JPS6131407A - Production of polymeric composition - Google Patents

Abstract

PURPOSE:To obtain easily the titled composition containing a uniformly dispersed polymer, e.g. rubber or resin, and crystalline 1,2-polybutadiene therein, by polymerizing butadiene in the presence of water and further the polymer, e.g. rubber or resin, in the solution state. CONSTITUTION:Butadiene is polymerized in the presence of water and further (A) a catalyst obtained by bringing a Co compound, e.g. cobalt octylate, into contact with an organometallic compound, e.g. n-buthyllithium, or hydride, e.g. LiAlH4, in the presence of a conjugated diene, e.g. butadiene, in a molar amount of 1-1,000 times that of the compound, (B) at least one of CS2, phenyl isothiocyanate and xanthogen compound, e.g. methyl xanthate, and (C) a polymer solution of a rubber, e.g. 1,4-polybutadiene, or a resin, e.g. polystyrene, to give the aimed composition.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention involves polymerizing butadiene in the coexistence of a solution of a polymer such as rubber or resin with water to form a crystalline 1.
．． The present invention relates to a method of making certain polymeric compositions containing 2-polybutadiene.

"Prior art" Cis-1,,4-$liptadiene rubber and crystallinity 1. ,2
- Methods for producing a polymer composition made of polybutadiene include a method of mechanically mixing the two products produced separately in advance, and a method of mixing solutions of each polymer (Japanese Patent Laid-Open No. 55-2
9535), a method of mixing jindioctactic 1.2-/liptadiene in a slurry state with a comb solution (Japanese Patent Publication No. 55-3182), a method of sequentially carrying out each polymerization in the same reactor (Japanese Patent Publication No. 1983-1993) -17666) are known and are used as adhesives with excellent bending resistance.

However, if crystalline 1,2-/liptadiene is produced in advance and mixed with a polymer such as Fuco9m or resin using an extruder or roll, crystalline 1,2-polybutadiene will be unevenly distributed and will not be sufficient. A homogeneous composition cannot be obtained.

Furthermore, if an attempt is made to mix the two in the form of a solution or slurry, there is a drawback that sulfurization occurs during mixing, making it impossible to obtain the desired composition.

Furthermore, Japanese Patent Publication No. 49-17666 describes a generally well-known so-called solution polymerization using an organic solvent.

However, in this method, after polymerizing cis-1,4-polybutadiene, crystallinity of 1.2-7f! Polymerization of liptadiene has the disadvantage that the viscosity of the polymerization system becomes extremely high, which not only makes stirring insufficient but also makes it difficult to transfer the polymer. For this purpose, there were difficulties in that the amount of polymer in the polymerization system had to be reduced, the total length of the solvent had to be increased, and the amount of crystalline 1,2-polybutadiene had to be kept low.

"Problems to be Solved by the Invention" The present inventors have conducted extensive studies and found that by polymerizing butadiene in the presence of water and in the coexistence of a polymer such as gum or resin, Polymer crystalline 1,2-
Poly! It has become possible to produce a specific polymer composition consisting of tadiene with low viscosity and homogeneity.

Furthermore, Japanese Patent Publication No. 49-17666 and Japanese Patent Publication No. 55-295
Polymer compositions such as No. 35 containing not only rubber but also resins such as ethylene vinyl acetate copolymer polystyrene and crystalline 1,2-polybutadiene have been successfully prepared.

``Means for Solving the Problems'' That is, the present invention provides a solution in which (a) a cobalt compound (A) and an organometallic compound of a metal of Groups I to III of the Periodic Table or a hydride thereof (B) are added to a polymer solution in advance. and 1 for (A)
The catalyst obtained by contacting in the presence of ~1000 times the mole of conjugated diene and (b) at least one selected from carbon disulfide, phenylisothiocyanic acid and xanthogen compounds were allowed to coexist in the presence of water. The present invention relates to a method for producing a polymer composition, which comprises polymerizing butadiene.

