JPS6123637A - Polymer particle and its production - Google Patents

Abstract

PURPOSE:To facilitate the formation of polymer particles containing a crystalline polymer containing a high proportion of unsaturated hydrocarbon groups in the side chains, by adding two specified catalyst components stepwise to the reaction system and emulsion-polymerizing a conjugated diene monomer in this system. CONSTITUTION:A cobalt compound (e.g., cobalt caprylate) is reacted with an organometallic compound or hydride of a metal of Group I -III of the periodic table (e.g., trimethylaluminum) in the presence of 1-1,000mol, per mol of the cobalt compound, of a conjugated diene compound (e.g., butadiene). Polymer seeds dispersed by emulsification in water (e.g., polybutadiene latex) are allowed to absorb the resulting first catalyst component solution. A conjugated diene monomer and a second catalyst component comprising a sulfur compound such as carbon disulfide are added to the reaction system and the mixture is polymerized to obtain polymer particles containing a crystalline polymer having at least 70% unsaturated hydrocarbon groups in the side chains.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to
This relates to polymer particles in which a crystalline polymer containing a high proportion of unsaturated hydrocarbon groups in the side chain and another polymer coexist within the same particle, and a method for producing these polymer particles. .

[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. -79169), coating agents (% 1987-98160), asphalt compositions (JP 5-O-i35114), thermal adhesives (JP-A 56-98160),
6-13674, JP-A-56-89934), Photosensitive tree Wi for flexible printing plates (% 1982-120)
No. 04 2% 1982-64301), for carpets, e-packing agents (JP 51-72683), foams (JP 55-73071, JP 52-72683)
2-43873) and other fields.

However, since such crystalline polymers generally require the use of organometallic compounds as catalysts in their synthesis, it is difficult to polymerize them in an aqueous system.Therefore, they are usually produced by solution polymerization; When using organic solvents under such conditions, it is not only necessary to ensure safety against the odor, toxicity, or flammability of organic solvents, but also the organic solvents must be removed and recovered, resulting in complicated handling. It is inferior in workability and has limitations in its applications.

In order to solve these problems and enable the crystalline polymer to be used for various purposes while ensuring high workability and safety, the polymer must be
Aqueous dispersion or emulsified dispersion using water as a dispersion medium (
Hereinafter, it will simply be referred to as an "aqueous dispersion." ) is very advantageous. By the way, in order to make the crystalline polymer obtained by the above-mentioned solution polymerization into an aqueous dispersion,
This crystalline polymer may be dissolved in a solvent, and the resulting solution may be emulsified and dispersed in water in the presence of an emulsifier. However, the aqueous dispersion obtained by such a method has the following drawbacks: (1) Because the polymer has high crystallinity and a relatively high melting point, the solvents that can be used are very limited;
Moreover, in order to completely dissolve this polymer in a solvent, high temperature and high pressure conditions are required.

Not easy to manufacture.

■ It is difficult to make the particle size of the polymer solution particles (oil droplets) that make up the dispersed phase small and uniform, resulting in poor dispersion stability, so it is difficult to maintain the dispersion in a stable state for a long period of time. I can't.

(2) rC requires a large amount of emulsifier for sufficient emulsification and dispersion, and -f: reduces the water resistance of the polymer.

However, it does not necessarily have sufficient industrial utility value.

[Object of the Invention] 1. The present invention has been made against the above background, and its purpose is to provide an unsaturated hydrocarbon group in the side chain, which is useful for various applications. The object of the present invention is to provide polymer particles in which a high proportion of a crystalline polymer and other polymers coexist within the same particle, and a manufacturing method that can efficiently and easily manufacture the polymer particles.

[Structure of the invention]

The feature of the polymer particles of the present invention is that they are obtained by polymerizing conjugated diene monomers. A crystalline polymer having ro% or more of unsaturated hydrocarbon groups in its side chain and a polymer different from this polymer coexist within the same particle.

