JP4165002B2 - Conjugated diene polymerization catalyst, method for preparing the same, and method for producing conjugated diene-based polymer - Google Patents

Description

【００２８】
表１から以下のことが分かる。
成分（Ａ）と成分（Ｂ）との混合・熟成を行わない比較例１〜３において、成分（Ｃ）／成分（Ａ）の比率を増加させると、反応率は上昇するものの、灰分およびゲル量が増加する傾向がある。
これらに比べ、成分（Ａ）と成分（Ｂ）との混合・熟成を行った実施例１〜３においては、それぞれ成分（Ｃ）／成分（Ａ）の比率が同じである比較例１または２と比べ、高いシス１，４−結合含有量を維持したまま反応率が高く、灰分及びゲル量が非常に少ない。また、実施例４においては、触媒量を減量しているにも拘らず、十分な反応率で、灰分およびゲル量が非常に少ない高シス−１，４結合含有量のポリブタジエンが得られている。
【００２９】
【発明の効果】
以上の本発明によれば、高重合活性を有し、高シス−１，４結合含有量で、ゲル含有量および灰分（ポリマー中に残存する触媒残渣）が著しく減少した共役ジエン系重合体の製造が可能な重合触媒が提供される。本発明の重合触媒を用いて製造される共役ジエン系重合体、特に高シス−１，４−ポリブタジエンは、上記の特性を有することから特にＨＩＰＳ用の強靭化剤として好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymerization catalyst for a conjugated diene and a method for producing a conjugated diene polymer using the same, and more specifically, a conjugated diene having a high cis-1,4 bond content, a low gel content, and an extremely low ash content. The present invention relates to a polymerization catalyst for a conjugated diene having a high polymerization activity from which a polymer is obtained, and a method for producing a conjugated diene polymer using the same.
[0002]
[Prior art]
Conjugated diene polymers, in particular polybutadiene having a high cis-1,4 bond content (hereinafter sometimes referred to as high cis polybutadiene), are used as tires and various industrial products as rubbers with high resilience and low heat build-up. Used in the manufacture of rubber products. In addition to the above properties, it is also used as a toughening material such as impact-resistant polystyrene (HIPS) taking advantage of excellent transparency and low-temperature properties.
[0003]
Usually, HIPS is produced by dissolving high cis polybutadiene as a toughening material in styrene and radical polymerizing the resulting solution. At that time, polybutadiene is required to have a high cis-1,4 bond content and a low gel content and ash (catalyst residue). This is because when the cis-1,4 bond content is low, the impact resistance of HIPS at low temperatures is reduced, and when the gel and ash content is high, these become defects in HIPS and impact resistance. It is because it reduces. In order to prevent such problems, the above styrene solution is filtered in a filtration step before polymerization. However, if the gel content is high, the filter medium is clogged, the filtration speed is reduced, and the replacement frequency of the filter medium is reduced. This is also because it increases the productivity.
[0004]
In order to obtain polybutazine having a high cis-1,4 bond content and a low gel and ash content, various polymerization methods have been proposed. For example, JP-A-7-188341 discloses a catalyst comprising an alkylaluminum chloride and a trialkylaluminum selected from divalent cobalt salts, diethylaluminum chloride and diethylaluminum sesquichloride in an inert hydrocarbon polymerization medium containing water. Japanese Patent Application Laid-Open No. 10-330428 discloses a method for polymerizing 1,3-butadiene using a cobalt compound, a trialkylaluminum compound, a halogen-containing aluminum compound, and water. A method of polymerizing 1,3-butadiene using a polymerization catalyst in which a compound and water are each in a specific ratio is disclosed.
By these polymerization methods, polybutadiene having a high cis-1,4 bond content and a low gel content can be obtained, but the ash content is not yet satisfactory.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of such circumstances, and an object of the present invention is a conjugated diene system having high polymerization activity, high cis 1,4 bond content, extremely low gel content and ash content. An object of the present invention is to provide a polymerization catalyst capable of producing a polymer and a method for producing a conjugated diene polymer having the above-described properties.
[0006]
As a result of intensive studies to achieve the above object, the present inventor prepared a cobalt compound, a trialkylaluminum compound, a halogen-containing organoaluminum compound and water as components, and mixed and aged these components in a specific order. The inventors have found that the object can be achieved by using a catalyst, and have completed the present invention.
