JPH10158315A - New anionic polymerization initiator and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an anionic polymerization initiator for producing a polymer used in an impact-resistant styrene-based resin composition excellent in balance between physical properties of impact resistance and gloss. SOLUTION: This anionic polymerization initiator is a low-molecular weight polymer prepared by reacting a mixture containing a conjugated diene-based monomer and a polyvinyl aromatic compound in the presence of an organolithium compound at a molar ratio of the polyvinyl aromatic compound/ organolithium compound within the range of 0.1-2.0 and has (A) 2-40wt.% total polyvinyl aromatic compound content in the initiator, (B) 500-20,000 weight- average molecular weight (Mw ) thereof, measured by a get permeation chromatography and expressed in terms of polystyrene and (C) 1.2-3.5 molecular weight distribution (Mw /Mn ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel anionic polymerization initiator, and more particularly to a polymerization initiator suitable for anionic polymerization of a conjugated diene monomer or an aromatic vinyl monomer. When a conjugated diene-based polymer or an aromatic vinyl-conjugated diene-based block copolymer produced by using the anionic polymerization initiator of the present invention is used as a toughening agent for an impact-resistant styrene-based resin, the impact strength and gloss are increased. A resin excellent in the balance of the above is obtained. Further, it is a useful initiator for producing polymers used for applications such as adhesives, asphalt modifiers, coating agents, and other industrial uses.

[0002]

2. Description of the Related Art Polystyrene is used for various purposes because of its excellent rigidity, transparency, gloss, etc. and good moldability. However, this polystyrene has a major drawback of poor impact resistance, and various unvulcanized rubbers have been used as toughening agents to improve this drawback. Above all, an impact-resistant styrene resin obtained by radical polymerization of a styrene monomer in the presence of an unvulcanized rubber and graft polymerization of a rubber-like polymer is industrially widely produced.

As the unvulcanized rubber used for this purpose, there are polybutadiene and styrene-butadiene copolymer. In particular, polybutadiene is widely used for imparting excellent impact resistance. Conventionally, when producing such a polybutadiene or styrene-butadiene copolymer, a monoorganic lithium compound such as n-butyllithium or sec-butyllithium has been most commonly used as a polymerization initiator.

It has also been reported that a reaction product containing a monoorganic lithium compound and a polyvinyl aromatic compound is used as a polymerization initiator. For example, a reaction product of a monoorganic lithium compound and a polyvinyl aromatic compound (JP-A-48-103690), a reaction of a monoorganic lithium compound with a conjugated diene compound or a monoaromatic vinyl compound, Product obtained by reacting an aromatic compound (US Patent No. 200300334);
Or a monoorganic lithium compound, a conjugated diene compound,
Polymerization initiators such as a product obtained by simultaneously reacting a poly (vinyl aromatic compound) and a polyvinyl aromatic compound (JP-B-43-25510 and JP-B-51-44987) are known.

In recent years, impact-resistant styrene resins have been used for
With the spread of housing and other parts of home electric appliances, axle parts, office equipment parts, daily necessities and toys, more excellent various characteristics are required,
There is a strong demand for an impact-resistant styrene-based resin having an excellent balance between appearance characteristics and impact resistance. Conventionally, as a method of improving the impact-resistant styrene resin, a solution viscosity of a conjugated diene polymer is specified (Japanese Patent Publication No. 58-4934), and a relationship between a solution viscosity of the conjugated diene polymer and Mooney viscosity is specified. (JP-B-53-44188), specifying the relationship between the solution viscosity of a conjugated diene-based polymer and the tensile modulus and swelling degree of a crosslinked organic peroxide (JP-A-60-2500)
No. 1) has been proposed. However, in these methods, the balance between impact resistance and gloss is improved as compared with the case where conventional polybutadiene is used, but it is not always satisfactory.

On the other hand, Japanese Patent Application Laid-Open No. 61-143415,
JP-A-63-165413, JP-A-2-1321
No. 12, JP-A-2-208312 and the like propose a method for improving impact resistance and appearance characteristics by using a styrene-butadiene block copolymer having a specific structure. However, when these methods are examined in detail, it has been found that there is no practically satisfactory balance between impact resistance and appearance characteristics. As described above, at present, satisfactory impact-resistant styrene resins have not been obtained with conventional polybutadiene rubbers or styrene-butadiene copolymers produced from conventional anionic polymerization initiators.

[0007]

As described above, it is difficult to improve the conflicting balance between impact resistance and gloss to a satisfactory level with a rubbery polymer produced with a conventional anionic polymerization initiator. However, an object of the present invention is to provide a novel anionic polymerization initiator for solving the above-mentioned problems.

[0008]

In the present invention, as a result of a detailed study on obtaining an impact-resistant styrenic resin having an excellent balance between physical properties of impact resistance and gloss, a specific structure which has not been studied hitherto has been obtained. By using a toughening agent produced by the anionic polymerization initiator having the above, it was clear that the above object was achieved, and the present invention was completed.

