brought into contact with the polymer seed particles.
Let it absorb. Step (1): A second catalyst component is added to the system obtained in step (I) to perform polymerization. The present invention will be explained in detail below. The aqueous dispersion of polymer seed particles used in the step (I) is constituted by containing a conjugated diene monomer in the polymer seed particles, and such an aqueous dispersion can be prepared, for example, by the following method. I can do it. The first method for preparing an aqueous dispersion is to add an amount equivalent to 200 parts by weight or less to 100 parts by weight of the polymer seed particles to an aqueous dispersion (emulsion or suspension) containing polymer seed particles as a dispersed phase. An example of this method is to add a conjugated diene monomer and mix and stir the mixture. Here, if the amount of conjugated diene monomer used is excessive with respect to the polymer seed particles, the amount of conjugated diene monomer remaining in the dispersion medium without being absorbed by the polymer seed particles will increase. As a result, unexpected new polymer particles are generated, which is undesirable. The aqueous dispersion used in step (I) above is not particularly limited, and may be obtained by emulsion polymerization, for example, with a particle size of 0.05
An emulsion made of dispersed particles of ~6 μm or a suspension made of dispersed particles with a particle size of 1 to 100 μm obtained by suspension polymerization can be used. Polymers constituting such dispersed particles include polystyrene, polybutadiene, styrene-butadiene copolymer,
Examples include acrylonitrile-butadiene copolymers, acrylic ester copolymers, metaagelene ester copolymers, polyisoprene, butadiene-isoprene copolymers, polychloroprene, and others. The aqueous dispersion may be formed by redispersing a polymer obtained by solution polymerization or the like in water using an emulsifier, for example, c
Known dispersions such as IS-1, 4 polyisoprene dispersions, natural rubber latex or concentrates thereof, etc. can also be used. A second method for preparing an aqueous dispersion involves preparing an emulsion containing a conjugated diene monomer and carrying out emulsion polymerization.
When the polymerization conversion rate reaches 99% or less, preferably 90% or less, a polymerization terminator may be added to stop the polymerization. As the above polymerization terminator, the process (
1) or in step (II), any catalyst can be used as long as it does not cause loss of activity of the first or second catalyst component, such as N,N-diethylhydroxylamine, tetraethylenepentamine, etc. Amine compound; p-tert-butylcatechol, di-tert-amylhydroquinone, α-nitrone-β
- Phenol compounds such as naphthol; hydrazine compounds such as phenylhydrazine; and sodium nitrite. As the conjugated diene monomer contained in the polymer seed particles in the above aqueous dispersion, those having 4 to 5 carbon atoms such as butadiene and isoprene can be used, and in particular
, 3-butadiene are preferred. Moreover, these conjugated diene monomers can also be used after being dissolved in an organic solvent, if necessary. Examples of such organic solvents include aromatic hydrocarbon compounds such as benzene, toluene, and xylene; aliphatic hydrocarbon compounds such as pentane, hexane, heptane, and octane; and halogenated hydrocarbon compounds such as methylene chloride, ethylene dichloride, trichloroethane, and chlorobenzene. Hydrogen compounds; Ester solvents such as ethyl acetate, propyl acetate, butyl acetate, ethyl octylate, 8-caprolactone, r-valerolactone; methanol, ethanol, isopropyl alcohol, n-butanol, 5eC-butanol, octatool, ethylene glycol Alcohol solvents; ketone solvents such as acetone, methyl ethyl ketone, acetophenone, acetylacetone; nitrile solvents such as acetonitrile, adiponitrile, benzonitrile; C-caprolactone, propiolactam, butyrolactam, valerolactone, N-methylpyrrolidone, N -Ethylpyrrolidone, N-
Methylformamide, N-ethylformamide, N・N