[0007]
[Means for Solving the Problems]
According to the present invention, selected from (A) the period iron group of Table 8-10, or a platinum group transition metal compound, (B) the Periodic Table 1-3 group elements and 1 to 13 group elements (C) a halogen-containing organoaluminum compound and (D) a compound having active hydrogen, and (1) the above components (A) and (B) in an inert solvent , Mixing and aging at a temperature of 0 to 80 ° C. for 0.1 to 24 hours at a ratio of component (B) / component (A) of 0.05 to 0.9 (molar ratio ) gave (2) mature Narueki and component (C) and the component (D) a conjugated diene polymer catalyst and characterized by being obtained by mixing and conjugated diene polymer which comprises polymerizing a conjugated diene using a polymerization catalyst A manufacturing method is provided.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to preferred embodiments of the invention.
The polymerization catalyst for conjugated dienes of the present invention comprises (A) a transition metal compound, (B) an organometallic compound of an element selected from Group 1 to 3 elements and 11 to 13 elements in the periodic table, and (C) a halogen-containing compound. It is characterized in that an organoaluminum compound and (D) a compound having active hydrogen are used as components, and these components are mixed and aged in the order described below.
[0009]
First, each component of the polymerization catalyst of the present invention will be described.
The transition metal compound of component (A) is an iron group and platinum group compound of groups 8 to 10 (former group VIII) of the periodic table, and examples thereof include a cobalt compound and a nickel compound. More preferred are cobalt compounds, for example, cobalt inorganic salts such as cobalt chloride, cobalt bromide, cobalt nitrate; cobalt acetate, cobalt oxalate, cobalt acetylacetate, cobalt octenoate, cobalt naphthenate, cobalt malonate And organic acid salts such as Particularly preferred is cobalt octenoate.
[0010]
As an organometallic compound of an element selected from Group 1 (former IA) to Group 3 (former IIIA) and Group 11 (former IB) to Group 13 (former IIIB) of the periodic table of component (B) Examples include organoaluminum compounds, organolithium compounds, organomagnesium compounds, organozinc compounds, organoboron compounds and the like, and halogen-containing compounds thereof. Specifically, for example, methyl lithium, butyl lithium, neopentyl lithium, benzyl lithium, trimethylsilylmethyl lithium, bistrimethylsilylmethyl lithium, dibutyl magnesium, dihexyl magnesium, dimethyl zinc, diethyl zinc, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum Alkyl metal compounds such as trihexyl aluminum, trioctyl aluminum and tridecyl aluminum; halogen-containing organometallic compounds such as ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride and ethyl aluminum dichloride; Diethylaluminum hydride Ageraru and hydrogenated organic metal compounds such as sesqui ethylaluminum hydride. These can be used alone or in combination of two or more. More preferred is an organoaluminum compound represented by the general formula R ₃ Al (R is a hydrocarbon group having about 1 to 10 carbon atoms), and triisobutylaluminum is particularly preferred.
[0011]
Table with component halogen-containing organic aluminum compound (C) has the general formula R _3-n AlX n (the number of R is a hydrocarbon group having 1 to 10 about carbon atoms, X is a halogen atom, n represents 1-2) Examples thereof include diethylaluminum monochloride, diethylaluminum monobromide, dibutylaluminum monochloride, dicyclohexylaluminum monochloride, duphenylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and the like. Of these, diethylaluminum monochloride is preferable.
[0012]
Examples of the component (D) compound having active hydrogen include water; lower alcohols such as methyl alcohol and ethyl alcohol; carboxylic acids such as formic acid, acetic acid and benzoic acid; and amine compounds such as ammonia and aniline. Of these, water is preferred.
[0013]
In the polymerization catalyst of the present invention, the order of addition of the above-mentioned components is important, and the target gel content and ash content cannot be reduced by simply mixing the components.
First, component (A) and component (B) are mixed in an inert solvent and aged. Here the two components, in the proportions component (B) / component (A) is from 0.05 to 0.9 (molar ratio), used at a ratio preferably will be 0.2 to 0.9 (mole ratio) To do . If this molar ratio is too small, the gel content of the polymer produced increases, and if it is too large, the polymerization activity decreases, which is not preferable. Mixing and aging of the catalyst components are usually performed at a temperature of 0 to 80 ° C., preferably 10 to 40 ° C., and aging is usually about 0.1 to 24 hours. As the inert solvent, a polymerization solvent described later is preferably used.
[0014]
Next, the obtained ripening liquid, component (C), and component (D) are mixed. At this time, for example, the following mixing method can be used.
(1) After mixing a component (C) and a component (D), this and an aging liquid are mixed.
(2) The aging liquid, component (C) and component (D) are mixed simultaneously.
(3) After mixing the ripening liquid and component (C), it is further mixed with component (D).
(4) After mixing the ripening liquid and component (D), it is further mixed with component (C).
Among these methods, the method (1) or (2) is preferable, and the method (1) is more preferable.
In the method (1), when mixing the component (C) and the component (D), it is preferable to mix in an inert solvent, a conjugated diene, or an inert solvent solution of a conjugated diene. The mixing temperature at this time is usually 0 to 80 ° C., preferably 10 to 40 ° C., and the mixing time is usually about 0.1 second to 1 hour.