The features of the method for producing polymer particles of the present invention are as follows:
The compound and (B) the organometallic compound or hydride of a metal from Groups ■ to ■ of the periodic table are combined with the former E (Al
A green component solution obtained by contacting the Konosilte compound in the presence of a conjugated diene compound of 1 to 1000 times the mole is absorbed into a polymer seed emulsified and dispersed in water. , then the conjugated diene monomer and (
1)) Polymerization is carried out by adding a second catalyst component consisting of at least one compound selected from the group of carbon disulfide, phenylisothiocyanic acid, and 1,000 yen compounds.

The present invention will be explained in detail below.

First, the manufacturing method of the present invention will be described.

What is particularly distinctive about the manufacturing method of the present invention?

The catalyst used is a first catalyst component solution and a second catalyst component solution, which will be detailed later.
It is a specific catalyst that is composed of many catalyst components and exhibits PR mediating action only when both catalyst components are combined, and each of these catalyst components is further processed in the following steps (Il and Step
) is added stepwise to the reaction system dispersion to carry out one polymerization.

Step (I): In a dispersion in which polymer seeds are preliminarily dispersed in water, the catalyst component bath liquid of Feed 1 is brought into contact with and absorbed by the polymer seeds.

Step (11): A conjugated diene monomer is added to the system obtained in step a(I), and a z-th catalyst component is further added to carry out polymerization.

The first ML medium acid component solution, a cobalt compound and (B
1 An organometallic compound or a hydrogen compound formed by the gold maple in Groups 1 and 2 of the periodic table.

1 to 1000 times the molar amount of t to the above-mentioned captive cobalt compound
It can be obtained by contacting in the presence of a cl-conjugated diene compound.

Further, the second catalyst component is -carbon disulfide.

It consists of at least one compound selected from phenylisothiocyanic acid and a chemical compound.

Examples of the cobalt compound (A) for forming the first catalyst component solution include organic compounds such as cobalt octylate, cobalt naphthenate, cobalt benzoate, cobalt shorate, cobalt malonate, and cobalt acetate. Acid salts, cobalt bisacetylacetonate, cobalt trisacetylacetonate.

Cobalt complexes such as cobalt acetoacetate ethyl ester, triphenylphosphine complexes of cobalt bromide, tri-m-)lylphosphine/packing of cobalt bromide, tri-m-thousylphosphine complexes of conjugated cobalt, and cobalt halides. Triarylphosphine complexes of cobalt chloride, pyridine complexes of cobalt chloride, β-picoline complexes of cobalt chloride, pyridine derivative complexes of cobalt chloride, ethyl alcohol complexes of cobalt chloride, (1,8-citadiene )(1-(21-methyl-8-butenyl)-π-
Allyl] cobalt, tris-π-allylconolt, bicyclo(B,8,0)-octidienyl-1,5-cyclooctadieneconolt, bis-(π-allyl)-
Cobalt halide (however, the halogens are I, Br.

Either CI. ), monovalent or zero-valent cobalt complexes such as octacarbonyl diconolt. These conomalt compounds may be used alone or in combination of two or more.

As (B) an organometallic compound or hydride of a metal of groups I to II of the periodic table for forming the first catalyst component solution, a compound that reduces a cobalt compound is preferably used. Metals from Groups 1 to M of the Periodic Table'''C1'i
, Ia, lt), la, jib, [la, 1llb
Group metals are used and the colors are Ia, la, l1la on this instep.
The preferred metal is Li
.

Examples of the metal include Na, Mg, Zn, and AI, and particularly preferred metals include Li and AA. Preferred organometallic compounds or metal hydride compounds include alkyl derivatives having 1 to 6 carbon atoms or hydrogenated derivatives of the above metals, such as ethyllithium, n-butyllithium, 5ee-zotyllithium, 1-butyllithium, etc. organolithium compounds, organozinc compounds such as diethylzinc and dimethylzinc.

Organomagnesium compounds such as butylmagnesium chloride, ethylmagnesium bromide, dibutylmagnesium, dibutylmagnesium.

Trimethylaluminum, triethylaluminum, triisobutylaluminum, 1J-n-thylaluminum, tridodecylaluminum.

