JP6726329B2 - Method for producing polybutadiene - Google Patents

Description

The present invention relates to a method for producing polybutadiene.

In recent years, environmental problems have been emphasized and regulations on carbon dioxide emissions have been tightened, and it is required to suppress the amount of petroleum raw materials used. In addition, since the petroleum raw materials are finite and the supply amount is decreasing year by year, the price of the petroleum raw materials is expected to soar in the future, and the use of raw materials made of petroleum resources is limited.
Therefore, as part of the construction of a recycling-based society, the use of biomass, which replaces fossil fuels, has been drawing attention as a way to break away from fossil fuels. In the field of materials such as rubber materials, production of various materials using raw materials derived from biomass is also drawing 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, ethanol, ethylene and tiglic acid derived from biomass.

JP, 2014-024915, A

However, 1,3-butadiene synthesized from a biomass-derived raw material is usually accompanied by a large amount of impurities. Therefore, even if an attempt is made to synthesize polybutadiene from this 1,3-butadiene, there is a fear that the polymerization does not proceed sufficiently and the molecular weight of the obtained polybutadiene does not become sufficiently high. As a countermeasure to this problem, for example, a method of removing the above impurities as much as possible by high-level purification such as distillation or extractive distillation prior to the polymerization, but this method requires additional equipment, which results in cost reduction. It is disadvantageous from a viewpoint.
It should be noted that 1,3-butadiene synthesized from a non-biomass-derived material, for example, a petroleum-derived material, may be accompanied by some impurities. Therefore, even when polybutadiene is synthesized using 1,3-butadiene synthesized from such a petroleum-derived raw material, it is the current situation that 1,3-butadiene is usually purified in advance by extractive distillation or the like.

Therefore, an object of the present invention is to provide a method for producing polybutadiene, which can solve the above-mentioned conventional problems and can produce polybutadiene at low cost.

As a result of earnest studies for achieving the above-mentioned object, the present inventors have found that polybutadiene can be used even when 1,3-butadiene used as a material for polymerization of polybutadiene is accompanied by a predetermined amount of an oxygen-containing compound. They have found that they can be manufactured, and have completed the present invention.

That is, the method for producing polybutadiene of the present invention is a butadiene-containing composition containing 1,3-butadiene and 0.001 to 3.0 parts by mass of an oxygen-containing compound with respect to 100 parts by mass of 1,3-butadiene. It is characterized by including a polymerization step of polymerizing 1,3-butadiene by using a product. According to this production method, polybutadiene can be produced 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 method for producing polybutadiene of the present invention, from the viewpoint of sufficiently suppressing carbon dioxide emission and producing polybutadiene by obtaining a butadiene-containing composition without depending on petroleum resources, the 1,3-butadiene is used. Is preferably 1,3-butadiene obtained by synthesizing ethanol derived from biomass.

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 preferably 85 mass% or more. As a result, polybutadiene can be obtained more reliably while avoiding an increase in cost associated with a sophisticated refining operation.

In the method for producing polybutadiene of the present invention, in the polymerization step, the butadiene-containing composition is blended with a rare earth element compound and an organometallic compound, wherein the blending amount of the organometallic compound is 100 parts of the butadiene-containing composition 100. It is preferably 0.1 to 6.0 parts by mass with respect to parts by mass. This makes it possible to increase the conversion rate at the time of converting the monomer into the polymer and increase the molecular weight of the obtained polymer.

Further, in the method for producing polybutadiene of the present invention, in the polymerization step, an anionic polymerization initiator is blended in the butadiene-containing composition, and the amount of the anionic polymerization initiator blended is 1,3-butadiene 100. It is preferably 0.003 to 3.0 parts by mass with respect to parts by mass. This makes it possible to increase the conversion rate at the time of converting the monomer into the polymer and increase the molecular weight of the obtained polymer.

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

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

<Butadiene-containing composition>
The butadiene-containing composition used in the production method of one example of the present invention (hereinafter, may be referred to as “the butadiene-containing composition of one example of the present invention”) includes 1,3-butadiene, an oxygen-containing compound, and And other ingredients.

