JP6612531B2 - Method for producing polybutadiene - Google Patents

Description

  The present invention relates to a method for producing polybutadiene.

In recent years, environmental issues have been emphasized, and regulations on the emission of carbon dioxide have been strengthened, and there has been a demand for reducing the amount of petroleum raw materials used. In addition, since petroleum raw materials are limited and the supply amount is decreasing year by year, the price of petroleum raw materials is expected to rise in the future, and there is a limit to the use of raw materials made of petroleum resources.
Therefore, as part of building a recycling-oriented society, attention is focused on the use of biomass to replace fossil fuels by moving away from fossil fuels. Similarly, in the field of materials such as rubber materials, production of various materials using raw materials derived from biomass has attracted attention, and various studies have been made on this.

  For example, Patent Document 1 discloses that a biomass polybutadiene rubber is synthesized using a mixture of 1,3-butadiene synthesized from butanol derived from biomass, ethanol, ethylene, and tiglic acid.

JP 2014-024915 A

However, 1,3-butadiene synthesized from biomass-derived raw materials is usually accompanied by a large amount of impurities. For this reason, even if an attempt is made to synthesize polybutadiene from this 1,3-butadiene, there is a possibility that the polymerization does not proceed sufficiently and the molecular weight of the resulting polybutadiene does not become sufficiently high. As a countermeasure to this problem, for example, there is a method of removing the above impurities as much as possible by advanced purification such as distillation or extractive distillation prior to the polymerization. However, this method requires additional equipment and is costly. It is disadvantageous from the viewpoint.
It should be noted that some impurities may also accompany 1,3-butadiene synthesized from non-biomass derived, for example, petroleum derived raw materials. Therefore, when synthesizing polybutadiene using 1,3-butadiene synthesized from such petroleum-derived raw materials, the present situation is that 1,3-butadiene is usually purified in advance by extraction distillation or the like.

  Accordingly, an object of the present invention is to provide a polybutadiene production method capable of solving the above conventional problems and producing polybutadiene at low cost.

  As a result of intensive studies to achieve the above object, the present inventors have determined that polybutadiene is used even when 1,3-butadiene used as a material for polymerizing polybutadiene is accompanied by a predetermined amount of oxygen-containing compound. The inventors have found that it can be manufactured and have completed the present invention.

That is, the polybutadiene production method of the present invention comprises 1,3-butadiene and a butadiene-containing composition containing 0.001 to 3.0 parts by mass of an oxygen-containing compound with respect to 100 parts by mass of the 1,3-butadiene. And a polymerization step of polymerizing 1,3-butadiene using the product. According to this manufacturing method, polybutadiene can be manufactured at low cost.
In the present invention, the “oxygen-containing compound” refers to a compound having at least one oxygen atom in the molecule.

  In the polybutadiene production method of the present invention, from the viewpoint of sufficiently suppressing carbon dioxide emission, and from the viewpoint of producing a polybutadiene by obtaining a butadiene-containing composition without depending on petroleum resources, the 1,3-butadiene is obtained. However, it is preferable that it is 1,3-butadiene obtained by synthesizing biomass-derived ethanol.

  In the method for producing polybutadiene of the present invention, the oxygen-containing compound contains an oxygen-containing neutral compound (neutral oxygen-containing compound) as a constituent component, and the proportion of the oxygen-containing neutral compound in the oxygen-containing compound is It is preferable that it is 85 mass% or more. As a result, polybutadiene can be obtained more reliably while avoiding an increase in cost associated with sophisticated purification operations.

  In the method for producing polybutadiene of the present invention, in the polymerization step, a rare earth element compound and an organometallic compound are blended with the butadiene-containing composition, and the blending amount of the organometallic compound is such that the butadiene-containing composition 100 is mixed. It is preferable that it is 0.1-6.0 mass parts with respect to a mass part. Thereby, while being able to raise the conversion rate at the time of converting from a monomer to a polymer, the molecular weight of the obtained polymer can be raised.

  Further, in the polybutadiene production method of the present invention, in the polymerization step, an anionic polymerization initiator is blended with the butadiene-containing composition, wherein the blending amount of the anionic polymerization initiator is the 1,3-butadiene 100. It is preferable that it is 0.003-3.0 mass parts with respect to a mass part. Thereby, while being able to raise the conversion rate at the time of converting from a monomer to a polymer, the molecular weight of the obtained polymer can be raised.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of polybutadiene which can solve the said problem of the said prior art and can manufacture polybutadiene at low cost can be provided.