That is, the present invention relates to (1) a method of preparing a mixture of a monomer containing a conjugated diene monomer and a polyvinyl aromatic compound by using a polyvinyl aromatic compound /
A low molecular weight polymer reacted in the presence of an organic lithium compound having a molar ratio of the organic lithium compound in the range of 0.1 to 2.0, wherein (A) the total polyvinyl aromatic compound content in the initiator is Two
40% by weight (B) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(C) an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5, (2) a hydrocarbon solvent in which 30 to 50,000 ppm of a polar organic compound is present, A mixture of a monomer containing a conjugated diene monomer and a polyvinyl aromatic compound has a molar ratio of polyvinyl aromatic compound / organic lithium compound of 0.1.
(A) The total polyvinyl aromatic compound content in the initiator is 2 to 2 by reacting in the presence of an organolithium compound in the range of 1 to 2.0.
40% by weight (B) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(C) a method for producing an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5;

(3) In a hydrocarbon solvent, a mixture of a monomer containing 1 to 99% by weight of the total amount of the conjugated diene monomer and a polyvinyl aromatic compound is prepared.
Polymerization is started in the presence of an organolithium compound having a molar ratio of the organolithium compound in the range of 0.1 to 2.0, and then the remaining conjugated diene-based monomer is continuously or intermittently introduced into the reaction system. (A) The total polyvinyl aromatic compound content in the initiator is 2 to 2
40% by weight (B) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(C) a method for producing an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5, (4) a hydrocarbon containing 30 to 50,000 ppm of a polar organic compound In a solvent, a mixture of a monomer containing 1 to 99% by weight of the total amount of the conjugated diene-based monomer and a polyvinyl aromatic compound has a molar ratio of polyvinyl aromatic compound / organic lithium compound of 0.1 to 2. By starting the reaction in the presence of an organolithium compound in the range of 0, and then continuously or intermittently feeding the remaining conjugated diene-based monomer into the reaction system. Total polyvinyl aromatic compound content is 2 to
40% by weight (B) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(C) a method for producing an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5.

Hereinafter, the present invention will be described in detail. The production of the anionic polymerization initiator of the present invention is produced by a method of reacting a mixture of a conjugated diene monomer and a monomer containing a polyvinyl aromatic compound in the presence of an organic lithium compound, and the reaction product is produced. And an anionic polymerization initiator such as a conjugated diene monomer or an aromatic vinyl monomer. The first method for producing the anionic polymerization initiator of the present invention comprises:
In a hydrocarbon solvent in which a polar compound is present, a mixture of a conjugated diene monomer and a monomer containing a polyvinyl aromatic compound is produced by completing the reaction in the presence of an organolithium compound.

In the second production method, 1 to 99% by weight, preferably 1% by weight of the total amount of the conjugated diene monomer in a hydrocarbon solvent is used.
A reaction of a mixture of 0 to 80% by weight and a monomer containing a polyvinyl aromatic compound is started in the presence of an organolithium compound, and then the remaining conjugated diene-based monomer is continuously introduced into the reaction system. It is manufactured by completing the reaction after addition and supply of all the conjugated diene-based polymers. The addition time of the remaining conjugated diene-based monomer can be arbitrarily selected. Alternatively, the remaining conjugated diene-based monomer is sequentially supplied in one to several portions, and after the supply of the monomer mainly containing all the conjugated diene-based monomers is completed, the reaction is continued. Manufactured by completing.

In the third production method, the total amount of the conjugated diene-based monomer in a hydrocarbon solvent containing a polar compound is 1 to
A reaction of a mixture of a monomer containing 99% by weight, preferably 10 to 80% by weight and a polyvinyl aromatic compound is started in the presence of an organolithium compound, and then the remaining conjugated diene monomer is reacted. It is manufactured by continuously adding it into the system and completing the reaction after the supply of all the conjugated diene-based polymers is completed. The addition time of the remaining conjugated diene-based monomer can be arbitrarily selected. Alternatively, the remaining conjugated diene-based monomer as a main component is sequentially supplied once to several times separately, and after all conjugated diene-based monomers have been supplied, the reaction is continued. Manufactured by completing.

Examples of the hydrocarbon solvent used for preparing the initiator of the present invention include aliphatic hydrocarbons such as butane, pentane and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, benzene, toluene, xylene, ethylbenzene, and the like. Aromatic hydrocarbons such as diethylbenzene are used,
One type or two or more types may be arbitrarily combined. Preferred examples include hexane and cyclohexane. Further, as the polar compound to be added to the hydrocarbon solvent, a tertiary monoamine, a tertiary diamine, a cyclic or chain ether, or the like is used.

Examples of tertiary monoamines include trimethylamine, triethylamine, methyldiethylamine,
1,1-dimethoxyamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine,
Compounds such as N, N-dimethylformamide diisopropyl acetal, N, N-dimethylformamide, dicyclohexyl acetal and the like can be mentioned.

