JPH0564163B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of the Invention] The present invention relates to a crystalline polymer containing a high proportion of unsaturated hydrocarbon groups in side chains obtained by polymerization of a conjugated diene monomer and another polymer in the same particle. The present invention relates to a method for producing polymer particles that coexist with the present invention. [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. Coating agents (JP-A-56-98160), asphalt compositions (JP-A-50-135114), thermal adhesives (JP-A-50-13674, Japanese Patent Publication No. 56-89934
Publication No.), Photosensitive resin for flexo printing plates (Unexamined Japanese Patent Publication No. 1983), Photosensitive resin for flexographic printing plates
-12004, JP-A-52-64301), carpet packing agent (JP-A-51-72683), foam (JP-A-55-73071, JP-A-52)
-43873 Publication) 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 in solution, it is not only necessary to ensure safety against the odor, toxicity, or flammability of organic solvents, but also to remove and recover the organic solvents. It is complicated, has poor workability, and has limitations in its applications. In order to solve these problems and make the crystalline polymer usable for various purposes while ensuring high workability and safety, the polymer must be dispersed in water. It is extremely advantageous to use it in the form of an aqueous dispersion or an aqueous emulsified dispersion (hereinafter simply referred to as "aqueous dispersion"). 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, since the aqueous dispersion obtained by such a method has high crystallinity and a relatively high melting point, the solvents that can be used are very limited, and moreover, the solvents that can be used are very limited. Polymer solution particles (oil droplets) that make up the dispersed phase require high temperature and high pressure conditions to completely dissolve the polymer in a solvent, making it difficult to manufacture.
It is difficult to make the particle size small and uniform, and the dispersion stability is poor, so the dispersion cannot be maintained in a stable state for a long period of time. It has drawbacks such as requiring a large amount of emulsifier, which reduces the water resistance of the polymer, and does not necessarily have sufficient industrial utility value. [Object of the Invention] The present invention has been made against the above-mentioned background, and its object is to provide a material with a high proportion of unsaturated hydrocarbon groups in its side chain, which is useful for various uses. An object of the present invention is to provide a production method that can efficiently and easily produce polymer particles in which a crystalline polymer and other polymers coexist in the same particle. [Structure of the Invention] The method for producing polymer particles of the present invention is characterized by (A) a cobalt compound and (B) a cobalt compound from groups 1 to 10 of the periodic table.
A first catalyst component solution obtained by contacting an organometallic compound or hydride of a Group 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). , a second compound comprising a conjugated diene monomer and (D) at least one compound selected from the group of carbon disulfide, phenylisothiocyanate and xanthogen compounds;
The point is that a catalyst component is added to carry out polymerization. The present invention will be explained in detail below. First, the manufacturing method of the present invention will be described. Particularly distinctive features of the manufacturing method of the present invention are:
The catalyst to be used is a specific one that is composed of a first catalyst component solution and a second catalyst component, which will be described in detail later, and exhibits a catalytic effect only when both catalyst components are combined, and each of these catalyst components is added stepwise to the reaction system dispersion in the following steps () and () to carry out polymerization. Step (): In a dispersion formed by dispersing polymer seeds in water in advance, the first catalyst component solution is brought into contact with and absorbed by the polymer seeds. Step (): A conjugated diene monomer is added to the system obtained in step (), and a second catalyst component is further added to perform polymerization. The first catalyst component solution contains (A) a cobalt compound and (B) an organometallic compound or a hydrogen compound formed by a metal from Groups 1 to 3 of the periodic table.
1 to 1000 times the mole of the cobalt compound (A)
(C) Obtained by contacting in the presence of a conjugated diene compound. Further, the second catalyst component includes (D) carbon disulfide,
It consists of at least one compound selected from phenylisothiocyanate and xanthogen compounds. Examples of the cobalt compound (A) for forming the first catalyst component solution include organic acid salts such as cobalt octylate, cobalt naphthenate, cobalt benzoate, cobalt oxalate, cobalt malonate, and cobalt acetate; Cobalt complexes such as cobalt acetylacetonate, cobalt trisacetylacetonate, cobalt acetoacetate ethyl ester, triphenylphosphine complex of cobalt bromide, tri-m-tolylphosphine complex of cobalt bromide, tri-m-tolylphosphine complex of cobalt bromide Triarylphosphine complexes of cobalt halides such as xylylphosphine complexes, pyridine complexes of cobalt chloride, pyridine derivative complexes of cobalt halides such as β-picoline complexes of cobalt chloride, ethyl alcohol complexes of cobalt chloride, (1 ,3-butadiene)[1-(2-methyl-3-putenyl)-π
-allyl]cobalt, tris-π-allylcobalt, bicyclo-[3,3,0]-octidienyl-
1,5-cyclooctadiene cobalt, bis-
Examples include monovalent or zero-valent cobalt complexes such as (π-allyl)-halogenocobalt (where the halogen is any one of I, Br, and Cl) and octacarbonyl dicobalt. These cobalt compounds can be used alone or in combination of two or more. As (B) an organometallic compound or hydride of a metal of groups 1 to 10 of the periodic table for forming the first catalyst component solution, a compound that reduces a cobalt compound is preferably used. Metals from Groups to Groups of the Periodic Table include a, b, a, b,
Metals of groups a and b can be used, among which metals of a,
Groups a and a are preferred; preferred metals include Li, Na, K, Mg, Zn, and Al; particularly preferred metals include Li and Al. 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, sec.