(Polybutadiene production method)
Hereinafter, embodiments of the method for producing polybutadiene of the present invention will be described in detail.
An example of the method for producing polybutadiene according to the present invention (hereinafter sometimes referred to as “an example production method”) is 1,3-butadiene and 0.001 to 100 parts by mass of 1,3-butadiene. It includes a polymerization step of polymerizing 1,3-butadiene using a butadiene-containing composition containing 2.0 parts by mass of an oxygen-containing compound.

<Butadiene-containing composition>
The butadiene-containing composition used in the production method of the present invention (hereinafter sometimes referred to as “an butadiene-containing composition of the present invention”) is 1,3-butadiene, an oxygen-containing compound, and an optional compound. And other components.

-1,3-butadiene
The 1,3-butadiene contained in the butadiene-containing composition of an example of the present invention is not particularly limited and is appropriately selected depending on the purpose, for example, through a step of heating ethanol to a high temperature under a metal catalyst. Examples include 1,3-butadiene obtained. Specifically, the above process can be performed by flowing N ₂ gas through a reactor filled with a metal catalyst, adding ethanol to the gas stream, and heating the gas in the reactor.
In addition, in the said process, by-products, such as alkenes, such as 1-butene and 2-butene, alcohol, an aldehyde, carboxylic acid, ether, ester, a ketone, can usually be produced | generated besides 1,3-butadiene.

Here, it is preferable that the ethanol is biomass-derived ethanol from the viewpoint of sufficiently suppressing the emission amount of carbon dioxide and from the viewpoint of not depending on petroleum resources. In other words, the 1,3-butadiene contained in the butadiene-containing composition is preferably 1,3-butadiene obtained by synthesizing ethanol derived from biomass as a raw material.
In addition, since 1.3-butadiene synthesized from ethanol derived from biomass usually contains a certain amount of oxygen-containing compound as impurities, a butadiene-containing composition of an example of the present invention can be easily obtained to produce polybutadiene. From this viewpoint, it is preferable to use 1,3-butadiene obtained by synthesizing ethanol derived from biomass.

-Oxygenated compounds-
The butadiene-containing composition of an example of the present invention contains at least an oxygen-containing compound. Here, when 1,3-butadiene is synthesized from ethanol in the presence of a catalyst, alcohols, aldehydes, ethers, esters, ketones, and the like, which are oxygen-containing compounds, can be produced more or less. Therefore, according to the present invention, it is possible to prepare polybutadiene at a low cost by preparing an example butadiene-containing composition of the present invention without the need to remove these by high-level purification.

  Here, the oxygen-containing compound includes a neutral oxygen-containing compound (hereinafter sometimes referred to as “oxygen-containing neutral compound”) and a non-neutral oxygen-containing compound (hereinafter referred to as “oxygen-containing non-neutral compound”). And may be classified as follows.)

Examples of the oxygen-containing neutral compound include ethers, esters, and ketones.
Specific examples of the ether include ethoxyethylene, diethyl ether, tetrahydrofuran, and 3-methylfuran. Specific examples of the ester include ethyl acetate and methyl acetate. Specific examples of the ketone include methyl vinyl ketone, methyl ethyl ketone (2-butanone), diacetyl (2,3-butanedione), and methyl isobutyl ketone. These oxygen-containing neutral compounds may be contained singly or in combination of two or more.

Examples of the oxygen-containing non-neutral compound include alcohols, aldehydes, and carboxylic acids.
Specific examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, crotyl alcohol and the like. Specific examples of the aldehyde include formaldehyde, acetaldehyde, methacrolein, crotylaldehyde and the like. Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, crotonic acid and the like.

The oxygen-containing compound content (total content of oxygen-containing neutral compound and oxygen-containing non-neutral compound) in the butadiene-containing composition of one example of the present invention is 0.001 with respect to 100 parts by mass of 1,3-butadiene. There is no particular limitation as long as it is within the range of -2.0 parts by mass. If the content of the oxygen-containing compound is less than 0.001 part by mass with respect to 100 parts by mass of 1,3-butadiene, high purification is required after the synthesis of 1,3-butadiene, which may increase the production cost. There is. Further, if the content of the oxygen-containing compound is more than 3.0 parts by mass with respect to 100 parts by mass of 1,3-butadiene, there is a possibility that the polymerization of 1,3-butadiene (production of polybutadiene) itself cannot be performed.
From the same viewpoint, the content of the oxygen-containing compound in the butadiene-containing composition of an example of the present invention is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of 1,3-butadiene, and 0.03 -2.0 mass parts is more preferable.