Examples of tertiary diamines include N, N,
N ', N'-tetramethyldiaminomethane, N, N,
N ′, N′-tetramethylethylenediamine, N, N,
N ′, N′-tetramethylpropanediamine, N, N,
N ', N'-tetramethyldiaminobutane, N, N,
N ', N'-tetramethyldiaminopentane, N, N,
Compounds such as N ′, N′-tetramethylhexanediamine, diperidinopentane, diperidinoethane and the like can be mentioned. Examples of the chain ether include dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.

Examples of the cyclic ether include tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-
Bis (2-oxolanyl) propane, 1,1-bis (2
-Oxolanyl) ethane, 2,2-bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, and compounds such as 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane. . Among the polar compounds, tertiary diamine N,
N, N ', N'-tetramethylethylenediamine and the chain ether, tetrahydrofuran, are preferred.
In using the polar compound, one kind or two or more kinds may be arbitrarily combined.

The amount of the polar compound used is 3 to the hydrocarbon solvent used in producing the anionic polymerization initiator.
0 to 50,000 ppm, preferably 2 to 50,000 ppm.
The range is from 00 to 20,000 ppm. 30 usage
When the amount is less than ppm, the molecular weight distribution of the obtained anionic polymerization initiator is widened, and when the obtained polymer is used for an impact-resistant styrenic resin, the balance between gloss and impact strength is unfavorably poor. If the amount exceeds 50,000 ppm, it is difficult to separate the polar compound and the polymerization solvent in the solvent recovery step after the production of the polymer, which is not preferable.

The conjugated diene monomer used in the present invention includes 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene,
Examples thereof include methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene, and the like, and one kind or a combination of two or more kinds is used. Preferred monomers include 1,3-butadiene and isoprene.
The amount of the conjugated diene monomer is not particularly limited, but is preferably in the range of 3 mol to 100 mol per 1 mol of the monoorganic lithium compound.

The production of the anionic polymerization initiator having a specific structure used in the present invention may be carried out by using a conjugated diene monomer as an essential component. It is also possible to use a mixture with the monomer as a conjugated diene-based monomer. For example, an anionic polymerization initiator can be prepared using a mixture of an aromatic vinyl-based monomer. Examples of the aromatic vinyl-based monomer include styrene, p-methylstyrene, α-methylstyrene, 3,5-dimethylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like, or a combination of two or more. May be used.

The organic lithium compound used in the present invention is a monoorganic lithium compound such as n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium and benzyllithium. Preferably, a monoorganic lithium compound of n-butyl lithium and sec-butyl lithium is used.

The monomer containing a polyvinyl aromatic compound used in the present invention is a polyvinyl aromatic compound alone or a mixture of a polyvinyl aromatic compound and an aromatic vinyl monomer. Examples of polyvinyl aromatic compounds include o, m and p-divinylbenzene, o, m and p
-Diisopropenylbenzene, 1,2,4-trivinylbenzene, 1,2-vinyl-3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4- Divinyl biphenyl, 3,
5,4'-trivinylbiphenyl, 1,2-divinyl-
3,4-dimethylbenzene, 1,5,6-trivinyl-
3,7-diethylnaphthalene and the like, which can be used alone or in combination of two or more. Particularly, divinylbenzene and diisopropenylbenzene are preferable, and divinylbenzene and diisopropenylbenzene include o-,
There are m- and p- isomers, and divinylbenzene and diisopropenylbenzene which are a mixture of these isomers are practically satisfied.

Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, α-methylstyrene,
5-dimethylstyrene, ethylvinylbenzene, vinylxylene, vinylnaphthalene, etc., and may be used alone or in combination of two or more. The content of the aromatic vinyl monomer in the monomer containing the polyvinyl aromatic compound is in the range of 100/0 to 10/90 by weight ratio of polyvinyl aromatic compound / aromatic vinyl monomer. Preferably,
It is in the range of 100/0 to 50/50.

The amount of the polyvinyl aromatic compound used for preparing the anionic polymerization initiator of the present invention is in the range of 0.1 to 2.0 mol based on the organolithium compound. Preferably, from 0.15 to 1.5, more preferably from 0.2 to 1.5
It is in the range of 1.0. A polymer obtained using an anionic polymerization initiator prepared with a polyvinyl aromatic compound / monoorganic lithium compound molar ratio of less than 0.1 has gloss and impact strength when used in an impact-resistant styrenic resin. Is inferior in balance. On the other hand, if it exceeds 2.0, only those having a wide molecular weight distribution of the anionic polymerization initiator can be obtained, and when the obtained polymer is used for an impact-resistant styrene resin, giant particles are formed. It is not preferable because glossiness is easily reduced.

