JP2018053120A - Polybutadiene composition with suppressed adhesiveness and manufacturing method therefor, and styrene resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polybutadiene composition having lower solution viscosity by suppressing aggregation of polybutadiene each other or adhesion to a manufacturing facility, and a styrene resin composition using the same.SOLUTION: There is provided a polybutadiene composition containing 20 to 50 pts.wt., of polybutadiene (A), satisfying conditions with cis-1,4-structure of 65 to 95 mol%, vinyl-1,2-structure of 4 to 30 mol%, and 5 wt.% styrene solution viscosity at 25°C (St-cp) of 100 or less and manufactured by a metallocene catalyst, and 50 to 80 pts.wt., of polybutadiene (B) other than polybutadiene (A), satisfying conditions with cis-1,4-structure of 30 to 99 mol%, vinyl-1,2-structure of 1 to 14 mol%, and a ratio between 5 wt.% styrene solution viscosity at 25°C and Mooney viscosity at 100°C (St-cp/ML) of 1.40 or less, as total 100 pts.wt.SELECTED DRAWING: None

Description

  The present invention relates to a polybutadiene composition with suppressed tackiness, a method for producing the same, and a styrene resin composition using the same.

  Polybutadiene produced with a metallocene catalyst has a special microstructure (high cis-high vinyl structure) among existing polybutadienes, so it is used for materials for tires and shoe soles, and is also applicable to styrene-based resins. It has been studied (Patent Documents 1 to 4). However, polybutadiene produced with a metallocene catalyst has a linear molecular chain, a high solution viscosity, and it is difficult to reduce the size of particles when making a styrene resin composition, and the cold flow is high and difficult to handle during storage and transportation. , Etc. have problems to be improved.

  Therefore, Patent Document 5 discloses a rubber composition in which polybutadiene produced by a metallocene catalyst and other polybutadiene having predetermined physical properties are combined to reduce the solution viscosity while maintaining a high-cis-vinyl structure. Further, it has been reported that the cold flow property is improved and the particle size of the styrenic resin is easily reduced.

JP-A-9-291108 JP-A-10-273574 Japanese Patent Laid-Open No. 2002-265677 JP 2002-338740 A Japanese Patent No. 5757373

  However, in the above-described method, when the rubber composition is produced, the polybutadienes are aggregated and fixed to the production equipment, thereby reducing the productivity. Furthermore, there is a demand for a rubber composition having a lower solution viscosity. However, the problem is that the sticking to the production facility becomes more prominent and the productivity further decreases.

  Therefore, an object of the present invention is to provide a polybutadiene composition having a lower solution viscosity and a styrene-based resin composition using the same, by suppressing aggregation of polybutadienes and adhesion to a production facility.

The present invention
(A1) cis-1,4-structure is 65 to 95 mol%, (a2) vinyl-1,2-structure is 4 to 30 mol%, and (a3) 5 wt% styrene solution viscosity at 25 ° C. (St 20 to 50 parts by weight of polybutadiene (A) produced by a metallocene catalyst, wherein -cp) satisfies the condition of 100 or less;
(B1) cis-1,4-structure is 30 to 99 mol%, (b2) vinyl-1,2-structure is 1 to 14 mol%, and (b3) 5 wt% styrene solution viscosity at 25 ° C. and 100 Polybutadiene (B) other than polybutadiene (A), which satisfies the condition that the ratio (St-cp / ML _{1 + 4} ) to the Mooney viscosity at 0 ° C. is 1.40 or less, the total amount is 100 parts by weight with 50 to 80 parts by weight. A polybutadiene composition containing as described above.

The present invention
(C1) cis-1,4-structure is 50 to 98 mol%, (c2) vinyl-1,2-structure is 1 to 12 mol%, and (c3) 5 wt% styrene solution viscosity at 25 ° C. (St -Cp) is 60 or less, and (c4) the ratio of 5 wt% styrene solution viscosity at 25 ° C to Mooney viscosity at 100 ° C (St-cp / ML _{1 + 4} ) is 1.9 or less, and (c5) cold flow rate Is a method for producing a polybutadiene composition having a value of 0.27 or less,
(A1) cis-1,4-structure is 65 to 95 mol%, (a2) vinyl-1,2-structure is 4 to 30 mol%, and (a3) 5 wt% styrene solution viscosity at 25 ° C. (St 20 to 50 parts by weight of polybutadiene (A) produced by a metallocene catalyst, wherein -cp) satisfies the condition of 100 or less;
(B1) cis-1,4-structure is 30 to 99 mol%, (b2) vinyl-1,2-structure is 1 to 14 mol%, and (b3) 5 wt% styrene solution viscosity at 25 ° C. and 100 Polybutadiene (B) other than polybutadiene (A), which satisfies the condition that the ratio (St-cp / ML _{1 + 4} ) to the Mooney viscosity at 0 ° C. is 1.40 or less, the total amount is 100 parts by weight with 50 to 80 parts by weight. In this way, the polybutadiene composition is mixed.

  The present invention is a styrene resin composition comprising the polybutadiene composition described above and a styrene resin.

  According to the present invention, it is possible to provide a polybutadiene composition having a lower solution viscosity and a styrene-based resin composition using the same, by suppressing aggregation of polybutadienes and adhesion to a production facility.

(Polybutadiene (A))
The cis-1,4-structure content of polybutadiene (A) is 65 to 95 mol%, preferably 70 to 95 mol%, and more preferably 75 to 92 mol%. The vinyl-1,2-structure content of the polybutadiene (A) is 4 to 30 mol%, preferably 5 to 25 mol%, more preferably 7 to 15 mol%. The trans-1,4-structure content of polybutadiene (A) is preferably 5 mol% or less, more preferably 4.5 mol% or less, and 0.5 to 4 mol%. Further preferred. If the content of cis-1,4-structure and vinyl-1,2-structure in the microstructure of polybutadiene (A) is outside the above range, the reactivity of polybutadiene (A) (graft reaction and crosslinking reactivity) Etc.) is not suitable, and when used as an additive, the rubber-like properties are reduced, affecting the balance of physical properties and appearance.

  In the present invention, it is particularly important to use the polybutadiene (A) having the above microstructure as a raw material. Compared with the case where other diene rubbers are used, the effect on the improvement of physical properties appears remarkably.

The molecular weight of the polybutadiene (A) is preferably in the following range as a molecular weight in terms of polystyrene. That is, the number average molecular weight (Mn) is preferably 10 × 10 ⁴ to 40 × 10 ⁴ , and more preferably 15 × 10 ⁴ to 30 × 10 ⁴ . The weight average molecular weight (Mw) is preferably 20 × 10 ^{4 to} 100 × 10 ⁴ , and more preferably 30 × 10 ⁴ to 80 × 10 ⁴ . When the molecular weight of the polybutadiene (A) is larger than the above range, there may be a problem of an increase in gel content, and when the molecular weight of the polybutadiene (A) is smaller than the above range, the productivity may be lowered.