Furthermore, the ratio of the oxygen-containing neutral compound in the oxygen-containing compound in the butadiene-containing composition of an example of the present invention is not particularly limited and is appropriately selected depending on the purpose, but is preferably 85% by mass or more, 89 The mass% or more is more preferable. When the ratio is 85% by mass or more, polybutadiene can be obtained more reliably while avoiding an increase in cost associated with a high-level purification operation.
In addition, the content of 1,3-butadiene, the content of oxygen-containing neutral compounds, and the content of oxygen-containing non-neutral compounds in the butadiene-containing composition can be measured using gas chromatography.

-Other ingredients-
The butadiene containing composition of an example of this invention can contain other components other than the 1, 3- butadiene mentioned above and an oxygen-containing compound in the range which does not impair the objective of this invention.
Examples of other components include methane, ethane, ethylene, propylene, 1-butene, 2-butene, 1,2-butadiene, methylbutene, and 1-pentene. These other components may be contained singly or in combination of two or more.
In addition, the butadiene-containing composition of an example of the present invention may be dissolved in a solvent such as hexane, cyclohexane, and toluene in advance before polymerizing 1,3-butadiene. Here, the solvent in this case is not included in the butadiene-containing composition.

<Preparation of butadiene-containing composition>
The butadiene-containing composition can be prepared, for example, from a reaction product containing 1,3-butadiene obtained by heating ethanol to a high temperature under a metal catalyst as described above. Usually, the reaction product includes oxygen-containing compounds such as alcohols, aldehydes, carboxylic acids, ethers, esters, and ketones as by-products in addition to 1,3-butadiene. Therefore, for example, the reaction product is purified by a simple method so that the content of these oxygenated compounds is within the range of 0.001 to 2.0 parts by mass with respect to 100 parts by mass of 1,3-butadiene. By doing so, a butadiene-containing composition can be prepared at a low cost.

Examples of the purification method include a method in which the reactant dissolved in a solvent such as hexane is brought into contact with an adsorbent and the oxygenated compound in the reactant is partially removed. Specifically, a method of adding an adsorbent to a reactant dissolved in a solvent and allowing to stand for a predetermined time, a method of treating a reactant dissolved in a solvent by column chromatography including a filler for a predetermined time, and these The method etc. which combined these are mentioned. Examples of the adsorbent include activated alumina, molecular sieves, and silica gel. Examples of the filler include activated alumina, molecular sieves, and silica gel. Each of these adsorbents and fillers may be used alone or in combination of two or more.
The removal ratio of the oxygen-containing compound can be appropriately adjusted by changing the type of the adsorbent or filler, or changing the contact time or mass ratio between the reactant and the adsorbent or filler.

  Here, when using the method of adding an adsorbent to the reactant dissolved in the solvent described above and allowing to stand, the standing time is not particularly limited and is appropriately selected according to the purpose. From the viewpoint of obtaining a butadiene-containing composition, it is preferably 12 hours or longer, more preferably 24 hours or longer, and preferably 120 hours or shorter, more preferably 100 hours or shorter, from the viewpoint of suppressing deterioration in productivity and low cost. .

Moreover, when using the method processed by the column chromatography mentioned above, as the processing time, it does not restrict | limit especially, It selects suitably according to the objective, From a viewpoint of obtaining a desired butadiene containing composition, 1 hour or more From the viewpoint of suppressing the deterioration of productivity and low cost, it is preferably 3 hours or shorter, and more preferably 2 hours or shorter.
In addition, it is preferable that the treatment time by the column chromatography described above is 6 hours or more, because the productivity of the butadiene-containing composition, and thus the productivity of polybutadiene decreases, and the production cost per unit amount of polybutadiene increases. Absent.

  And in preparation of a butadiene containing composition, it is preferable not to include the process of refine | purifying the said reaction material by distillation or extractive distillation. Advanced purification, such as distillation or extractive distillation, may require additional equipment and increase manufacturing costs.