- Organolithium compounds such as butyllithium and t-butyllithium, organozinc compounds such as diethylzinc and dimethylzinc, organomagnesium compounds such as butylmagnesium chloride, ethylmagnesium bromide, dibutylmagnesium and dihexylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,
Organoaluminum compounds such as tridodecylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and tetraethylaluminoxane, and metal hydride compounds such as lithium aluminum hydride, sodium boron hydride, and lithium boron hydride may be mentioned. can.
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 involves first adding a specific amount of (A) a cobalt compound and (B) an organometallic compound or a metal hydride compound of Group 1 of the periodic table in the presence of (C) a conjugated diene compound. contact,
The key is to let it react. In this preparation, the amount of the conjugated diene compound (C) used is preferably 1 to 1000 mol, more preferably 6 to 300 mol, per 1 mol of the cobalt compound (A), and (B) The amount of the group organometallic compound or metal hydride compound used is 0.3 per mole of cobalt compound (A).
The amount is preferably 100 mol, more preferably 0.9 to 50 mol. The temperature during preparation is preferably -78°C to 100°C, more preferably -30°C to 50°C.
By stirring the solvent and catalyst component as necessary during preparation, the reaction between (A) the cobalt compound and (B) the organometallic compound or hydrogen metal compound can be uniformly carried out. Here, the solvent used for the preparation has a solubility in water of less than 10 ^-3 % by weight, easily absorbs the conjugated diene monomer added in step (), and serves as an absorption aid for the monomer. Preferably one that works. Such solvents include n-hexane, n-heptane,
Examples include n-pentane and refined kerosene. When this solvent is used together with a solvent such as toluene, xylene, or cyclohexane, which has a solubility in water of more than 10 ^-3 % by weight, the solvent having a solubility in water of 10 ^-3 % by weight or less is added to the first catalyst component solution. preferably 0.5% by weight or more, particularly preferably carbon disulfide (D) constituting the second catalyst component,
Although there are no particular restrictions on the use of phenylisothiocyanic acid and xanthogen compounds, it is desirable to remove dissolved oxygen by bubbling with nitrogen gas or the like prior to use. As a xanthogen compound, the general formula

〔Effect of the invention〕

According to the production method of the present invention, a first catalyst component solution is first absorbed into a polymer seed having a predetermined particle size, and then a conjugated diene monomer and a second catalyst component are absorbed into the polymer seed. As is clear from the examples described below, an aqueous dispersion of polymer particles in which an industrially extremely useful crystalline conjugated diene polymer and other polymers coexist within the same particle can be obtained. can be easily produced with high yield. 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 it is possible to easily modify the crystalline polymer. I can do it. 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., and are extremely 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, adhesives, and also in rubbers. It is also suitable for organic fillers for resins, etc., 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. Example 1 Volume 100 replaced with nitrogen gas in advance
Cobalt octylic acid 0.2 mol/ml in a pressure-resistant container
7.5 ml of n-hexane solution and 11 ml of cyclohexane were added, and a magnetic rotor was inserted and the bottle was capped. and 2.6 ml of 1,3-butadiene (room temperature 20°C)
After adding 9.0 ml of n-hexane solution of 0.5 mol of triisobutylaluminum, the magnetic rotor was rotated vigorously for 10 minutes while cooling the container in ice water. A catalyst component solution of No. 1 was obtained. To 10 ml of this catalyst component solution, 100 ml of distilled water bubbled with nitrogen gas and 2 g of sodium lauryl sulfate were added, and this was subjected to ultrasonic waves (ultrasonic output 300 W, ultrasonic frequency 19 KHz) under a nitrogen gas atmosphere.
A dispersion with dispersed particles having a particle size of 0.05 to 0.2 μm was prepared. This will be referred to as catalyst dispersion liquid 1. Next, 1 g (solid content equivalent weight) of polybutadiene latex "#700" (manufactured by Japan Synthetic Rubber Co., Ltd.) whose average particle diameter of dispersed particles (polymer seeds) is 0.3 μm obtained by emulsion polymerization was added. Dilute to 80 ml with distilled water, put it in a pressure-resistant container with a capacity of 300 ml, and bubble it with nitrogen gas.