Organic aluminum compounds such as diethylaluminium chloride, diimbutylaluminum chloride, ethylaluminum chloride, ethylaluminum dichloride, and tetraethylaluminum dichloride; metal hydrides such as lithium aluminum hydride, sodium borosonol hydride, and lithium boron hydride; Compounds can be mentioned. These metal compounds can be used alone or in combination of two or more.

The method of preparing the first catalyst component solution is extremely important. The method for preparing this catalyst component solution is as follows: First, in the presence of a conjugated diene compound, a specific amount of a conjugated diene compound and an organometallic compound or a metal hydride compound of Groups 1.II and II of the periodic table. contact.

The key is to let it react. During this preparation (the amount of q-conjugated diene compound used is 1 mole of tetracobalt compound)
-1000 mol is preferable, more preferably 6-800 mol
(B) Periodic Table No. 1. The amount of the organometallic compound or metal hydride compound of groups (1) and (2) to be used is preferably 0.8 to 100 mol, more preferably 0.9 to 50 mol, per 1 mol of the tetracobalt compound. The temperature during preparation is preferably -78C to 100C, more preferably -80C to 50C. By stirring the solvent and the catalyst component as necessary during the preparation, the reaction between the cobalt compound (A) and the (Bl organometallic compound or hydrogen metal compound) can be uniformly carried out. The solvent used for this has a solubility in water of 10
-6% by weight or less, it is preferable to easily absorb the conjugated diene monomer added in step (n), and to act as an absorption aid for the monomer. Examples of such solvents include n-hexay, n-hebuty, n-peethane, purified solvent oil, and the like. This solvent has a solubility in water of 10-3 weight 1.1 m,! > Large @ big toluene, xylene. When used in combination with a solvent such as cyclohesensan, the solubility in water is 10-'wt-
Preferably 0.5 weight or more, particularly preferably 2 weight or more of the solvent added to the conjugated genomonomer added in step (n) may be used. Also.

A solvent having a solubility in water of 1O-5 by weight or less.

The content in the first polymerization catalyst component solution is preferably at least 10% by weight.

Constituting the second catalyst component (l: carbon sulfide.

There are no particular restrictions on the use of phenylisothiocyanic acid and xanthogen compounds, and it is desirable to remove dissolved oxygen in advance by bubbling with Shichisei gas or the like prior to use.

Examples of the xanthogen compound include compounds having the general formula -0-C-S-, methyl xanthogen/acid, ethyl xanthogen FR, In-propyl xanthogen/acid, and isopropyl xanthogen acid.

n-ditylthousandtonic acid, aec-ditylthousandtogen #, 6-butylthousandtonic acid, n-pentylthousandtonic acid, n-hezothylthousandtonic acid, n-hezotylthousandtonic acid, n-octyl Sensu Toge/drink, 2
-The ethyl thousands of thousands of thousands, toogenic acid / phenyl thousands / thousands of thousands, pct ') thousandsu -tags, such as drying / acid
vIRs and the lithium, sodium, potassium salts and dimethyl chloride/disulfides of these chlorinated acids.

Diethylxanthogen disulfide, di-n-propyl chloride/togen disulfide, diisozorobil chlorine/disulfide, di-n-ditylxanthogen disulfide, di-L-zotel chlorine disulfide, z
-Thousand disulfides such as ethylhexyl disulfide and diphenyl xanthogen disulfide are preferably used. Among these, particularly preferred are 100% xanthate/disulfide, particularly dimethyl 100% disulfide, diisopropylxanthogen disulfide, and diphenylxanthogen disulfide.

The amount of the second catalyst component used is (A
) Preferably 0.01 to 1 mole of cobalt compound
The amount is 100 mol, more preferably 0.8 to 10 mol.

The conjugated diene monomer used in step (n) is particularly preferably one having a return prime number of 4 to 5, such as butadiene and isoprey. Further, in addition to these conjugated genomonomers, a small amount of oleinos, etc. can also be allowed to coexist in the reaction system. Moreover, these conjugated genomonomers 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 heptane; pentane, heptane, and heptane.