-1,3-Butadiene-
The 1,3-butadiene contained in the butadiene-containing composition of the example of the present invention is not particularly limited and is appropriately selected depending on the purpose, for example, via a step of heating ethanol to a high temperature under a metal catalyst. The 1,3-butadiene obtained may be mentioned. Specifically, the above step can be performed by flowing N ₂ gas into a reactor filled with a metal catalyst, adding ethanol to this gas flow, and heating this in the reactor.
In addition, in addition to 1,3-butadiene, usually, by-products such as alkenes such as 1-butene and 2-butene, alcohols, aldehydes, carboxylic acids, ethers, esters, ketones and the like can be produced in the above process.

Here, the ethanol is preferably biomass-derived ethanol from the viewpoint of sufficiently suppressing the emission of carbon dioxide and the viewpoint of not depending on petroleum resources. In other words, 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.
Since 1.3-butadiene synthesized from the biomass-derived ethanol usually contains a certain amount of oxygen-containing compounds as impurities, it is easy to obtain a butadiene-containing composition according to an example of the present invention to produce polybutadiene. From this viewpoint as well, it is preferable to use 1,3-butadiene obtained by synthesizing ethanol derived from biomass.

-Oxygen-containing compound-
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, more or less oxygen-containing compounds such as alcohols, aldehydes, ethers, esters and ketones can also be produced. Therefore, according to the present invention, it is possible to produce polybutadiene at a low cost by preparing the butadiene-containing composition of the present invention without the need to remove them by a high degree of 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, “oxygen-containing non-neutral compound”). May be referred to as)).

Examples of the oxygen-containing neutral compound include ethers, esters, ketones and the like.
Specific examples of ethers 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), methyl isobutyl ketone, and the like. These oxygen-containing neutral compounds may be contained alone or in combination of two or more.

Examples of the oxygen-containing non-neutral compound include alcohols, aldehydes, carboxylic acids and the like.
Specific examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and crotyl alcohol. 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 content of the oxygen-containing compound (the total content of the oxygen-containing neutral compound and the 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. When the content of the oxygen-containing compound is less than 0.001 part by mass relative to 100 parts by mass of 1,3-butadiene, a high degree of purification is required after the synthesis of 1,3-butadiene, which may increase the manufacturing cost. There is. 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, polymerization of 1,3-butadiene (production of polybutadiene) itself may be impossible.
From the same viewpoint, the content of the oxygen-containing compound in the butadiene-containing composition of the example of the present invention is preferably 0.01 to 2.0 parts by mass, and 0.03 parts by mass with respect to 100 parts by mass of 1,3-butadiene. ˜2.0 parts by mass is more preferred.

Further, the proportion of the oxygen-containing neutral compound in the oxygen-containing compound in the butadiene-containing composition of one example of the present invention is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 85% by mass or more, It is more preferably at least mass%. When the ratio is 85% by mass or more, polybutadiene can be obtained more reliably while avoiding an increase in cost associated with a sophisticated refining operation.
In addition, the content of 1,3-butadiene, the content of the oxygen-containing neutral compound, and the content of the oxygen-containing non-neutral compound in the butadiene-containing composition can be measured using gas chromatography.

-Other ingredients-
The butadiene-containing composition of one example of the present invention can contain other components other than the above-mentioned 1,3-butadiene and the oxygen-containing compound within a range that does not impair the object of the present invention.
Other components include methane, ethane, ethylene, propylene, 1-butene, 2-butene, 1,2-butadiene, methylbutene, 1-pentene and the like. These other components may be contained alone or in combination of two or more.
The butadiene-containing composition of the present invention may be dissolved in a solvent such as hexane, cyclohexane or toluene 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, in addition to 1,3-butadiene, oxygen-containing compounds such as alcohols, aldehydes, carboxylic acids, ethers, esters and ketones are also contained as by-products in the above reaction products. Therefore, for example, the reaction product is purified by a simple method so that the content of these oxygen-containing 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, the butadiene-containing composition can be prepared at low cost.