The total content of the polyvinyl aromatic compound in the anionic polymerization initiator is in the range of 2 to 40% by weight.
When the amount is less than 2% by weight, when the obtained polymer is used as an impact-resistant styrenic resin, the balance between gloss and impact strength is poor, which is not preferable. If it exceeds 40% by weight, only an anionic polymerization initiator having a wide molecular weight distribution can be obtained, and gel formation may occur in some cases, which is not preferable. Further, when the obtained polymer is used as an impact-resistant styrene resin, giant particles are easily formed, and the gloss is reduced, which is not preferable. The temperature at the time of producing the anionic polymerization initiator of the present invention is in the range of 10 ° C to 140 ° C,
Preferably it is in the range of 35 ° C to 110 ° C. The reaction time generally depends on the reaction temperature during preparation, but ranges from 5 minutes to 24 hours.

The anionic polymerization initiator prepared by the method of the present invention has a weight average molecular weight (Mw) of 5 in terms of polystyrene measured by gel permeation chromatography.
In the range of 100 to 20,000, preferably 100
It is in the range of 0 to 10,000. Weight average molecular weight 2
When a polymer obtained using an anionic polymerization initiator exceeding 000 is used for an impact-resistant styrenic resin,
The balance between gloss and impact strength is poor, which is not preferred. 500
If it is less than 1, the molecular weight distribution of the anionic polymerization initiator becomes undesirably wide.

The molecular weight distribution (Mw / Mn) is from 1.2 to
It is in the range of 3.5, preferably in the range of 1.2 to 2.5. When a polymer obtained using an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of more than 3.5 is used for an impact-resistant styrene-based resin, large particles are easily formed and gloss is reduced. Not preferred. The anionic polymerization initiator produced in the present invention is a very useful initiator for solution-polymerizing at least one conjugated diene monomer and / or at least one aromatic vinyl monomer in a hydrocarbon solvent. Useful for

Examples of the conjugated diene monomer include 1,3
-Butadiene, isoprene, 2,3-dimethyl-1,3
-Butadiene, 1,3-pentadiene, 3-methyl-
1,3-pentadiene, 1,3-heptadiene, 1,3
-Hexadiene and the like, used alone or in combination of two or more. Preferred monomers include 1,3-butadiene and isoprene. Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, α-methylstyrene, 3,5-dimethylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like. Used. Particularly, styrene is preferred.

As the hydrocarbon solvent used in the solution polymerization,
Aliphatic hydrocarbons such as butane, pentane and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene are used. Preferred examples include hexane and cyclohexane. Conjugated diene polymer or aromatic vinyl-
As a method for producing a conjugated diene-based copolymer, an anionic polymerization initiator of the present invention is prepared, and then a conjugated diene-based monomer and / or an aromatic vinyl monomer are added to initiate a polymerization reaction. And a method in which the anionic polymerization initiator of the present invention is added to a reactor containing a conjugated diene-based monomer and / or an aromatic vinyl monomer and the polymerization reaction is started to produce the polymer. Used.

The polymer produced by using the anionic polymerization initiator of the present invention is, for example, a compound represented by the following general formula (1) c- (B) n (2) c- (AB) n (3) c- ( BA) n (4) c- (BAB) n (5) c- (ABA) n (6) c- (BABA) n (7) c -(ABAB) n (where B is a conjugated diene polymer or a random copolymer of a conjugated diene and an aromatic vinyl compound, and a taper block in which the ratio of the aromatic vinyl compound gradually increases is used. A represents a polymer block mainly composed of an aromatic vinyl compound, c represents a residue of an anionic polymerization initiator, n is an integer of 1 to 10, and is a mixture of each. May be used.).

C- (B) n type, c- (AB) n type, c- (
BA) n type, c- (BAB) n type, c- (AB-
A) n-type polymers or block copolymers are preferred. Further, as toughening agents for impact-resistant styrene resins, c- (B) n-type, c- (AB) n-type, c- (BA) n type is preferably used.

The conjugated diene-based polymer or aromatic vinyl-conjugated diene-based copolymer produced by using the anionic polymerization initiator of the present invention is a low-molecular-weight polymer having a specific structure, that is, a low-molecular-weight polymer. Is obtained by adding a residual double bond of the polyvinyl aromatic compound of the above to the polymer. As a result, for example, when it is used for an impact-resistant styrene resin composition, it is characterized in that it is possible to greatly improve the balance between impact strength and gloss of the resin.

The conjugated diene-based polymer or the aromatic vinyl-conjugated diene-based copolymer produced by using the anionic polymerization initiator of the present invention can be used as long as its basic properties are not impaired. Various modifications such as introduction of a carboxyl group, an ester group, a nitrile group, a sulfonic acid group, an amino group, etc. may be achieved by the reaction. Further, the block copolymer may contain various additives as needed, for example, inorganic fillers such as calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, clay, talc, glass beads, glass fibers, and organic reinforcing agents such as carbon black. , Carbon fiber, organic fiber such as synthetic fiber, coumarone indene resin,
Adhesives such as terpene resins, organic peroxides, inorganic peroxides, crosslinkers such as sulfur, paraffinic,
It is also possible to use an appropriate amount of a naphthene-based or aroma-based oil, various pigments, dyes, flame retardants, antistatic agents, lubricants, plasticizers, other extenders, or mixtures thereof.