Aliphatic hydrocarbon compounds such as octane; methylene chloride,
Halogenated hydrocarbon compounds such as ethylene dichloride, trichloroethane, and chlorobenzene; Ester solvents such as ethyl acetate, globyl acetate, butyl acetate, ethyl octylate, 6-caprolactone, and γ-valerolactone; Bill alcohol, In-
Butanol.

Alcohol solvents such as 5ee-citanol, octatool, and ethylene glycol; Ketone heating mediums such as acetone, methyl ethyl keto/, acetophenone, and acetylacetone; Nitrile solvents such as acetonitrile, adiponitrile, and benzonitrile; 6-cagulactam, propiolactam , butyrolactam, parerolactam, N-
Amide yarn bath ropes such as methylpyrrolidone, N-ethylpyrrolidone, N-methylformamide 1', N-ethylformamide, and N,N-dimethylformamide can be mentioned. Among these, ester solvents are particularly preferred.

Furthermore, these organic solvents can also be used as solvents for the second catalyst component.

Next, the manufacturing method of the present invention will be explained in more detail.

First, in step (I), an emulsifier, the above-mentioned first catalyst component solution, and an aqueous dispersion in which polymer seeds are dispersed are added to an aqueous dispersion medium, and these are stirred and mixed to form one polymer seed. Absorb the first catalyst component solution. Note that, if the emulsifier contained in the polymer seed dispersion at this time sufficiently emulsifies and disperses the system, the emulsifier may not be used.

In order to effectively absorb the first catalyst component solution into the polymer seeds, the first catalyst component solution must be prepared in advance by -f:
The particle size is preferably 5 μm or less, more preferably 1 μm.
finely dispersed in water in the presence of an emulsifier to form an emulsion so that the particle size is less than m.

The emulsifier is not particularly limited, and examples include anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium sialylthylsulfoconolate, formalin condensate of naphthalenesulfonic acid, and polyol. 1,000-diethylene nonylphenol ether.

It is also possible to use a nonionic surfactant such as polyethylene glycol monostearate or sorbitan monostearate in combination.

Next, in Step a (It), a conjugated diene monomer was added to the system obtained in Step (I) and mixed and stirred.

This conjugated diene monomer is absorbed into the polymer seed which has absorbed the first catalyst component solution dispersed in the system. Then, a second polymerization catalyst component is further added.

The polymerization reaction is carried out at a temperature of -5 to 80C, preferably 0 to 50C.

The aqueous dispersion in which the polymer seeds are dispersed used in the step (■) is not particularly limited.
A polyethylene latex consisting of dispersed particles, polycitadiene latex, styrene-styrene copolymer latex, acrylic ester copolymer latex, methacrylic ester copolymer latex, and any other known latex can be used. . In addition, a polymer obtained by solution polymerization etc. is redispersed in water using an emulsifier to form a polymer at ℃, for example, eta-1+4
A known dispersion such as a polyisozolene dispersion, natural rubber latex, or a container thereof can also be used.

The above-mentioned polymer seeds are produced by introducing carboxyl groups onto their surfaces and subjecting them to so-called calze-cyl modification, and by using a persulfate-based polymerization initiator in the production of polymerized seeds. Second, it is possible to improve the dispersion stability of the polymer seeds, thereby reducing the amount of emulsifier used reciprocally and improving the mechanical stability and chemical stability of the polymer seeds.

The amount of non-polymerized seeds used is preferably 0.001 to 100 parts by weight per 1 part by weight of the conjugated diene monomer.

More preferably, it is 001 to 101 parts by weight.

Note: 1. Water used in the production method of the present invention.

That is, it is desirable to remove dissolved oxygen from water as a dispersion medium and water required during polymerization in advance by bubbling with nitrogen gas or using a water-soluble dissolved oxygen removing agent such as sodium dithionite.

In addition, the aqueous dispersion medium used (and leaked) in the step (I) has high water solubility and is used in the bath of the first catalyst component solution for the purpose of promoting absorption of the first polymerization catalyst component into the polymer seeds. Acetic acid, lower alkanols, methyl acetate, acetonitrile, etc. can be used as swelling agents.These solvents can be used at a ratio of 1 to 100 parts to water. In order to maintain a good dispersion state of the polymer particles, it is desirable to use the polymer at a ratio of 10- or less, preferably 5- or less.