<Polybutadiene polymerization (production of polybutadiene)>
In the manufacturing method of an example of this invention, it is required to include the superposition | polymerization process of superposing | polymerizing 1, 3- butadiene using a butadiene containing composition. In the polymerization step, 1,3-butadiene is polymerized in the butadiene-containing composition. The polymerization method of 1,3-butadiene is not particularly limited and is appropriately selected depending on the purpose, and examples thereof include coordination polymerization and anionic polymerization. Further, in any polymerization method, an arbitrary component can be blended in the butadiene-containing composition in the polymerization step, and thereby polymerization can be started.

-Coordination polymerization-
In the production method of an example of the present invention, 1,3-butadiene can be polymerized by coordination polymerization using a butadiene-containing composition. Specifically, 1,3-butadiene can be polymerized by blending a butadiene-containing composition dissolved in a solvent such as hexane with a component that catalyzes coordination polymerization. Here, the components that catalyze coordination polymerization suitable in the present invention are also referred to as rare earth element compounds (hereinafter also referred to as “component (A)”) and organometallic compounds (hereinafter referred to as “component (B)”). Furthermore, an aluminoxane compound (hereinafter also referred to as “component (C)”), a halogen compound (hereinafter also referred to as “component (D)”), an ionic compound (hereinafter referred to as “component (E)”). A compound that can be an anionic ligand (hereinafter referred to as “component (F)”) and the like.
In addition, when blending into the butadiene-containing composition, the catalyst composition is prepared by previously mixing the components selected from the components (A) and (B) and any of the components (C) to (F). The catalyst composition may be prepared and blended with the butadiene-containing composition, or each of the above components may be blended alone with the butadiene-containing composition.

--Rare earth element compound (component (A))-
The component (A) can be a rare earth element-containing compound having a metal-nitrogen bond (MN bond) or a reaction product of the rare earth element-containing compound and a Lewis base. Examples of the rare earth element-containing compound include scandium, yttrium, and a compound containing a lanthanoid element composed of an element having an atomic number of 57 to 71. The lanthanoid elements are specifically lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
Examples of the Lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like.
The said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

  Here, it is preferable that the rare earth element-containing compound or the reaction product of the rare earth element-containing compound and the Lewis base does not have a bond between the rare earth element and carbon. This is because when the reaction product of the rare earth element-containing compound and the Lewis base does not have a rare earth element-carbon bond, the reaction product is stable and easy to handle.

-Organometallic compound (component (B))-
The component (B) has the formula (S2)
YR ⁴ _a R ⁵ _b R ⁶ _c (S2)
Wherein Y is a metal element selected from the group consisting of Group 1, Group 2, Group 12, and Group 13; R ⁴ and R ⁵ are hydrocarbons having 1 to 10 carbon atoms A group or a hydrogen atom, which may be the same or different; R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms; R ⁶ is the same as or different from the above R ⁴ or R ⁵ And when Y is a Group 1 metal element, a is 1 and b and c are 0, and Y is a Group 2 metal element and a Group 12 metal element. In the case, a and b are 1 and c is 0, and when Y is a Group 13 metal element, a, b and c are 1). Can do.

The component (B) has the formula (S3)
AlR ⁷ R ⁸ R ⁹ (S3)
(In the formula, R ⁷ and R ⁸ are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and may be the same or different; R ⁹ is a hydrocarbon group having 1 to 10 carbon atoms. R ⁹ is preferably an organoaluminum compound represented by R ⁷ or R ⁸ which may be the same or different.
Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and trihexyl. Aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, it includes isobutyl aluminum dihydride and the like, particularly, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred.
The said organoaluminum compound may be used individually by 1 type, and may be used in combination of 2 or more type.

--Aluminoxane compound (component (C))-
(C) A component is a compound obtained by making an organoaluminum compound and a condensing agent contact. By using the component (C), the catalytic activity in the polymerization reaction system can be further improved. Therefore, the reaction time can be further shortened and the reaction temperature can be further increased.
Here, as an organoaluminum compound, what was mentioned above as a (B) component, its mixture, etc. are mentioned, Especially the mixture of trimethylaluminum and trimethylaluminum and triisobutylaluminum is preferable.
As a condensing agent, what is normally used in this technical field is mentioned.