  The molecular weight distribution (Mw / Mn) of the polybutadiene (A) is preferably 2.80 or less, more preferably 1.50 to 2.60, and further preferably 1.80 to 2.40. preferable. By controlling the molecular weight distribution within such a range, it is possible to easily control the rubber particle diameter when used as a modifier of the styrenic resin, and to make the particle diameter size uniform. Further, by controlling the molecular weight distribution in such a range, the gloss (glossiness) and grafting properties are improved, and the impact strength is also improved.

  The gel content of the polybutadiene (A) is preferably 0.060% by weight or less, more preferably 0.020% by weight or less, and further preferably 0.0001 to 0.010% by weight. By controlling the gel content in a small region in this way, it is possible to prevent as much as possible the clogging of the filter that removes the gel that is undissolved when dissolved in the solvent. Moreover, the problem of fish eyes can be prevented by reducing the gel content.

  The intrinsic viscosity [η] measured in toluene at 30 ° C., which is an index of the molecular weight of the polybutadiene (A), is preferably from 0.1 to 10, and more preferably from 1 to 8.

  The cold flow rate (CF) of the polybutadiene (A) is preferably 1.0 g / 10 min or less, more preferably 0.9 g / 10 min or less, and further preferably 0.8 g / 10 min or less. .

The polybutadiene (A) has a 5% by weight styrene solution viscosity (St-cp) at 25 ° C. of 100 or less, preferably 20 to 95, and more preferably 50 to 90. The Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of the polybutadiene (A) is preferably 10 to 45, more preferably 15 to 35, and still more preferably 20 to 25. The ratio (St-cp / ML _{1 + 4} ) of the 5% by weight styrene solution viscosity (St-cp) and the Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of the polybutadiene (A) is 1.0 to 5.0. Is more preferable, 2.5 to 4.5 is more preferable, and 3.5 to 4.0 is still more preferable.

(Method for producing polybutadiene (A))
The polybutadiene (A) is produced by a metallocene catalyst, and more specifically, is produced by polymerizing butadiene using a metallocene catalyst. Polybutadiene (A), for example, polymerizes butadiene using a catalyst comprising (A1) a metallocene complex of a transition metal compound and (A2) an ionic compound of a non-coordinating anion and a cation and / or an alumoxane. Can be manufactured. Alternatively, polybutadiene (A) is (A1) a metallocene complex of a transition metal compound, (A2) an ionic compound of a non-coordinating anion and a cation, and (A3) an organic metal of a group 1 to 3 element of the periodic table It can be produced by polymerizing butadiene using a compound and a catalyst comprising (A4) water.

Examples of the metallocene complex of the transition metal compound as the component (A1) include metallocene complexes of Group 4 to 8 transition metal compounds in the periodic table. More specifically, a metallocene type complex of a Group 4 transition metal compound of the periodic table such as titanium or zirconium (for example, CpTiCl ₃ ), a metallocene of a Group 5 transition metal compound of the periodic table such as vanadium, niobium, tantalum or the like. And metallocene type complexes of Group 6 transition metal compounds such as chromium, and metallocene type complexes of Group 8 transition metal compounds such as cobalt and nickel. Among these, metallocene type complexes of Group 5 transition metal compounds of the periodic table are preferably used.

As metallocene type complexes of Group 5 transition metal compounds of the periodic table, (1) RM · L _a , (2) R _n MX _2−n · L _a , (3) R _n MX _3−n · L _a , (4) RMX ₃ · L _a , (5) RM (O) X ₂ · L _a , (6) R _n MX _3-n (NR ′) and other compounds represented by general formulas may be mentioned (wherein , N is 1 or 2, and a is 0, 1 or 2. Among _{them, RM · L a, RMX 3} · L a, RM (O) X 2 · L compound represented by the general formula _a is preferred.

  M is a group 5 transition metal compound in the periodic table, specifically vanadium (V), niobium (Nb), or tantalum (Ta), and vanadium is preferable.

  R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group. Examples of the substituent in the substituted cyclopentadienyl group, substituted indenyl group, or substituted fluorenyl group include methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, and hexyl. Examples thereof include linear aliphatic hydrocarbon groups or branched aliphatic hydrocarbon groups; aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, and benzyl; hydrocarbon groups containing silicon atoms such as trimethylsilyl. Further, a ring in which a cyclopentadienyl ring is bonded to a part of X with a bridging group such as dimethylsilyl, dimethylmethylene, methylphenylmethylene, diphenylmethylene, ethylene, or substituted ethylene is also included.

  X represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or an amino group. All Xs may be the same or different from each other. Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include linear aliphatic hydrocarbon groups such as methyl, ethyl and propyl or branched aliphatic hydrocarbon groups; aromatics such as phenyl, tolyl, naphthyl and benzyl. A hydrocarbon group etc. are mentioned. Furthermore, hydrocarbon groups containing silicon atoms such as trimethylsilyl are also included. Of these, methyl, benzyl, trimethylsilylmethyl and the like are preferable. Specific examples of the alkoxy group include methoxy, ethoxy, phenoxy, propoxy, butoxy and the like. Furthermore, amyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, and methylthio may be used. Specific examples of the amino group include dimethylamino, diethylamino, diisopropylamino, bistrimethylsilylamino and the like. Among these, as X, hydrogen, fluorine atom, chlorine atom, bromine atom, methyl, ethyl, butyl, methoxy, ethoxy, dimethylamino, diethylamino, bistrimethylsilylamino and the like are preferable.

  L is a Lewis base and is a general inorganic or organic compound having Lewis basicity capable of coordinating to a metal. Of these, compounds having no active hydrogen are particularly preferred. Specific examples include ethers, esters, ketones, amines, phosphines, silyloxy compounds, olefins, dienes, aromatic compounds, alkynes, and the like.

  NR ′ is an imide group, and R ′ is a hydrocarbon substituent having 1 to 25 carbon atoms. Specific examples of R ′ include linear aliphatic hydrocarbon groups such as methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, hexyl, octyl and neopentyl, Branched aliphatic hydrocarbon group; aromatic hydrocarbon group such as phenyl, tolyl, naphthyl, benzyl, 1-phenylethyl, 2-phenyl-2-propyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, etc. Is mentioned. Furthermore, hydrocarbon groups containing silicon atoms such as trimethylsilyl are also included.

Among these metallocene type complexes of Group 5 transition metal compounds of the periodic table, vanadium compounds in which M is vanadium are particularly preferred. For _{example, RV · L a, RVX ·} L a, R 2 V · L a, RVX 2 · L a, R 2 VX · L a, RVX 3 · L a, such as _{RV (O) X 2 · L} a is preferably _{, RV · L a, RVX 3} · L a, RV (O) X 2 · L a is more preferable.