Next, the polymer particles obtained by the above-described manufacturing method of the present invention will be described.

One integrated particle of the present invention comprises a polymer constituting the polymer seed used in step (I), and a conjugated diene monomer that is added to the reaction system dispersion at the step mark and absorbed into the polymer seed r. It is a composite polymer particle formed by coexisting within the same particle a crystalline polymer formed by polymerization of .

The crystalline polymer constituting the polymer particles is highly crystalline and contains 70Qt- or more unsaturated hydrocarbon groups in its side chains. If the content of side chain vinyl groups in the crystalline polymer is less than 70% +-'F-, the crystallinity of the polymer will decrease and the melting point will be low, resulting in difficulty in using it for various purposes. The polymer dissolves during drying or processing, making it impossible to maintain sufficient heat resistance.

The content ratio of vinyl groups in the side chains of a crystalline polymer refers to the infrared absorption spectrum of this polymer.
The nine results obtained were analyzed using the analytical method. The melting point of the crystalline polymer can be controlled within a range of 200° C. or lower by changing the type or amount of the organic solvent used for the conjugated diene monomer and the second catalyst component. Organic solvents that have a large effect on lowering the melting point of crystalline polymers include esters, alcohols, ketones, aldehydes,
Examples include organic solvents having polar groups such as nitrile, amide, and sulfokide. Further, the degree of crystallinity of the crystalline polymer varies depending on the reaction conditions, etc., but is usually 101 or more, usually 30% or more, and further 50% or more.

The melting point of the polymer in the polymer particles of the present invention is
This can be achieved by appropriately selecting a polymer having high affinity with the crystalline polymer synthesized in step (6) as a polymer seed. Examples of polymers having high affinity for crystalline polymers include polybutadiene, getadiene-styrene copolymer, butadiene-acrylonitrile copolymer, cts-x, 4-polyinozolene, and natural rubber. By selecting the type and composition ratio in consideration of the properties of these polymers, such as their melting point, it becomes possible to control the melting point of the final polymer within a range of 200°C or less. .

Additionally, as the average particle size of the polymer particles increases, the dispersion stability (of the aqueous dispersion) decreases and the polymer particles tend to settle, which poses a practical problem when used in the form of an aqueous dispersion. Come. 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. Corresponding 5 μm or less, preferably 2 μm
m or less, more preferably 1 μfi, 1. Dispersion stability can be improved by setting the following conditions.

The particle size of the polymer particles can be controlled by selecting the particle size of the polymer seeds.

〔Effect of the invention〕

According to the production method of the present invention, the first catalyst component solution is first absorbed into a polymer seed having a predetermined particle size, and then the conjugated diene monomer and the second catalyst component are absorbed into the polymer seed P. As is clear from the examples described later, by carrying out the polymerization reaction, an industrially extremely useful crystalline conjugated diene polymer and other polymers coexist in the same particle. Dispersions can be easily produced in high yields.

In addition, by appropriately selecting the polymer constituting the polymer seed, it is possible to control the melting point, etc. of the resulting polymer, and modification of the crystalline polymer can be easily achieved. . Such crystalline polymers 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 very wide variety of applications, especially in the form of aqueous dispersions, such as paper coating compositions, carpet backing agents, coatings, strength and heat resistance of these various materials. , effective for modification.

[Embodiments of the invention]

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 In a pressure-resistant container with a capacity of 1004 ml, which had been purged with nitrogen gas in advance, 7.511 L of a solution of 0.2 molar conoltooctylic acid in n-hexane was added, and then cyclohexane I was added.
IIILt was added, a magnetic rotor was added, and the container was capped. Then, after adding 2.6 m of 1,3-butadiene (volume at room temperature of 20°C), the container was cooled in ice water while the magnet was rotated vigorously for 10 minutes, and then triimbutylaluminum was added. 0.5 mol/1 n-hexane solution9. Od was added and the mixture was stirred violently for about 15 minutes to obtain a first catalyst component solution. To this catalyst component solution 1OrIL,
100% of distilled water and 211% of sodium lauryl sulfate that had been heated with nitrogen gas were added, and this was heated under a nitrogen gas atmosphere by ultrasonic waves (ultrasonic output: 300 W, ultrasonic frequency: 19 KHz) until the particle size of the dispersed particles was 0.
A dispersion of 0.05-0.2 μm was prepared. This will be referred to as catalyst dispersion l.

