JP2007186533A - Manufacturing method of powder-containing ethylene oxide copolymer resin and packaging method - Google Patents

Manufacturing method of powder-containing ethylene oxide copolymer resin and packaging method Download PDF

Info

Publication number
JP2007186533A
JP2007186533A JP2004257709A JP2004257709A JP2007186533A JP 2007186533 A JP2007186533 A JP 2007186533A JP 2004257709 A JP2004257709 A JP 2004257709A JP 2004257709 A JP2004257709 A JP 2004257709A JP 2007186533 A JP2007186533 A JP 2007186533A
Authority
JP
Japan
Prior art keywords
powder
ethylene oxide
copolymer resin
oxide copolymer
containing ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2004257709A
Other languages
Japanese (ja)
Inventor
Alain Vallee
アライン ヴァリー
Paul-Andre Lavoie
ポール−アンドレ ラヴォワ
Michiyuki Kono
通之 河野
Manabu Kikuta
学 菊田
Tetsuya Touzaki
哲也 東崎
Hiroyuki Hiruko
博幸 蛭子
Masaki Tezuka
正樹 手塚
Takao Yokohashi
貴生 横橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Avestor LP
Original Assignee
Avestor LP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Avestor LP filed Critical Avestor LP
Priority to JP2004257709A priority Critical patent/JP2007186533A/en
Priority to PCT/JP2005/015750 priority patent/WO2006025374A1/en
Publication of JP2007186533A publication Critical patent/JP2007186533A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Packages (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a powder-containing ethylene oxide copolymer resin, comprising an ethylene oxide copolymer and a powder mixed with and dispersed in the copolymer, that suffers from no decrease in molecular weight of the resin by mechanical shear or the like, and a packaging method of the resin obtained by the same. <P>SOLUTION: The manufacturing method comprises a step where a powder containing an electrochemically active substance is mixed with and dispersed in an ethylene oxide copolymer resin solution comprising an ethylene oxide copolymer resin, comprised of 80-95 wt.% of ethylene oxide and 5-20 wt.% of an oxirane compound copolymerizable with ethylene oxide, and a solvent thereby to give a powder-containing ethylene oxide copolymer resin solution, a step where the solvent is removed from the powder-containing ethylene oxide copolymer resin solution thereby to give a flowable powder-containing ethylene oxide copolymer resin, a step where the flowable powder-containing ethylene oxide copolymer resin is pelletized or granulated, and a step where the pelletized or granulated powder-containing ethylene oxide copolymer resin is dried. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、粉体含有エチレンオキシド系共重合体樹脂の製造方法及び包装方法に関し、さらに詳しくは、押し出し成形加工の原料として使用するのに適した、粉体をエチレンオキシド系共重合体樹脂に分散させた粉体含有エチレンオキシド系共重合体樹脂の製造方法及び包装方法に関する。   The present invention relates to a production method and a packaging method of a powder-containing ethylene oxide copolymer resin, and more specifically, a powder suitable for use as a raw material for extrusion molding is dispersed in an ethylene oxide copolymer resin. The present invention relates to a method for producing and packaging a powder-containing ethylene oxide copolymer resin.

成形体、フィルム等の製造に使用される熱可塑性樹脂の加工においては、押出機を用いた押出し成形がしばしば行われている。この押出し成形では、あらかじめペレット化した樹脂を用い、これを溶融し、可塑剤等の添加剤等を混合して押出機に供給するのが一般的である。   In the processing of thermoplastic resins used for the production of molded articles, films and the like, extrusion molding using an extruder is often performed. In this extrusion molding, a resin pelletized in advance is generally melted, and an additive such as a plasticizer is mixed and supplied to an extruder.

しかしながら、エチレンオキシド系共重合体樹脂は、熱あるいは機械的なシェアーによって部分的に分解して分子量低下を生じる。そのため、特に樹脂に酸化バナジウム系化合物のような酸化性を有する粉体を混練機にて溶融混合して分散させた後、押出し成形すると、樹脂の分子量低下をもたらすという問題があった。   However, the ethylene oxide copolymer resin is partially decomposed by heat or mechanical shear to cause a decrease in molecular weight. For this reason, in particular, there is a problem that when a powder having an oxidizing property such as a vanadium oxide-based compound is melt-mixed and dispersed in a kneader and then extruded, the molecular weight of the resin is reduced.

樹脂に粉体を分散させる方法としては、例えば特開２００２−２８４８８７号公報に、含水率が０．５重量％以上のエチレン−ビニルアルコール共重合体樹脂（ＥＶＯＨ）を押出機に導入し、この押出機内で含水かつ溶融状態のＥＶＯＨに対し、無機微粒子の水分散溶液を配合して溶融混練する方法が開示されている。   As a method for dispersing the powder in the resin, for example, JP-A No. 2002-284887 introduces an ethylene-vinyl alcohol copolymer resin (EVOH) having a water content of 0.5% by weight or more into an extruder. A method is disclosed in which an aqueous dispersion of inorganic fine particles is blended and melt-kneaded with water-containing and molten EVOH in an extruder.

しかし、この方法では押出機内で樹脂に無機微粒子を均一に分散させるため、押出機に導入する樹脂の含水率や混練する無機微粒子の添加量を制御しなければならず、設備や運転方法が複雑となる。また、押出機から出てくる樹脂の含水率が５〜４０重量％と高いため、本発明で用いるエチレンオキシド系共重合体樹脂にこの方法を適用した場合、樹脂に粘着性が残り、押出しの後工程であるペレット化（粒状化）が困難となる。また、エチレンオキシド系共重合体樹脂の融点が比較的低いために乾燥工程であまり熱をかけることができず、乾燥工程に長時間を要することになり、経済的ではない。
特開２００２−２８４８８７号公報 However, in this method, the inorganic fine particles are uniformly dispersed in the resin in the extruder, so the water content of the resin introduced into the extruder and the amount of inorganic fine particles to be kneaded must be controlled, and the equipment and operation method are complicated. It becomes. Also, since the water content of the resin coming out of the extruder is as high as 5 to 40% by weight, when this method is applied to the ethylene oxide copolymer resin used in the present invention, the resin remains sticky, and after the extrusion Pelletization (granulation) as a process becomes difficult. In addition, since the melting point of the ethylene oxide copolymer resin is relatively low, it is difficult to apply heat in the drying process, which requires a long time for the drying process, which is not economical.
JP 2002-284887 A

本発明は、上記の問題点に鑑みてなされたものであり、押出し成形等に使用し得る粉体含有エチレンオキシド系共重合体樹脂の製造方法であって、機械的シェアーによる樹脂分子量の低下がほとんどない製造方法を提供することを目的とする。また、得られた粉体含有エチレンオキシド系共重合体樹脂の性能を長期間維持する包装方法を提供することを目的とする。   The present invention has been made in view of the above-described problems, and is a method for producing a powder-containing ethylene oxide copolymer resin that can be used for extrusion molding or the like, and the resin molecular weight is hardly reduced due to mechanical shear. The aim is to provide no manufacturing method. Another object of the present invention is to provide a packaging method for maintaining the performance of the obtained powder-containing ethylene oxide copolymer resin for a long period of time.

本発明の製造方法は、エチレンオキシド系共重合体樹脂に粉体を混合して分散させた、粉体含有エチレンオキシド系共重合体樹脂の製造方法であって、エチレンオキシド８０〜９５重量％と、このエチレンオキシドと共重合可能なオキシラン化合物５〜２０重量％とからなるエチレンオキシド系共重合体樹脂と溶媒からなるエチレンオキシド系共重合体樹脂溶液に、電気化学的活性物質を含有してなる粉体を混合して分散させて、粉体含有エチレンオキシド系共重合体樹脂溶液を調製する工程と、前記粉体含有エチレンオキシド系共重合体樹脂溶液から溶媒を除去して流動性を有する粉体含有エチレンオキシド系共重合体樹脂を得る工程と、前記流動性を有する粉体含有エチレンオキシド系共重合体樹脂をペレット化又は粒状化する工程と、前記ペレット化又は粒状化された粉体含有エチレンオキシド系共重合体樹脂を乾燥する工程とを含むものとする（請求項１）。   The production method of the present invention is a method for producing a powder-containing ethylene oxide copolymer resin in which a powder is mixed and dispersed in an ethylene oxide copolymer resin, wherein 80 to 95% by weight of ethylene oxide and the ethylene oxide A powder containing an electrochemically active substance is mixed with an ethylene oxide copolymer resin comprising 5 to 20% by weight of an oxirane compound copolymerizable with an ethylene oxide copolymer resin solution comprising a solvent. A step of preparing a powder-containing ethylene oxide copolymer resin solution by dispersing, and a powder-containing ethylene oxide copolymer resin having fluidity by removing the solvent from the powder-containing ethylene oxide copolymer resin solution And pelletizing or granulating the powder-containing ethylene oxide copolymer resin having fluidity, and The serial pelletizing or granulated powder containing ethylene oxide copolymer resin and a process of drying (claim 1).

