JP6359246B2 - Praseodymium compound and method for producing the same - Google Patents
Praseodymium compound and method for producing the same Download PDFInfo
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本発明は、新規なプラセオジム化合物およびその製造方法に関するものである。 The present invention relates to a novel praseodymium compound and a method for producing the same.
特許文献１には、プラセオジムトリイソプロポキシドを用いて、２，６−ジメチルヘプタンジオン（ｄｉｂｍ）と配位子交換することで、Ｐｒ(ＯｉＰｒ)n (ｄｉｂｍ)3 - nを合成している。しかし、報告されている化合物は、ｎが１又は２の化合物のみである。 Patent Document 1, using praseodymium triisopropoxide, 2,6-dimethyl-heptane-dione (dibm) and by ligand exchange, Pr (OiPr) n (dibm ) 3 - are synthesized n . However, the only reported compounds are those where n is 1 or 2.
特許文献２にはトリス（２，２，６，６−テトラメチル−３，５−ヘプタンジオナト）プラセオジムを重合触媒として用い、エチルアルミニウムセスキクロライド及びジブチルマグネシウムを助触媒とするブタジエンの重合例が開示されているが、触媒を多量に使用する必要がある。 Patent Document 2 discloses an example of butadiene polymerization using tris (2,2,6,6-tetramethyl-3,5-heptanedionato) praseodymium as a polymerization catalyst and co-catalyzing ethylaluminum sesquichloride and dibutylmagnesium. However, it is necessary to use a large amount of catalyst.
非特許文献１にはトリス（２，４−ヘキサンジオナト）プラセオジムの合成法が開示されているが、トリス（２，６−ジメチルヘプタン−３，５−ジオナト）プラセオジムについては記載されていない。 Non-Patent Document 1 discloses a method for synthesizing tris (2,4-hexanedionato) praseodymium, but does not describe tris (2,6-dimethylheptane-3,5-dionato) praseodymium.
本発明は、新規なプラセオジム化合物およびその製造方法を提供することを目的とする。 An object of the present invention is to provide a novel praseodymium compound and a method for producing the same.
本発明は、新規なプラセオジム化合物およびその製造方法を提供することを目的とする。 An object of the present invention is to provide a novel praseodymium compound and a method for producing the same.
本発明は、新規なプラセオジム化合物およびその製造方法を提供する。なお、上記プラセオジム化合物は、オレフィン重合触媒や化学蒸着用化合物として用いることができる。 The present invention provides a novel praseodymium compound and a method for producing the same. The praseodymium compound can be used as an olefin polymerization catalyst or a chemical vapor deposition compound.
本発明のガドリニウム化合物は、トリス（２，６−ジメチルヘプタン−３，５−ジオナト）プラセオジムである。 The gadolinium compound of the present invention is tris (2,6-dimethylheptane-3,5-dionato) praseodymium.
上記のトリス（２，６−ジメチルヘプタン−３，５−ジオナト）プラセオジムは、プラセオジム化合物と２，６−ジメチルヘプタン−３，５−ジオンとを溶媒中で反応させることで得られる。 The tris (2,6-dimethylheptane-3,5-dionato) praseodymium is obtained by reacting a praseodymium compound and 2,6-dimethylheptane-3,5-dione in a solvent.
上記のプラセオジム化合物としては、プラセオジムアルコキシドおよびハロゲン化プラセオジムなどが挙げられる。 Examples of the praseodymium compound include praseodymium alkoxide and praseodymium halide.
上記のプラセオジムアルコキシドとしては、例えば、プラセオジムエトキシド、プラセオジムｎ−プロポキシド、プラセオジムイソプロポキシド、プラセオジムブトキシドなどが挙げられる。 Examples of the praseodymium alkoxide include praseodymium ethoxide, praseodymium n-propoxide, praseodymium isopropoxide, praseodymium butoxide and the like.
上記のハロゲン化プラセオジムとしては、例えば、三フッ化プラセオジム、三塩化プラセオジム、三臭化プラセオジム、三ヨウ化プラセオジムなどが挙げられる。 Examples of the above-mentioned praseodymium halide include praseodymium trifluoride, praseodymium trichloride, praseodymium tribromide, praseodymium triiodide, and the like.
上記の溶媒としては、例えば、水、メタノール、エタノール、ｎ−プロパノール、イソプロピルアルコール、ｎ−ブタノール、イソブチルアルコール、ｔ−ブチルアルコール、アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、ジメチルエーテル、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、テトラヒドロピラン、ジオキサン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、シクロペンタン、シクロヘキサン、ベンゼン、トルエン、キシレン、クメン、シメンなどが挙げられる。 Examples of the solvent include water, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, t-butyl alcohol, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, dioxane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, benzene, toluene, xylene, cumene, For example, cymene.
これらの溶媒は、一種用いてもよく、二種以上を組み合わせて用いてもよい。 These solvents may be used alone or in combination of two or more.
反応温度は−３０〜１５０℃の範囲が好ましく、０〜１００℃の範囲が特に好ましい。 The reaction temperature is preferably in the range of -30 to 150 ° C, particularly preferably in the range of 0 to 100 ° C.
反応時間は１分〜１２時間の範囲が好ましく、５分〜５時間が特に好ましい。 The reaction time is preferably in the range of 1 minute to 12 hours, particularly preferably 5 minutes to 5 hours.