Next, 1 g of polybutadiene latex R #700J (manufactured by Nippon Gosei Co., Ltd.) whose average particle size of dispersed particles (polymer seeds) is 0.3 μm obtained by emulsion polymerization (
(solid content equivalent weight) was diluted with distilled water to make 80 g, which was placed in a pressure-resistant container with a capacity of 300 d, and after bubbling with nitrogen gas at ℃, 22111/catalyst dispersion 1 was added thereto and plugged. . and the container at room temperature for about 15 minutes.
The first catalyst component solution was absorbed into the latex polymer seeds by vigorous shaking for a minute. Thereafter, the container was cooled in ice water, 6.2 g of 1,3-butadiene was added, and the mixture was lightly shaken. Next, 1 rnl of a solution of 0.1 mol/l of carbon disulfide in methyl acetate, which is the second catalyst component, was added, and the container was shaken at room temperature (20°C) for 2 hours.

No coagulation was observed in the latex thus obtained. Furthermore, when this latex was left to stand for a long time, it was confirmed that a stable dispersion state was maintained without separation of the dispersed particles.

Example 2 In place of 6.2 g of 1,3-butadiene used in the polymerization step of Example 1, 310 g of 1,3-butadiene was used. □
No, 171. Yo, □ka, □□, □ An aqueous dispersion of 1 coalesced particles was obtained.

Example 3 Instead of the polybutadiene latex r''700J used in the polymerization process of Example 1, a styrene-butadiene copolymer latex [÷0599J] with an average particle size of dispersed particles (polymer seeds) of 0.1 μm was used. (Japanese synthetic rubber■
Example 1 except that 1 g (solid content equivalent) of
An aqueous dispersion of polymer particles was obtained in the same manner as above.

Example 4 Instead of the polybutadiene latex "÷700" used in the polymerization process of Example 1, the average particle size of dispersed particles (polymer 7-de) produced by soap and free polymerization was 0. 7μm polystyrene latex rIM
An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1, except that MJTEXJ (manufactured by Japan Synthetic Rubber Company) 39 (solid content equivalent weight) was used.

Example 5 Instead of the polybutadiene latex r''700J used in the polymerization process of Example 1, cis with an average particle size of dispersed particles (polymer seeds) of 07 μin was produced by re-emulsifying the polymer. -1+' Polyisoprene latex "Maxprene 1R900J (manufactured by Tetsusei Kagaku ■)"
An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1.

Regarding the polymer particles obtained in Examples 1 to 5 above.

(1) Conversion rate (yield) of 1.8-1 tadiene monomer.

(2) Polymer composition ratio, i.e. polymer seed fa)
The weight ratio (a:b) of the conjugated diene monomer absorbed in the seed (1)), and (3) the average particle size of the polymer particles (by dynamic light scattering method).

(4) Melting point of the polymer (by differential scanning calorimetry needle).

(A) Miyanami ratio of vinyl groups in the polymer (based on infrared absorption spectrum Morero dust analysis).

When examining each item, the results shown in the first article were obtained.

Table 1 Furthermore, in order to clarify the particle structure of the polymer particles of the present invention, the cross section of the white particles was observed at ℃ using a transmission electron microscope. As a sample, the aqueous dispersion (latex) obtained in Example 4 was dyed with 0's O4, water was further evaporated to form polymer particles into powder, and this powder was embedded in a resin. After solidification, the obtained block was sliced into thin slices using an ultramicrotome. 1st
The figure was thus obtained. 1 is an electron micrograph showing a cross section of a polymer particle.

This means that in polystyrene particles with a diameter of about 1 μm,
It can be seen that syndiotactic 1,2-polybutadiene crystals (dot-dyed areas) exist in the form of needles.