Examples of the purification method include a method of partially removing the oxygen-containing compound in the reaction product by bringing the reaction product dissolved in a solvent such as hexane into contact with an adsorbent or the like. Specifically, a method of adding an adsorbent to a reaction product dissolved in a solvent and allowing it to stand for a predetermined time, a method of treating the reaction product dissolved in a solvent for a predetermined time by column chromatography with a filler, and these And the like. Examples of the adsorbent include activated alumina, molecular sieves, silica gel and the like. Examples of the filler include activated alumina, molecular sieves, silica gel and the like. 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 the filler, or changing the contact time or mass ratio between the reactant and the adsorbent or the filler.

Here, when using a method of adding an adsorbent to the reaction product dissolved in the above-mentioned solvent and standing still, the standing time is not particularly limited and is appropriately selected according to the purpose, but desired From the viewpoint of obtaining a butadiene-containing composition, 12 hours or more is preferable, 24 hours or more is more preferable, and 120 hours or less is preferable and 100 hours or less is more preferable from the viewpoint of suppressing deterioration of productivity and low cost. ..

When using the above-mentioned method of treating by column chromatography, the treatment time is not particularly limited and may be appropriately selected depending on the purpose, but from the viewpoint of obtaining the desired butadiene-containing composition, 1 hour or more. Is preferable, and from the viewpoint of suppressing deterioration of productivity and low cost, 3 hours or less is preferable, and 2 hours or less is more preferable.
In addition, when the treatment time by the above-mentioned column chromatography is 6 hours or more, the productivity of the butadiene-containing composition, and thus the productivity of polybutadiene decreases, and the production cost per unit amount of polybutadiene increases, which is preferable. Absent.

The preparation of the butadiene-containing composition preferably does not include the step of purifying the reaction product by distillation or extractive distillation. Advanced purification, such as distillation or extractive distillation, may require additional equipment and increase manufacturing costs.

<Polymerization of 1,3-Butadiene (Production of Polybutadiene)>
The production method of one example of the present invention needs to include a polymerization step of polymerizing 1,3-butadiene using the butadiene-containing composition. In the polymerization step, 1,3-butadiene is polymerized in the butadiene-containing composition. The method for polymerizing 1,3-butadiene is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include coordination polymerization and anionic polymerization. In addition, in any of the polymerization methods, in the polymerization step, the butadiene-containing composition can be blended with any component, and thereby the polymerization can be initiated.

-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 adding a component that catalyzes coordination polymerization to a butadiene-containing composition dissolved in a solvent such as hexane. Here, as the component that catalyzes the coordination polymerization suitable in the present invention, a rare earth element compound (hereinafter, also referred to as “(A) component”) and an organometallic compound (hereinafter, also referred to as “(B) component”). ), an aluminoxane compound (hereinafter, also referred to as “(C) component”), a halogen compound (hereinafter, also referred to as “(D) component”), an ionic compound (hereinafter, also referred to as “(E) component”). It is also possible to add a compound capable of becoming an anionic ligand (hereinafter referred to as “(F) component”).
In addition, at the time of compounding with the butadiene-containing composition, the catalyst composition is prepared by previously mixing the above-mentioned components (A) and (B), and optionally selected from the components (C) to (F). This catalyst composition may be prepared and added to the butadiene-containing composition, or the above components may be added to the butadiene-containing composition alone.

---Rare earth element compound ((A) component)---
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 compounds containing a lanthanoid element composed of elements having atomic numbers 57 to 71. The lanthanoid element is specifically lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
Examples of the Lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins and the like.
The component (A) may be used alone or in combination of two or more.

Here, the rare earth element-containing compound or the reaction product of the rare earth element-containing compound and the Lewis base preferably has no 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 handling becomes easy.

---Organometallic compound (component (B))---
The component (B) has the formula (S2)
YR ⁴ _a R ⁵ _b R ⁶ _c ... (S2)
(In the formula, 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. 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 R ⁴ or R ⁵ above. A is 1 and b and c are 0 when Y is a Group 1 metal element, 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 metal element of Group 13, a, b and c are 1). You can

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. And R ⁹ may be the same as or different from R ⁷ or R ⁸ above).
Examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, 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, isobutylaluminium dihydride and the like can be mentioned, and particularly triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutyl hydride. Aluminum is preferred.
The organoaluminum compounds may be used alone or in combination of two or more.