（合成例）
以下に本発明に基づく合成例について具体的に記載する。
プラセオジム含量の測定は、ＩＣＰ発光分析法にて行った。測定には、バリアンジャパン社製ＩＣＰ発光分光分析装置 Ｖｉｓｔａ ＭＰＸ型を用いた。
(Synthesis example)
The synthesis example based on this invention is described concretely below.
The praseodymium content was measured by ICP emission spectrometry. For measurement, an ICP emission spectrometer Vista MPX type manufactured by Varian Japan was used.
（合成例１）
３００ｍｌのナシ形二つ口フラスコに高純度化学研究所製トリイソプロポキシプラセオジムを０．６４ｇ（２．０１ｍｍｏｌ）、２，６−ジメチルヘプタンジオンを０．９５ｇ（６．０５ｍｍｏｌ）および脱水トルエン１０ｍｌを加え、マグネティックスターラーにて攪拌した。トルエン還流下で２０時間反応を行い、トルエンを留去し、減圧乾固した。得られた固体を１１０℃にて２時間減圧乾固し、トリス（２，６−ジメチルヘプタンジオナト）プラセオジムを得た。収量０．３８ｇ（０．６３ｍｍｏｌ）、収率３１％。
生成物の核磁気共鳴スペクトル（ＮＭＲ）の結果、１Ｈ−ＮＭＲ δ（ｐｐｍ）：−０．８（３６Ｈ）、０．３、０．７（計６Ｈ）、１３．７（３Ｈ） ただし、測定溶媒はＣ６Ｄ６を用いた。
(Synthesis Example 1)
In a 300 ml pear-shaped two-necked flask, 0.64 g (2.01 mmol) of triisopropoxy praseodymium manufactured by High Purity Chemical Laboratory, 0.95 g (6.05 mmol) of 2,6-dimethylheptanedione and 10 ml of dehydrated toluene were added. In addition, the mixture was stirred with a magnetic stirrer. The reaction was carried out for 20 hours under toluene reflux, and the toluene was distilled off and dried under reduced pressure. The obtained solid was dried under reduced pressure at 110 ° C. for 2 hours to obtain tris (2,6-dimethylheptanedionato) praseodymium. Yield 0.38 g (0.63 mmol), yield 31%.
As a result of nuclear magnetic resonance spectrum (NMR) of the product, 1 H-NMR δ (ppm): -0.8 (36H), 0.3, 0.7 (total 6H), 13.7 (3H) However, C 6 D 6 was used as a measurement solvent.
（ＩＣＰ発光分析)
合成例１において合成されたトリス（２，６−ジメチルヘプタン−３，５−ジオナト）プラセオジムについて、ＩＣＰ発光分析法にてプラセオジムの含量を算出した。分析測定を２回行い、測定値が理論値とほぼ同等の数値を示したことから、一個のプラセオジム原子あたり、三個の２，６−ジメチルヘプタン−３，５−ジオン配位子が結合していることが示唆された。その分析結果を表１に示した。
(ICP emission analysis)
For the tris (2,6-dimethylheptane-3,5-dionato) praseodymium synthesized in Synthesis Example 1, the praseodymium content was calculated by ICP emission spectrometry. Analytical measurement was performed twice, and the measured value showed a value almost equal to the theoretical value. Therefore, three 2,6-dimethylheptane-3,5-dione ligands were bonded per one praseodymium atom. It was suggested that The analysis results are shown in Table 1.
（重合触媒用途)
合成例１において合成されたトリス（２，６−ジメチルヘプタン−３，５−ジオナト）プラセオジムは、例えば共役ジエン重合用触媒として用いることができる。
(Application for polymerization catalyst)
Tris (2,6-dimethylheptane-3,5-dionato) praseodymium synthesized in Synthesis Example 1 can be used as a catalyst for conjugated diene polymerization, for example.
（共役ジエン重合例)
内容量１．５Ｌのオートクレーブの内部を窒素置換し、トルエン３１５ｍｌ及びブタジエン１８０ｍｌからなる溶液を仕込んだ。次いで、トリエチルアルミニウム（ＴＥＡ）のトルエン溶液（２ｍｏｌ／Ｌ）１．２５ｍｌを添加した。次に、トリス（２，６−ジメチル−３，５−ヘプタンジオナト）プラセオジムのトルエン溶液（０．０２ｍｏｌ／Ｌ）１．５ｍｌを添加した後、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートのトルエン溶液（０．４３ｍｏｌ／Ｌ）０．１４ｍｌを添加した。４０℃で２５分間重合した後、老化防止剤を含むエタノール溶液３ｍｌを添加し、重合を停止した。オートクレーブの内部を放圧した後、重合液にエタノールを投入し、ポリブタジエンを回収後、８０℃で３時間真空乾燥した。得られたポリブタジエンは、収量９．５０ｇ、シス体比率９８．２％であった。
(Examples of conjugated diene polymerization)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 315 ml of toluene and 180 ml of butadiene was charged. Next, 1.25 ml of a toluene solution (2 mol / L) of triethylaluminum (TEA) was added. Next, 1.5 ml of a toluene solution (0.02 mol / L) of tris (2,6-dimethyl-3,5-heptanedionato) praseodymium was added, and then a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.14 ml (0.43 mol / L) was added. After polymerization at 40 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution, and polybutadiene was recovered, followed by vacuum drying at 80 ° C. for 3 hours. The obtained polybutadiene had a yield of 9.50 g and a cis-isomer ratio of 98.2%.
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