上記において、前記粉体としては有機物粉体又は無機物粉体を用いることができる（請求項２，３）。   In the above, organic powder or inorganic powder can be used as the powder (claims 2 and 3).

電気化学的活性物質としては、遷移金属酸化物系化合物、リン酸塩系化合物、カーボン、グラファイト及びカーボン−グラファイトからなる群から選択された１種又は２種以上を用いることができる（請求項４）。   As the electrochemically active substance, one or more selected from the group consisting of transition metal oxide compounds, phosphate compounds, carbon, graphite, and carbon-graphite can be used. ).

エチレンオキシドと共重合可能なオキシラン化合物としては、ブチレンオキシドを用いることができる（請求項５）。   Butylene oxide can be used as the oxirane compound copolymerizable with ethylene oxide (Claim 5).

上記エチレンオキシド系共重合体樹脂溶液中に粉体を混合して分散させる工程で、低粘度で混合することにより樹脂の機械的劣化による分子量低下を防止することが好ましい（請求項６）。   In the step of mixing and dispersing the powder in the ethylene oxide copolymer resin solution, it is preferable to prevent a decrease in molecular weight due to mechanical deterioration of the resin by mixing at a low viscosity.

上記粉体含有エチレンオキシド系共重合体樹脂溶液から溶媒を除去して流動性を有する粉体含有エチレンオキシド系共重合体樹脂を得る工程は、粉体含有エチレンオキシド系共重合体樹脂溶液を予備濃縮する第一段階と、取り出し機能を備えた撹拌機を用いて低温で撹拌することによりさらに溶媒除去を行う第二段階からなることが好ましい（請求項７）。   The step of obtaining a fluid-containing powder-containing ethylene oxide copolymer resin by removing the solvent from the powder-containing ethylene oxide copolymer resin solution comprises preconcentrating the powder-containing ethylene oxide copolymer resin solution. Preferably, the method comprises one stage and a second stage in which the solvent is further removed by stirring at a low temperature using a stirrer having a take-out function (Claim 7).

上記粉体含有エチレンオキシド系共重合体樹脂をペレット化又は粒状化する工程は、ペレット化又は粒状化される樹脂を予備冷却し、次いで冷媒によって冷却しながらペレット化又は粒状化する段階を含むことが好ましい（請求項８）。   The step of pelletizing or granulating the powder-containing ethylene oxide copolymer resin may include precooling the resin to be pelletized or granulated and then pelletizing or granulating while cooling with a refrigerant. Preferred (claim 8).

上記粉体含有エチレンオキシド系共重合体樹脂を乾燥する工程は、減圧下で不活性ガスを導入しながら乾燥を行う段階を含むことが好ましい（請求項９）。   The step of drying the powder-containing ethylene oxide copolymer resin preferably includes a step of drying while introducing an inert gas under reduced pressure (claim 9).

本発明の粉体含有エチレンオキシド系共重合体樹脂の包装方法は、上記いずれかの製造方法により得られた粉体含有エチレンオキシド系共重合体樹脂を、吸湿及び酸素による性能劣化を防止するために不活性ガス雰囲気下で包装容器に充填するものとする（請求項１０）。   The packaging method for the powder-containing ethylene oxide copolymer resin of the present invention is not suitable for preventing the powder-containing ethylene oxide copolymer resin obtained by any of the above production methods from deteriorating performance due to moisture absorption and oxygen. The packaging container is filled under an active gas atmosphere (claim 10).

本発明の製造方法によれば、熱的劣化や機械的劣化による分子量低下がなく、安定した物性を有する粉体含有エチレンオキシド系共重合体樹脂が得られる。   According to the production method of the present invention, it is possible to obtain a powder-containing ethylene oxide copolymer resin having stable physical properties without lowering the molecular weight due to thermal degradation or mechanical degradation.

また、本発明の包装方法によれば、上記得られた樹脂が保管中に水分や酸素に曝されることがないので、分子量低下が抑えられ、初期の性能が長期間維持される。   In addition, according to the packaging method of the present invention, since the obtained resin is not exposed to moisture or oxygen during storage, a decrease in molecular weight is suppressed and the initial performance is maintained for a long time.

以下、本発明に係る粉体含有エチレンオキシド系共重合体樹脂の製造方法について詳述するが、以下の例示は本発明の範囲を拘束するものではなく、本発明の趣旨を損なわない範囲で適宜変更して実施しうるものである。   Hereinafter, the production method of the powder-containing ethylene oxide copolymer resin according to the present invention will be described in detail. However, the following examples are not intended to limit the scope of the present invention, and are appropriately changed within the scope of the present invention. Can be implemented.

１．粉体含有エチレンオキシド系共重合体樹脂の混合・分散工程
本発明の製造方法では、まずエチレンオキシド系共重合体樹脂と溶媒からなるエチレンオキシド系共重合体樹脂溶液に粉体を添加し、低粘度で混合して分散させる。これにより、分子量の低下がなく、粉体が均一に分散した樹脂を得ることが可能となる。粘度は、具体的には、温度６０℃で１，０００Ｐａ・ｓ以下であることが好ましい。 1. Mixing / dispersing step of powder-containing ethylene oxide copolymer resin In the production method of the present invention, powder is first added to an ethylene oxide copolymer resin solution composed of an ethylene oxide copolymer resin and a solvent, and mixed at a low viscosity. And disperse. Thereby, it is possible to obtain a resin in which the powder is uniformly dispersed without lowering the molecular weight. Specifically, the viscosity is preferably 1,000 Pa · s or less at a temperature of 60 ° C.

本発明で用いるエチレンオキシド系共重合体樹脂は、エチレンオキシド８０〜９５重量％とこのエチレンオキシドと共重合可能なオキシラン化合物５〜２０重量％（両者の合計で１００重量％）とが共重合してなるものである。分子量は樹脂の用途等によって異なり、特に限定されるものではないが、通常は重量平均分子量で５万〜２０万程度である。   The ethylene oxide copolymer resin used in the present invention is obtained by copolymerizing 80 to 95% by weight of ethylene oxide and 5 to 20% by weight of oxirane compounds copolymerizable with this ethylene oxide (100% by weight in total). It is. The molecular weight varies depending on the use of the resin and is not particularly limited, but is usually about 50,000 to 200,000 in terms of weight average molecular weight.

エチレンオキシドと共重合可能なオキシラン化合物としては、プロピレンオキシド、ブチレンオキシド、メチルグリシジルエーテル、エチルグリシジルエーテル、プロピルグリシジルエーテル、ブチルグリシジルエーテル、アリルグリシジルエーテルを挙げることができ、これらのうちの１種又は２種以上を用いることができる。これらの中で特に好ましいのはブチレンオキシドである。   Examples of the oxirane compound copolymerizable with ethylene oxide include propylene oxide, butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, and allyl glycidyl ether, one or two of these. More than seeds can be used. Of these, butylene oxide is particularly preferred.

次に、粉体は、有機物、無機物又は両者の混合物のいずれでもよく、電気化学的活性物質を含むことが好ましい。電気化学的活性物質の例としては、遷移金属酸化物系化合物、リン酸塩系化合物、カーボン、グラファイト及びカーボン−グラファイト混合物が挙げられ、これらの２種以上の混合物であってもよい。遷移金属酸化物系化合物の例としては、酸化バナジウム系化合物、酸化マンガン系化合物、酸化チタン系化合物が挙げられる。リン酸塩系化合物の例としてはリン酸鉄が挙げられる。   Next, the powder may be organic, inorganic or a mixture of both, and preferably contains an electrochemically active substance. Examples of the electrochemically active substance include transition metal oxide compounds, phosphate compounds, carbon, graphite, and carbon-graphite mixtures, and may be a mixture of two or more of these. Examples of transition metal oxide compounds include vanadium oxide compounds, manganese oxide compounds, and titanium oxide compounds. An example of the phosphate compound is iron phosphate.