As the component (C), for example, the formula (S4)
-(Al (R ¹⁰ ) O) _n- (S4)
(Wherein, R ¹⁰ is a hydrocarbon group having 1 to 10 carbon atoms, wherein the halogen and / or may be substituted with an alkoxy group in some hydrocarbon group; R ¹⁰ is between the repeating units And may be the same or different; n is 5 or more).

The molecular structure of the aluminoxane may be linear or cyclic. N is preferably 10 or more. Furthermore, examples of the hydrocarbon group for R ¹⁰ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is particularly preferable. The said hydrocarbon group may be used individually by 1 type, and may be used in combination of 2 or more type. As the hydrocarbon group for R ¹⁰ , a combination of a methyl group and an isobutyl group is preferable.

Examples of the component (C) include TMAO, for example, product name: TMAO-341 manufactured by Tosoh Finechem.
Moreover, as (C) component, MMAO, for example, the product name: MMAO-3A by Tosoh Finechem Co., Ltd. is mentioned.
Furthermore, as the component (C), PMAO, for example, product name: TMAO-211 manufactured by Tosoh Finechem Co., Ltd. may be mentioned. Among these, TMAO and MMAO are preferable from the viewpoint of enhancing the effect of improving the catalytic activity, and TMAO is more preferable from the viewpoint of further enhancing the effect of improving the catalytic activity.

-Halogen compound (component (D))-
Component (D) is a halogen-containing compound that is a Lewis acid (hereinafter also referred to as “(D-1) component”), a complex compound of a metal halide and a Lewis base (hereinafter referred to as “(D-2) component”). And at least one compound selected from the group consisting of organic compounds containing active halogen (hereinafter also referred to as “component (D-3)”).

These compounds react with a component (A), that is, a rare earth element-containing compound having an MN bond, or a reaction product of the rare earth element-containing compound and a Lewis base, to form a cationic transition metal compound or a halogenated transition. A metal compound and / or a transition metal compound in which electrons are insufficient at the transition metal center are generated.
By using the component (D), the cis-1,4 bond amount of polybutadiene can be improved.

As the component (D-1), for example, a halogen-containing compound containing an element from Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14, Group 15 or the like In particular, aluminum halides or organometallic halides are preferred.
Examples of halogen-containing compounds that are Lewis acids include titanium tetrachloride, tungsten hexachloride, tri (pentafluorophenyl) borate, methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide. , Butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquichloride, aluminum G Examples include bromide, tri (pentafluorophenyl) aluminum, dibutyltin dichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, antimony trichloride, antimony pentachloride, etc., especially ethyl aluminum dichloride, ethyl aluminum dibromide, diethyl Aluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, and ethylaluminum sesquibromide are preferred.
As halogen, chlorine or bromine is preferable.
The halogen-containing compound that is the Lewis acid may be used alone or in combination of two or more.

Examples of the metal halide used to obtain the component (D-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. In particular, magnesium chloride, calcium chloride, barium chloride, zinc chloride, manganese chloride, and copper chloride are preferred, and more particularly, magnesium chloride. Siumu, zinc chloride, manganese chloride, copper chloride are preferable.
As the Lewis base used to obtain the component (D-2), a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, and an alcohol are preferable, for example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphosphate phosphate. Phenyl, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone, propionitrileacetone, valerylacetone, ethylacetylacetone, methyl acetoacetate, ethyl acetoacetate , Phenylacetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versa Kkusan (Shell Chemical Co., Ltd. under the trade name, C ₁₀ synthetic acids composed of a mixture of isomers of monocarboxylic acids), triethylamine, N, N- dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl alcohol , Stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol and the like, and in particular, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.
The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

  Examples of component (D-3) include benzyl chloride.

--Ionic compound (component (E))-
(E) A component consists of a non-coordinating anion and a cation. Examples of the non-coordinating anions include tetravalent boron anions such as tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl). Borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl ] Borate, tridecahydride-7,8-dicarboundeborate and the like.
The said non-coordinating anion may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Here, examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. Examples of the tri (substituted phenyl) carbonyl cation include tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation.
Examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.
Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
The said cation may be used individually by 1 type, and may be used in combination of 2 or more type.

The compounds selected and combined from the above non-coordinating anions and cations include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, and trityltetrakis (penta). Fluorophenyl) borate ([Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]), tris (pentafluorophenyl) boron [B (C ₆ F ₅ ) ₃ ] and the like.