The conjugated diene-based polymer or aromatic vinyl-conjugated diene-based copolymer produced using the anionic polymerization initiator of the present invention is useful as a toughening agent for impact-resistant styrene-based resins. Usually, as a method for producing an impact-resistant styrene resin, a conjugated diene-based polymer or an aromatic vinyl-conjugated diene-based copolymer is dissolved in a mixture with an aromatic vinyl monomer or a copolymerizable monomer. However, a method of performing graft polymerization by a bulk polymerization method, a bulk suspension polymerization method, or a solution polymerization method while stirring so that a uniform stress is applied to the rubber solution is preferable.

The conjugated diene-based polymer or aromatic vinyl-conjugated diene-based copolymer produced by using the anionic polymerization initiator of the present invention is also useful as a material for a hot melt pressure-sensitive adhesive composition having excellent adhesive properties. It is. When used as a hot-melt pressure-sensitive adhesive composition, a pressure-sensitive adhesive resin, a softening agent, and a reinforcing resin can be blended with the conjugated diene-based polymer of the present invention or the aromatic vinyl-conjugated diene-based copolymer. .

The pressure-sensitive adhesive resin is one which has been conventionally used as a tackifier in a hot-melt pressure-sensitive adhesive.
Coumarone / indene resin, phenolic resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, terpene / phenol resin, polyterpene resin, xylene / formaldehyde resin, synthetic polyterpene resin, aromatic hydrocarbon resin, aliphatic cyclic Hydrocarbon resins, oligomers of monoolefins and diolefins, hydrogenated hydrocarbon resins, hydrocarbon-based tackifying resins, polybutene, polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, hydrogenated rosin and monoalcohol or polyhydric Examples include esters with alcohols and turpentine tackifiers. The softener is a petroleum softener,
Paraffin, vegetable oil-based softener, plasticity and the like. Reinforcement resin such as polystyrene, polyethylene, polypropylene ethylene-propylene copolymer, ethylene butene copolymer, ethylene-vinyl acetate copolymer, relatively low molecular weight thermoplastic polyester resin, polyamide resin, polyphenylene ether resin, etc. Can be used.

The conjugated diene-based polymer or aromatic vinyl-conjugated diene-based copolymer produced using the anionic polymerization initiator of the present invention can be obtained by appropriately selecting the ratio of the polymer to asphalt. , Road pavement, waterproof,
It can be used for rust prevention, coating for automobile base, roofing, pipe coating, joint use, etc. In particular, the polymer is useful as a polymer for solving the problems of asphalt containing a conventional block copolymer, such as a melt viscosity that is too high, phase separation during storage, and the like. Asphalt includes straight asphalt, semi-blown asphalt, blown asphalt, tar, pitch,
Furthermore, cutback asphalt to which oil is added can be mentioned, and these may be arbitrarily mixed and used. This asphalt composition can be blended with optional additives in optional amounts as needed. Examples of additives include inorganic fillers such as clay, talc, calcium carbonate, zinc oxide, and glass beads; aggregates such as crushed stone, gravel and sand; fibrous reinforcing materials such as glass fiber and asbestos; and carbon black. Organic reinforcing agents, coumarone indene resin, tackifying resin such as terpene resin, paraffinic,
Softening agents such as naphthene-based and aroma-based oils, thermoplastic resins such as polyolefin-based resins, polystyrene-based resins, and polyvinyl chloride-based resins, natural rubber, polybutadiene rubber,
Synthetic rubbers such as styrene-butadiene rubber and nitrile rubber are exemplified.

When a conjugated diene polymer or an aromatic vinyl-conjugated diene polymer produced using the anionic polymerization initiator of the present invention is used for shoe soles, automobile parts, industrial parts, etc. Fillers and / or organic fillers, softeners and thermoplastics can be included. Examples of the inorganic filler and / or the organic filler include calcium carbonate, crecu, silica, zinc white, magnesium carbonate, magnesium silicate, talc, diatomaceous earth, dolomite, mica powder, aluminum sulfate, barium sulfate, graphite, and glass fiber. , Carbon black, high styrene resin, coumarone / indene resin, phenol / formaldehyde resin,
Modified melamine resin, petroleum resin, lignin, wood flour, carbon fiber and the like can be mentioned. Examples of the softener include lubricating oils, paraffinic process oils, naphthenic process oils, aroma-based process oils, paraffin, vaseline, asphalt, vegetable oils (castor oil, cottonseed oil, rapeseed oil, soybean oil, etc.), rosin, fatty acids, and the like. Can be As the thermoplastic resin, olefin resin, styrene resin, acrylate resin, vinyl chloride resin, polyamide resin,
Examples include polyester resins, polycarbonate resins, polyphenylene ether resins, polyphenylene sulfide resins, polyacetal resins, and polyurethane resins. Among them, olefin resins such as polyethylene, polypropylene and ethylene-propylene copolymer, and styrene resins such as polystyrene and rubber-modified impact-resistant polystyrene are preferably used.