粉体の好ましい例としては、酸化バナジウム系化合物と必要に応じて用いられるカーボン粉末とからなり、両者の配合比率が、酸化バナジウム系化合物：カーボン粉末＝１００〜９０：０〜１０（重量％、両者の合計で１００重量％）であるものが挙げられる。酸化バナジウム系化合物の例としては、Ｖ２Ｏ５、Ｖ３Ｏ８等や、ＬｉｘＶ３Ｏ８（ｘ：１．０〜１．４）のようなそれらのリチウム化物等が挙げられる。 As a preferable example of the powder, it consists of a vanadium oxide compound and a carbon powder used as necessary, and the blending ratio of both is vanadium oxide compound: carbon powder = 100 to 90: 0 to 10 (% by weight, The total of both is 100% by weight). Examples of vanadium oxide compounds include V 2 O 5 , V 3 O 8, and lithiated compounds such as Li x V 3 O 8 (x: 1.0 to 1.4).

粉体の平均粒径は、特に限定されないが、通常は１〜１０μｍの範囲である。   Although the average particle diameter of powder is not specifically limited, Usually, it is the range of 1-10 micrometers.

粉体の添加量は、樹脂の重量に対して好ましくは１〜１０倍の範囲であり、より好ましくは１〜４倍の範囲である。   The addition amount of the powder is preferably in the range of 1 to 10 times, more preferably in the range of 1 to 4 times the weight of the resin.

なお、粉体含有樹脂の用途に応じて、酸化防止剤、防腐剤、耐光性向上剤等の添加物をさらに添加してもよい。   Depending on the use of the powder-containing resin, additives such as an antioxidant, a preservative, and a light resistance improver may be further added.

樹脂の希釈溶解に用いる溶媒としては、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素系溶媒；ジメトキシエタン、エチレングリコールジメチルエーテル等のエチレングリコールジアルキルエーテル類の溶媒；テトラヒドロフラン、ジオキサン等の環状エーテル系溶媒、メタノール、エタノール等のアルコール類の溶媒；アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、アセトン等の共極性溶媒；あるいは水等が挙げられる。中でも、トルエン、キシレンがコストの面から好ましい。   Examples of the solvent used for diluting and dissolving the resin include aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; solvents of ethylene glycol dialkyl ethers such as dimethoxyethane and ethylene glycol dimethyl ether; cyclics such as tetrahydrofuran and dioxane. Examples include ether solvents, solvents of alcohols such as methanol and ethanol; polar solvents such as acetonitrile, N, N-dimethylformamide and acetone; or water. Of these, toluene and xylene are preferable from the viewpoint of cost.

溶媒の量は、溶液中の樹脂固形分が５〜７０重量％となる量が好ましく、１０〜４０重量％となる量がより好ましい。   The amount of the solvent is preferably such that the resin solid content in the solution is 5 to 70% by weight, and more preferably 10 to 40% by weight.

混合・分散の際に用いる装置は特に限定されないが、撹拌翼（ヘリカルリボン翼、スーパーブレンド翼、マックスブレンド翼、フルゾーン翼等）を備える反応器や、プロシェアーミキサー、コンビミックス等が好ましい例として挙げられる。用いる装置によって使用条件が異なるので、装置に応じた条件を設定する。   The apparatus used for mixing / dispersing is not particularly limited, but preferred examples include reactors equipped with stirring blades (helical ribbon blades, super blend blades, max blend blades, full zone blades, etc.), proshear mixers, combimixes, etc. Can be mentioned. Since the use conditions differ depending on the apparatus to be used, conditions according to the apparatus are set.

混合時の溶液の温度は４０〜１００℃が好ましく、６０〜８０℃がより好ましい。   40-100 degreeC is preferable and the temperature of the solution at the time of mixing has more preferable 60-80 degreeC.

２．粉体含有エチレンオキシド系共重合体樹脂溶液の溶媒除去工程
本製造方法における溶媒除去工程は、粉体含有エチレンオキシド系共重合体樹脂溶液から溶媒として用いた溶剤を揮発除去して、流動性を有する粉体含有エチレンオキシド系共重合体樹脂を得る工程であり、溶媒除去の程度は樹脂が完全に溶媒を含まないものとなっている必要はなく、溶媒が所定の濃度以下になっていればよい。 2. Solvent removal step of powder-containing ethylene oxide copolymer resin solution The solvent removal step in this production method is a powder having fluidity by volatilizing and removing the solvent used as a solvent from the powder-containing ethylene oxide copolymer resin solution. This is a step of obtaining a body-containing ethylene oxide copolymer resin, and the degree of solvent removal does not require the resin to be completely free of solvent, as long as the solvent is at a predetermined concentration or lower.

溶媒除去工程は、粉体含有エチレンオキシド系共重合体樹脂溶液から、溶媒として用いた溶剤を低温で一部揮発させる第一段階（予備濃縮）と、第１段階を経た粉体含有エチレンオキシド系共重合体樹脂溶液を取り出し機能を備えた撹拌装置に移し、所定の濃度まで低温で溶剤を除去する第二段階との二段階からなるものとすることが好ましい。これにより粉体含有エチレンオキシド系共重合体樹脂の熱劣化や機械的劣化による分子量低下を防止できるだけでなく、所望の形態で粉体含有エチレンオキシド系共重合体樹脂を取り出すことが可能となる。従って、後のペレット化（粒状化）工程を考慮すれば非常に生産性が良好であり、かつ経済的に優れた方法となる。これら二段階の溶媒除去工程について以下により具体的に述べる。   The solvent removal step consists of a first stage (pre-concentration) in which the solvent used as a solvent is partially volatilized from the powder-containing ethylene oxide copolymer resin solution at a low temperature, and the powder-containing ethylene oxide copolymer that has undergone the first stage. The combined resin solution is preferably transferred to a stirrer equipped with a function, and is composed of two stages including a second stage in which the solvent is removed at a low temperature to a predetermined concentration. This not only prevents the powder-containing ethylene oxide copolymer resin from lowering the molecular weight due to thermal deterioration and mechanical deterioration, but also enables the powder-containing ethylene oxide copolymer resin to be taken out in a desired form. Therefore, considering the subsequent pelletization (granulation) step, the productivity is very good and the method is economically excellent. These two-stage solvent removal steps will be described more specifically below.

（１）第一段階
第一段階の溶媒除去工程は、溶液中の溶媒量（溶媒濃度）が好ましくは２５〜６０重量％、より好ましくは３０〜５０重量％となるまで濃縮する工程である。溶媒濃度が２５重量％未満となると、樹脂溶液の粘度が急激に上昇し、高動力の撹拌機が必要となると共に蒸発槽からの取り出しが困難となる。 (1) First Step The first step of solvent removal is a step of concentration until the amount of solvent (solvent concentration) in the solution is preferably 25 to 60% by weight, more preferably 30 to 50% by weight. When the solvent concentration is less than 25% by weight, the viscosity of the resin solution rises rapidly, requiring a high power stirrer and making it difficult to take out from the evaporation tank.

溶媒除去に用いる装置は特に限定されないが、減圧可能な撹拌型蒸発槽が好ましい。撹拌翼としては、例えばヘリカルリボン翼、スーパーブレンド翼、マックスブレンド翼、フルゾーン翼が使用できる。また、プロシェアーミキサー、コンビミックス等を使用することもできる。使用条件は、装置に応じた条件を設定する。   Although the apparatus used for solvent removal is not specifically limited, The stirring type evaporation tank which can be pressure-reduced is preferable. As the stirring blade, for example, a helical ribbon blade, a super blend blade, a max blend blade, or a full zone blade can be used. Moreover, a pro-shear mixer, a combination mix, etc. can also be used. Use conditions are set according to the device.

溶媒除去温度は４０〜１１０℃が好ましく、特に６０〜９０℃が好ましい。４０℃未満であると濃縮終了時の粘度が上昇し、１１０℃を超えると分子量の低下が認められる。   The solvent removal temperature is preferably 40 to 110 ° C, particularly preferably 60 to 90 ° C. When the temperature is lower than 40 ° C., the viscosity at the end of concentration increases, and when the temperature exceeds 110 ° C., a decrease in molecular weight is observed.

（２）第二段階
第二段階の溶媒除去工程では、溶媒濃度が好ましくは５〜３０重量％、より好ましくは１０〜２５重量％となるまで濃縮する。溶媒濃度が５重量％未満となると、高動力の撹拌機でも撹拌できず、取り出しが不可能となるおそれがあるだけでなく、機械的シェアーによって分子量の低下が生じることとなる。さらに樹脂の流動性がなくなるため、取り出しの際に形状を任意に変化させることが困難となる。 (2) Second Stage In the second stage solvent removal step, the solvent concentration is preferably 5 to 30% by weight, more preferably 10 to 25% by weight. When the solvent concentration is less than 5% by weight, not only a high-powered stirrer cannot be stirred, there is a possibility that the removal becomes impossible, but also the molecular weight is lowered due to mechanical shear. Furthermore, since the fluidity of the resin is lost, it is difficult to arbitrarily change the shape at the time of removal.