Example 6 Iik 100m installed in advance with nitrogen gas
Cobalt octino ν & 0.2 mol/
1 of n-hexane solution 'Z5WLJ' was added, a magnetic rotator was added, and the container was capped. Then 1,8-Zotazier/Z
Oml<volume at room temperature 210 tl'lC f) ft added,
＠Cool the rotor in water for 10 minutes without rotating it violently, then add Natori 1 cum boron hydride 0. z mol/
2, 2.5 mA of the IGO-propertool solution of No. 1 was added and reacted for 15 minutes to obtain a first catalyst component solution.
Added 100 mJ of distilled water of 9 ml and 2 g of sodium lauryl, and heated it with ultrasonic waves (ultrasonic output aoow, ultrasonic frequency 19 KHz) in a nitrogen gas atmosphere until the particle size of the dispersed particles increased. 0.05-0.
A dispersion of B 77m was prepared. This will be referred to as catalyst dispersion liquid 2.

Next, polycitadiene latex r”700 JIJ (
(solid content equivalent) diluted with distilled water to make a volume of 80ml
This was placed in a pressure-resistant container with a capacity of 800 m1, and after bubbling with nitrogen gas, it was placed in a 24 m! Catalyst Dispersion 2 was added to the container and the container was capped. Then, at room temperature, the container is
The first catalyst component solution was absorbed into the latex polymerized seeds by vigorous shaking for 5 minutes. The container was then cooled in ice water.

Add 6.2 I of 1,8-butadiene and further add 0.1 mol/'/ of carbon disulfide, which is the second catalyst component, to n-1,000/1 ff of solution! A was added and the container was shaken for 2 hours at room temperature (201:") to carry out polymerization. Regarding the latex obtained in this way, the characteristics of the ponds as described above were investigated, and it was found that the conversion rate (yield) 92%,
Average particle size of polymer particles: 0.54 μm, melting point of polymer: 16
8iC, the vinyl group content in the polymer was 96%, and the solid content was 6.4%. In addition, no coagulation was observed in this latex, and it was confirmed that the dispersed particles remained stable without agglomeration or separation even when left for a long time.

Silkworm coalescence - Example 7 Instead of the polybutadiene latex r"7.oOj used in the polymerization process of Example 1, natural rubber with an average particle size of 0.4 μm in dispersed particles (polymer seeds) was used. An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1, except that 6.2 g (solid content equivalent) of latex (produced in Fe1da, Malaysia) was used.

Regarding this aqueous dispersion, the same characteristics as those described above were investigated, and the results shown in Table 2 were obtained.

Table 2 Note that the polymer of the present invention obtained by using natural rubber latex and/or diene rubber latex as a dispersion of polymer seeds has a rubber-like appearance and has excellent tensile strength and flexural strength. It has strength and can be suitably used for tires, anti-vibration rubber, etc.