[0015]
When mixing the component (C) and the component (D), the component (D) / component (C) is preferably used in a ratio of 0.1 to 1.7 (molar ratio), more preferably. Is a ratio of 0.3 to 0.9 (molar ratio). If this molar ratio is too small, the cis 1,4-bond content of the produced polymer will be low, and if it is too large, the gel content of the produced polymer will increase.
[0016]
Moreover, it is preferable to use a component (C) in the ratio from which a component (C) / component (A) will be 10-1000 (molar ratio), More preferably, it is a ratio from 20-200 (molar ratio). . When this molar ratio is too small, the polymerization activity is lowered, and when it is too large, the ash content of the produced polymer increases, which is not preferable.
[0017]
The polymerization catalyst of the present invention prepared by mixing and aging in this order is a conjugated diene such as 1,3-butadiene, 1,3-pentadiene, 2,3-dimethylbutadiene, isoprene or the like. It is used to produce a conjugated diene polymer by polymerizing two or more kinds. As the conjugated diene, 1,3-butadiene is preferred.
[0018]
The polymerization catalyst of the present invention is usually used in an amount such that the component (A) is 0.001 to 0.02 mmol per mole of conjugated diene, but is not limited to this amount. The optimum amount can be determined appropriately so that the Mooney viscosity or the solution viscosity of the coalescence is within a predetermined range.
[0019]
The polymerization of the conjugated diene can be performed in the absence of a solvent, but is generally performed in a solvent. As the solvent, a solvent that does not affect the polymerization activity of the catalyst and dissolves the conjugated diene, the catalyst, and the produced polymer is preferable. Examples of the solvent for polymerization include saturated aliphatic hydrocarbons such as butane, pentane, n-hexane and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; 1-butene, cis-2-butene, trans Monoolefins such as 2-butene; aromatic hydrocarbons such as benzene, toluene, and xylene. These solvents can be used alone or in combination of two or more.
In the polymerization, known molecular weight regulators such as non-conjugated dienes such as allene, 1,2-butadiene and cyclooctadiene, and α-olefins such as ethylene and propylene can be used.
[0020]
The conjugated diene polymerization method is the same as the conventional conjugated diene polymerization method using a Ziegler type catalyst, and batch or continuous polymerization is used. Although superposition | polymerization temperature changes with solvents to be used, it is normally implemented in the range of -30-100 degreeC.
After completion of the polymerization, a substance (a polymerization terminator) that deactivates a polymerization catalyst such as water or alcohol is added to the polymerization system to stop the polymerization reaction, recover the unreacted conjugated diene, and then add the conjugated diene polymer solution. For example, the polymer is solidified as crumb by contacting with water vapor, etc., and the crumb is washed with water or alcohol to remove catalyst residues, and then the crumb is conventionally practiced as an extrusion dryer or hot air dryer. Dry by the drying method.
[0021]
By using the polymerization catalyst of the present invention, the microstructure (bonding mode) is cis-1,4 bond, the content is 90 mol% or more, and the gel content and ash content (catalyst residue) are significantly reduced. A high cis-1,4 conjugated diene polymer can be produced. When 1,3-butadiene is used as the conjugated diene, in addition to the processability and other properties equivalent to high cis-1,4-polybutadiene using a conventional Ziegler catalyst, high cis- 1,4-polybutadiene is obtained and can be used in various applications such as for tires and toughening materials of high impact polystyrene (HIPS).
[0022]
【Example】
The present invention will be specifically described below with reference to examples and comparative examples.
[0023]
Examples 1-4, Comparative Examples 1-3
Cobalt octenoate as component (A), triisobutylaluminum (Tibal) or diethylaluminum monochloride (DEAC) as component (B), diethylaluminum monochloride (DEAC) as component (C), and component (D) These components were used in molar ratios as shown in Table 1.
[0024]
First, component (A) and component (B) in the polymerization catalyst were mixed in toluene as an inert solvent and aged in nitrogen gas at 20 ° C. for 1 hour.
On the other hand, cis-2-butene as a polymerization solvent and 30% by weight of 1,3-butadiene with respect to this polymerization solvent were charged into a degassed and dried pressure vessel, and components (C) and ( D) was added and mixed and left at 20 ° C. for 1 minute.
Next, the ripening solution of the above component (A) and component (B) or component (A) is added to the cis-2-butene solution of 1,3-butadiene to which component (C) and component (D) are added. The component (A) was added in an amount of 0.005 mmol per mole of 1,3-butadiene (provided that 0.003 mmol in Example 4), and polymerization was carried out at 22 ° C. for 2 hours with stirring.