- Amide solvents such as dimethylformamide can be mentioned. Among these, ester solvents are particularly preferred. Further, these organic solvents can also be used as a solvent for the second catalyst component described later. The first catalyst component solution used in the process (phantom) of the present invention includes (A) an alkali metal (with a cobalt compound),
At least one kind selected from the group of organometallic compounds formed by metals of Groups I to II of the Periodic Table and metal hydrides formed by metals of Groups I to II of the Periodic Table. It can be obtained by contacting a metal or a compound in the presence of a zero-conjugated diene-based compound in an amount of 1 to 1000 times the mole of the cobalt compound (A). Examples of cobalt compounds for forming the catalyst component solution in item 1) include organic acid salts such as cobalt octylate, cobalt nantenate, cobalt benzoate, cobalt shorate, cobalt malonate, and cobalt acetate; bisacetyl; Cobalt complexes such as cobalt acetonate, cobalt trisacetylacetonate, cobalt acetoacetate ethyl ester, triphenylphosphine complex of cobalt bromide, trim-)lylphosphine complex of cobalt bromide, IJ m-ki of cobalt bromide Triarylphosphine complexes of cobalt halides such as silylphosphine complexes, pyridine complexes of cobalt chloride, β-picoline complexes of cobalt chloride, Nato halokenes (1), pyridine derivative complexes of cobalt chloride, ethyl alcohol complexes of cobalt chloride, ( 1,3-butadiene)(1-(
2-methyl-3-butenyl)-π-allyl]cobalt,
Tris-π-allyl cobalt, bicyclo-(3,3,0
)-octidienyl-1,5-cyclooctadiene cobalt, bis-(π-allyl)-halogenocobalt (however, the halogen is either Ianr*Cx), or monovalent or zero-valent cobalt such as octacarbonyl dicobalt. Examples include cobalt complexes. These cobalt compounds can be used alone or in combination of two or more. Of the group Φ) for forming the first catalyst component solution, sodium and lithium are preferably used as the alkali metals, and organometallic compounds or metals of Groups I to II of the periodic table. As the hydride, a compound that reduces a cobalt compound is preferably used. Metals from groups ① to ① of the periodic table and 1. Ia, Ib, Ila, Il
Metals of groups Ia, Ia, and Ib can be used, among which Ia
* Group I a + I a is preferable, and preferable metals include lithium, sodium, potassium, magnesium, zinc, and aluminum, and particularly preferable metals include lithium, magnesium, and aluminum. can. Further, preferable organometallic compounds or metal hydrides are as follows:
Alkyl derivatives having 1 to 6 carbon atoms or aqueous derivatives of the above metals are preferable, and organic lithium compounds such as ethyllithium, n-butyllithium, 5eC-butyllithium, and t-butyllithium, and organic lithium compounds such as diethylzinc and dimethylzinc are preferred. Zinc compounds, organomagnesium compounds such as butylmagnesium chloride, ethylmagnesium bromide, dibutylmagnesium, dihexylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trilohexylaluminum, tridodecylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, ethyl Examples include organoaluminum compounds such as aluminum sesquichloride, ethylaluminum dichloride, and tetraetheraluminoxane, and metal hydride compounds such as lithium aluminum hydride, sodium boron hydride, and lithium boron hydride. These metal compounds can be used alone or in combination of two or more. C) The conjugated diene compound for forming the first catalyst component solution is a compound having a carbon number such as butadiene or isoprene, which may be the same or different from the conjugated diene single case used in step (1). It mainly refers to conjugated diene compounds of 4 to 5, but is not limited thereto, and also includes oligomers or complexes of these conjugated diene compounds. The method of preparing the first catalyst component solution is extremely important. This method of preparing a catalyst component solution requires special equipment to prepare a cobalt compound (B) and a cobalt compound (B
) It is to contact and react with an alkali metal, an organometallic compound of groups 1 and 2 of the periodic table, or a metal hydride. In this preparation, the amount of the zero-conjugated diethylene compound used (1%) is 1 to 100% per mole of the cobalt compound.