第二段階で使用する装置は、取り出し機能を備えた溶媒除去装置であり、取り出し機能とは装置内容物を送り出すスクリュー等の機構や上部又は側部が大きく開放する機構である。具体例としては、（ａ）装置に送り出し機構を備えているものとして、二軸型押出機（ＫＲＣ）ニーダー、セルフクリーニング式リアクター（ＳＣＲ）、一軸押出機、（ｂ）それ自体が送り出し機能を備えているものとして、真空ドラムドライヤー、真空ベルト乾燥機、（ｃ）上部及び／又は側面に開放部を備えており、開放部から取り出しできるものとして、プロシェアーミキサー等が挙げられ、用いる装置によって、塊状（ブロック状）、棒状又はひも状（ストランド状）、板状（シート状）等の様々な形状にすることができる。使用条件は、装置に応じた条件を設定する。   The device used in the second stage is a solvent removal device having a take-out function, and the take-out function is a mechanism such as a screw for sending out the contents of the device or a mechanism in which the upper part or side part is largely opened. As a specific example, (a) Assuming that the apparatus is equipped with a feeding mechanism, a twin screw extruder (KRC) kneader, a self-cleaning reactor (SCR), a single screw extruder, (b) itself has a feeding function. As a thing equipped, a vacuum drum dryer, a vacuum belt dryer, (c) an upper part and / or a side face are provided with an open part, and those that can be taken out from the open part include a pro-shear mixer, etc. Various shapes such as a block shape, a bar shape or a string shape (strand shape), and a plate shape (sheet shape) can be used. Use conditions are set according to the device.

この段階での溶媒除去温度は、４０〜１１０℃が好ましく、５０〜９０℃がより好ましい。   The solvent removal temperature at this stage is preferably 40 to 110 ° C, more preferably 50 to 90 ° C.

３．粉体含有エチレンオキシド系共重合体樹脂のペレット化（粒状化）工程
上記工程を経て、装置に応じた形状で取り出された粉体含有エチレンオキシド系共重合体樹脂を最終製品としてペレット状（粒状）にする。その方法としては、塊状物を押出機等で一旦シート状やひも状等に成形しておき、この成型物を冷却して固化させてからペレット状（粒状）に加工する方法が好ましいが、塊状物から直接ペレット状（粒状）に成形することもできる。 3. Pelletization (granulation) process of powder-containing ethylene oxide copolymer resin The powder-containing ethylene oxide copolymer resin taken out in the shape corresponding to the device through the above process is made into pellets (granular) as the final product To do. The method is preferably a method in which the lump is once formed into a sheet or string with an extruder or the like, and then cooled to solidify and then processed into a pellet (granular). It can also be directly molded into a pellet form (granular form).

シート状やひも状等に成形してからペレット化（粒状化）するには、前述した溶媒除去装置の取り出し口（樹脂排出口）にポリマーポンプやギヤポンプ等を取り付けて、粉体含有エチレンオキシド系共重合体樹脂を溶媒除去装置から抜き取りつつ、更に連結した押出機で押し出す方法や、押出機の代わりにＴダイやロール等を用いる方法が好ましく用いられる。   To form into a sheet or string and then pelletize (granulate), attach a polymer pump, gear pump, etc. to the take-out port (resin discharge port) of the solvent removal device described above, and share the powder-containing ethylene oxide system. A method of extruding the polymer resin from the solvent removing apparatus and extruding it with a connected extruder, or a method of using a T die or a roll instead of the extruder is preferably used.

押出機としては、一軸型押出機、二軸型押出機、セルフクリーニング式リアクター（ＳＣＲ）等が挙げられるが、一定の厚さのシート状又は板状に押し出すためには、押出機にＴダイ又はノズルを装着して押し出すことが好ましい。   Examples of the extruder include a single-screw extruder, a twin-screw extruder, and a self-cleaning reactor (SCR). In order to extrude into a sheet or plate having a certain thickness, a T-die is inserted into the extruder. Or it is preferable to push out by attaching a nozzle.

押し出された成形物をペレット化するには、機械的劣化防止のため、低速回転で高動力を備えた装置を使用するのが好ましく、例としては成形ランナー用粉砕機、ペレタイザー（ストランドカット式、ホットカット式、シートカット式等）等が挙げられる。   In order to pelletize the extruded product, it is preferable to use an apparatus with high power at low speed rotation to prevent mechanical deterioration. Examples include a grinder for molding runners, a pelletizer (strand cut type, Hot cut type, sheet cut type, etc.).

また、ペレット状や微細粒子状に押し出すにはドロップフォーマーを使用するのが好ましい。   Moreover, it is preferable to use a drop former to extrude into pellets or fine particles.

押出機を使用する際の温度は好ましくは４０〜１１０℃、より好ましくは５０〜８０℃、真空度は好ましくは１〜２５ｋＰａ、より好ましくは５〜１５ｋＰａである。   The temperature when using the extruder is preferably 40 to 110 ° C, more preferably 50 to 80 ° C, and the degree of vacuum is preferably 1 to 25 kPa, more preferably 5 to 15 kPa.

なお、ペレット化（粒状化）の際には、装置への樹脂の融着防止のため、事前に樹脂を冷媒で冷却固化し、粉砕機等に冷媒と共に投入し、切断又は粉砕することが好ましい。この時、冷媒は出口の樹脂温度が好ましくは２０℃以下、より好ましくは１０℃以下、さらに好ましくは０℃以下となるように調整して導入する。冷媒の例としては、液体窒素、二酸化炭素、窒素ガス等が挙げられる。また、酸化防止のため、不活性ガスの雰囲気下でペレット化することが好ましい。   In the case of pelletization (granulation), in order to prevent fusion of the resin to the apparatus, it is preferable to cool and solidify the resin with a refrigerant in advance, and then add it to the pulverizer together with the refrigerant, and cut or crush it. . At this time, the refrigerant is introduced such that the resin temperature at the outlet is preferably 20 ° C. or lower, more preferably 10 ° C. or lower, and further preferably 0 ° C. or lower. Examples of the refrigerant include liquid nitrogen, carbon dioxide, nitrogen gas and the like. In order to prevent oxidation, it is preferable to pelletize in an inert gas atmosphere.

４．粉体含有エチレンオキシド系共重合体樹脂の溶媒除去・乾燥工程
上記ペレット化（粒状化）工程の後、ペレット状（粒状）の粉体含有エチレンオキシド系共重合体樹脂に残存する溶媒や水分を減圧下に置くことにより除去する。用いる装置としては、減圧可能で密閉できる容器を備えた装置であればよく、形状、材質等は特に限定されないが、容器の上部より減圧可能で、下部より不活性ガスを導入できるようになされたものが好適に使用できる。温度調節機能は特に必要ではないが、装備されていてもよい。装置の例としては、プロシェアーミキサーやナウターミキサー、真空乾燥機、真空棚段乾燥機等が挙げられる。 4). Solvent removal and drying process of powder-containing ethylene oxide copolymer resin After the above pelletization (granulation) process, the solvent and moisture remaining in the pellet-shaped (granular) powder-containing ethylene oxide copolymer resin are reduced under reduced pressure. Remove by placing in. The apparatus to be used may be an apparatus provided with a container that can be depressurized and sealed, and the shape, material, etc. are not particularly limited, but the depressurization can be performed from the upper part of the container, and an inert gas can be introduced from the lower part. A thing can be used conveniently. The temperature control function is not particularly required, but may be equipped. Examples of the apparatus include a proshear mixer, a nauter mixer, a vacuum dryer, and a vacuum shelf dryer.

例えば、プロシェアーミキサーを使用して溶媒除去・乾燥を行う場合、温度は樹脂の溶融、劣化がないように温度を０〜３０℃の範囲に保ちながら、圧力を好ましくは１〜１０ｋＰａ、より好ましくは３〜６ｋＰａの範囲に減圧し、残留溶媒・水分を除去する。このとき、必要に応じて容器の下部から不活性ガスを導入する。   For example, when solvent removal and drying are performed using a proshear mixer, the pressure is preferably 1 to 10 kPa, more preferably while keeping the temperature in the range of 0 to 30 ° C. so that the resin does not melt or deteriorate. Reduce the pressure in the range of 3 to 6 kPa to remove residual solvent and moisture. At this time, an inert gas is introduced from the lower part of the container as necessary.