（式中、Ｒは、アルキル基又はアリール基、Ｙは、水素、アルキル基、ハロゲン、シリル基からなる群から選択される少なくとも１つを示す。）に示されるアニオン性三座配位子前駆体が挙げられる（Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ，２３，ｐ ４７７８４７８７ （２００４）参照）。具体的には、ビス（２−ジフェニルホスフィノフェニル）アミン等のＰＮＰ配位子が挙げられる。 --Compound that can be an anionic ligand (component (F))-
As the component (F), for example, the formula (S5):

(Wherein, R represents an alkyl group or an aryl group, Y represents at least one selected from the group consisting of hydrogen, an alkyl group, a halogen, and a silyl group.) (See Organometallics, 23, p 4778787 (2004)). Specific examples include PNP ligands such as bis (2-diphenylphosphinophenyl) amine.

  The ratio of (B) component (organometallic compound) to (A) component ((B) component / (A) component) is 1 to 50 in terms of molar ratio from the viewpoint of improving the catalytic activity in the reaction system. preferable.

  The ratio of aluminum in the component (C) (aluminoxane compound) to the rare earth element in the component (A) is preferably 10 to 1000 in terms of molar ratio from the viewpoint of improving the catalytic activity in the reaction system.

  The ratio of (D) component (halogen compound) to (A) component ((D) component / (A) component) is 0.1 to 50 in terms of molar ratio from the viewpoint of improving the catalytic activity in the reaction system. Is preferred.

  The ratio of (E) component (ionic compound) to (A) component ((E) component / (A) component) is 0.1 to 10 in terms of molar ratio from the viewpoint of improving the catalytic activity in the reaction system. It is preferable.

  Here, in the method for producing polybutadiene as an example of the present invention, from the viewpoint of sufficiently activating the polymerization reaction, the blending amount of the component (A) (rare earth element compound) is 0 with respect to 100 parts by mass of the butadiene-containing composition. The amount is preferably 0.018 parts by mass or more, and more preferably 0.02 parts by mass or more. On the other hand, from the viewpoint of reducing the possibility of inactivating the polymerization reaction, the amount is preferably 0.032 parts by mass or less, and 0.03 parts by mass or less with respect to 100 parts by mass of the butadiene-containing composition. Further preferred.

Here, in the method for producing polybutadiene according to an example of the present invention, from the viewpoint of sufficiently activating the polymerization reaction and increasing the conversion rate when the monomer is converted into the polymer, the compounding amount of the organometallic compound is the butadiene-containing composition 100. The amount is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 2.0 parts by mass or more with respect to parts by mass.
Conversely, from the viewpoint of reducing the risk of inactivating the polymerization reaction and increasing the molecular weight of the resulting polymer, the amount of the organometallic compound is 6.0 parts by mass with respect to 100 parts by mass of the butadiene-containing composition. Or less, more preferably 5.0 parts or less.

-Anionic polymerization-
In the production method of an example of the present invention, 1,3-butadiene can be polymerized by anionic polymerization using a butadiene-containing composition. Specifically, 1,3-butadiene can be polymerized by blending an anionic polymerization initiator into a butadiene-containing composition dissolved or dispersed in a solvent such as hexane. Here, a suitable anionic polymerization initiator in the present invention includes hydrocarbyl lithium. Specific examples of the hydrocarbyl lithium include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tert-octyl lithium, n-decyl lithium, and phenyl lithium. , 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, a reaction product of diisopropenyl benzylene and butyl lithium, and the like.

  The amount of the anionic polymerization initiator added to the butadiene-containing composition is not particularly limited and is appropriately selected depending on the intended purpose, but is 0.003 to 3.0 with respect to 100 parts by mass of 1,3-butadiene. It is preferable that it is a mass part. The blending amount of the anionic polymerization initiator is 0.003 parts by mass or more with respect to 100 parts by mass of 1,3-butadiene, thereby sufficiently suppressing the stop of the polymerization reaction due to the presence of impurities in the system. The conversion rate when converting from monomer to polymer can be increased. Moreover, when the compounding amount of the anionic polymerization initiator is 3.0 parts by mass or less with respect to 100 parts by mass of 1,3-butadiene, the molecular weight of the obtained polymer can be increased, and a polymer having an appropriate molecular weight can be obtained. Can be obtained. From the same viewpoint, the amount of the anionic polymerization initiator is more preferably 0.003 to 1.0 part by mass with respect to 100 parts by mass of 1,3-butadiene.