Specific compounds represented by RMX ₃ · _{L a,} the (i) ~ (xvi) can be mentioned below.
(I) cyclopentadienyl vanadium trichloride and mono-substituted cyclopentadienyl vanadium trichloride (for example, methylcyclopentadienyl vanadium trichloride, ethylcyclopentadienyl vanadium trichloride, propylcyclopentadienyl vanadium trichloride, Isopropylcyclopentadienyl vanadium trichloride)
(Ii) 1,2-disubstituted cyclopentadienyl vanadium trichloride (for example, (1,2-dimethylcyclopentadienyl) vanadium trichloride)
(Iii) 1,3-disubstituted cyclopentadienyl vanadium trichloride (for example, (1,3-dimethylcyclopentadienyl) vanadium trichloride)
(Iii) 1,2,3-trisubstituted cyclopentadienyl vanadium trichloride (eg, (1,2,3-trimethylcyclopentadienyl) vanadium trichloride)
(Iv) 1,2,4-trisubstituted cyclopentadienyl vanadium trichloride (for example, (1,2,4-trimethylcyclopentadienyl) vanadium trichloride)
(V) Tetra-substituted cyclopentadienyl vanadium trichloride (for example, (1,2,3,4-tetramethylcyclopentadienyl) vanadium trichloride)
(Vi) penta-substituted cyclopentadienyl vanadium trichloride (for example, (pentamethylcyclopentadienyl) vanadium trichloride)
(Vii) indenyl vanadium trichloride (viii) substituted indenyl vanadium trichloride (eg, (2-methylindenyl) vanadium trichloride)
(Ix) monoalkoxides, dialkoxides, trialkoxides in which the chlorine atoms of the compounds of (i) to (viii) are substituted with alkoxy groups (for example, cyclopentadienyl vanadium tri-t-butoxide, cyclopentadienyl vanadium tri-i- Propoxide, cyclopentadienyl vanadium dimethoxychloride, etc.)
(X) A methyl product in which the chlorine atom of (i) to (ix) is substituted with a methyl group (xi) R and X are bonded by a hydrocarbon group or a silyl group (for example, (t-butylamido) dimethyl (η5 -Cyclopentadienyl) silane vanadium dichloride, etc.)
(Xii) A methyl form in which the chlorine atom in (xi) is substituted with a methyl group (xiii) A monoalkoxy form in which the chlorine atom in (xi) is substituted with an alkoxy group or a monochloro form in a dialkoxy form (xiv) (xiii) in methyl Amides in which the chlorine atom of the compound (xv) (i) to (viii) substituted with a group is substituted with an amide group (for example, cyclopentadienyltris (diethylamide) vanadium, cyclopentadienyltris (i-propylamide) Vanadium, etc.)
(Xvi) a methyl compound in which the chlorine atom in (xv) is substituted with a methyl group

Specific examples of the compound represented by the above RM (O) X ₂ include the following (A) to (D).
(I) Cyclopentadienyloxovanadium dichloride, methylcyclopentadienyloxovanadium dichloride, benzylcyclopentadienyloxovanadium dichloride, (1,3-dimethylcyclopentadienyl) oxovanadium dichloride, and chlorine of these compounds A methyl compound (B) in which an atom is substituted with a methyl group, and R and X bonded by a hydrocarbon group or a silyl group (for example, (t-butylamido) dimethyl (η5-cyclopentadienyl) silane oxovanadium chloride, etc. Amidochlorides, or methyl compounds in which the chlorine atom of these compounds is substituted with a methyl group)
(C) Cyclopentadienyloxovanadium dimethoxide, cyclopentadienyloxovanadium di-i-propoxide, and methyl compounds obtained by substituting the chlorine atom of these compounds with a methyl group (d) (cyclopentadienyl) bis ( Diethylamido) oxovanadium

  Among the ionic compounds of the non-coordinating anion and cation of the component (A2), examples of the non-coordinating anion include tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate. , Tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate and the like. On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

  Specific examples of the carbonium cation include tri-substituted carbonium cations such as a triphenyl carbonium cation and a tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation. Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation and the like; N, N-dimethylanilinium cation, N N, N-dialkylanilinium cation such as N, diethylanilinium cation and dialkylammonium cation such as di (i-propyl) ammonium cation. Specific examples of the phosphonium cation include a triarylphosphonium cation such as a triphenylphosphonium cation.

  As the ionic compound, those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used. Among them, as ionic compounds, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1 ′ -Dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferable. An ionic compound can be used individually by 1 type, and can also be used in combination of 2 or more type.

Moreover, you may use an alumoxane as (A2) component. The alumoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and includes a chain alumoxane or a cyclic alumoxane represented by the general formula (—Al (R ′) O) _n (R ′ Is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group, where n is the degree of polymerization and is 5 or more, preferably 10 or more). Examples of R ′ include methyl, ethyl, propyl, and isobutyl groups, with a methyl group being preferred.

  Examples of the organoaluminum compound used as a raw material for alumoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. An alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used.

  A typical example of the condensing agent is water, but in addition to this, an arbitrary one that undergoes a condensation reaction of the trialkylaluminum, for example, adsorbed water such as an inorganic substance, diol, and the like.

  The (A1) component and the (A2) component may be further combined with an organometallic compound of Group 1 to 3 elements of the periodic table as the (A3) component to polymerize a conjugated diene. The addition of the component (A3) has an effect of increasing the polymerization activity. Examples of organometallic compounds of Group 1 to 3 elements of the periodic table include organoaluminum compounds, organolithium compounds, organomagnesium compounds, organozinc compounds, and organoboron compounds.

  Specific compounds include methyl lithium, butyl lithium, phenyl lithium, bistrimethylsilylmethyl lithium, dibutyl magnesium, dihexyl magnesium, diethyl zinc, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, boron trifluoride, triphenyl boron and the like. It is done. Further, organometallic halogen compounds such as ethyl magnesium chloride, dimethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride and ethylaluminum dichloride; hydrogenated organometallic compounds such as diethylaluminum hydride and sesquiethylaluminum hydride are also included. An organometallic compound can be used individually by 1 type, and can also be used in combination of 2 or more type.

As a combination of the above catalyst components, as component (A1), RMX ₃ such as cyclopentadienyl vanadium trichloride (CpVCl ₃ ), or cyclopentadienyl oxovanadium dichloride (CpV (O) Cl ₂ ), etc. A combination of trialkylcarbenium tetrakis (pentafluorophenyl) borate as the RM (O) X ₂ and (A2) component, and a trialkylaluminum such as triethylaluminum as the (A3) component is preferable. When an ionic compound is used as the component (A2), the above-described alumoxane may be combined as the component (A3).

  The blending ratio of each component varies depending on various conditions and combinations, but the molar ratio (A2) / (A1) of the metallocene complex of the component (A1) and the alumoxane of the component (A2) is preferably 1 to 100,000. More preferably, it is 10-10000. The molar ratio (A2) / (A1) between the (A1) component metallocene complex and the (A2) component ionic compound is preferably 0.1 to 10, and preferably 0.5 to 5. More preferred. The molar ratio (A3) / (A1) between the metallocene complex of component (A1) and the organometallic compound of component (A3) is preferably 0.1 to 10,000, more preferably 10 to 1,000. .