It is preferably 0 mol, more preferably 6 to 300 mol, and the amount of φ) alkali metal, organometallic compound or metal hydride of Group 1 and I of the periodic table to be used is (A)
The amount is preferably from 0.3 to 100 mol, more preferably from 0.9 to 50 mol, per mol of the cobaltized adduct. The temperature during preparation is preferably -78°C to 100°C, more preferably -30°C to 50°C. By stirring the solvent and the catalyst component as necessary during preparation, the reaction between (A) the cobalt compound and (B) the alkali metal, organometallic compound, or metal hydride can be uniformly carried out. Here, the solvents used for preparation include solvents with low solubility in water such as n-hexane, n-hebutane, n-pentane, and purified solvent oil, or water-soluble solvents such as toluene', xylene, and cyclohexane. Although a solvent having a relatively high solubility in the former solvent or a mixed solvent of this solvent and the latter solvent can be preferably used. The second catalyst component (
5) comprises at least one compound selected from carbon disulfide, phenylisothiocyanate and xanthogen compounds. Although there are no particular limitations on the use of these second catalyst components, it is desirable to remove dissolved oxygen in advance by bubbling with nitrogen gas or the like prior to use. The xanthogen compound has the general formula R-0-C-
8-, such as methylxanthate, ethylxanthate, n-propylxanthate, isopropylxanthate, n-butylxanthate,
5ec-butylxanthogenic acid, 6-butylxanthonic acid, n-pentylxanthenoic acid, n-hexylxanthogen H1n-heptylxanthonic acid, n-octylxanthonic acid, 2-ethylhexylxanthenoic acid, phenylxanthokenic acid, Xanthate acids such as p-tolylxanthate; and lithium, sodium, potassium salts of these xanthate acids; and dimethylxanthogen disulfide, diethylxanthogen disulfide, di-n-propylxanthogen disulfide, diisopropylxanthogen disulfide, di-n-
Xanthogen disulfides such as butylxanthogen disulfide, di-t-butylxanthogen disulfide, 2-ethylhexylxanthogen disulfide, diphenylxanthogen disulfide, and ethylphenylxanthogen disulfide are preferably used. Among these, xanthogen disulfide is particularly preferred, and dimethylxanthogen disulfide, diisopropylxanthogen disulfide, and diphenylxanthogen disulfide are particularly preferred. The usage of the second catalyst component is to add the first catalyst component solution)
Preferably 0.01 to 1 per mole of cobalt compound
00 mol, more preferably 0.3 to 10 mol. Next, the manufacturing method of the present invention will be explained in more detail. First, in step (1), an aqueous dispersion of polymer seed particles containing a conjugated diene monomer obtained by the method described above and separately the first catalyst component solution described above are added to water. Mix and stir the aqueous dispersion obtained by dispersing,
A first catalytic acid solution is absorbed into the polymer seed particles. In order to effectively absorb the first catalyst component solution into the polymer seed containing the conjugated diene monomer, the first catalyst component solution must have a particle size that is equal to the particle size of the polymer seed particles. It is preferable to finely disperse it in water in the presence of an emulsifier to form an emulsion so that it is equal to or lower than . The emulsifiers that can be used here are particularly limited, and examples include anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dialkylsulfate, formalin condensate of naphthalenesulfonic acid, etc. In addition, nonionic surfactants such as polyoxyethylene nonylphenol ether, polyethylene glycol monostearate, and sorbitan monostearate can also be used in combination. Moreover, the aqueous dispersion obtained in the above step (1) is
In order to promote the absorption of the first polymerization catalyst component into the polymer seed, it contains acetone, lower alkanol, methyl acetate, acetonitrile, etc. as a swelling agent that has high water solubility and can serve as a solvent for the solution of the first catalyst component. can do. These solvents can be used at a ratio of 1 to 100% based on water, but in order to maintain a good dispersion state of the polymer particles, they should be used at a ratio of 10% or less, preferably 5% or less. It is desirable that Next, in step (If), a second polymerization catalyst component is added to the system obtained in step (I), and the temperature is -5 to 8.
Polymerization is carried out at 0°C, preferably from 0 to 50°C. Such polymerization odor

[ can carry out the polymerization reaction at a polymerization conversion rate of approximately 100% without performing a special treatment to terminate the polymerization reaction, but the polymerization conversion rate depends on the polymerization termination agent, such as potassium salt or sodium salt of dimethyldithiocarbamic acid. It can be controlled by adding thiocarbamate compounds such as ammonium salts, thiuram disulfide compounds such as tetramethylthiuram disulfide, etc. to the system. Note that the water used in the production method of the present invention, that is, water as a dispersion medium and water required during polymerization, is prepared by bubbling with nitrogen gas or using a water-soluble dissolved oxygen remover such as sodium dithionite in advance. It is desirable to remove dissolved oxygen by In the production method of the present invention, the polymerization reaction tank system used is not particularly limited, and a homopolymerization reaction tank system or a multistage polymerization reaction tank system in which a plurality of stirred polymerization reaction tanks are connected in series may be used. However, a multi-stage polymerization reaction tank system is preferably used because the polymerization conditions can be easily controlled and polymer particles having uniform quality can be obtained. FIG. 1 schematically represents a multistage polymerization reaction tank system that can be suitably used in the production method of the present invention. In Figure 1, 8(1)
~8(12) are stirring type polymerization reaction vessels connected in series, and polymerization reaction vessels 8(1) to 8(7) in the previous stage are connected to each other in series.