The present invention will be explained in detail below. Examples of the cobalt compound (A) used in the method of the present invention include organic acid salts such as cobalt octylate, cobalt naphthenate, cobalt benzoate, cobalt oxalate, cobalt malonate, and cobalt acetate, and bisacetylacetonate. Cobalt, cobalt complexes such as cobalt trisacetylacetonate, cobalt acetoacetate ethyl ester, triphenylphosphine complex of cobalt bromide, copal bromide) Q)! J
m-tolylphosphine complex, of cobalt bromide) I
Triarylphosphine complexes of cobalt halide such as J m -xylylphosphine complexes, pyridine complexes of cobalt chloride, β-picoline complexes of cobalt chloride, pyridine derivative complexes of cobalt halide such as Nato, ethyl alcohol complexes of cobalt chloride, ( 1,3-butadiene)
[1-(2-methyl-3-phthynyl)-π-allyl]cobalt, tris-π-allylcobalt, bicyclo-[3
,3,0]-]octidienyl-1,5-cyclooctadienecobaltbis-(π-allyl)-hekopal) (however, as halo r % I * Br 1 ct
Either. ), monovalent or zero-valent cobalt complexes such as octacarbonyl dicobalt. One type or two or more types of these cobalt compounds can be used.

As the organometallic compound or hydride (B) of a metal of groups 1 to 2 of the periodic table, a compound that reduces a cobalt compound is preferably used. Metals in Groups ■~■ of the periodic table include I
a+Ib+IIa+IIb+IHa.

Metals of group Ib can be used, among which Ia+I[a+1
Group 11a is preferred, and preferred metals include Li, Na, K, Mg, Zn,
Particularly preferred metals include At, A
I can give you an A.

Also preferred are organometallic compounds or metal hydride compounds (B
), the above metal has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
12, more preferably 1 to 6 alkyl derivatives or hydrogenated derivatives, organic lithium compounds such as ethyllithium, n-butyllithium, I@(+-butyllithium, t-butyllithium, diethylzinc, dimethylzinc Organozinc compounds such as butylmagnesium chloride, ethylmagnesium bromide, dibutylmagnesium, dihexylmagnesium, trimethylaluminum, triethylaloonium, triisobutylalkinium, tri-n-hexylaluminum, tridodecyl7/L' onium, diethylaluminium chloride, diisobutylaluminum chloride, ethylaluzunium sesquichloride, ethylaluminum cyclolide, tetraethylaluminoxane tri(octyl)alkinium, tri(
Organic aluminum compounds such as n-dodecyl)aluminum, di(octyl)aluminum halide, di(dodecyl)aluminum halide, lithium aluminum hydride, sodium? Ronhydride, lithium? Mention may be made of hydrogenated metal compounds such as ronhydrides. These metal compounds can be used alone or in combination of two or more.

The use of carbon disulfide and/or phenylisothiocyanate as component (C) used in the present invention is not particularly limited, but it is preferable to remove dissolved oxygen in advance by nitrogen bubbling or the like.

Examples of the xanthogen compounds include general formula ntogonic acid, ethylxanthogen M, n-zorobylxanthogenic acid, isozolopylxanthogenic acid, n-butylxanthogenic acid, get+-butylxanthogenic acid, 6
-Butylxanthate, n-pentylxanthate, n-hexylxanthate, n-hebutylxanthate, n-octylxanthanoate, 2-ethylhexylxanthate, phenylxanthate, p-tolylxanthate, etc. xanthogenic acids and lithium, sodium, potassium salts of these xanthic acids and dimethylxanthogen disulfide, diethylxanthogen disulfide, di-n-zolopylxanthogen disulfide, diisoderopylxanthogen disulfide, di-n-butylxanthogen disulfide , t-butylxanthogen disulfide, 2-ethylhexylxanthogen disulfide, diphenylxanthogen disulfide, and ethylphenylxanthogen disulfide. Among these, xanthogen disulfide is particularly preferred, and dimethylxanthogen disulfide, diisozolopylxanthogen disulfide, and diphenylxanthogen disulfide are particularly preferred.