  Furthermore, it is preferable to add water as the component (A4). The molar ratio (A3) / (A4) between the organometallic compound (A3) and the water (A4) is preferably 0.66 to 5, and preferably 0.7 to 3.0. More preferred.

  There is no restriction | limiting in particular in the addition order of said catalyst component. Moreover, hydrogen can coexist as needed at the time of superposition | polymerization. The amount of hydrogen present is preferably 500 mmol or less or 12 L or less at 1 atm at 20 ° C., more preferably 1.2 L or less at 50 mmol or 20 at 1 atm with respect to 1 mol of butadiene.

  In addition to butadiene monomers, conjugates such as isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene. Diene; acyclic monoolefin such as ethylene, propylene, butene-1, butene-2, isobutene, pentene-1, 4-methylpentene-1, hexene-1 and octene-1; cyclic monoolefin such as cyclopentene, cyclohexene and norbornene And / or aromatic vinyl compounds such as styrene and α-methylstyrene; a small amount of non-conjugated diolefins such as dicyclopentadiene, 5-ethylidene-2-norbornene, and 1,5-hexadiene.

  The polymerization method is not particularly limited, and solution polymerization or bulk polymerization using 1,3-butadiene itself as a polymerization solvent can be applied. As a polymerization solvent, aromatic hydrocarbons such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; 1-butene, Examples include olefinic hydrocarbons such as 2-butene; hydrocarbon solvents such as mineral spirits, solvent naphtha, and kerosene; and halogenated hydrocarbon solvents such as methylene chloride.

  In addition, it is preferable to perform prepolymerization at a predetermined temperature using the above catalyst. The prepolymerization can be performed by a gas phase method, a solution method, a slurry method, a bulk method, or the like. The solid or solution obtained in the prepolymerization can be separated and used in the main polymerization, or the main polymerization can be continued without separation.

  The polymerization temperature is preferably in the range of −100 to 200 ° C., more preferably in the range of −50 to 120 ° C. The polymerization time is preferably in the range of 2 minutes to 12 hours, and more preferably in the range of 5 minutes to 6 hours.

  After carrying out the polymerization for a predetermined time, the polymerization is stopped by adding a polymerization terminator. Thereafter, the inside of the polymerization tank is released as necessary, and post-treatment such as washing and drying is performed. In order to obtain polybutadiene, it is necessary to improve the dispersibility of the added polymerization terminator. By improving the dispersibility of the polymerization terminator, the polymerization catalyst and the polymerization terminator can be reacted efficiently to deactivate the polymerization catalyst.

  The polybutadiene (A) may be modified. Specific examples include those branched with a transition metal catalyst for modification. However, the modification makes the production process of the polybutadiene (A) complicated, and may lead to a decrease in quality due to an increase in gel due to an increase in side reactions. Therefore, it is preferable to use unmodified polybutadiene (A).

(Polybutadiene (B))
The cis-1,4-structure content of the polybutadiene (B) other than the polybutadiene (A) blended with the polybutadiene (A) is 30 to 99 mol%, preferably 60 to 98 mol%, preferably 90 to More preferably, it is 97 mol%. The vinyl-1,2-structure content of the polybutadiene (B) is 1 to 14 mol%, preferably 1.5 to 9 mol%, and more preferably 2 to 4 mol%. The trans-1,4-structure content of polybutadiene (B) is preferably 5 mol% or less, more preferably 4.5 mol% or less, and 0.5 to 4 mol%. Further preferred. A polybutadiene composition obtained by blending with polybutadiene (A) when the content of cis-1,4-structure and vinyl-1,2-structure in the microstructure of polybutadiene (B) is outside the above t range. The impact resistance of the object (C) may be lowered.

The molecular weight of the polybutadiene (B) is preferably in the following range as the molecular weight in terms of polystyrene. That is, the number average molecular weight (Mn) is preferably 3 × 10 ⁴ to 30 × 10 ⁴ , and more preferably 8 × 10 ^{4 to} 20 × 10 ⁴ . The weight average molecular weight (Mw) is preferably 15 × 10 ^{4 to} 100 × 10 ⁴ , and more preferably 25 × 10 ⁴ to 80 × 10 ⁴ . If the molecular weight of the polybutadiene (B) is larger than the above range, the solution viscosity tends to increase. If the molecular weight of the polybutadiene (B) is smaller than the above range, a problem of productivity may occur.

  The molecular weight distribution (Mw / Mn) of the polybutadiene (B) is preferably 5.00 or less, more preferably 1.50 to 4.50, and further preferably 2.00 to 4.00. preferable. By controlling the molecular weight distribution within such a range, it is possible to easily control the rubber particle diameter when used as a modifier of the styrenic resin, and to make the particle diameter size uniform.

The 5 wt% styrene solution viscosity (St-cp) at 25 ° C. of the polybutadiene (B) is preferably 20 to 80, and more preferably 25 to 60. The Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of the polybutadiene (B) is preferably 60 or less, more preferably 10-50, and even more preferably 15-40. The ratio (St-cp / ML _{1 + 4} ) of 5% by weight styrene solution viscosity (St-cp) and the Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of polybutadiene (B) is 1.40 or less, and 1.10. It is preferable that it is -1.37, and it is more preferable that it is 1.20-1.34.

(Method for producing polybutadiene (B))
The polybutadiene (B) is preferably produced by a cobalt-based catalyst, and more specifically is preferably produced by polymerizing butadiene using a cobalt-based catalyst. Examples of the cobalt-based catalyst include a catalyst system composed of a cobalt catalyst, an organoaluminum compound, and water.

  Cobalt catalysts include cobalt chloride, cobalt bromide, cobalt nitrate, cobalt octylate (ethylhexanoate), cobalt naphthenate, cobalt acetate, cobalt malonate, etc .; cobalt bisacetylacetonate, cobalt trisacetylacetonate , Ethyl acetoacetate cobalt, organic base complexes such as pyridine complexes and picoline complexes of cobalt salts, and ethyl alcohol complexes. Of these, octylic acid (ethylhexanoic acid) cobalt is preferable. Regarding the usage-amount of a cobalt-type catalyst, it can adjust suitably so that it may become polybutadiene (B) which has a desired physical property.

  Examples of organoaluminum compounds include trialkylaluminum; dialkylaluminum chloride, dialkylaluminum bromide, alkylaluminum sesquichloride, alkylaluminum sesquibromide, alkylaluminum dichloride, alkylaluminum dibromide, and other halogen-containing organoaluminum compounds; dialkylaluminum hydride, alkylaluminum Examples thereof include organic aluminum hydride compounds such as sesquihydrite. An organoaluminum compound can be used individually by 1 type, and can also be used together 2 or more types.

  Specific examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum.