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph of a cross section of a polymer particle showing the particle structure of the polymer particle. ■-Continued amendment (voluntary) October 9, 1985 Patent Office k i'G:, 75 Ka 1MffB
1A21, Indication of the case Japanese Patent Application No. 59-142222 2, Name of the invention ↓81, i1i combined particles and their manufacturing method 3, Relationship with the amendment case No. 11-24 Chome Name (417) Japan Synthetic Rubber Co., Ltd. 4, Agent J Okano Bill Name (7875) Patent Attorney Masahiko Oi Telephone: 824-2041 5. Amendment (1) Invention of Specification jl Detailed Explanation Column 6, Contents of Correction: ``Preferably 0.5% by weight or more, particularly preferably, based on the first catalyst component solution.'' (2) Specification, page 11, lines 13 to 16? It is also preferable that the solubility of T in water is 10% by weight. ” to be deleted. (3) Specification page 14, line 20 to page 15, line 11-
1. Delete "It is preferable among children." (4) In the first line of page 21 of the specification, [Polymer particles settle 1] is corrected to "Polymer particles separate and float." (A) [Latex r'1M on page 25, line 14 of the specification]
MJTEXJ J ``Latex r1MMVTI:!:
Xj Correct to J. (6) The display rl:o, 8J in the polymer composition ratio column of Table 2 on page 31 of the specification is corrected to 1-1:0.9J. (7) The following sentence is added between the second and third lines of page 32 of the specification. [Example 8] A tetofhydrofuran solution having a cobalt chloride depth of 02...ol/β, prepared by preparing cobalt chloride and pyridine at a ratio of 1':5.1, was placed in a pressure-resistant container that had been previously purged with nitrogen.
After cooling the container to 5°C, 0.11 part of 1,3-tutadiene was added and stirred for 30 minutes. This I-Rium Aluminum High Tri F'0.2
mol/ρ of 1--Shicht 1" Furan solution tt 21.
2 parts were added and stirred for 30 minutes without cooling to obtain a first catalyst component solution.・To the second catalyst component solution, 0.2 parts of 1-lium totesolhenzenesulfonate (solid content) and 10 parts of distilled water bubbled with nitrogen gas were added, and pre-dispersed using a homomixer in a nitrogen gas atmosphere. After that, emulsify and disperse using a super 1' wave pomosizer to prepare a dispersion. This will be referred to as catalyst dispersion liquid 3. Natural rubber latex (Malaysia) in a pressure-resistant reaction vessel
15.5 parts (solid content) and 48 parts of distilled water were added, the yarn was sufficiently bubbled with nitrogen gas, and then cooled to 5τ5. Next, Catalyst Dispersion 3 was added and stirred well for about 3 minutes, 3.1 parts of 1.3-butatsuene was added and stirred for 30 minutes, and then carbon disulfide
．． 6 mol/7! One month of n-hexane solution was added and polymerization was carried out while keeping the temperature at 5°C for 3 hours and stirring slowly. In the above polymerization, the polymerization yield was The obtained polymer had a melting point of 200°C by differential thermal scanning calorimetry; IL, and a Morero infrared absorption spectrum.
The content of hinyl groups determined by the analysis method was 97%. Example 9 0.2 mol of cobalt naphthenate/0.396 jH of isochlorohexane solution was placed in a pressure-resistant container that had been purged with nitrogen.
After adding B, the container was cooled to 5° C., and 0.11 part of (1),3-butatsuene was added and stirred for 30 minutes. To this, butyl lithium 0.2 mol/β n-hexane solution 0.9
8 parts were added and stirred for 30 minutes while cooling to obtain a first catalyst component solution.To this catalyst component solution, 02 parts (solid content) of sodium dodecylhensensulfonate and distilled water bubbled with nitrogen gas were added. 10 parts were added and predispersed using a homomixer under a nitrogen gas atmosphere, and then emulsified and dispersed using an ultrasonic homogenizer to obtain a dispersion. This will be referred to as catalyst dispersion 4. 1 Example 8
Instead of the natural rubber latex (produced in Felda, Malaysia) used in the polymerization process of
(manufactured by ++1 Honsei Rubber Co., Ltd.) i. Polymerization 4
b1) In the above polymerization, the polymerization yield was 97%'.

Claims (1)

[Scope of Claims] 1) A crystalline polymer having 70% or more of unsaturated hydrocarbon groups in its side chains, which is obtained by polymerizing a conjugated diene monomer;
A polymer particle characterized in that this polymer and a different polymer coexist within the same particle. 2) The polymer particles according to claim 1, wherein the crystalline polymer constituting the polymer particles is syndiotactic 1,2-polybutadiene. 3) (A) Cobalt compound and (B) Group I of the periodic table ~
A first catalyst component obtained by contacting an organometallic compound or hydride of a Group III metal in the presence of a conjugated diene compound (C) in an amount of 1 to 1000 times the mole of the cobalt compound (A). The solution is adsorbed onto polymer seeds emulsified in water and then mixed with a polymer seed comprising a conjugated diene monomer and (D) at least one compound selected from the group of carbon disulfide, phenylisothiocyanate and xanthogen compounds. 2. A method for producing polymer particles, which comprises adding and polymerizing the catalyst component of item 2.