---Aluminoxane compound ((C) component)---
The component (C) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. By using the component (C), the catalytic activity in the polymerization reaction system can be further improved. Therefore, therefore, the reaction time can be further shortened and the reaction temperature can be further raised.
Here, examples of the organoaluminum compound include those described above as the component (B), a mixture thereof, and the like. Particularly, trimethylaluminum and a mixture of trimethylaluminum and triisobutylaluminum are preferable.
Condensing agents include those commonly used in the art.

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 May be the same or different; and n is 5 or more).

The molecular structure of the aluminoxane may be linear or cyclic. Further, 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, an isobutyl group, and the like, and a methyl group is particularly preferable. The above hydrocarbon groups may be used alone or in combination of two or more. 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 Co., Ltd.
Examples of the component (C) include MMAO, for example, product name: MMAO-3A manufactured by Tosoh Finechem Co., Ltd.
Furthermore, as the component (C), PMAO, for example, product name: TMAO-211 manufactured by Tosoh Finechem Co., Ltd. can also be mentioned. Among these, TMAO and MMAO are preferable from the viewpoint of enhancing the effect of improving the catalytic activity, and TMAO is further preferable from the viewpoint of further enhancing the effect of improving the catalytic activity.

---Halogen compound ((D) component)---
The 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, also referred to as “(D-2) component”). And a compound containing an active halogen (hereinafter, also referred to as “component (D-3)”).

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

As the component (D-1), for example, a halogen-containing compound containing an element of Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14 or Group 15 and the like. In particular, an aluminum halide or an organic metal halide is preferable.
Examples of the halogen-containing compound which is a Lewis acid include titanium tetrachloride, tungsten hexachloride, tri(pentafluorophenyl)borate, methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide. , Butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum chloride, methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, aluminum Examples include tribromide, tri(pentafluorophenyl)aluminum, dibutyltin dichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, antimony trichloride, antimony pentachloride, and the like. In particular, ethyl aluminum dichloride, ethyl aluminum dibromide, Diethyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride and ethyl aluminum sesquibromide are preferable.
The halogen is preferably chlorine or bromine.
The above-mentioned halogen-containing compounds that are Lewis acids 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, and iodine. Calcium iodide, 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 preferable, and magnesium chloride, zinc chloride, manganese chloride and copper chloride are particularly preferable.
The Lewis base used for obtaining the component (D-2) is preferably a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound or an alcohol, and examples thereof include tributyl phosphate, tri-2-ethylhexyl phosphate and triphosphate. Phenyl, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone, propionitrileacetone, valerylacetone, ethylacetylacetone, methyl acetoacetate, ethyl acetoacetate , Phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid (trade name of Shell Chemical Co., Ltd. , A synthetic acid composed of a mixture of isomers of C ₁₀ monocarboxylic acid), triethylamine, N,N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1- Decanol, lauryl alcohol, etc. are mentioned, and especially tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, lauryl alcohol are preferable.
The number of moles of the Lewis base is 0.01 to 30 moles, preferably 0.5 to 10 moles, per mole of the metal halide. The use of the reaction product with the Lewis base can reduce the amount of metal remaining in the polymer.

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

---Ionic compound ((E) component)---
The component (E) is composed of a non-coordinating anion and a cation. As the non-coordinating anion, a tetravalent boron anion, for example, tetraphenyl borate, 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, trideca hydride-7,8-dicarbaundecaborate and the like can be mentioned.
The non-coordinating anion may be used alone or in combination of two or more.
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 cations include trisubstituted carbonium cations and tri-substituted carbonium cations such as tri(substituted phenyl)carbonium cations. Examples of tri(substituted phenyl)carbonyl cations 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- Examples include N,N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.
Examples of phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.
The above cations may be used alone or in combination of two or more.

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

（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, formula (S5):

(In the formula, R represents an alkyl group or an aryl group, and Y represents at least one selected from the group consisting of hydrogen, an alkyl group, a halogen, and a silyl group.) Anionic tridentate ligand precursor The body (see Organometallics, 23, p 47784787 (2004)). Specific examples include PNP ligands such as bis(2-diphenylphosphinophenyl)amine.