  Examples of the dialkylaluminum chloride include dimethylaluminum chloride and diethylaluminum chloride. Examples of the dialkylaluminum bromide include dimethylaluminum bromide and diethylaluminum bromide. Examples of the alkylaluminum sesquichloride include methylaluminum sesquichloride and ethylaluminum sesquichloride. Examples of the alkylaluminum sesquibromide include methylaluminum sesquibromide and ethylaluminum sesquibromide. Examples of the alkylaluminum dichloride include methylaluminum dichloride and ethylaluminum dichloride. Examples of the alkylaluminum dibromide include methylaluminum dibromide and ethylaluminum dibromide.

  Examples of the dialkylaluminum hydride include diethylaluminum hydride and diisobutylaluminum hydride. Examples of the alkylaluminum sesquihydride include ethylaluminum sesquihydride and isobutylaluminum sesquihydride.

  The mixing ratio of the organoaluminum compound and water is preferably 1.5 to 3 in terms of aluminum / water (molar ratio) since polybutadiene (B) having desired physical properties is easily obtained. More preferably, it is -2.5.

  Furthermore, in order to obtain polybutadiene (B) having desired physical properties, non-conjugated dienes such as cyclooctadiene, allene and methylallene (1,2-butadiene); α-olefins such as ethylene, propylene and 1-butene It is also possible to use molecular weight regulators such as A molecular weight regulator can be used individually by 1 type, and can also use 2 or more types together.

  There is no particular limitation on the polymerization method of butadiene, and bulk polymerization (bulk polymerization) in which a monomer is polymerized while using a conjugated diene compound monomer such as 1,3-butadiene as a polymerization solvent, or polymerization is performed in a state where the monomer is dissolved in the solvent. Solution polymerization or the like can be applied. Solvents used in the solution polymerization include aromatic hydrocarbons such as toluene, benzene and xylene; saturated aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; Examples include olefinic hydrocarbons such as cis-2-butene and trans-2-butene; petroleum solvents such as mineral spirits, solvent naphtha, and kerosene; halogenated hydrocarbons such as methylene chloride. Among these, toluene, cyclohexane, or a mixed solvent of cis-2-butene and trans-2-butene is preferably used.

  The polymerization temperature is preferably in the range of −30 to 150 ° C., more preferably in the range of 30 to 100 ° C., and further preferably 70 to 80 ° C. from the viewpoint that polybutadiene (B) having desired physical properties can be easily obtained. The polymerization time is preferably in the range of 1 minute to 12 hours, and more preferably in the range of 5 minutes to 5 hours.

  After the polymerization reaction reaches a predetermined polymerization rate, an anti-aging agent can be added as necessary. Anti-aging agents include phenol-based anti-aging agents such as 2,6-di-t-butyl-p-cresol (BHT), phosphorus-based anti-aging agents such as trinonylphenyl phosphite (TNP), and 4,6 -Sulfur-based anti-aging agents such as -bis (octylthiomethyl) -o-cresol and dilauryl-3,3'-thiodipropionate (TPL). One type of anti-aging agent can be used alone, or two or more types can be used in combination. The addition amount of the antioxidant is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the polybutadiene (B).

  After carrying out the polymerization for a predetermined time, the inside of the polymerization tank is released as necessary, and further post-treatment such as washing and drying steps is performed, whereby polybutadiene (B) having desired characteristics can be produced.

(Polybutadiene composition)
The polybutadiene composition of the present invention contains polybutadiene (A) and polybutadiene (B). Thus, by blending the polybutadiene (A) produced with the metallocene catalyst with the highly branched polybutadiene (B), the cold flow can be improved and the solution viscosity can be lowered. Furthermore, by improving the cold flow, handling properties, processability and shape retention are improved, and by reducing the solution viscosity, the controllability of the particle diameter can be improved.

  The compounding quantity of polybutadiene (A) is 20-50 weight part with respect to a total of 100 weight part of polybutadiene (A) and polybutadiene (B), It is preferable to set it as 25-45 weight part, It is 30-40 weight part. It is more preferable. When the blending amount of the polybutadiene (A) is less than the above range, the effects such as impact resistance strength of the polybutadiene (A) are weakened. When the blending amount of the polybutadiene (A) is larger than the above range, the cold flow rate is high and the solution viscosity is also high, which causes problems in deterioration of workability and shape retention due to increased adhesiveness.

  The compounding quantity of polybutadiene (B) is 50-80 weight part with respect to a total of 100 weight part of polybutadiene (A) and polybutadiene (B), It is preferable to be 55-75 weight part, It is 60-70 weight part. Is more preferable. When the blending amount of the polybutadiene (B) is less than the above range, the effect of improving the cold flow rate is low and the solution viscosity is also high. In addition, since the adhesiveness is increased, a problem occurs in workability and shape retention. When there are more compounding quantities of polybutadiene (B) than the said range, effects, such as impact strength which polybutadiene (A) has, will become weak.

  The polybutadiene composition of the present invention may be composed of polybutadiene (A) and polybutadiene (B) (the total of polybutadiene (A) and polybutadiene (B) is 100% by weight), and if necessary, other diene rubbers Etc. may be included. Examples of other diene rubbers include polybutadiene different from polybutadiene (A) and polybutadiene (B), and natural rubber. The total of the polybutadiene (A) and the polybutadiene (B) is preferably 60 to 100% by weight, more preferably 70 to 99% by weight, further preferably 80 to 98% by weight, and 90 to It is particularly preferably 97% by weight, and most preferably 95 to 96% by weight.

  As a blending method of polybutadiene (A) and polybutadiene (B), a method of blending polybutadiene (A) and polybutadiene (B) in a solid state with a roll or the like, polybutadiene (A) and polybutadiene (B) are mixed with toluene or cyclohexane. A method of blending in the state of a solution dissolved in a solvent such as It is preferable to blend in a solution state rather than blending in a solid state.

  The cis-1,4-structure content of the polybutadiene composition is preferably 50 to 98 mol%, preferably 70 to 97 mol%, and more preferably 90 to 95 mol%. The vinyl-1,2-structure content of the polybutadiene composition is 1 to 12 mol%, preferably 2 to 9 mol%, and more preferably 3 to 8 mol%. The trans-1,4-structure content of polybutadiene (B) is preferably 30 mol% or less, more preferably 5 mol% or less, and even more preferably 1 to 3 mol%.

The 5 wt% styrene solution viscosity (St-cp) at 25 ° C. of the polybutadiene composition is preferably 60 or less, more preferably 20 to 57, and even more preferably 30 to 54. The Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of the polybutadiene composition is preferably 10-50, more preferably 15-40, and even more preferably 20-30. The ratio (St-cp / ML _{1 + 4} ) of the 5 wt% styrene solution viscosity (St-cp) to the Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of the polybutadiene composition is preferably 1.90 or less. .20 to 1.85 is preferable, and 1.40 to 1.80 is more preferable.

The molecular weight of the polybutadiene composition is preferably in the following range as the molecular weight in terms of polystyrene. That is, the number average molecular weight (Mn) is preferably 5 × 10 ^{4 to} 20 × 10 ⁴ , and more preferably 8 × 10 ⁴ to 15 × 10 ⁴ . The weight average molecular weight (Mw) is preferably 20 × 10 ^{4 to} 60 × 10 ⁴ , and more preferably 30 × 10 ⁴ to 40 × 10 ⁴ . The molecular weight distribution (Mw / Mn) of the polybutadiene composition is preferably 5.00 or less, more preferably 1.50 to 4.00, and even more preferably 2.00 to 3.00. .