In step (1), an aqueous dispersion of polymer seed particles used in step (1) is produced, and in subsequent polymerization reaction vessels 8(8) to 8(12), step (1) and step (It) are carried out. will be carried out. 1 to 6 are raw materials necessary for producing the aqueous dispersion (emulsion) of polymer seed particles used in step (I) (e.g., a polymerizable monomer, an aqueous dispersion medium containing an emulsifier, etc., 9 active agent molecules) 7 and 11 are sources of reaction terminators. 12 is a supply source of the first catalyst component solution, 13 is a supply source of an aqueous dispersion medium containing an emulsifier, etc., and these supply sources 12.1
The first catalyst component solution and the aqueous dispersion medium supplied from 3 are stirred and emulsified by a homogenizer 9, and then supplied to polymerization reaction vessels 8 (8) and (9). 10 is a supply source of the second catalyst component solution, and this second catalyst component solution is supplied to the polymerization reaction tank (9) (IQ). The polymer particles will be described. The polymer particles of the present invention are obtained by polymerizing the polymer constituting the polymer seed particles used in step (1) and the conjugated diene monomer contained in the polymer seed particles. It is a composite polymer particle formed by coexisting in the same particle with a crystalline polymer formed by The content ratio of vinyl groups in the side chains of a crystalline polymer is determined by measuring the infrared absorption spectrum of this polymer using Mor e r o analysis method. This is the result of the analysis.The melting point of the crystalline polymer constituting the polymer particles can be adjusted to 200% by changing the type or amount of the organic solvent used in the conjugated diene monocap and the second catalyst component. It can be controlled within the range below ℃.As organic solvents that have a large effect on lowering the melting point of crystalline polymers,
Examples include organic solvents having polar groups such as esters, alcohols, ketones, aldehydes, nitriles, amides, and sulfoxides. Further, the degree of crystallinity of the crystalline polymer varies depending on the reaction conditions, etc., but is usually 10% or more, usually 30% or more, and further 50% or more. In order to control the melting point of the polymer in the polymer particles of the present invention, a polymer having high affinity with the crystalline polymer synthesized in step (It) is used as a polymer seed particle containing a conjugated diene monomer. This can be achieved by appropriately selecting the combination. Polymers with high affinity for crystalline polymers include polybutadiene, butadiene-
Examples include styrene copolymer, butadiene-acrylonitrile copolymer, cis-1e4 polyisoprene, and natural rubber. By selecting the type and composition ratio of these polymers in consideration of their properties, such as their melting point, it is possible to control the melting point of the final polymer within a range of 200°C or less. Become. Additionally, as the average particle size of the polymer particles increases, the dispersion stability of the aqueous dispersion decreases, causing the polymer particles to float and separate. cause trouble. The dispersion stability of polymer particles is affected by the density of the polymer particles, the viscosity of the aqueous dispersion medium, the concentration of solids, etc., but the particle size of the polymer particles should be adjusted to approximately the range in which the particles can move due to thermal motion. The dispersion stability can be improved by setting the diameter to 5 μm or less, preferably 2 μm or less, and more preferably 1 μm or less. The particle size of the polymer particles can be controlled by selecting the particle size of the polymer seeds. When the polymer constituting the polymer seed is styrene-butadiene rubber, natural rubber, ethylene-propylene rubber, butadiene rubber, or polystyrene, the crystalline polymer is in the form of fine fibers in the polymer particles, Constitute polymer/fiber composite particles. Such polymer/fiber composite particles can be easily formed into a film by air-drying or the like, and can form a highly reinforced film, so they can be suitably used for various purposes described below. Further, polymer particles obtained by the production method of the present invention, comprising a small amount (both one kind of monomer) selected from the group of conjugated diolefins, aromatic vinyls, acrylic esters, methacrylic esters, and vinyl cyanide, may also be used. Polymer or copolymer of 50 to 95 units and crystalline 1,2-polybutadiene containing 80 units or more of 1,2-vinyl bonds 50 to 95 units