  Here, in the case of employing anionic polymerization in the production method of an example of the present invention, the content of the oxygen-containing neutral compound in the butadiene-containing composition is 0.001 to 2 with respect to 100 parts by mass of 1,3-butadiene. It is particularly preferable that the proportion of oxygen-containing non-neutral compound in the oxygen-containing compound in the butadiene-containing composition is 8 parts by mass or more. When the content of the oxygen-containing neutral compound and the ratio of the oxygen-containing non-neutral compound are within the above ranges, the molecular weight is relatively large (for example, the number average molecular weight (Mn) in terms of polystyrene is 100,000 or more). Polybutadiene can be obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to the following Example at all, In the range which does not change the summary, it can change suitably.

<Preparation of solid catalyst for butadiene synthesis>
In 100 mL of water, 0.22 g of Cu (OCOCH ₃ ) ₂ .H ₂ O (Cu salt), 1.37 g of Zn (NO ₃ ) ₂ .6H ₂ O (Zn salt), and ZrO (NO ₃ ) ₂ .2H 0.98 g of ₂ O (Zr salt) was dissolved to obtain an aqueous solution. This aqueous solution was impregnated with 11 g of silica (Grade 646, 35-60 mesh, pore 150 angstrom) manufactured by Sigma-Aldrich, dried at 80 ° C. for 8 hours, and calcined at 500 ° C. for 2 hours to obtain Cu, Zn and Zr. A solid catalyst supported on silica was prepared.

<Preparation of butadiene-containing composition>
After charging 10 g of the prepared solid catalyst into a fixed bed flow reactor, N ₂ gas is flowed at a flow rate of 190 mL / min, and biomass-derived ethanol is added to the N ₂ gas flow at a rate of 300 mL / min. The reaction was conducted at a reaction temperature of 500 ° C. under atmospheric pressure. And the gas produced | generated by reaction was bubbled in the hexane cooled at -30 degreeC, and the solution which dissolves the composition containing a butadiene (1, 3- butadiene) as a reaction material in hexane was obtained. . To 1300 g of the obtained solution, 100 g of activated alumina (alumina oxide (active), granular) manufactured by Kanto Chemical Co., Ltd. and 100 g of molecular sieves (Molecular Sieve 4A) manufactured by Kanto Chemical Co., Ltd. were added and allowed to stand at room temperature for 24 hours. I put it. Thereafter, the supernatant was taken out and concentrated by simple distillation at room temperature to obtain a butadiene-containing composition A.
Further, the butadiene-containing composition obtained in the same manner as described above was further treated by column chromatography for 10 minutes to prepare a butadiene-containing composition B. Here, as a column chromatography column filler (solid phase), 500 g of activated alumina (alumina oxide (active), granular) manufactured by Kanto Chemical Co., Ltd., and molecular sieves (Molecular Sieve 4A manufactured by Kanto Chemical Co., Ltd.) ) 500 g was used.
Further, except that the treatment time was changed from 10 minutes to 30 minutes, 1 hour, 2 hours, and 6 hours, the butadiene-containing compositions C, D, E, and F were prepared in the same manner as the preparation of the butadiene-containing composition B. Each was prepared.
And the composition of these butadiene containing compositions AF was analyzed using the gas chromatograph made from Agilent.

<Manufacture of polybutadiene 1>
In a glove box under a nitrogen atmosphere, 448 μmol of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) as a rare earth element compound and trityltetrakis (pentafluorophenyl) borate as an ionic compound in a glass container Was charged in a predetermined amount with 448 μmol and triisobutylaluminum as an organometallic compound, and 10 mL of toluene was added to form a catalyst solution. Next, the catalyst solution was taken out from the glove box, and the catalyst solution was stirred for 15 minutes using an ultrasonic device.
Thereafter, 50 g of a butadiene-containing composition selected from the above-mentioned butadiene-containing compositions A to F (the concentration of butadiene is 20%) and the above-mentioned stirring in a 100 mL pressure-resistant stainless steel reactor sufficiently dried and purged with nitrogen A predetermined amount of the used catalyst solution was blended, and a polymerization reaction (coordination polymerization) was attempted at 50 ° C. for 3 hours. For reference, a polymerization reaction (coordination polymerization) was attempted in the same manner as described above, using 1,3-butadiene that was synthesized from petroleum-derived raw materials and then subjected to extractive distillation.
Table 1 shows the type and composition of the selected butadiene-containing composition, the blending amount of the organometallic compound, and the like.