The method of preparing the catalyst used in the process of the invention is of critical importance. The method for preparing the catalyst used in the present invention is to first add a specific amount of cobalt compound (A) in the presence of a conjugated diene and a cobalt compound (A) listed in Table 1 of the periodic table. (1) and (2) group organometallic compounds or metal hydride compounds (B) are subjected to a contact reaction. The molar ratio of conjugated diene/Co compound during this preparation was 1
The molar ratio of (B)/(A) is preferably 0.3 to 100, more preferably 0.9 to 50. The temperature during preparation is preferably -78°C to 100°C, more preferably -30°C to 50°C. (A) and (B) by stirring the solvent and catalyst component as necessary during preparation.
) can be carried out uniformly.

Preferably, the solvent used for preparing the catalyst is toluene, benzene, xylene, hexane, hezotane, refined solvent oil, etc. Stirring is sufficient to uniformly mix the inside.The preparation time is The temperature is usually 5 minutes to 2 hours, although it depends on the temperature during preparation.

Component (C) may be added in advance to the aqueous suspension or emulsion of the monomer or monomer solvent solution, or added to the polymerization system simultaneously with the addition of the reaction product of the cobalt compound described above. Good too. Of these, the former is preferred.

The above component (C) is 0 per mole of cobalt compound (A).
．． 01 to 100 mol is preferable, and 0.3 to 10 mol is more preferable.

The water used in the polymerization of the present invention is preferably one that has been previously freed of dissolved oxygen by nitrogen bubbling or the like.

Polymers used in the present invention include natural rubber,
Cis-1,4-polybutadiene, cis-1,4-polyisolune, 1,2-polybutadiene, polybutadiene using an organolithium compound as a polymerization catalyst, butadiene-styrene copolymer, butadiene-isoprene copolymer, isozolene- Styrene copolymer, styrene-citadiene-styrene pro-copolymer, styrene-isoprene-styrene block copolymer, ethylene-propylene copolymer,
Co-9 polymers such as polyethylene-propylene-tertiary monomer copolymer, butyl rubber, emulsion polymerization styrene-citadiene copolymer, emulsion polymerization acrylonitrile-butadiene copolymer, acrylic (co)polymer, etc. can.

Among these rubbers, cis-1,4-polyisoprene, cis-1,4-polybutadiene, 1.2-polybutadiene,
Polybutadiene using an organolithium compound as a polymerization catalyst,
Particularly preferred are butadiene-styrene copolymers, ethylene-zoropyrene copolymers, and the like.

Furthermore, polystyrene, acrylonitrile-styrene copolymer, ethylene vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride,
Resins such as phenol resin, polyester, polyethylene, polypropylene polyvinyl acetate, polymethacrylate, polyvinylidene chloride polyvinyl ether, polyvinyl ketone polyamide, trans-1,4-polybutadiene, trans-1,4-polyethylene, and the like can also be mentioned. Among these, particularly preferred are TEHA, -ristyrene, and ethylene-vinyl acetate copolymer resins.

During polymerization, the organic solvent for dissolving the polymer is an aromatic hydrocarbon solvent such as benzene, toluene, or xylenato;
Resin group hydrocarbon solvents such as pentane hexane, heptane, octane; halodanized hydrocarbon compounds such as methylene chloride, ethylene dichloride, trichloroethane, chlorobenzene; ethyl acetate, propyl acetate, butyl acetate, ethyl octylate, -monocaprolactone, Ester solvents such as r-valerolactone; Alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, c-butanol, octatool, and ethylene glycol; Ketone solvents such as acetone, methyl ethyl ketone, acetophenone, and acetylacetone; Nitrile solvents such as a7tonitrile, adiponitrile, benzonitrile; C-casololactam, propiolactam, butyrolactam, parerolactam, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylformamide, N
- Amide solvents such as ethylformamide and N,N-trimethylformamide can be mentioned.

The amount of the solvent is preferably 0 to 1000% by weight, more preferably 0 to 300% by weight based on the monomer.

The present invention can also be achieved by dissolving the polymer in the monomer butadiene without using any solvent.

The present invention is carried out by using the above-mentioned polymers, resins, catalyst compounds, solvents, and the like.

Specifically, for example, water and butadiene are added to a solution of the above-mentioned polymer dissolved in a solvent, and the catalysts (A) and (B) prepared by the above-mentioned method are added, and after stirring, the pore-forming agent is added. and carbon disulfide (or phenylisothianic acid, a xanthogen compound) and polymerize while stirring. However, the method is not limited to this method.