  The adhesive strength of the polybutadiene composition is preferably 0.30 to 0.65 kg, and more preferably 0.40 to 0.60 kg.

  The cold flow rate (CF) of the polybutadiene composition is preferably 0.27 g / 10 min or less, and more preferably 0.2 to 0.25 g / 10 min.

(Styrenic resin composition)
The styrene resin composition of the present invention is a rubber-reinforced styrene resin composition (hereinafter abbreviated as HIPS polymer) containing a styrene resin and a polybutadiene composition. Thus, by using a polybutadiene composition with improved solution viscosity and cold flow, handling properties, processability, shape retention, controllability of rubber particle diameter are improved, and styrene resin composition with excellent impact strength You can get things.

  The styrenic resin constituting the continuous phase of the HIPS polymer is obtained by polymerizing a styrenic monomer conventionally known for producing HIPS polymers. Styrene monomers include side chain alkyl-substituted styrenes such as styrene, α-methylstyrene, α-ethylstyrene; vinyl toluene, vinyl xylene, ot-butyl styrene, pt-butyl styrene, p-methyl. Examples thereof include nuclear alkyl-substituted styrenes such as styrene; halogenated styrenes such as monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene; p-hydroxystyrene, o-methoxystyrene, vinylnaphthalene, and the like. Among these, styrene and α-methylstyrene are preferable, and styrene is more preferable. A styrene-type monomer can be used individually by 1 type, and can also be used in combination of 2 or more type.

  The weight average molecular weight of the styrene resin constituting the continuous phase of the HIPS polymer is preferably 50,000 or more, and more preferably 100,000 to 400,000.

  The polybutadiene composition is preferably contained in 0.5 to 25 parts by weight, more preferably 1 to 20 parts by weight, in 100 parts by weight of the HIPS polymer. When the content of the polybutadiene composition is less than the above range, the effect of the present invention is hardly obtained, the content of the polybutadiene composition is increased, and the impact resistance of the resin is improved. When the content of the polybutadiene composition is more than the above range, it becomes difficult to control the rubber particle diameter due to the increase in viscosity of the styrene solution. However, it can also be avoided by diluting with a solvent.

  The polybutadiene composition is preferably in a state of being dispersed in the form of particles in the styrene resin constituting the continuous phase of the HIPS polymer. The size (particle diameter) of the dispersed particles of the polybutadiene composition is preferably 0.1 to 7.0 μm, more preferably 0.3 to 6.0 μm, and 0.5 to 5.0 μm. More preferably. The polybutadiene composition preferably has a chemical bond such as a graft bond with the styrene resin, but may be occluded without a chemical bond such as a graft bond.

  As a method for producing the HIPS polymer, a method of polymerizing a styrene monomer in the presence of a polybutadiene composition is adopted, and a bulk polymerization method and a bulk suspension polymerization method are economically advantageous methods. The polymerization may be batch or continuous.

  An example of the bulk polymerization method will be described. The polybutadiene composition (0.5 to 25% by weight) is dissolved in a styrene monomer (99.5 to 75% by weight), and in some cases, a solvent and a molecular weight regulator. Then, a polymerization initiator or the like is added to convert the rubber composition into a rubber particle in which the polybutadiene composition is dispersed to a styrene monomer conversion rate of 10 to 40%. Until the rubber particles are produced, the rubber phase forms a continuous phase. Further, when the polymerization is continued, the HIPS polymer is produced by polymerizing the styrene monomer up to a conversion rate of 50 to 99% through a phase change (particle formation step) that becomes a dispersed phase as rubber particles.

  A raw material solution mainly composed of a styrene monomer and a polybutadiene composition is polymerized in, for example, a complete mixing reactor. The complete mixing reactor is not particularly limited as long as the raw material solution maintains a uniform mixed state in the reactor, and preferably has a stirring blade of a type such as a helical ribbon, a double helical ribbon, or an anchor. It is preferable that a draft tube is attached to the helical ribbon type stirring blade to further enhance the vertical circulation in the reactor.

  In production of the HIPS polymer, in addition to the above polybutadiene composition, a styrene-butadiene copolymer, ethylene-propylene, ethylene-vinyl acetate, acrylic rubber, or the like can be used as necessary. Moreover, you may blend the resin manufactured by these methods. Furthermore, you may manufacture by mixing the polystyrene-type resin which does not contain the HIPS polymer manufactured by these methods.

  HIPS polymers include stabilizers such as antioxidants and UV absorbers, mold release agents, lubricants, colorants, various fillers and various plasticizers, higher fatty acids, organic polymers as necessary during and after production. Known additives such as siloxane, silicone oil, flame retardant, antistatic agent and foaming agent may be added. The HIPS polymer can be used for various known molded products, but is excellent in flame retardancy, impact strength, and tensile strength, and is therefore suitable for injection molding used in the fields of electrical and industrial applications.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples.

(Mooney viscosity)
Mooney viscosity (ML _{1 + 4} ) was measured at 100 ° C. according to JIS K6300.

(Styrene solution viscosity)
As the styrene solution viscosity (St-cp), 5 g of polymer was dissolved in 95 g of styrene monomer, and the solution viscosity at 25 ° C. (unit: centipoise (cp)) was measured.

(Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn))
The number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were calculated using a standard polystyrene calibration curve using HLC-8220 GPC (trade name) manufactured by Tosoh Corporation. The column used was Shodex GPC KF-805 L columns (trade name), and two were connected in series. The measurement conditions were a column temperature of 40 ° C. in THF.

(Micro structure)
The microstructure was performed by infrared absorption spectrum analysis. Specifically, 740 cm ^-1 (cis-1,4-structure), 967 cm ^-1 (trans-1,4-structure) was calculated from the absorption intensity ratio of 910 cm ^-1 (vinyl-1,2-structure) .

(Adhesive force)
The adhesive strength was evaluated using a Toyo Seiki Tack Tester (trade name: PICMA TACK TESTER II). Specifically, various polybutadienes were molded with a press so as to have a thickness of 2 mm, and the test conditions were UP SPEEDS: 300 cm / mm, DOWN SPEEDS: 300 cm / mm, and SUBMINY TIME: 0 seconds.

(Cold flow speed)
As the cold flow rate (CF), the polymer is kept at 50 ° C., sucked with a glass tube having an inner diameter of 6.4 mm for 10 minutes by a differential pressure of 180 mmHg, and sucked per minute by measuring the weight of the sucked polymer. The amount of polymer obtained was measured.

(Particle size)
Regarding the particle size, only the polystyrene portion forming the matrix of the styrene resin composition (HIPS polymer) was dissolved in dimethylformamide. A part of the solution was dispersed in an electrolytic solution composed of a solvent dimethylformamide and a dispersing agent ammonium thiocyanate by using a Coulter counter device (trade name: Multicider III type) manufactured by Beckman Coulter Co. The average particle size was determined.