The conjugated diene-based polymer or aromatic vinyl-conjugated diene-based copolymer produced by using the anionic polymerization initiator of the present invention is a vinyl aromatic hydrocarbon which does not satisfy the requirements of the present invention. Block copolymer elastomer of styrene and conjugated diene (generally having a vinyl aromatic hydrocarbon content of 60% by weight or less) or block copolymer resin of vinyl aromatic hydrocarbon and conjugated diene (generally containing vinyl aromatic hydrocarbon) (The amount is more than 60% by weight) to improve moldability and adhesive properties.

Further, the conjugated diene-based polymer or aromatic vinyl-conjugated diene-based copolymer produced by using the anionic polymerization initiator of the present invention is also used as a modifier for the above-mentioned various thermoplastic resins. can do. When the above-mentioned composition is produced using the conjugated diene-based polymer of the present invention or the aromatic vinyl-conjugated diene-based copolymer, various kinds of components commonly used for mixing high-molecular substances depending on the composition of the components are used. It can be prepared by using a mixing device, for example, a single-screw or multi-screw extruder, a mixing roll, a bumper mixer, a kneader and the like, and it is preferable to mix in a molten state.

The composition can also be obtained by, for example, mixing the solutions of the respective components and then removing the solvent by heating. The block copolymer of the present invention and the composition obtained by adding various additives to the block copolymer may be any conventionally known molding method, for example, extrusion, injection molding, hollow molding, etc., a sheet, a foam, It can be easily formed into a wide variety of practically useful products such as films, injection molded products of various shapes, hollow molded products, compressed air molded products, etc.
It can be used for electric cables, food packaging containers, various automobile parts, industrial supplies, etc.

[0042]

EXAMPLES Some examples will be shown below to show specific embodiments of the present invention. However, these examples are intended to explain the technical contents of the present invention more specifically, and limit the present invention. Not something. Various measurements were made according to the following methods. [Weight average molecular weight of anionic polymerization initiator] measured by GPC (gel permeation chromatography),
It is the calculated molecular weight in terms of polystyrene. (GPC measurement conditions) Measuring model LC Module 1 solvent manufactured by Waters Solvent Chloroform column Shodex K-801 1 K-802 1 K-803 1 (3 in total) Column temperature 35 ° C Delivery flow rate 1.0 ml / Min Sample concentration 0.1% by weight Sample injection amount 0.1ml Detector Showex RI Shodex RI SE-61

[Weight average molecular weight of polymer] Measured by GPC (gel permeation chromatography)
It is the calculated molecular weight in terms of polystyrene. (GPC measurement conditions) Measurement model LC Module 1 solvent manufactured by Waters THF (tetrahydrofuran) Column PL gel manufactured by Polymer Laboratories × 3 Column temperature 35 ° C Liquid sending flow rate 0.4 ml / min Sample concentration 0.1 wt% Sample injection amount 0 .1 ml detector Showex Denko Shodex RI SE-61

[Microstructure] Using an infrared spectrophotometer (FT-IR1650 manufactured by PerkinElmer), the SBR was measured.
Is based on the Hampton method (Analytical Chemistry, 21 , 923 (194
9)) and BR were measured by the Morero method (Chim Ind 41 , 758 (1959)). [Bound styrene content] UV spectrophotometer (Hitachi UV20
0) was measured by a standard method. [Izod impact strength] The obtained composition was compression-molded to prepare a 3.2 mm-thick test piece, which was subjected to JIS-K-7.
Measured according to 110.

[Gloss] Gloss (incidence angle: 60 °) of the gate portion and the end gate portion was measured and averaged according to ASTM D-638. [Rubber particle diameter] An electron micrograph was taken of the obtained resin by an ultra-thin section method, and the rubber particles in the photograph were 800 to 1000.
The particle diameter of each of the particles was measured and weight averaged. That is, average rubber particle diameter = Σn D ⁴ / Σn D ³ (n is the number of rubber particles having a particle diameter D)

(I) Preparation of Anionic Polymerization Initiator (Examples 1 to 3) A 10 L internal volume stirrer and a jacketed autoclave were washed, dried and purged with nitrogen, and then dried under the conditions shown in Table 1. Add 1,3-butadiene, cyclohexane, tetrahydrofuran and divinylbenzene, then add n-butyllithium and add
The reaction time was adjusted. The anionic polymerization initiator prepared under the conditions shown in Table 1 was soluble in cyclohexane and had no gel. The divinylbenzene used for the preparation of the catalyst contained 56% by weight of an isomer mixture (m-divinylbenzene = 40% by weight, p-divinylbenzene = 16% by weight),
Commercially available divinylbenzene with the balance being ethylvinylbenzene = 44% by weight was used.