不活性ガスの例としては窒素ガス、ヘリウムガス、アルゴンガス等が挙げられ、導入ガスは必要に応じて好適温度に加温する。   Examples of the inert gas include nitrogen gas, helium gas, and argon gas, and the introduced gas is heated to a suitable temperature as necessary.

５．粉体含有エチレンオキシド系共重合体樹脂の包装方法
上記によりペレット化（粒状化）された粉体含有エチレンオキシド系共重合体樹脂は、乾燥後、水分や酸素に曝されることにより吸湿や性能劣化を起こすので、これを防止するために、容器への充填前に、減圧可能な混合槽を使用して不活性ガスを導入し、水分ないしは湿った空気を置換することが好ましい。不活性ガスとしては上記と同様、窒素ガス、ヘリウムガス、アルゴンガス等が用いられる。必要であれば混合槽内を減圧にして置換速度を上げることができる。また、上記混合槽から包装容器までの充填ラインに乾燥空気又は窒素等の不活性ガスを流すことが好ましい。 5). Packaging Method for Powder-Containing Ethylene Oxide Copolymer Resin The powder-containing ethylene oxide copolymer resin pelletized (granulated) as described above is exposed to moisture and oxygen after drying, resulting in moisture absorption and performance deterioration. In order to prevent this, in order to prevent this, it is preferable to introduce an inert gas using a depressurized mixing tank and replace moisture or moist air before filling the container. As the inert gas, nitrogen gas, helium gas, argon gas or the like is used as described above. If necessary, the replacement rate can be increased by reducing the pressure in the mixing tank. Moreover, it is preferable to flow inert gas, such as dry air or nitrogen, to the filling line from the said mixing tank to a packaging container.

製品の包装容器としては、空気の混入を防ぐためにガス透過性及び透湿性の低い材質からなる袋が好ましく、例えば、内面が樹脂コーティングされたアルミラミネート袋が好適に用いられる。袋は、充填直前に窒素等の不活性ガスを流し、予め入っている空気を追い出すことが好ましい。必要に応じて、製品充填後にもノズル等を用いて不活性ガスを袋の内部に導入してから袋の開口部を密閉する。   The product packaging container is preferably a bag made of a material having low gas permeability and moisture permeability in order to prevent air from being mixed in. For example, an aluminum laminated bag whose inner surface is resin-coated is preferably used. The bag is preferably flushed with an inert gas such as nitrogen immediately before filling to expel the pre-filled air. If necessary, after filling the product, an inert gas is introduced into the bag using a nozzle or the like, and then the opening of the bag is sealed.

以上の各工程を経ることにより、熱的及び機械的劣化による分子量低下のない、安定した物性の粉体含有エチレンオキシド系共重合体樹脂が得られる。   By passing through the above steps, a powder-containing ethylene oxide copolymer resin having stable physical properties free from molecular weight reduction due to thermal and mechanical deterioration can be obtained.

以下に本発明の実施例を示すが、本発明はこれに限定されるものではない。   Examples of the present invention are shown below, but the present invention is not limited thereto.

なお、以下の合成例及び実施例中の共重合体の分子量（重量平均分子量）の測定はゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析により行った。測定条件は以下の通りである。   In addition, the measurement of the molecular weight (weight average molecular weight) of the copolymer in the following synthesis examples and Examples was performed by gel permeation chromatography (GPC) analysis. The measurement conditions are as follows.

カラム：Ｇｕａｒｄ ｃｏｌｕｍｎ ＰＷＸＬ ＋ Ｇ５０００ＰＷＸＬ
＋ Ｇ４０００ＰＷＸＬ ＋ Ｇ３０００ＰＷＸＬ
＋ Ｇ２５００ＰＷＸＬ（以上、東ソー（株）製）
カラムサイズ：７．８ｍｍφ×３０ｃｍ
カラム温度：４０℃
溶離液：アセトニトリル／０．０８Ｍ−酢酸ナトリウム溶液＝５０／５０（溶量比）
流速：１．０ｍｌ／ｍｉｎ
検出器：示差屈折検出器
標準物質：東ソー（株）製ポリエチレンオキシド、分子量２，０００〜９００，０００ Column: Guard column PWXL + G5000PWXL
+ G4000PWXL + G3000PWXL
+ G2500PWXL (above, manufactured by Tosoh Corporation)
Column size: 7.8mmφ × 30cm
Column temperature: 40 ° C
Eluent: acetonitrile / 0.08M-sodium acetate solution = 50/50 (solution ratio)
Flow rate: 1.0 ml / min
Detector: Differential refraction detector Standard material: Polyethylene oxide manufactured by Tosoh Corporation, molecular weight 2,000 to 900,000

［合成例１］
撹拌翼を備えた１００リットルの加圧反応容器に脱水トルエン３５ｋｇ、触媒としてのナトリウムメチラート５ｇを仕込み、９０℃まで加温後、圧力２００ｋＰａ以下、温度１２０℃以下になるよう調整した。樹脂原料としてのエチレンオキシド及び１，２−ブチレンオキシドを９０：１０の割合（重量比）で合計量１５ｋｇ仕込み、反応させて共重合体溶液１を得た。共重合体の分子量を調べたところ、１１３０００であった。 [Synthesis Example 1]
A 100 liter pressurized reaction vessel equipped with a stirring blade was charged with 35 kg of dehydrated toluene and 5 g of sodium methylate as a catalyst, heated to 90 ° C., and adjusted to a pressure of 200 kPa or less and a temperature of 120 ° C. or less. A total amount of 15 kg of ethylene oxide and 1,2-butylene oxide as resin raw materials were charged at a ratio of 90:10 (weight ratio) and reacted to obtain a copolymer solution 1. When the molecular weight of the copolymer was examined, it was 113,000.

［実施例１］
合成例１により得られた共重合体溶液１の５０ｋｇを撹拌翼と分散翼を備えた２００リットルのコンビミックスに仕込み、トルエン１００ｋｇを添加して、液体温度６０℃に調整した。続けて、リチウム化酸化バナジウム／カーボン粉末混合物（ＵＳ Ａｖｅｓｔｏｒ ＬＬＣ製、リチウム化酸化バナジウム／カーボン粉末＝９５：５（重量比、以下同様））３５ｋｇを添加し、３０分間撹拌し、均一な分散溶液を調整した後、減圧によりトルエン含有量が４０重量％になるまでトルエンを留去し、濃縮溶液を得た。得られた濃縮溶液をプロシェアーミキサーへ移し、トルエン含有量が１５重量％になるまでトルエンをさらに減圧留去した。得られた濃縮物は装置上部から直接塊状にて取り出した。取り出した塊状物を炭酸ガスにて１０℃以下まで冷却し、成形ランナー用粉砕機にて粒状に粉砕した後、ナウターミキサーに移し、温度２５℃、圧力４ｋＰａにて減圧乾燥した。乾燥後の粒状物は、窒素雰囲気下でアルミラミネート袋（内面ポリエチレン樹脂コーティング、以下同様）に移し、ヒートシールにより密閉した。 [Example 1]
50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200 liter combination mix equipped with a stirring blade and a dispersion blade, and 100 kg of toluene was added to adjust the liquid temperature to 60 ° C. Subsequently, 35 kg of a lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC, lithiated vanadium oxide / carbon powder = 95: 5 (weight ratio, the same applies hereinafter)) was added, and the mixture was stirred for 30 minutes to obtain a uniform dispersion solution Then, toluene was distilled off under reduced pressure until the toluene content became 40% by weight to obtain a concentrated solution. The obtained concentrated solution was transferred to a proshear mixer, and toluene was further distilled off under reduced pressure until the toluene content became 15% by weight. The obtained concentrate was taken out directly from the upper part of the apparatus as a lump. The taken-up lump was cooled to 10 ° C. or less with carbon dioxide gas, pulverized into granules with a molding runner pulverizer, transferred to a Nauter mixer, and dried under reduced pressure at a temperature of 25 ° C. and a pressure of 4 kPa. The dried granular material was transferred to an aluminum laminate bag (inner surface polyethylene resin coating, the same applies hereinafter) under a nitrogen atmosphere and sealed by heat sealing.