Further, in the present invention, the polymerization temperature is from 0°C to 80°C, preferably from 5°C to 50°C.

According to the present invention, since the polymerization system is maintained in a suspended state, the viscosity inside the reactor is low and the temperature can be easily controlled. Additionally, a small amount of surfactant may be added to the reaction system to stabilize the suspended state.

The composite material obtained in the present invention can be used as reinforcing rubber, extrusion processable rubber, impact-resistant resin, heat-resistant processing resin, and reinforcing resin.

"Examples" The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded.

Example 1゜(Preparation of catalyst) A stirrer coated with Teflon on a pressure-resistant pin of 1QQd which had been purged with nitrogen in advance, and 0.20 mol of cobalt octylic acid/
After adding 9.0 ml of Ritter cyclohexane solution, the frame was molded. After adding 6 ml of butadiene, place it in a water tank at 0°C, and without rotating the stirrer vigorously, add a 0.4 mol/liter hexane solution of n-butyllithium.
9. Oa/added. The reaction mixture was reacted for about 15 minutes, and then used as a reaction solution in the polymerization described below.

(Polymerization) cis-1,4-
4 Liptadiene rubber (manufactured by Nippon Gosei Gam Co., Ltd., JSRB
After replacing the mixture with nitrogen, 160 mJ of deoxidized toluene was added to the mixture to completely dissolve the cis-1,4-polyptadiene rubber.

Next, 200 mA'i of deoxidized water was added, and then 8.0 ml of butadiene 40f9 and reacted cobalt solution (0.6 part remole as 12 part amount) were added, followed by stirring and mixing.
After thorough mixing, add 2 parts of sodium dodecyl sulfate aqueous solution 5 parts.
ml and 0.6 mmol of carbon disulfide were added. 20℃
Polymerization was carried out for 1 hour.

Fum and polymerized crystallinity in autoclave 1.2
- Polybutadiene was obtained in a dispersed state in the form of a low viscosity crumb slurry. After the polymerization was completed, the crumb-like polymer was recovered using a Tetron cloth, coagulated with alcohol using methanol containing BT (Tl), and vacuum-dried at 50°C.

Dem and crystallinity1. ．． 20.4 g (polymerization rate of butadiene: -c'271)'e was obtained as a polymer composition of 2-yJe liptadiene. As a result of DSC analysis of the polymer composition, the vitrification temperature 'rg was -121.0°C, and the melting point Tm was -11.5°C and 188.5°C. The resulting polymer had a homogeneous composition.

Comparative Example 1 20 I of cis-1,4-polybutadiene was placed in a 80011 autoclave, the atmosphere was replaced with nitrogen, and 320 ml of deoxygenated toluene was added. 80 g of butadiene and the reaction solution of Example 1, 16.0 liters (1.2 mmol of cobalt) were added, and 1.2 mol of extracted carbon sulfide was added with thorough stirring, and heated to 20°C for 1 hour. Time polymerization was performed. The viscosity inside the autoclave became extremely high during polymerization, and about 10 minutes after the start of multiple polymerization, it became impossible to stir the mixture sufficiently, but the polymerization continued. Even after the polymerization was completed, the autoclave had to be dismantled in order to remove the polymer inside, which would have been extremely difficult for industrial production. B) Coagulation was performed with methanol containing 1% IT and vacuum drying at 50°C, to obtain a composite of 37.4.81'lr. (The polymerization rate of butadiene was 21.8 degrees) According to DSC analysis, Tg-120°C, Tm-11,0°C, 1188°C.

Example 2. ~19゜Amount of alcohol, amount of butadiene, and reaction mixture of Example 1? Composites were obtained in the same manner by varying the amount of rut liquid and the amount of carbon disulfide, and using other polymers in place of cis-1,4-/lysotadiene.

The results are shown in Table-1.

Example 20 Using the same recipe as in Example 2, 2831 composites were obtained by increasing the polymerization scale and using a 10 ton autoclave.

100 parts of this composite was kneaded with carbon black zinc white, stearic acid, etc. according to the following formulation, and then mixed with a vulcanizing agent and an accelerator using a roll, and heated to 145°C.
- Vulcanization was performed for 40 minutes.