From the viewpoint of improving the catalytic activity in the reaction system, the ratio of the component (B) (organic metal compound) to the component (A) (component (B)/component (A)) is 1 to 50 in terms of molar ratio. 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 the component (D) (halogen compound) to the component (A) (component (D)/component (A)) 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 the component (E) (ionic compound) to the component (A) (component (E)/component (A)) 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 of an example of the present invention, from the viewpoint of sufficiently activating the polymerization reaction, the amount of the component (A) (rare earth element compound) blended is 0 with respect to 100 parts by mass of the butadiene-containing composition. It is preferably 0.018 parts by mass or more, and more preferably 0.02 parts by mass or more. On the contrary, from the viewpoint of reducing the risk of inactivating the polymerization reaction, it is preferably 0.032 parts by mass or less, and preferably 0.03 parts by mass or less with respect to 100 parts by mass of the butadiene-containing composition. More preferable.

Here, in the method for producing polybutadiene of an example of the present invention, from the viewpoint of sufficiently activating the polymerization reaction and increasing the conversion rate at the time of converting from a monomer to a polymer, the amount of the organometallic compound added is butadiene-containing composition 100. It is preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, and further preferably 2.0 parts by mass or more with respect to parts by mass.
On the contrary, from the viewpoint of reducing the risk of inactivating the polymerization reaction and increasing the molecular weight of the obtained polymer, the amount of the organometallic compound is 6.0 parts by mass relative to 100 parts by mass of the butadiene-containing composition. It is preferably not more than 5.0 parts, more preferably not more than 5.0 parts.

-Anionic polymerization-
In the production method of one example of the present invention, 1,3-butadiene can be polymerized by anionic polymerization using the butadiene-containing composition. Specifically, 1,3-butadiene can be polymerized by adding an anionic polymerization initiator to a butadiene-containing composition dissolved or dispersed in a solvent such as hexane. Here, as the anionic polymerization initiator suitable in the present invention, hydrocarbyllithium can be mentioned. Specific examples of 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-naphthyllithium, 2-butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, cyclopentyllithium, a reaction product of diisopropenylbenzene and butyllithium, and the like.

The amount of the anionic polymerization initiator to be added to the butadiene-containing composition is not particularly limited and may be 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 preferably part by mass. When the 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, it is possible to sufficiently suppress the termination of the polymerization reaction due to the presence of impurities in the system. It is possible to increase the conversion rate when converting from a monomer to a polymer. 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. Obtainable. From the same viewpoint, the compounding 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, when anionic polymerization is adopted in the production method of one example of the present invention, the content of the oxygen-containing neutral compound in the butadiene-containing composition is 0.001-2 with respect to 100 parts by mass of 1,3-butadiene. It is particularly preferable that the content is 0.0 part by mass and the proportion of the oxygen-containing non-neutral compound in the oxygen-containing compound in the butadiene-containing composition is 8% 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 polystyrene equivalent number average molecular weight (Mn) is 100,000 or more). Polybutadiene can be obtained.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples and can be appropriately modified without departing from the scope of the invention.

<Preparation of solid catalyst for butadiene synthesis>
Of water _{100mL, Cu (OCOCH 3) 2} · H 2 O (Cu _{salt) 0.22g, Zn (NO 3)} 2 · 6H 2 O (Zn salts) 1.37 g, 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 Å) manufactured by Sigma-Aldrich Co., followed by drying at 80° C. for 8 hours and firing 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 filling 10 g of the prepared solid catalyst in a fixed bed flow type reactor, N ₂ gas was caused to flow at a flow rate of 190 mL/min, and ethanol derived from biomass was added at a rate of 300 mL/min to this N ₂ gas flow. The reaction temperature was 500° C. and atmospheric pressure was applied. Then, the gas generated by the reaction was bubbled into hexane cooled to −30° C. to obtain a solution obtained by dissolving the composition containing butadiene (1,3-butadiene) as a reactant in hexane. .. To 1300 g of the obtained solution, 100 g of activated alumina (alumina oxide (active), granular) manufactured by Kanto Chemical Co., Inc. and 100 g of molecular sieves (Molecular Sieves 4A) manufactured by Kanto Chemical Co., Ltd. were added, and the mixture was allowed to stand at room temperature for 24 hours. I put it. Then, 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 above was further treated by column chromatography for 10 minutes to prepare a butadiene-containing composition B. Here, as a packing material (solid phase) of a column for column chromatography, 500 g of activated alumina (alumina oxide (active), granular) manufactured by Kanto Chemical Co., Inc. and molecular sieves (Molecular Sieves 4A manufactured by Kanto Chemical Co., Ltd.) are used. ) 500 g was used.
Further, the butadiene-containing compositions C, D, E, and F were prepared in the same manner as in the preparation of the butadiene-containing composition B, except that the treatment time was changed from 10 minutes to 30 minutes, 1 hour, 2 hours, and 6 hours. Each was prepared.
Then, the compositions of these butadiene-containing compositions A to F were analyzed using a gas chromatograph manufactured by Agilent.