22 ml of catalyst dispersion 1 was added and the mixture was stoppered. Then shake the container vigorously for about 15 minutes at room temperature.
A solution of the catalyst components was absorbed into the latex polymer seeds. The container is then cooled in ice water,
6.2 g of 1,3-butadiene was added and gently shaken. Next, the second catalyst component, carbon disulfide
1 ml of a 0.1 mol/ml methyl acetate solution was added and the container was shaken for 2 hours at room temperature (20°C).
No coagulum 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 could be maintained without separation of the dispersed particles. Example 2 1,3 used in the polymerization step of Example 1
An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1, except that 3.1 g of 1,3-butadiene was used instead of 6.2 g of -butadiene. Example 3 In place of the polybutadiene latex "#700" used in the polymerization process of Example 1, a styrene-butadiene copolymer latex "#0599" in which the average particle size of dispersed particles (polymer seeds) was 0.1 μm was used.
(manufactured by Japan Synthetic Rubber Co., Ltd.) An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1, except that 1 g (solid content equivalent) was used. Example 4 Instead of the polybutadiene latex "#700" used in the polymerization process of Example 1, dispersed particles (polymer seeds) produced by soap-free polymerization and having an average particle size of 0.7 μm were used. Polystyrene latex “IMMVTEX” (Japan Synthetic Rubber Co., Ltd.)
An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1, except that 3 g (weight in terms of solid content) (manufactured by Co., Ltd.) was used. Example 5 Instead of the polybutadiene latex "#700" used in the polymerization process of Example 1, dispersed particles (polymer seeds) produced by re-emulsifying the polymer and having an average particle size of 0.7 μm were used. An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1, except that cis-1,4 polyisoprene latex "Maxprene IR900" (manufactured by Seitetsu Kagaku Co., Ltd.) was used. Regarding the polymer particles obtained in Examples 1 to 5 above, (1) the conversion rate (yield) of 1,3-butadiene monomer, (2) the polymer composition ratio, that is, the polymer seed ( Weight ratio of a) to the polymer (b) of the conjugated diene monomer absorbed in this seed (a:b) (3) Average particle size of the polymer particles (by dynamic light scattering method), ( 4) Melting point of the polymer (by differential scanning calorimetry); (5) Content ratio of vinyl groups in the polymer (by infrared absorption spectrum Morero analysis method). The results are shown in Table 1. was gotten.

[Table] Furthermore, in order to clarify the particle structure of the polymer particles obtained by the production method of the present invention, the cross section of the particles was observed using a transmission electron microscope.
As a sample, the aqueous dispersion (latex) obtained in Example 4 was dyed with O _s O ₄ , water was evaporated to form polymer particles into powder, and this powder was wrapped in resin. The blocks were embedded and solidified, and the resulting blocks were sliced into thin slices using an ultramicrotome. FIG. 1 is an electron micrograph showing the cross section of the polymer particles thus obtained. According to this, it can be seen that syndiotactic 1,2-polybutadiene crystals (black dyed parts) exist in the form of needles in polystyrene particles having a particle size of about 1 μm. Example 6 Volume 100 replaced with nitrogen gas in advance
Cobalt octylic acid 0.2 mol/ml in a pressure-resistant container
7.5 ml of n-hexane solution was added, a magnetic rotator was added, and the bottle was capped. Next, 20 ml of 1,3-butadiene (capacity at room temperature of 20°C) was added, and after cooling in ice for 10 minutes while rotating the magnetic rotor vigorously, 22.5 ml of an iso-propanol solution containing 0.2 mol of sodium boron hydride was added.
A first catalyst component solution was obtained by reacting for 15 minutes. To 10.9 ml of this catalyst component solution, 100 ml of distilled water bubbled with nitrogen gas and 2 g of sodium laurate were added, and this was subjected to ultrasonic waves (ultrasonic output 300 W, ultrasonic frequency
19KHz) to prepare a dispersion with dispersed particles having a particle size of 0.05 to 0.2 μm. This will be referred to as catalyst dispersion liquid 2. Next, polybutadiene latex “#700” 1
g (solid content equivalent) was diluted with distilled water to make a volume of 80 ml, and this was placed in a pressure-resistant container with a capacity of 300 ml.