<Manufacture of polybutadiene 2>
In a 100 mL pressure-resistant glass container sufficiently dried and purged with nitrogen, a butadiene-containing composition selected from the butadiene-containing compositions A to F dissolved in hexane and n-butyllithium as an anionic polymerization initiator are placed. Quantitative, 0.003 mmol of 2-2′-di (tetrahydrofuryl) propane as a randomizer was blended, and a polymerization reaction (anionic polymerization) was attempted at 50 ° C. for 3 hours. For reference, a polymerization reaction (anionic polymerization) was attempted in the same manner as described above using 1,3-butadiene that was synthesized from petroleum-derived raw materials and then subjected to extractive distillation.
Table 1 shows the kind and composition of the selected butadiene-containing composition, the blending amount of the anionic polymerization initiator, and the like.

  The following evaluation was performed with respect to the polybutadiene which could be manufactured by said coordination polymerization or anion polymerization. The results are shown in Table 1.

<Analysis of Number Average Molecular Weight (Mn), Weight Average Molecular Weight (Mw) and Molecular Weight Distribution (Mw / Mn) of Polybutadiene>
Gel permeation chromatography (GPC) (GPC device: manufactured by Tosoh Corporation, HLC-8220GPC; column: manufactured by Tosoh Corporation, TSKgel GMHXL-2; detector: differential refractometer (RI)) as a standard The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of polybutadiene in terms of polystyrene were calculated. The measurement temperature was 40 ° C. and the elution solvent was THF.

  From Table 1, using a butadiene-containing composition containing 1,3-butadiene and 0.001 to 2.0 parts by mass of an oxygen-containing compound with respect to 100 parts by mass of the 1,3-butadiene, It can be seen that polybutadiene can be produced at low cost by polymerizing 3-butadiene.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of polybutadiene which can manufacture polybutadiene at low cost can be provided.

Claims (4)

Using 1,3-butadiene and a butadiene-containing composition containing 0.001 to 2.0 parts by mass of an oxygen-containing compound with respect to 100 parts by mass of 1,3-butadiene, Including a polymerization step to polymerize,
The oxygen-containing compound contains an oxygen-containing neutral compound as a constituent component, and the proportion of the oxygen-containing neutral compound in the oxygen-containing compound is 85% by mass or more,
The oxygen-containing neutral compounds is at least one of ether and ester le,
When the oxygen-containing neutral compound contains an ether, the ether is at least one of ethoxyethylene, diethyl ether, tetrahydrofuran, and 3-methylfuran.   The method for producing polybutadiene according to claim 1, wherein the 1,3-butadiene is 1,3-butadiene obtained by synthesizing ethanol derived from biomass. In the polymerization step, a rare earth element compound and an organometallic compound are blended in the butadiene-containing composition, and the blending amount of the organometallic compound is 0.1 to 100 parts by mass with respect to 100 parts by mass of the butadiene-containing composition. 6.0 parts by mass, and the organometallic compound has the formula (S2):
YR ⁴ _a R ⁵ _b R ⁶ _c (S2)
Wherein Y is a metal element selected from the group consisting of Group 1, Group 2, Group 12, and Group 13; R ⁴ and R ⁵ are hydrocarbons having 1 to 10 carbon atoms A group or a hydrogen atom, which may be the same or different; R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms; R ⁶ is the same as or different from the above R ⁴ or R ⁵ And when Y is a Group 1 metal element, a is 1 and b and c are 0, and Y is a Group 2 metal element and a Group 12 metal element. Wherein a and b are 1 and c is 0, and when Y is a Group 13 metal element, a, b and c are 1). Or the manufacturing method of the polybutadiene of 2.   In the polymerization step, an anionic polymerization initiator is blended with the butadiene-containing composition, and the blending amount of the anionic polymerization initiator is 0.003 to 3.3 with respect to 100 parts by mass of the 1,3-butadiene. The manufacturing method of the polybutadiene of Claim 1 or 2 which is 0 mass part.