(Examples 4 to 6) An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed, dried and purged with nitrogen. Then, under the conditions shown in Table 1, 80 g of dried 1,3-butadiene, cyclohexane, Tetrahydrofuran and divinylbenzene were added, followed by n-butyllithium. Then, the remaining 1,3-butadiene 120g
Was continuously added to the reactor over 1 hour, and then reacted for an additional 30 minutes. The reaction temperature was 75 ° C. The anionic polymerization initiator prepared under the conditions shown in Table 1 was soluble in cyclohexane and had no gel. The divinylbenzene used for the preparation of the catalyst contains 56% by weight of an isomer mixture (m-divinylbenzene = 40% by weight, p-divinylbenzene = 16% by weight), and the balance is ethylvinylbenzene = 44% by weight. Commercially available divinylbenzene was used.

(Examples 7 to 9) An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed, dried and purged with nitrogen. Then, under the conditions shown in Table 1, 80 g of dried 1,3-butadiene, cyclohexane and Divinylbenzene was added, followed by n-butyllithium. Thereafter, 120 g of the remaining 1,3-butadiene was continuously added to the reactor over 1 hour, and then the mixture was further reacted for 30 minutes. The reaction temperature was 75 ° C. The anionic polymerization initiator prepared under the conditions shown in Table 1 was soluble in cyclohexane and had no gel.

The divinylbenzene used in the preparation of the catalyst was
56% by weight of an isomer mixture (m-divinylbenzene = 40
% By weight, p-divinylbenzene = 16% by weight), and the remainder was ethylvinylbenzene = 44% by weight. Further, in Example 8, m-divinylbenzene was used, and the molecular weight distribution curve of the obtained anionic polymerization initiator H is shown by a solid line in FIG.

Example 10 As a polar compound, N,
N, N ', N'-tetramethylethylenediamine (TM
An anionic polymerization initiator was prepared in the same manner as in Example 1 except that EDA) was used. (Example 11) An anionic polymerization initiator was prepared in the same manner as in Example 1 except that m-diisopropenylbenzene was used as the polyvinyl aromatic compound.

(Comparative Examples 1 to 5) Under the conditions shown in Table 2,
An anionic polymerization initiator was prepared in the same manner as in Example 1. When the molar ratio of divinylbenzene / n-butyllithium was adjusted to 2.2, the molecular weight distribution of the anionic polymerization initiator was widened, and when the divinylbenzene content in the anionic polymerization initiator was 43% by weight, A gel formed. The molecular weight distribution curve of the anionic polymerization initiator N obtained in Comparative Example 3 is shown by a dotted line in FIG.

[0052]

[Table 1]

[0053]

[Table 2]

(II) Production of Polybutadiene An autoclave with a stirrer and a jacket having an internal volume of 10 L was washed, dried and purged with nitrogen, and then purified and dried under the conditions shown in Tables 3 and 4 in advance. -Butadiene and cyclohexane were added, then tetrahydrofuran was added as a 1,2-vinyl regulator, and an anionic polymerization initiator shown in Table 1 was further added to initiate polymerization at 60 ° C. After the completion of the polymerization, methanol was added to completely inactivate the living polymer. As a stabilizer, 2,6-di-tert-butyl-4-methylphenol was added to the polymer solution thus obtained in an amount of 0.2 to 100 parts by weight of the polymer.
5 parts by weight, and the solvent was removed by steam stripping.
C.), and the rubber sample No. shown in Table 3 was dried.
3, 4, and 8 polybutadienes were obtained.

(III) Production of styrene-butadiene block copolymer An autoclave with a stirrer and a jacket having an internal volume of 10 L was washed, dried and purged with nitrogen, and then purified in advance under the conditions shown in Tables 3 and 4. Then, dried 1,3-butadiene and cyclohexane were added, then tetrahydrofuran was added as a 1,2-vinyl regulator, and an anionic polymerization initiator shown in Table 1 was further added to initiate polymerization at 60 ° C. After completion of the reaction, styrene was subsequently added, and polymerization was continued. After the completion of the polymerization, methanol was added to completely inactivate the living polymer. To the polymer solution thus obtained, 2,6-di-tert-butyl-4-methylphenol was added as a stabilizer in an amount of 0.5 part by weight per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. Subsequently, the sample was dried with a hot roll (110 ° C.), and the rubber sample Nos. 1, 2, 5 to 7, and 9 to 15 styrene butadiene block copolymers were obtained.

[0056]

[Table 3]

[0057]

[Table 4]

(IV) Production of Impact-Resistant Styrenic Resin Composition Next, using the various polymers shown in Tables 3 and 4 by the bulk polymerization method described below, I got Table 5 for the stirrer and jacketed reactor,
Ethylbenzene and styrene were added in the types and ratios shown in Table 6 and then the rubber samples N shown in Tables 3 and 4 were added.
o. As a rubber and a stabilizer of 1,3,4,6,7,9 to 12,14,15, n-octadecyl-3- (3 ′,
0.3 parts by weight of 5'-di-tert-butyl-4'-hydroxyphenyl) propionate and 0.05 parts by weight of t-dodecylmercaptan were added and dissolved by stirring.