5% by weight and having a particle size of 0.05 to 1 μm can be used for various purposes described below, and are particularly useful. [Effects of the Invention] The production method of the present invention For example, polymer seed particles pre-contained with a conjugated diene monomer. By absorbing the first catalyst component solution and then absorbing the second catalyst component to carry out the main reaction, a very industrially useful crystalline conjugated diene polymer can be produced, as will be clear from the examples described below. Polymer particles in which the polymer and other polymers coexist within the same particle can be easily produced in high yield. By pre-containing a conjugated diene monomer in the polymer seed particles and then adding a catalyst to carry out polymerization, it is possible to carry out polymerization without significantly changing the emulsion polymerization process used in ordinary synthetic rubber production, and with the addition of some additional equipment. Since it can be implemented by providing it, it has the advantage of being easy to industrialize. Further, by preparing the first catalyst component solution as an aqueous dispersion in advance and mixing and stirring this with an aqueous dispersion of polymer seed particles containing a conjugated diene monomer, the first catalyst component solution and the polymer This is advantageous in that the first catalyst component solution can be efficiently absorbed into the polymer seed particles as a result of the increased opportunity for contact with the seed particles. In addition, by appropriately selecting the type of polymer constituting the polymer seed particles, the composition ratio of the polymer and the conjugated diene monomer contained in the polymer seed particles, etc., as a result,
The melting point or fine structure of the obtained polymer can be controlled, and the polymer can be easily modified. Such polymers are crystalline polymers that have a high proportion of vinyl groups in their side chains, have a high degree of crystallinity, have a high melting point, and are excellent in impact resistance, solvent resistance, etc. It can be used in a wide variety of applications, especially in the form of aqueous dispersions, such as paper coating compositions, carpet backing agents, asphalt compositions, foam rubbers, paints. It is suitable for adhesives, adhesives, and organic fillers for rubber or resin, and is effective for improving and modifying the strength and heat resistance of these various materials. [Embodiments of the Invention] Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, "part" and "chi"
represents Higashisagibe and Egatachi. (Example 1) Natural rubber latex (produced in 'elda, Malaysia 1) with an average particle size of dispersed particles of 0.4 μm was prepared with a solid content of 15.5 μm.
1 part and 48 parts of distilled water were placed in a pressure-resistant reaction vessel, and the system was sufficiently bubbled with nitrogen gas. Next, after cooling the system to 5° C., 3.1 parts of 1,3-butadiene was added and stirred for 30 minutes to allow the latex particles (seed particles) to absorb 1,3-butadiene. This will be referred to as "seed dispersion A." After putting 0.33 parts of a 2 mol/1 n-hexane solution of cobalt octylic acid Q into a pressure-resistant container that had been purged with nitrogen in advance, 0.56 parts of cyclohexane was added thereto and the mixture was thoroughly stirred. After the system was cooled to 5° C., 0.11 part of 3-butadiene was added and stirred for 30 minutes. To this was added 0.39 parts of an n-hexane solution containing 0.5 mol/f of triisobutylaluminum, and the mixture was stirred for 30 minutes while being cooled to obtain a first catalyst component solution. This first catalyst component solution was mixed with 0.2 parts of sodium dodecylbenzenesulfonate (solid content) and 1 liter of distilled water bubbled with nitrogen! was added and predispersed using a homomixer under a nitrogen gas atmosphere, and then emulsified and dispersed using a homogenizer (manufactured by Manton Galarin, "15M type") to form an aqueous dispersion with a particle size of 0.1 to 0.3 μm. Prepared. This is called "first catalyst dispersion A." This first catalyst dispersion A is added to the previously prepared seed dispersion A.