濃縮物の濃縮直後（ペレット化又は粒状化前、以下同様）の分子量、粒状物のヒートシール直後、１ヶ月保管後の、それぞれの分子量を表１に示す。   Table 1 shows the molecular weight immediately after concentration of the concentrate (before pelletization or granulation, the same applies hereinafter), and immediately after heat sealing of the granular material and after storage for 1 month.

［実施例２］
合成例１により得られた共重合体溶液１の５０ｋｇをマックスブレンド翼を備えた２００リットルの反応器に仕込み、トルエン１００ｋｇを添加して、液体温度８０℃に調整した。続けて、リチウム化酸化バナジウム／カーボン粉末混合物（ＵＳ Ａｖｅｓｔｏｒ ＬＬＣ製）４５ｋｇを添加し、６０分間撹拌し、均一な分散溶液を調整した後、減圧によりトルエン含有量が５０重量％になるまでトルエンを留去し、濃縮溶液を得た。この濃縮溶液をセルフクリーニング式リアクター（ＳＣＲ）の反応器へ移送し、トルエン含有量が２０重量％になった溶融物を取り出し、さらに真空ドラムドライヤーへ導入して残留トルエンを留去したフレーク状成形物を得た。得られたフレーク状成形物を窒素ガスにて冷却しながら、ペレタイザーでペレット状に裁断した。得られたペレットを真空棚段乾燥機へ移し、温度３０℃、圧力６ｋＰａにて減圧乾燥した。乾燥後のペレットは、窒素雰囲気下でアルミラミネート袋に移し、ヒートシールにより密閉した。 [Example 2]
50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200-liter reactor equipped with a Max Blend blade, and 100 kg of toluene was added to adjust the liquid temperature to 80 ° C. Subsequently, 45 kg of a lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added and stirred for 60 minutes to prepare a uniform dispersion, and then toluene was added until the toluene content was reduced to 50% by weight under reduced pressure. Distilled off to obtain a concentrated solution. This concentrated solution is transferred to a reactor of a self-cleaning reactor (SCR), and the molten product with a toluene content of 20% by weight is taken out and introduced into a vacuum drum dryer to remove residual toluene to form a flaky shape. I got a thing. The obtained flake shaped product was cut into pellets with a pelletizer while being cooled with nitrogen gas. The obtained pellets were transferred to a vacuum shelf dryer and dried under reduced pressure at a temperature of 30 ° C. and a pressure of 6 kPa. The dried pellets were transferred to an aluminum laminate bag under a nitrogen atmosphere and sealed by heat sealing.

濃縮物の濃縮直後の分子量、ペレットのヒートシール直後、１ヶ月保管後の、それぞれの分子量を表１に示す。   Table 1 shows the molecular weight immediately after concentration of the concentrate and the molecular weight immediately after heat sealing of the pellet and after storage for 1 month.

［実施例３］
合成例１により得られた共重合体溶液１の５０ｋｇをヘリカルブレンド翼を備えた３５０リットルの反応器に仕込み、トルエン１５０ｋｇを添加して、液体温度５５℃に調整した。続けて、リチウム化酸化バナジウム／カーボン粉末混合物（ＵＳ Ａｖｅｓｔｏｒ ＬＬＣ製）２２．５ｋｇを添加し、１５分間撹拌し、均一な分散溶液を調整した後、減圧によりトルエン含有量が６５重量％になるまでトルエンを留去し、濃縮溶液を得た。この濃縮溶液を、コーティング用ノズルから真空ベルトクーラーのベルト上へ移送し、減圧にて乾燥しながら、トルエン含有量が５重量％のシート状成形物を得た。得られたシート状成形物を、窒素ガスにて冷却しながらペレタイザーでペレット状に裁断した。得られたペレットを真空棚段乾燥機へ移し、温度３０℃、圧力６ｋＰａにて減圧乾燥した。乾燥後のペレットは、窒素雰囲気下でアルミラミネート袋に移し、ヒートシールにより密閉した。 [Example 3]
50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 350 liter reactor equipped with a helical blend blade, and 150 kg of toluene was added to adjust the liquid temperature to 55 ° C. Subsequently, 22.5 kg of a lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added and stirred for 15 minutes to prepare a uniform dispersion solution, and then the toluene content was reduced to 65% by weight under reduced pressure. Toluene was distilled off to obtain a concentrated solution. This concentrated solution was transferred from a coating nozzle onto a belt of a vacuum belt cooler, and a sheet-like molded product having a toluene content of 5% by weight was obtained while drying under reduced pressure. The obtained sheet-like molded product was cut into pellets with a pelletizer while being cooled with nitrogen gas. The obtained pellets were transferred to a vacuum shelf dryer and dried under reduced pressure at a temperature of 30 ° C. and a pressure of 6 kPa. The dried pellets were transferred to an aluminum laminate bag under a nitrogen atmosphere and sealed by heat sealing.

濃縮物の濃縮直後の分子量、ペレットのヒートシール直後、１ヶ月保管後の、それぞれの分子量を表１に示す。   Table 1 shows the molecular weight immediately after concentration of the concentrate and the molecular weight immediately after heat sealing of the pellet and after storage for 1 month.

［実施例４］
合成例１により得られた共重合体溶液１の５０ｋｇをヘリカルブレンド翼を備えた３５０リットルの反応器に仕込み、トルエン１５０ｋｇを添加して、液体温度５５℃に調整した。続けて、リチウム化酸化バナジウム／カーボン粉末混合物（ＵＳ Ａｖｅｓｔｏｒ ＬＬＣ製）２２．５ｋｇを添加し、１５分間撹拌し、均一な分散溶液を調整した後、減圧によりトルエン含有量が６０重量％になるまでトルエンを留去し、濃縮溶液を得た。この濃縮溶液を続けて減圧ラインを装備した一軸押出機に導入し、減圧下でトルエンを留去しながらノズルより押出すことでトルエン含有量１０％のストランド状成形物を得た。得られたストランド状成形物を炭酸ガスにて５℃に冷却しながら、ペレタイザー（ストランドカット式）にてカットし、ペレットを得た。得られたペレットは実施例１と同様にして乾燥後、アルゴンガスを密閉したグローブボックス中でアルミラミネート袋に移し、ヒートシールして密閉した。 [Example 4]
50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 350 liter reactor equipped with a helical blend blade, and 150 kg of toluene was added to adjust the liquid temperature to 55 ° C. Subsequently, 22.5 kg of a lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added, and the mixture was stirred for 15 minutes to prepare a uniform dispersion, and then the toluene content was reduced to 60% by weight under reduced pressure. Toluene was distilled off to obtain a concentrated solution. This concentrated solution was continuously introduced into a single screw extruder equipped with a decompression line, and extruded from a nozzle while distilling off toluene under reduced pressure to obtain a strand-like molded product having a toluene content of 10%. The obtained strand-shaped molded product was cut with a pelletizer (strand cut type) while being cooled to 5 ° C. with carbon dioxide gas to obtain pellets. The obtained pellets were dried in the same manner as in Example 1, then transferred to an aluminum laminate bag in a glove box sealed with argon gas, and sealed by heat sealing.

濃縮物の濃縮直後の分子量、ペレットのヒートシール直後、１ヶ月保管後の、それぞれの分子量を表１に示す。   Table 1 shows the molecular weight immediately after concentration of the concentrate and the molecular weight immediately after heat sealing of the pellet and after storage for 1 month.

［実施例５］
合成例１により得られた共重合体溶液１の１ｋｇをヘリカルブレンド翼を備えた１０リットルの反応器に仕込み、キシレン１ｋｇを添加して、液体温度６０℃に調整した。続けて、リチウム化酸化バナジウム／カーボン粉末混合物（ＵＳ Ａｖｅｓｔｏｒ ＬＬＣ製）３．５ｋｇを添加し、窒素雰囲気下で６０分間撹拌し、均一な分散溶液を調整した後、減圧によりトルエン含有量が１５重量％になるまでトルエンを留去し、さらに撹拌を停止してトルエン含有量が２％になるまで濃縮した。濃縮物は反応器上部から直接塊状で取り出した。取り出した塊状物は炭酸ガスにて１０℃以下まで冷却し、成形ランナー用粉砕機にて粒状に粉砕した後、ペレタイザー（ホットカット式）に導入し、ペレットを得た。得られたペレットをナウターミキサーに移し、窒素ガスを導入しながら温度２５℃、圧力８ｋＰａにて減圧乾燥した。乾燥後の粒状物を窒化雰囲気下でアルミラミネート袋に移し、ヒートシールにより密閉した。 [Example 5]
1 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 10-liter reactor equipped with a helical blend blade, and 1 kg of xylene was added to adjust the liquid temperature to 60 ° C. Subsequently, 3.5 kg of a lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added, and the mixture was stirred for 60 minutes under a nitrogen atmosphere to prepare a uniform dispersion solution. Toluene was distilled off until it reached%, and further stirring was stopped to concentrate the toluene content to 2%. The concentrate was taken out in bulk directly from the top of the reactor. The taken-up lump was cooled to 10 ° C. or less with carbon dioxide gas, pulverized into granules with a molding runner pulverizer, and then introduced into a pelletizer (hot cut type) to obtain pellets. The obtained pellets were transferred to a Nauter mixer and dried under reduced pressure at a temperature of 25 ° C. and a pressure of 8 kPa while introducing nitrogen gas. The dried granular material was transferred to an aluminum laminate bag under a nitriding atmosphere and sealed by heat sealing.