Formulation Table I Liptadiene Composite Material 100 parts Carbon brane (HAF type) 50 parts Aromatic oil 10 parts Zinc white
4 parts stearic acid 2
part accelerator, MSA 0.5 part accelerator, DM 1.0 part sulfur
2.0 parts "I N-oxydiethylene-2-penzothiazole sulfene electronic book" 2 G2-→nzothiazyl sulfide Table 2 shows the results.
Shown below.

Comparative Example 2゜ (Preparation of Polymer) After purging the autoclave of 800111 with nitrogen, toluene 3007/l/l treated with nitrogen bubbling and Citadiene 30I were charged with gold, and then - triisobutylalonium 0.5
Mol/liter toluene solution s, O*/ ,! : ,
Copal octylate) 0.2 mol/liter toluene solution 2.5 tnl and carbon disulfide 0.2 mol/liter toluene solution 2.5 ml were added, and at 20°C
Polymerization was carried out for many hours, but some polymer precipitated during the polymerization.
It became impossible to stir sufficiently.

After the polymerization was completed, coagulation was performed using methanol containing part 1 of BIT'i, and the polymer was dried in vacuum. The yield of polymer is 23
．． The melting point of 2 g of the 0 polymer was 197°C, and 1. , 2-bond gold content was 98%.

(Preparation of complex) Cis-1,4-polybutadiene complex 9M20ON? Wrap the above 1,2-polybutadiene 20 onto a 6-inch roll.
．． A sample for evaluation was prepared by adding 9'f sucrose and thoroughly kneading the mixture.

By visual inspection, it was found that L2-polybutadiene was scattered and solidified in granular form in some parts, indicating that the dispersibility was not good. We conducted an evaluation. The results are shown in Table-2.

Comparative Example 3: Using cis-1,4-polybutadiene as is, Example 20
Cargane etc. were blended and evaluated in the same manner as above.

The results are shown in Table-2.

Example 21 (Preparation of catalyst).

A Teflon-coated stirrer and 0.20% of cobalt octylic acid were placed in a 100 WLl pressure-resistant bottle that had been purged with nitrogen in advance.
After adding 9 d of tercyclohexane solution (mol/s), the flask was capped. After adding butadiene 4'ILl, the mixture was placed in a water path at 0° C., and 54 ml of a 0.1 mol/liter isozorobyl alcohol solution of sodium borohydride was added while vigorously rotating a stirrer. The reacted cobalt solution was reacted for about 15 minutes and used in the following polymerization.

(Preparation of polymer) Cis-1,4-
Ilisoprene Co., Ltd. (Nippon Gosei Co., Ltd.) a,
After adding JSRBROI) 10 II and replacing with nitrogen,
Toluene 1 treated with BA oxygen by nitrogen bubbling
60d was added to completely dissolve the cis-1,4-polybutadiene rubber. Next, deoxidized water at 200mA! i
After adding tadiene 40I and the above reaction cobalt solution 22
．． 3 ttl (:0.6 mmol as parto)
After the addition, the mixture was stirred and mixed, and after thorough mixing, 2 volumes of an aqueous solution of sodium dodecyl sulfate and 0.6 mmol of carbon disulfide were added. Polymerization was carried out at 20°C for 1 hour. The gum in the autoclave and the polymerized crystalline 1,2-polybutadiene were obtained in a dispersed state in the form of a low-viscosity crumb slurry. After the polymerization was completed, the sifram-like polymer was recovered using Tetron cloth, coagulated with dialcohol in methanol containing 1% BIT, and vacuum dried at 50°C. Rubber and crystalline 1,2-polybutadiene A polymer composition of 32.0.9 (polymerization rate of sitadiene of 55%) was obtained. DSC analysis results of the polymer composition showed that the vitrification temperature Tg was -72°C melting point and Tm was 175.0°C. .cis-1,,4-/lysozolene and crystallinity 1
．． It was visually confirmed that 2-polybutadiene 1 was homogeneously mixed.

Example 22 (Preparation of catalyst) A Teflon-coated stirring bar and 10 m/liter of a 0.25 mol/liter toluene solution of cobalt octylic acid were placed in a 1,00 ml pressure bottle which had been purged with nitrogen in advance, and then the bottle was capped.