<Production 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 trityl tetrakis(pentafluorophenyl)borate as an ionic compound are placed in a glass container. Was charged in a predetermined amount, and 10 mL of toluene was added to prepare a catalyst solution. Then, the catalyst solution was taken out from the glove box, and the catalyst solution was stirred for 15 minutes using an ultrasonic device.
Then, 50 g of the 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 are placed in a 100 mL pressure-resistant stainless steel reactor that has been sufficiently dried and purged with nitrogen. A predetermined amount of the completed catalyst solution was mixed, and a polymerization reaction (coordination polymerization) was tried at 50° C. for 3 hours. Further, for reference, a polymerization reaction (coordination polymerization) was attempted in the same manner as above using 1,3-butadiene which was synthesized from a petroleum-derived raw material and then subjected to extractive distillation.
Table 1 shows the type and composition of the selected butadiene-containing composition and the blending amount of the organometallic compound.

<Production of polybutadiene 2>
A butadiene-containing composition selected from the above-mentioned butadiene-containing compositions A to F dissolved in hexane and n-butyllithium as an anionic polymerization initiator were placed in a 100 mL pressure-resistant glass container that had been sufficiently dried and purged with nitrogen. Quantification, 0.003 mmol of 2-2'-di(tetrahydrofuryl)propane as a randomizer was blended, and a polymerization reaction (anionic polymerization) was tried at 50°C for 3 hours. Also, for reference, a polymerization reaction (anionic polymerization) was attempted in the same manner as above using 1,3-butadiene that was synthesized from a petroleum-derived raw material and then subjected to extractive distillation.
Table 1 shows the type and composition of the selected butadiene-containing composition, the compounding amount of the anionic polymerization initiator, and the like.

The following evaluation was performed on the polybutadiene that could be produced by the above coordination polymerization or anionic 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>
By gel permeation chromatography (GPC) (GPC device: Tosoh Corp., HLC-8220GPC; column: Tosoh Corp., TSKgel GMHXL-2 bottles; detector: differential refractometer (RI)), based on monodisperse polystyrene As the number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of polybutadiene in terms of polystyrene were calculated. The measurement temperature was 40° C. and the eluting solvent was THF.

From Table 1, 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 1,3-butadiene was used. It is understood 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 (2)

Using a butadiene-containing composition containing 1,3-butadiene and 0.001-2.0 parts by mass of an oxygen-containing compound with respect to 100 parts by mass of 1,3-butadiene, 1,3-butadiene was obtained. Including a polymerization step to polymerize,
The 1,3-butadiene is 1,3-butadiene obtained by synthesizing biomass-derived ethanol,
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 0.1 to 100 parts by mass of the butadiene-containing composition. 6.0 parts by mass,
The rare earth element compound has a metal-nitrogen bond,
The organometallic compound has the formula (S2):
YR ⁴ _a R ⁵ _b R ⁶ _c ... (S2)
(In the formula, 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. 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 R ⁴ or R ⁵ above. A is 1 and b and c are 0 when Y is a Group 1 metal element, 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 metal element of Group 13, a, b and c are 1). A method for producing polybutadiene. The oxygen-containing compound comprises an oxygen-containing neutral compounds as a constituent component, the ratio of the oxygen-containing neutral compounds oxygenates in is not less than 85 mass%, the production method of the polybutadiene according to claim 1.