濃縮物の濃縮直後の分子量、ペレットのヒートシール直後、１ヶ月保管後の、それぞれの分子量を表１に示す。   Table 1 shows the molecular weight immediately after concentration of the concentrate and the molecular weight immediately after heat sealing of the pellet and after storage for 1 month.

［比較例１］
合成例１により得られた共重合体溶液１の１０ｋｇを撹拌翼と分散翼を備えた２００リットルのコンビミックスに仕込み、トルエン１００ｋｇを添加して、液温を６０℃に調整した。続けてリチウム化酸化バナジウム／カーボン粉末混合物（ＵＳ Ａｖｅｓｔｏｒ ＬＬＣ製）４０ｋｇを添加し、６０分間撹拌した後、減圧によりトルエン含有量が１５％になるまで濃縮したが、高粘度のため途中で撹拌不能となり、コンビミックス底部からの取り出しが困難となった。 [Comparative Example 1]
10 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200 liter combination mix equipped with a stirring blade and a dispersion blade, and 100 kg of toluene was added to adjust the liquid temperature to 60 ° C. Subsequently, 40 kg of a lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added, and the mixture was stirred for 60 minutes, and then concentrated to 15% by toluene under reduced pressure. It became difficult to take out from the bottom of the combination mix.

［比較例２］
合成例１により得られた共重合体溶液１の５０ｋｇを撹拌翼と分散翼を備えた２００リットルのコンビミックスに仕込み、トルエン１００ｋｇを添加して、液温を６０℃に調整した。続けてリチウム化酸化バナジウム／カーボン粉末混合物（ＵＳ Ａｖｅｓｔｏｒ ＬＬＣ製）３５ｋｇを添加し、３０分間撹拌し、均一な分散溶液を調製した後、減圧によりトルエン含有量が４０重量％になるまでトルエンを留去し、濃縮溶液を得た。さらに、濃縮溶液をプロシェアーミキサーに移し、トルエン含有量が３重量％になるまで撹拌しながらトルエンをさらに減圧留去した。得られた濃縮物を温度６０℃の状態で装置上部から塊状で直接取り出した。以下の操作は実施例１と同様に行った。 [Comparative Example 2]
50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200 liter combination mix equipped with a stirring blade and a dispersion blade, and 100 kg of toluene was added to adjust the liquid temperature to 60 ° C. Subsequently, 35 kg of a lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added and stirred for 30 minutes to prepare a uniform dispersion, and then the toluene was retained until the toluene content was reduced to 40% by weight under reduced pressure. To give a concentrated solution. Furthermore, the concentrated solution was transferred to a proshear mixer, and toluene was further distilled off under reduced pressure while stirring until the toluene content became 3% by weight. The obtained concentrate was directly taken out as a lump from the upper part of the apparatus at a temperature of 60 ° C. The following operations were performed in the same manner as in Example 1.

濃縮物の濃縮直後の分子量、ペレットのヒートシール直後、１ヶ月保管後の、それぞれの分子量を表１に示す。   Table 1 shows the molecular weight immediately after concentration of the concentrate and the molecular weight immediately after heat sealing of the pellet and after storage for 1 month.

［比較例３］
実施例１において、成形ランナー用粉砕機で、気温２７℃、相対湿度８２％の環境下で粉砕を行った。粉砕開始から２０分経過後に、粉砕機内部で塊状物が溶融・融着し、粉砕継続が不可能となった。 [Comparative Example 3]
In Example 1, it grind | pulverized by the grinder for shaping | molding runners in the environment of air temperature 27 degreeC and relative humidity 82%. After 20 minutes from the start of pulverization, the lump was melted and fused in the pulverizer, and pulverization could not be continued.

［比較例４］
実施例２において、裁断して得られたトルエン含有量５重量％のペレットを真空棚段乾燥機に移し、温度３５℃、圧力３０ｋＰａにて減圧乾燥した。５時間乾燥後のトルエン含有量は２重量％であり、未乾燥状態であった。続けて、このペレットを、気温２７℃、相対湿度８２％の空気環境下でポリエチレン製袋に移し、ヒートシールにより密閉した。 [Comparative Example 4]
In Example 2, pellets having a toluene content of 5% by weight obtained by cutting were transferred to a vacuum shelf dryer and dried under reduced pressure at a temperature of 35 ° C. and a pressure of 30 kPa. The toluene content after drying for 5 hours was 2% by weight and was in an undried state. Subsequently, the pellets were transferred to a polyethylene bag in an air environment at an air temperature of 27 ° C. and a relative humidity of 82%, and sealed by heat sealing.

濃縮物の濃縮直後の分子量、ペレットのヒートシール直後、１ヶ月保管後の、それぞれの分子量を表１に示す。   Table 1 shows the molecular weight immediately after concentration of the concentrate and the molecular weight immediately after heat sealing of the pellet and after storage for 1 month.

［比較例５］
実施例２において、セルフクリーニング式リアクターの反応器の減圧度を５０ｋＰａ、温度を８０℃に変更した以外は同様にして、樹脂溶液を濃縮した。真空ドラムドライヤーから取り出した組成物は、溶媒濃度３５重量％であり、流動性を有し、固体化できないため、シートを成形できなかった。 [Comparative Example 5]
In Example 2, the resin solution was concentrated in the same manner except that the pressure reduction degree of the reactor of the self-cleaning reactor was changed to 50 kPa and the temperature was changed to 80 ° C. Since the composition taken out from the vacuum drum dryer had a solvent concentration of 35% by weight and had fluidity and could not be solidified, a sheet could not be formed.

Figure 2007186533
Figure 2007186533

本発明の製造方法により得られた粉体含有エチレンオキシド系共重合体樹脂は、例えばリチウム二次電池の正極材料等に好適に用いることができる。   The powder-containing ethylene oxide copolymer resin obtained by the production method of the present invention can be suitably used for, for example, a positive electrode material of a lithium secondary battery.

Claims (10)