[0025]
A very small amount of a 2 wt% methanol solution of an anti-aging agent (2,6-di-tert-butyl-4-methylphenol) is added to the polymer solution to stop the polymerization and recover unreacted 1,3-butadiene. After that, water vapor was blown into the polymer solution to separate polybutadiene as crumb, and the crumb was sufficiently washed with water, and then dried under reduced pressure at 70 ° C. for 12 hours. The resulting polybutadiene was measured for microstructure, gel content and ash content. In addition, cis 1,4-bond content (cis 1,4 amount), gel content (gel amount) and ash were measured by the following methods. Table 1 shows the reaction rate (conversion) and the results.
[0026]
[Cis 1,4-bond content]
It was measured by 1H-NMR and ¹³ C-NMR.
[Gel content]
About 4 g of polybutadiene was placed in an 80-mesh stainless steel wire mesh container of known weight and immersed in 500 ml of toluene at room temperature for 48 hours. The soot taken out from the solvent was thoroughly washed with the above solvent and dried under reduced pressure at 60 ° C., and then the weight of the soot was measured and determined from the weight increase.
〔ash〕
About 2 g of polybutadiene was put in a crucible of known weight, and this was ashed by heating to 550 ° C. for 20 hours in an electric furnace. After the crucible was cooled to room temperature in a desiccator, the weight of the crucible was measured and determined from the increase in weight.
[0027]

[0028]
Table 1 shows the following.
In Comparative Examples 1 to 3 where mixing and aging of component (A) and component (B) is not performed, increasing the ratio of component (C) / component (A) increases the reaction rate, but ash and gel The amount tends to increase.
In comparison with these, in Examples 1 to 3 in which the component (A) and the component (B) were mixed and aged, Comparative Example 1 or 2 in which the ratio of component (C) / component (A) was the same. The reaction rate is high while maintaining a high cis 1,4-bond content, and the amount of ash and gel is very small. Moreover, in Example 4, although the amount of catalyst was reduced, polybutadiene having a high cis-1,4 bond content with a very low ash content and gel amount was obtained with a sufficient reaction rate. .
[0029]
【The invention's effect】
According to the present invention described above, a conjugated diene polymer having a high polymerization activity, a high cis-1,4 bond content, and a marked reduction in gel content and ash content (catalyst residue remaining in the polymer). A polymerization catalyst that can be produced is provided. The conjugated diene polymer produced using the polymerization catalyst of the present invention, particularly high cis-1,4-polybutadiene, is particularly suitable as a toughening agent for HIPS because it has the above properties.

Claims (6)

(A) cycle iron group of Table 8-10, or a platinum group transition metal compound, an organometallic compound of an element selected from the (B) Periodic Table 1-3 group elements and 1 to 13 group elements, (C) a halogen-containing organic aluminum compound and, (D) and the compound component having active hydrogen, (1) the above components in an inert solvent (a) and component (B), component (B) / component ( at a ratio a) is 0.05 to 0.9 (molar ratio), 0.1 to 24 hours at a temperature 0 to 80 ° C., mixed and aged, (2) the resulting ripe Narueki and component (C ) And a component (D) are mixed, The conjugated diene polymerization catalyst characterized by the above-mentioned. The molar ratio of the above components is such that component (B) / component (A) is 0. 2 to 0.9, component (C) / component (A) from 10 to 1000 and component (D) / component (C) is a conjugated diene polymerization catalyst as claimed in claim 1 is 0.1 to 1.7. (A) The conjugated diene polymerization catalyst according to claim 1 or 2, wherein the transition metal compound of group 8 to group 10 of the periodic table is a cobalt compound. (B) An organometallic compound of an element selected from Group 1-3 elements and Group 11-13 elements of the periodic table is represented by the general formula R _Three The conjugated diene polymerization catalyst according to any one of claims 1 to 3, which is an organoaluminum compound represented by Al (R is a hydrocarbon group having 1 to 10 carbon atoms). (A) cycle iron group of Table 8-10, or a platinum group transition metal compound, an organometallic compound of an element selected from the (B) Periodic Table 1-3 group elements and 1 to 13 group elements, In preparing a catalyst comprising (C) a halogen-containing organoaluminum compound and (D) a compound having active hydrogen as a component, (1) component (A) and component (B) described above in an inert solvent , (B) / component (a) so that the ratio of 0.05 to 0.9 (molar ratio), 0.1 to 24 hours at a temperature 0 to 80 ° C., were mixed and aged, was obtained (2) process for the preparation of conjugated diene polymerization catalyst characterized by mixing ripe Narueki and component (C) and the component (D). A method for polymerizing a conjugated diene polymer, wherein the conjugated diene is polymerized using the polymerization catalyst according to any one of claims 1 to 4 .