After bubbling with nitrogen gas, 24 ml of Catalyst Dispersion 2 was added to the flask and the flask was capped. The container was then vigorously shaken for about 15 minutes at room temperature to absorb the first catalyst component solution into the latex polymerized seeds. After that, cool the container in ice water and
- Add 6.2 g of butadiene, then add 1 ml of n-hexane solution containing 0.1 mol of carbon disulfide, which is the second catalyst component, and perform polymerization by shaking the container at room temperature (20°C) for 2 hours. Summer. Regarding the latex obtained in this way, we investigated various properties as mentioned above, and found that the conversion rate (yield) was 92%, the average particle diameter of the polymer particles was 0.54 μm, the melting point of the polymer was 168°C, and the Results showed that the content of vinyl groups in the coalescence was 96%, and the solid content was 6.4%. In addition, no coagulation was observed in this latex, and it was confirmed that the latex could maintain a stable state without agglomeration or separation of dispersed particles even when left for a long time. Example 7 Instead of the polybutadiene latex "#700" used in the polymerization process of Example 1, 6.2 g of natural rubber latex (produced in Felda, Malaysia) with an average particle size of dispersed particles (polymer seeds) of 0.4 μm was used ( An aqueous dispersion of polymer particles was obtained in the same manner as in Example 1, except that the amount of solid content 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] 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 exhibits a rubber-like appearance and has extremely excellent tensile strength,
It has bending strength and can be suitably used for tires, anti-vibration rubber, etc. Example 8 0.45 part of a tetrahydrofuran solution containing cobalt chloride and pyridine in a ratio of 1:5.7 and having a cobalt chloride concentration of 0.2 mol/was placed in a pressure-resistant container that had been purged with nitrogen in advance, and the container was cooled to 5°C. 0.11 part of 1,3-butadiene was added and stirred for 30 minutes. To this was added 1.2 parts of a tetrahydrofuran solution containing 0.2 mol of sodium aluminum hydride, and the mixture was stirred for 30 minutes while being cooled to obtain a first catalyst component solution. To this catalyst component solution, 0.2 parts of sodium dodecylbenzenesulfonate (solid content) and 10 parts of distilled water bubbled with nitrogen gas were added, predispersed using a homomixer under a nitrogen gas atmosphere, and then emulsified using an ultrasonic homogenizer. A dispersion was prepared by dispersing. This will be referred to as catalyst dispersion liquid 3. 15.5 parts (solid content) of natural rubber latex (produced in Felda, Malaysia) and distilled water in a pressure-resistant reaction vessel.
After adding 48 parts and bubbling the system sufficiently with nitrogen gas, the system was cooled to 5°C. Next, catalyst dispersion 3 was added and stirred well for about 15 minutes, further 3.1 parts of 1,3-butadiene was added and stirred for 30 minutes, and then 0.11 parts of an n-hexane solution containing 0.6 mol of carbon disulfide was added. Polymerization was carried out with gentle stirring for 3 hours while maintaining the temperature at 5°C. In the above polymerization, the polymerization yield was 98%. In addition, the obtained polymer has a melting point of 200°C as measured by a differential scanning calorimeter, and an infrared absorption spectrum.
Vinyl group content is 97% by Morero analysis method
It was hot. Example 9 After putting 0.39 parts of a cyclohexane solution containing 0.2 mol of cobalt naphthenate in a pressure-resistant container that had been previously purged with nitrogen, the container was cooled to 5° C., 0.11 parts of 1,3-butadiene was added, and the mixture was stirred for 30 minutes. Add 0.2 mol/n-hexane solution of butyllithium to this.
0.98 part was added and stirred for 30 minutes while cooling to obtain a first catalyst component solution. Distilled water bubbled with 0.2 parts of sodium dodecylbenzenesulfonate (solid content) and nitrogen gas into this catalyst component solution.
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 liquid 4. Instead of the natural rubber latex (produced in Felda, Malaysia) used in the polymerization process of Example 8, 15.5 parts (solid content) of styrene-butadiene copolymer latex "#1500" (manufactured by Nippon Gosei Rubber Co., Ltd.) was used. In addition, polymerization was carried out in the same manner as in Example 8 except that catalyst dispersion 4 was used instead of catalyst dispersion 3. In the above polymerization, the polymerization yield was 97%. In addition, the obtained polymer has a melting point of 200°C as measured by a differential scanning calorimeter, and an infrared absorption spectrum.
Vinyl group content is 96% by Morero analysis method
It was hot.

[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.

Claims (1)

[Claims] 1 (A) a cobalt compound and (B) an organometallic compound or hydride of a metal from Groups 1 to 3 of the periodic table, and (C) a conjugated diene in an amount of 1 to 1000 times the mole of the cobalt compound (A). The first catalyst component solution obtained by contacting in the presence of the compound is absorbed into the polymer seeds emulsified and dispersed in water, and then the conjugated diene monomer and (D) carbon disulfide, phenylisothiocyanate and A method for producing polymer particles, which comprises adding a second catalyst component consisting of at least one compound selected from the group of xanthogen compounds and performing polymerization.