To this, 1 × 10 ^-4 mol of di-tert-butyl peroxide was added per 1 mol of the monomer,
Polymerization was performed at 110 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Further, after heating at 230 ° C. for 30 minutes, unreacted products were removed under reduced pressure, and the obtained polymer was pulverized and formed into pellets by an extruder. Tables 5 and 6 show the physical properties of the obtained impact-resistant styrenic resin composition. As is clear from the results of the examples, the impact-resistant styrene resin composition produced using the polybutadiene or styrene-butadiene block copolymer obtained using the anionic polymerization initiator of the present invention has a glossy It can be seen that the balance between the strength and the impact strength is excellent. On the other hand, as shown in Comparative Examples 1 to 4, when the styrene butadiene block copolymer obtained using the anionic polymerization initiator out of the range of the present invention is used, the impact strength or the gloss is inferior. In both cases, no excellent impact-resistant styrenic resin composition was obtained.

(V) Production of ABS resin Using the same reactor as in Example 1, ethylbenzene, styrene and acrylonitrile were added in the types and ratios shown in Tables 5 and 6, and then in Tables 3 and 4. Rubber sample No. 4 shown in Table 4. 2,5,8,13 rubbers and stabilizers as n
Octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate
3 parts by weight and 0.05 parts by weight of t-dodecyl mercaptan were added and dissolved by stirring. To this, di-tert-butyl peroxide was added in an amount of 1 × 10
^-4 mol added, 110 ° C for 3 hours, 140 ° C for 5 hours,
Polymerization was performed at 180 ° C. for 2 hours. Further, at 230 ° C., 30
After heating for 1 minute, unreacted products were removed under reduced pressure, and the resulting polymer was pulverized and formed into pellets with an extruder to obtain an ABS resin. The physical properties of the obtained ABS resin composition are shown in Tables 5 and 6.

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

The anionic polymerization initiator of the present invention is useful for producing a conjugated diene polymer or an aromatic vinyl-conjugated diene block copolymer used in an impact-resistant styrene resin composition. When the polymer produced by the anionic polymerization initiator of the present invention is used in an impact-resistant styrenic resin composition, physical properties such as impact resistance and gloss are compared with those of a conventional impact-resistant styrenic resin composition. Excellent balance,
Wide variety of applications such as electronic devices such as TVs and VTRs, home appliances such as air conditioners and refrigerators, general equipment such as OA office equipment, stationery, toys, leisure sports goods, household goods, building materials and housing parts, and food containers. It has an industrially superior effect that it can be used for

[Brief description of the drawings]

FIG. 1 shows an anionic polymerization initiator H and an anionic polymerization initiator N
2 shows the molecular weight distribution curve of the sample.

Claims (4)

[Claims] 1. A mixture of a monomer containing a conjugated diene monomer and a polyvinyl aromatic compound having a molar ratio of polyvinyl aromatic compound / organic lithium compound of 0.1 to 2.0.
A low molecular weight polymer reacted in the presence of an organolithium compound in the range of (A) wherein the total polyvinyl aromatic compound content in the initiator is 2 to 2
40% by weight (B) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(C) An anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5. 2. The method according to claim 1, wherein the polar organic compound is 30 to 50,000 p.
pm, a mixture of a monomer containing a conjugated diene monomer and a polyvinyl aromatic compound in a hydrocarbon solvent having a polyvinyl aromatic compound / organic lithium compound molar ratio of 0.1 to 2.0. (A) a total polyvinyl aromatic compound content of 2 to 40% by weight (B) a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (B) Mw) is 500
(C) A method for producing an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5. 3. A mixture of a monomer containing 1 to 99% by weight of the total amount of a conjugated diene monomer and a polyvinyl aromatic compound in a hydrocarbon solvent, in a molar ratio of polyvinyl aromatic compound / organic lithium compound. Is in the range of 0.1 to 2.0 in the presence of an organolithium compound, and then the remaining conjugated diene-based monomer is continuously or intermittently supplied into the reaction system for reaction. (A) The total polyvinyl aromatic compound content in the initiator is 2 to
40% by weight (B) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(C) A method for producing an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5. 4. The method according to claim 1, wherein the polar organic compound is 30 to 50,000 p.
pm in a hydrocarbon solvent, a mixture of a monomer containing 1 to 99% by weight of the total amount of the conjugated diene-based monomer and a polyvinyl aromatic compound is used in a molar ratio of polyvinyl aromatic compound / organic lithium compound. Is in the range of 0.1 to 2.0 in the presence of an organolithium compound, and then the remaining conjugated diene-based monomer is continuously or intermittently supplied into the reaction system for reaction. (A) The total polyvinyl aromatic compound content in the initiator is 2 to
40% by weight (B) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(C) A method for producing an anionic polymerization initiator having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5.