was added and stirred for 30 minutes while maintaining the temperature at 5°C. Next, 0.11 parts of an n-hexane solution containing 0.6 m01/1 of carbon disulfide (hereinafter referred to as "second catalyst solution A") was added to this solution, and the mixture was heated for 3 hours while controlling the temperature at 5°C. The first polymerization was carried out with slow stirring. In the above polymerization, the combined yield was 95%, and no coagulum was observed. When the obtained polymer was examined, it was found that Melting point measured by wrinkle meter is 200℃
The content ratio of vinyl groups was determined to be 98- by Morer analysis of infrared absorption spectrum. (Example 2) 70 parts of 1.3-butadiene, 30 parts of styrene, 5.0 parts of potassium stearate, 0.1 part of potassium phosphate, and 0.06 part of sodium ethylenediaminetetraacetate. Ferrous sulfate Q, 0.005 parts, sodium formaldehyde sulfoxylate) 0.03 parts, diisopropylbenzene hydroperoxide 0.03 parts, tertiary dodecyl mercaptan 0.2 parts, and distilled water 190 parts were replaced with nitrogen gas. The mixture was charged into a reactor and polymerization was started at 5° C. with stirring. Approximately 15 hours after starting the reaction, the Togane rate reached 72chi, so N. 0.15 parts of N-diethylhydroxylamine was added to the Togane system to stop the reaction. This is called “Seed Dispersion B”
shall be. Hereinafter, the above seed dispersion B was used instead of the seed dispersion in Example 1, and the amount of 5 in Example 1 was used.
Polymerization was carried out in the same manner as in Example except that the first catalyst dispersion A and the second catalyst solution A were used in an amount equivalent to twice the amount of the first catalyst dispersion A and the second catalyst solution A, and when the bundle conversion rate reached 70%, potassium dimethyldithiocarbamate was added. Polymerization was stopped by adding 0.1 part. As a result, a latex with excellent dispersion stability and no coagulum was obtained. When the obtained polymer was examined, the melting point was 200C by a differential scanning calorimeter, and the infrared absorption spectrum showed that Mo
The content of vinyl groups according to r e r -folding method is 95
%Met. (Example 3) Polymerization similar to that in Example 2 was carried out using the multistage polymerization reaction tank system shown in FIG. As a result, as in Example 2, it was possible to continuously and efficiently obtain a latex with good dispersion stability without the generation of coagulum. (Example 4) Commercially available acrylic yarn latex [AB203J (manufactured by Japan Synthetic Rubber Co., Ltd.) in a solid content of 124 parts and distilled water 4
00 parts were placed in a pressure-resistant reaction vessel, and the system was sufficiently bubbled with nitrogen gas. Next, after cooling the system to 5°C, 1.3
- 3.1 parts of butadiene was added and stirred for 30 minutes to absorb 1,3-butadiene into the seed particles. This will be referred to as "seed dispersion C." Add 0.3 cyclohexane solution of 0.2 mol/1 cobalt octylic acid to a pressure-resistant container that has been purged with nitrogen in advance.
After adding 9 parts, the system was cooled to 5°C and further heated to 1°3-
After adding 0.11 parts of butadiene, the mixture was stirred for 30 minutes. Add to this 0.2 mol of sodium boron hydride/
1.2 parts of the 1so-propertool solution of i was added and stirred for 30 minutes while cooling to obtain a first catalyst component solution. To this first catalyst component solution, 0.2 parts of sodium dodecylbenzenesulfonate (solid content) and 10 parts of distilled water bubbled with nitrogen were added, and the mixture was preliminarily dispersed using a homomixer under a nitrogen gas atmosphere. An aqueous dispersion was prepared by emulsification and dispersion using a "15M type" manufactured by Lin Co., Ltd.). This will be referred to as "first catalyst dispersion B." This first catalyst dispersion B is added to the previously prepared seed dispersion C.
was added and stirred for 30 minutes while maintaining the temperature at 5°C. Next, add the second catalyst solution A (carbon disulfide 0.6 mol
/1 n-hexane solution) was added, and 5
Polymerization was carried out with slow stirring for 3 hours while maintaining the temperature at °C. As a result, a latex with a polymerization yield of 97% and good dispersion stability with few coagulated substances was obtained. When the obtained polymer was examined, the melting point was 197° C. by differential scanning calorimetry, and the vinyl group content was 96° C. by Morero analysis. (Example 5) Cobalt chloride YI prepared at a weight ratio of cobalt chloride and pyridine of 1:5.7 was placed in a pressure-resistant container that had been purged with nitrogen in advance.