エチレンオキシド系共重合体樹脂に粉体を混合して分散させた、粉体含有エチレンオキシド系共重合体樹脂の製造方法であって、
エチレンオキシド８０〜９５重量％と、このエチレンオキシドと共重合可能なオキシラン化合物５〜２０重量％とからなるエチレンオキシド系共重合体樹脂と溶媒からなるエチレンオキシド系共重合体樹脂溶液に、電気化学的活性物質を含有してなる粉体を混合して分散させて、粉体含有エチレンオキシド系共重合体樹脂溶液を調製する工程と、
前記粉体含有エチレンオキシド系共重合体樹脂溶液から溶媒を除去して流動性を有する粉体含有エチレンオキシド系共重合体樹脂を得る工程と、
前記流動性を有する粉体含有エチレンオキシド系共重合体樹脂をペレット化又は粒状化する工程と、
前記ペレット化又は粒状化された粉体含有エチレンオキシド系共重合体樹脂を乾燥する工程と
を含むことを特徴とする粉体含有エチレンオキシド系共重合体樹脂の製造方法。 A method for producing a powder-containing ethylene oxide copolymer resin, in which a powder is mixed and dispersed in an ethylene oxide copolymer resin,
An electrochemically active substance is added to an ethylene oxide copolymer resin solution consisting of 80 to 95% by weight of ethylene oxide and 5 to 20% by weight of an oxirane compound copolymerizable with ethylene oxide and a solvent. Mixing and dispersing the contained powder to prepare a powder-containing ethylene oxide copolymer resin solution;
Removing the solvent from the powder-containing ethylene oxide copolymer resin solution to obtain a powder-containing ethylene oxide copolymer resin having fluidity; and
Pelletizing or granulating the powder-containing ethylene oxide copolymer resin having fluidity; and
And drying the pelletized or granulated powder-containing ethylene oxide copolymer resin. A method for producing a powder-containing ethylene oxide copolymer resin. 前記粉体として有機物粉体が用いられることを特徴とする、請求項１に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   2. The method for producing a powder-containing ethylene oxide copolymer resin according to claim 1, wherein an organic powder is used as the powder. 前記粉体として無機物粉体が用いられることを特徴とする、請求項１に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   The method for producing a powder-containing ethylene oxide copolymer resin according to claim 1, wherein an inorganic powder is used as the powder. 前記電気化学的活性物質が、遷移金属酸化物系化合物、リン酸塩系化合物、カーボン、グラファイト及びカーボン−グラファイトからなる群から選択された１種又は２種以上であることを特徴とする、請求項１〜３のいずれか１項に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   The electrochemically active material is one or more selected from the group consisting of transition metal oxide compounds, phosphate compounds, carbon, graphite, and carbon-graphite, Item 4. The method for producing a powder-containing ethylene oxide copolymer resin according to any one of Items 1 to 3. 前記エチレンオキシドと共重合可能なオキシラン化合物がブチレンオキシドであることを特徴とする、請求項１〜４のいずれか１項に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   The method for producing a powder-containing ethylene oxide copolymer resin according to any one of claims 1 to 4, wherein the oxirane compound copolymerizable with ethylene oxide is butylene oxide. 前記エチレンオキシド系共重合体樹脂溶液中に粉体を混合して分散させる工程で、低粘度で混合することにより前記樹脂の機械的劣化による分子量低下を防止することを特徴とする、請求項１〜５のいずれか１項に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   In the step of mixing and dispersing the powder in the ethylene oxide copolymer resin solution, the molecular weight reduction due to mechanical deterioration of the resin is prevented by mixing at a low viscosity. 6. The method for producing a powder-containing ethylene oxide copolymer resin according to any one of 5 above. 前記粉体含有エチレンオキシド系共重合体樹脂溶液から溶媒を除去して流動性を有する粉体含有エチレンオキシド系共重合体樹脂を得る工程が、粉体含有エチレンオキシド系共重合体樹脂溶液を予備濃縮する第一段階と、取り出し機能を備えた撹拌機を用いて低温で撹拌することによりさらに溶媒除去を行う第二段階からなることを特徴とする、請求項１〜６のいずれか１項に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   The step of removing the solvent from the powder-containing ethylene oxide copolymer resin solution to obtain a powder-containing ethylene oxide copolymer resin having fluidity includes pre-concentrating the powder-containing ethylene oxide copolymer resin solution. The powder according to any one of claims 1 to 6, comprising one stage and a second stage in which the solvent is further removed by stirring at a low temperature using a stirrer having a take-out function. Method for producing body-containing ethylene oxide copolymer resin. 前記粉体含有エチレンオキシド系共重合体樹脂をペレット化又は粒状化する工程が、ペレット化又は粒状化される樹脂を予備冷却し、次いで冷媒によって冷却しながらペレット化又は粒状化する段階を含むことを特徴とする、請求項１〜７のいずれか１項に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   The step of pelletizing or granulating the powder-containing ethylene oxide copolymer resin includes precooling the resin to be pelletized or granulated and then pelletizing or granulating while cooling with a refrigerant. The method for producing a powder-containing ethylene oxide copolymer resin according to any one of claims 1 to 7, which is characterized by the following. 前記粉体含有エチレンオキシド系共重合体樹脂を乾燥する工程が、減圧下で不活性ガスを導入しながら乾燥を行う段階を含むことを特徴とする、請求項１〜８のいずれか１項に記載の粉体含有エチレンオキシド系共重合体樹脂の製造方法。   9. The process according to claim 1, wherein the step of drying the powder-containing ethylene oxide copolymer resin includes a step of drying while introducing an inert gas under reduced pressure. Of producing a powder-containing ethylene oxide copolymer resin. 請求項１〜９のいずれか１項に記載の製造方法により得られた粉体含有エチレンオキシド系共重合体樹脂を、吸湿及び酸素による性能劣化を防止するために不活性ガス雰囲気下で包装容器に充填することを特徴とする、粉体含有エチレンオキシド系共重合体樹脂の包装方法。
The powder-containing ethylene oxide copolymer resin obtained by the production method according to any one of claims 1 to 9 is placed in a packaging container under an inert gas atmosphere in order to prevent performance deterioration due to moisture absorption and oxygen. A method for packaging a powder-containing ethylene oxide copolymer resin, which comprises filling.
JP2004257709A 2004-09-03 2004-09-03 Manufacturing method of powder-containing ethylene oxide copolymer resin and packaging method Pending JP2007186533A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2004257709A JP2007186533A (en) 2004-09-03 2004-09-03 Manufacturing method of powder-containing ethylene oxide copolymer resin and packaging method
PCT/JP2005/015750 WO2006025374A1 (en) 2004-09-03 2005-08-30 Process for producing particle-containing ethylene oxide copolymer resin and method of packaging

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2004257709A JP2007186533A (en) 2004-09-03 2004-09-03 Manufacturing method of powder-containing ethylene oxide copolymer resin and packaging method

Publications (1)

Publication Number Publication Date
JP2007186533A true JP2007186533A (en) 2007-07-26

Family

ID=36000026

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004257709A Pending JP2007186533A (en) 2004-09-03 2004-09-03 Manufacturing method of powder-containing ethylene oxide copolymer resin and packaging method

Country Status (2)

Country Link
JP (1) JP2007186533A (en)
WO (1) WO2006025374A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008033061A1 (en) 2007-07-18 2009-02-12 Hitachi, Ltd. Motor drive device and test method for this
JP2012507411A (en) * 2008-11-04 2012-03-29 ビーエーエスエフ ソシエタス・ヨーロピア Use of a composite film as a packaging material for an oxidation-sensitive polymer, a method for packaging an oxidation-sensitive polymer, and a package containing the composite film

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5518420A (en) * 1978-07-25 1980-02-08 Toray Ind Inc Preparation of conductive polyether polymer composition having improved moldability

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008033061A1 (en) 2007-07-18 2009-02-12 Hitachi, Ltd. Motor drive device and test method for this
JP2012507411A (en) * 2008-11-04 2012-03-29 ビーエーエスエフ ソシエタス・ヨーロピア Use of a composite film as a packaging material for an oxidation-sensitive polymer, a method for packaging an oxidation-sensitive polymer, and a package containing the composite film

Also Published As

Publication number Publication date
WO2006025374A1 (en) 2006-03-09

Similar Documents

Publication Publication Date Title
CN111253677B (en) Low-density polypropylene bead foam, and preparation method and application thereof
CA2497332A1 (en) Water soluble nonionic alkylene oxide resin and production process therefor
US4789597A (en) Incorporation of chemically reactive agents on resin particles
JPWO2006025600A1 (en) Method for storing positive electrode material composition for lithium secondary battery
WO2006025602A1 (en) Process for producing positive electrode material composition for lithium secondary battery
CN111533999B (en) Ultrahigh melt index polypropylene material and preparation method and application thereof
CN111251494B (en) Preparation method of low-melting-point weather-resistant auxiliary agent master batch
JP2007186533A (en) Manufacturing method of powder-containing ethylene oxide copolymer resin and packaging method
JP2006335905A (en) Manufacturing method of pelletized nonionic alkylene oxide-based resin
JP7167711B2 (en) Polyvinyl alcohol-based resin composition pellets and method for producing the polyvinyl alcohol-based resin composition pellets
EP2876131B1 (en) Method for producing resin composition containing active particles
JPH0512371B2 (en)
CN116940454A (en) Granulation of polymer stabilizer mixtures
JPS62169605A (en) Granulation of polycarbonate
EP0553653A2 (en) Granular vinyl chloride resin
JP2005060494A (en) Oxygen-absorbing resin composition and oxygen-absorbing packaging material
JP3120383B2 (en) Method for producing granulated polyarylene sulfide resin
CN113861889B (en) Adhesive resin for high-barrier bottle and preparation method thereof
JPS6049210B2 (en) Manufacturing method of synthetic resin powder
US20020167107A1 (en) Process for manufacturing granulated hydrophilic resin
JP3651510B2 (en) Oxygen absorption sheet
JP2023083106A (en) Method for producing resin composition, mixture, resin composition and molding
JP2514969B2 (en) Saran pellet manufacturing method and saran pellet
CN116329258A (en) Device and process for producing polypropylene fibers by chemical degradation method
WO2006025604A1 (en) Process for producing positive electrode material composition for lithium secondary battery