After adding 6 ml of butanoene, place it in a water path at 0°C and while rotating the stirrer vigorously, add 0.50 mol/liter toluene solution of triisobutylaluminum.
Added 5ml. The mixture was reacted for about 15 minutes and used as a reaction solution for polymerization.

(Polymerization) Polymerization and post-treatment were carried out in the same manner as in Example 20 in the presence of cis-1,,4-/lysozolene, using 9.8 rd of reacted cobalt solution (0.6 mmol as cobalt). 26.8 g of a polymerized composition of rubber and crystalline 1,2-polybutadiene (42 g as a polymerization rate of sitadiene)
俤) was obtained.

DSC analysis result of polymer composition: vitrification temperature Tg is -7
The 2°C melting point Tm was 188°C. It was visually confirmed that the cis-1,4-/lysozolene rubber and the crystalline 1,2-polybutadiene were homogeneously mixed.

Dinner 1 cis-1,4-yJ? Liptadiene rubber manufactured by Japan Synthetic Rubber Co., Ltd. JSRBROI 2 Solution polymerization SBR manufactured by Japan Synthetic Rubber Co., Ltd. JSR5L
552 tatami 3 Synthetic natural rubber J made by Japan Synthetic Rubber Co., Ltd.
SRlR2200 screen 4 Ethylene-Zolopyrene copolymerization-
"A Japan Synthetic Rubber @) JSREP24 Stain 5 Acrylonitrile-butadiene copolymer rubber JSRN23O8 manufactured by Japan Synthetic Rubber Co., Ltd. Acrylic rubber
JSRAR201 (manufactured by Nippon Gosei Co., Ltd.) 7 Polystyrene resin (manufactured by Mitsui Toatsu) -4 E'Rex 525 8
Ethylene vinyl acetate resin Ultrasen 633 manufactured by Toyo Soda Comparative Example 4 After purging an 800 ml autoclave with nitrogen, 400 ml of distilled water that had been previously subjected to nitrogen and 9 blinds and 100 g of butadiene were added.

5. Reacted cobalt solution prepared by the method of Example 22.
After adding 9 ml (0.36 mmol of cobalt), 0.36 mmol of carbon disulfide was added to initiate polymerization. Polymerization was carried out for 1 hour while maintaining the reaction temperature at 15°C. After the polymerization was completed, the polymer was taken on a cloth, immersed in methanol containing one portion of BHT, and then vacuum-dried at 50° C. overnight. As a result, 32.9 g of a gypsum-like polymer was obtained.

The melting point of the polymer was 192°C.

20 g of 1,2-,JP liptadiene thus obtained was added to 2500 ml of a toluene solution in which 200 g of cis-1,4-polybutadiene was melted, and after stirring vigorously,
Toluene was removed by steam stripping. When this polymer was dried using a roll at 120°C, it was a non-uniform composition in which lumps of 1,2-polybutadiene were observed scattered throughout the polymer.

This composition was vulcanized according to the same formulation as in Example 20. The results are shown in Table-2.

This composition had only a low tensile strength due to poor dispersion of 1,2-polybutadiene.

Extrusion test ASTM D2230 - Pay die screw diameter 10φ L/D = 8 Gui temperature 100°C Number of revolutions 2 Orpm "Effects of the invention" As is clear from the above, according to the present invention, the solution state of a polymer such as rubber or resin By polymerizing butadiene in the presence of 1.2-polybutadiene in the presence of water, a polymer composition in which a polymer such as rubber or resin and crystalline 1.2-polybutadiene are extremely uniformly dispersed in a low-viscosity reaction system can be obtained. can be obtained easily.

Claims (1)

[Claims] (a) A cobalt compound (A) and an organometallic compound of a metal in Groups I to III of the periodic table or its hydride (B) are added in advance to the polymer solution in an amount of 1 to 1000 times the mole of (A). A catalyst obtained by contacting in the presence of a conjugated diene and (
b) A method for producing a polymer composition, which comprises polymerizing butadiene in the presence of water in the coexistence of at least one selected from carbon disulfide, phenylisothiocyanic acid, and a xanthogen compound.