A tetrahydrofuran solution with a k degree of 0.2 mol/i.
After adding 45 parts and cooling the system to 5°C, 1,3-
0.11 part of butadiene was added and stirred for 30 minutes. To this, metallic sodium was suspended and dispersed in n-hexane 1,
5-fold IIT% (0.4 mol/1) solution at 0.31
The mixture was treated with Nr and stirred for 30 minutes while being cooled to obtain a first catalyst component solution. Add 0.2 parts of sodium dodecylbenzenesulfonate (solid content) and 10 parts of XM water bubbled with nitrogen gas to the conofi line component solution; pre-disperse with a homomixer under 5 nitrogen gas atmosphere, then emulsify with a homogenizer. Dispersion to prepare an aqueous dispersion. This will be referred to as "Our Catalyst Dispersion C". Seed dispersion A was prepared in the same manner as in Example 1, the first tuna hemorrhoid dispersion C was added thereto, and the mixture was heated at 5°C for 30 minutes.
Stir for a minute. Next, 0.11 parts of second catalyst solution A (0.6 mol of carbon disulfide/1 n-hexane solution) was added, and the polymerization was carried out with slow stirring for 3 hours while controlling the polymerization temperature at 5°C. went. The polymerization yield in the above polymerization reaction was 70%, and no coagulum was observed. Further, the melting point of the polymer determined in the same manner as described above was 188° C., and the content of vinyl groups was 93%. (Example 6) Cobalt naphthenate in a pressure-resistant container that has been purged with nitrogen in advance)
0.2 mol/1 dichlorohexane solution 0.39
After cooling the thread to 5° C., 0.11 part of 1,3-butadiene was added, followed by stirring for 30 minutes. Add to this 0.2 mo of sodium aluminum hydride.
1.2 parts of 1/II tetrahydrofuran solution was added and stirred for 30 minutes while cooling to obtain a first catalyst component solution. The above catalyst was used as the first catalyst component, and
As the catalyst component of A2, dimethylxanthogen disulfide Q, 5 mol/1 n-hexane solution 0.1
Polymerization was carried out in the same manner as in Example 4, except that 1 part was used. The polymerization yield in the above polymerization reaction was 20%, and a latex with good dispersion stability was obtained. In addition, the melting point of the polymer determined in the same manner as described above was 160 ° C.
The vinyl group content was 88%.

[Brief explanation of the drawing]

It is. 1 to 6...Raw material supply source 8(1) to 8(6)...Polymerization reaction tank 12...Supply source of first catalyst component solution]0...Second
Source of catalyst component solution ~・′,′

Claims (1)

[Claims] 1) In the step (I), an aqueous dispersion (A) of polymer seed particles containing a conjugated diene monomer, (A) a cobalt compound, (B) an alkali metal, a periodic table Group I~
Organometallic compounds containing metals of Group III and Periodic Table
A first compound containing at least one metal hydride selected from the group of metal hydrides containing Group I to Group III metals, and (C) a conjugated diene compound corresponding to 1 to 1000 times the mole of the cobalt compound (A). and an aqueous dispersion (b) of a catalyst component solution, and in step (II), a second catalyst component consisting of at least one compound selected from the group of carbon disulfide, phenylisothiocyanic acid and xanthogen compounds. A method for producing polymer particles, which comprises adding and polymerizing. 2) The average particle size of the dispersed particles made of the first catalyst component solution in the aqueous dispersion (b) is equal to or less than the average particle size of the polymer seed particles containing the conjugated diene monomer in the aqueous dispersion (a). A method for producing polymer particles according to claim 1. 3) The aqueous dispersion (a) of polymer seed particles containing a conjugated diene monomer emulsion polymerizes the monomer composition containing the conjugated diene monomer, and the conjugated diene monomer remains. 2. The method for producing polymer particles according to claim 1, wherein the polymer particles are obtained by stopping polymerization at a certain temperature. 4) The method for producing polymer particles according to claim 1, wherein the preparation of the aqueous dispersion (a) and steps (I) and (II) are carried out continuously using a multistage polymerization reaction tank system. .