(Graft rate)
1 g of HIPS polymer was added to 50 ml of a mixed solution of methyl ethyl ketone / acetone = 1/1 (weight ratio) and stirred vigorously for 1 hour to dissolve and swell. Next, the insoluble matter was allowed to settle using a centrifuge, and the supernatant was discarded by decantation. The methyl ethyl ketone / acetone insoluble matter thus obtained was dried under reduced pressure at 50 ° C., cooled in a desiccator, and weighed to obtain methyl ethyl ketone / acetone insoluble matter (MEK / AC-insol. (G)). Asked. Then, the graft ratio was calculated from the methyl ethyl ketone / acetone insoluble content and the rubber component amount (R (g)) calculated from the rubber component content.
Graft ratio = [MEK / AC-insol. (G) -R (g)] × 100 / R (g)

(Izod impact strength)
Measured according to JIS K7110 (notched).

(Dupont impact strength)
The 50% fracture energy was measured with a DuPont drop weight tester, and the value was defined as the Dupont impact strength.

(Production example of polybutadiene (A))
The inside of the polymerization autoclave having an internal volume of 1.5 L was purged with nitrogen, and 1 L of a raw material mixed solution (cyclohexane: 20 wt%, butadiene: 40 wt%, butene: 40 wt%) was charged and stirred. Then 19 μl of water was added and stirring was continued for 30 minutes at 500 rpm. At 20 ° C. and 1 atmosphere, 120 ml of hydrogen was metered in with an integrating mass flow meter, and then 1.6 mmol of triethylaluminum (TEA) was added. After stirring for 5 minutes, 6.8 μmol of vanadiumoxy (cyclopentadienyl) dichloride (CpV (O) Cl ₂ ), triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 10.2 μmol was sequentially added in a toluene solution, and polymerization was performed at a polymerization temperature of 50 ° C. and 500 rpm for 30 minutes. Then, 0.2355 mmol of 4,6-bis (octylmethyl) -o-cresol (cas-number: 110553-27-0) was added and stirred for 1 minute. Next, 6 ml of water was added as a reaction terminator, and the mixture was stirred for 1 minute at 700 rpm with a helical stirring blade. Then, polybutadiene (A) [polybutadiene (A-1) to polybutadiene (A-6)] was obtained by evaporating and drying the solvent and water. Table 1 shows the physical properties of the obtained polybutadiene (A). The difference between polybutadiene (A-1) to polybutadiene (A-6) is due to the difference in the amount of catalyst added.

(Production Example 1 of polybutadiene (B))
Polymer solution dehydrated in advance using molecular sieves in a stainless steel reaction tank with a stirrer (stirring blade diameter: 0.06 m) with an internal volume of 1.5 L substituted with nitrogen gas (tank diameter: 0.08 m) 1.0 L (1.3-butadiene: 30.0 wt%, cyclohexane: 70.0 wt%) was added. Next, under stirring, water, diethylaluminum chloride, cyclooctadiene, and cobalt octoate were added to carry out cis-1,4 polymerization. Ethanol containing 4,6-bis (octylthioethyl) -o-cresol is added to stop the polymerization, and then unreacted butadiene and 2-butenes are removed by evaporation. Thereafter, the solvent and water are evaporated and dried. As a result, polybutadiene (B) [polybutadiene (B-1) to polybutadiene (B-9)] was obtained. Table 2 shows the physical properties of the obtained polybutadiene (B). The difference between polybutadiene (B-1) to polybutadiene (B-9) is due to the mixing ratio of the substances.

(Production Example 2 of polybutadiene (B))
Polybutadiene (B-10) is a low-cis polybutadiene produced using a Li catalyst.

Example 1
A polybutadiene composition (C-1) in which 40% by weight of polybutadiene (A-1) and 60% by weight of polybutadiene (B-1) were blended was produced. Table 3 shows the physical properties of the resulting polybutadiene composition (C-1).

(Example 2)
A polybutadiene composition (C-2) blended with 40% by weight of polybutadiene (A-1) and 60% by weight of polybutadiene (B-2) was produced. Table 3 shows the physical properties of the resulting polybutadiene composition (C-2).

(Example 3)
A polybutadiene composition (C-3) in which 40% by weight of polybutadiene (A-1) and 60% by weight of polybutadiene (B-3) were blended was produced. Table 3 shows the physical properties of the resulting polybutadiene composition (C-3).

Example 4
A polybutadiene composition (C-4) was produced by blending 40% by weight of polybutadiene (A-1) and 60% by weight of polybutadiene (B-4). Table 3 shows the physical properties of the resulting polybutadiene composition (C-4).

(Example 5)
A polybutadiene composition (C-5) in which 40% by weight of polybutadiene (A-2) and 60% by weight of polybutadiene (B-5) were blended was produced. Table 3 shows the physical properties of the obtained polybutadiene composition (C-5).

(Example 6)
A polybutadiene composition (C-6) was prepared by blending 30% by weight of polybutadiene (A-2) and 70% by weight of polybutadiene (B-6). Table 3 shows the physical properties of the obtained polybutadiene composition (C-6).

(Example 7)
A polybutadiene composition (C-7) in which 20% by weight of polybutadiene (A-2) and 80% by weight of polybutadiene (B-6) were blended was produced. Table 3 shows the physical properties of the resulting polybutadiene composition (C-7).

(Example 8)
A polybutadiene composition (C-8) was prepared by blending 50% by weight of polybutadiene (A-2) and 50% by weight of polybutadiene (B-6). Table 3 shows the physical properties of the resulting polybutadiene composition (C-8).

Example 9
A polybutadiene composition (C-9) was prepared by blending 50% by weight of polybutadiene (A-6) and 50% by weight of polybutadiene (B-10). Table 3 shows the physical properties of the resulting polybutadiene composition (C-9).

(Comparative Example 1)
A polybutadiene composition (C-10) in which 46% by weight of polybutadiene (A-3) and 54% by weight of polybutadiene (B-7) were blended was produced. Table 4 shows the physical properties of the resulting polybutadiene composition (C-10).

(Comparative Example 2)
A polybutadiene composition (C-11) in which 48% by weight of polybutadiene (A-4) and 52% by weight of polybutadiene (B-8) were blended was produced. Table 4 shows the physical properties of the resulting polybutadiene composition (C-11).

(Comparative Example 3)
A polybutadiene composition (C-12) in which 60% by weight of polybutadiene (A-2) and 40% by weight of polybutadiene (B-6) were blended was produced. Table 4 shows the physical properties of the resulting polybutadiene composition (C-12).

(Comparative Example 4)
A polybutadiene composition (C-13) in which 50% by weight of polybutadiene (A-5) and 50% by weight of polybutadiene (B-9) were blended was produced. Table 4 shows the physical properties of the resulting polybutadiene composition (C-13).

Since polybutadiene (A) was soft and strongly tacky, the adhesive strength could not be measured. On the other hand, the polybutadiene composition (C) in which the polybutadiene (B) is mixed with the polybutadiene (A) is relaxed in the adhesive force, and the adhesive force can be measured. In particular, by reducing the St-cp / ML _{1 + 4} by branching the polybutadiene (B), the reduction in adhesive strength can be remarkably confirmed, and the productivity of the polybutadiene composition (C) is improved. I understand.

(Example 10)
The 1.0 L separable flask with a stirrer was replaced with nitrogen gas, and 368 g of styrene and 32 g of polybutadiene (C-4) were added and dissolved. Next, 0.08% by weight of n-dodecyl mercaptan was added and prepolymerized for 90 minutes while stirring at 130 ° C. until the conversion of styrene reached 30%. Next, 0.5 wt% polyvinyl alcohol aqueous solution was injected into the obtained prepolymerized solution in the same weight as the prepolymerized solution, and 0.20 parts by weight of benzoyl peroxide and 0.15 parts by weight of dicumyl peroxide were added. In addition, polymerization was conducted continuously with stirring at 100 ° C. for 2 hours, 125 ° C. for 3 hours, and 140 ° C. for 2 hours. The bead polymer was filtered from the polymerization reaction mixture obtained by cooling to room temperature, washed with water and dried. The obtained polymer was pelletized with an extruder to obtain a styrene-based resin composition. The obtained styrene resin composition was injection-molded to produce a physical property measurement test piece, and the physical property was measured. Table 5 shows the rubber particle diameter, graft ratio, Izod impact strength, and Dupont impact strength of the resulting styrene-based resin composition.

(Example 11)
A styrene resin composition was produced in the same manner as in Example 10 except that the polybutadiene composition (C-4) was changed to the polybutadiene composition (C-5). Table 5 shows the physical properties (particle diameter, graft ratio, Izod impact strength, and Dupont impact strength) of the obtained styrene-based resin composition.

(Example 12)
A styrene resin composition was produced in the same manner as in Example 10 except that the polybutadiene composition (C-4) was changed to the polybutadiene composition (C-6). Table 5 shows the physical properties (particle diameter, graft ratio, Izod impact strength, and Dupont impact strength) of the obtained styrene-based resin composition.

(Example 13)
A styrene resin composition was produced in the same manner as in Example 10 except that the polybutadiene composition (C-4) was changed to the polybutadiene composition (C-7). Table 5 shows the physical properties (particle diameter, graft ratio, Izod impact strength, and Dupont impact strength) of the obtained styrene-based resin composition.

(Comparative Example 8)
A styrene resin composition was produced in the same manner as in Example 10 except that the polybutadiene composition (C-4) was changed to the polybutadiene composition (C-10). Table 5 shows the physical properties (particle diameter, graft ratio, Izod impact strength, and Dupont impact strength) of the obtained styrene-based resin composition.

(Comparative Example 9)
A styrene resin composition was produced in the same manner as in Example 10, except that the polybutadiene composition (C-4) was changed to the polybutadiene composition (C-13). Table 5 shows the physical properties (particle diameter, graft ratio, Izod impact strength, and Dupont impact strength) of the obtained styrene-based resin composition.

  The particle diameter of the styrene-based resin composition prepared by using various polybutadiene compositions (C) which branch the polybutadiene (B) and achieve low solution viscosity while suppressing the adhesiveness between the polybutadienes is very small. Izod impact strength is also excellent, and application to high gloss styrene resin applications and high impact styrene resin applications can be expected.

  The polybutadiene composition according to the present invention is used for a wide range of applications, for example, home appliances / industrial uses for housings of televisions, air conditioners, refrigerators, facsimiles, telephones, etc., films / sheets used for packaging materials, food containers, etc. be able to. The polybutadiene composition according to the present invention can also be used for non-tire applications such as automobile tires and golf balls and shoe soles.

Claims (5)

(A1) cis-1,4-structure is 65 to 95 mol%, (a2) vinyl-1,2-structure is 4 to 30 mol%, and (a3) 5 wt% styrene solution viscosity at 25 ° C. (St 20 to 50 parts by weight of polybutadiene (A) produced by a metallocene catalyst, wherein -cp) satisfies the condition of 100 or less;
(B1) cis-1,4-structure is 30 to 99 mol%, (b2) vinyl-1,2-structure is 1 to 14 mol%, and (b3) 5 wt% styrene solution viscosity at 25 ° C. and 100 Polybutadiene (B) other than polybutadiene (A), which satisfies the condition that the ratio (St-cp / ML _{1 + 4} ) to the Mooney viscosity at 0 ° C. is 1.40 or less, the total amount is 100 parts by weight with 50 to 80 parts by weight. A polybutadiene composition comprising.   2. The polybutadiene composition according to claim 1, wherein the metallocene catalyst is a catalyst containing (A1) a metallocene complex of a vanadium metal, and (A2) an ionic compound of a non-coordinating anion and a cation and / or an alumoxane. (C1) cis-1,4-structure is 50 to 98 mol%, (c2) vinyl-1,2-structure is 1 to 12 mol%, and (c3) 5 wt% styrene solution viscosity at 25 ° C. (St -Cp) is 60 or less, and (c4) the ratio of 5 wt% styrene solution viscosity at 25 ° C to Mooney viscosity at 100 ° C (St-cp / ML _{1 + 4} ) is 1.9 or less, and (c5) cold flow rate The polybutadiene composition according to claim 1, wherein the polybutadiene composition is 0.27 or less. (C1) cis-1,4-structure is 50 to 98 mol%, (c2) vinyl-1,2-structure is 1 to 12 mol%, and (c3) 5 wt% styrene solution viscosity at 25 ° C. (St -Cp) is 60 or less, and (c4) the ratio of 5 wt% styrene solution viscosity at 25 ° C to Mooney viscosity at 100 ° C (St-cp / ML _{1 + 4} ) is 1.9 or less, and (c5) cold flow rate Is a method for producing a polybutadiene composition having a value of 0.27 or less,
(A1) cis-1,4-structure is 65 to 95 mol%, (a2) vinyl-1,2-structure is 4 to 30 mol%, and (a3) 5 wt% styrene solution viscosity at 25 ° C. (St 20 to 50 parts by weight of polybutadiene (A) produced by a metallocene catalyst, wherein -cp) satisfies the condition of 100 or less;
(B1) cis-1,4-structure is 30 to 99 mol%, (b2) vinyl-1,2-structure is 1 to 14 mol%, and (b3) 5 wt% styrene solution viscosity at 25 ° C. and 100 Polybutadiene (B) other than polybutadiene (A), which satisfies the condition that the ratio (St-cp / ML _{1 + 4} ) to the Mooney viscosity at 0 ° C. is 1.40 or less, the total amount is 100 parts by weight with 50 to 80 parts by weight. A method for producing a polybutadiene composition to be mixed.   A styrene resin composition comprising the polybutadiene composition according to any one of claims 1 to 3 and a styrene resin.