JP3857079B2 - Method for producing glycols - Google Patents

Description

【００３３】
上記一般式中、Ｒ^１及びＲ^２は、同−若しくは異なって、水素原子、メチル基、エチル基又はハロゲン原子を表す。Ｒ^３及びＲ^４は、同一若しくは異なって、アルキル基、アルコキシアルキル基又はアリール基を表すか、又は、Ｒ^３−Ｎ^＋−Ｒ^４は、Ｒ^３とＲ^４とが結合してピペリジン環又はモルホリニウム環を表す。Ｘ^１及びＸ^２は、同一若しくは異なって、水素原子、アルキル基又はハロゲン原子を表す。Ｙ⁻は、カウンターアニオンを表す。
【００３４】
上記ハロゲン原子としては特に限定されず、例えば、フッ素、塩素、臭素、ヨウ素等が挙げられる。
上記アルキル基又はアルコキシアルキル基は、総炭素数が１〜１８個であることが好ましい。このようなアルキル基としては特に限定されず、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等が挙げられる。より好ましくは、炭素原子数が１〜１２個であり、更に好ましくは、炭素原子数が１〜８個であり、最も好ましくは、炭素原子数が１〜６個である。
上記アリール基は、炭素数６〜１５個が好ましく、６〜１２個が更に好ましい。このようなアリール基としては特に限定されず、例えば、フェニル基、トリル基、キシリル基等が挙げられる。
上記ピペリジン環及び上記モルホリニウム環は、炭素原子数が１〜１３個であるアルキル基により１個又は２個以上の水素原子が置換されていてもよい。
【００３５】
上記一般式で表されるアンモニウム化合物の好ましい例としては、例えば、ジアリルジメチルアンモニウムクロライド、ジアリルジエチルアンモニウムクロライド等のジアリルジアルキルアンモニウムクロライド；ジメタリルジメチルアンモニウムクロライド等のジメタリルジアルキルアンモニウムクロライド等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００３６】
上記ジアリルアンモニウム基を分子内に２個以上有する化合物の好ましい具体例としては、例えば、下記式（１）〜（１０）で表される化合物等が挙げられる。
【００３７】
【化２】

【００３８】
上記式（１）〜（１０）で表される化合物の中でも、式（１０）で表されるＮ，Ｎ，Ｎ′，Ｎ′−テトラアリルジピペリジルプロパニウムジクロライドが更に好ましい。また、ジアリルアンモニウム基を分子内に２個以上有する化合物としては、式（１）〜（１０）で表される化合物以外にも、例えば、Ｎ，Ｎ′−ジメチル−Ｎ，Ｎ，Ｎ′，Ｎ′−テトラアリル−２−ブテン−１，４−ジアンモニウムジクロライドや、パラビニルフェニルメチルアンモニウム基及び／又はメタビニルフェニルメチルアンモニウム基を分子内に２個以上有する化合物として、例えば、Ｎ，Ｎ′−ジ（パラビニルフェニルメチル）エチレンジアンモニウムジクロライド、Ｎ，Ｎ′−ジ（メタビニルフェニルメチル）エチレンジアンモニウムジクロライド、Ｎ，Ｎ′−ジ（パラビニルフェニルメチル）プロピレンジアンモニウムジクロライド、Ｎ，Ｎ′−ジ（メタビニルフェニルメチル）プロピレンジアンモニウムジクロライド等が挙げられる。ここに掲げたものは代表例であり、これら以外にも例えば、フェニレンジアミンやその他ジアミン類と塩化アリル又は酢酸アリルで合成される化合物が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。尚、これらの化合物が有するカウンターアニオンは、クロライド系に限らず、他のものでもよい。
【００３９】
上記有機高分子架橋体の製造において、アンモニウム化合物とジアリルアンモニウム基を分子内に２個以上有する化合物との共重合比率としては特に限定されず、例えば、重量比で４０〜９９．９／６０〜０．１となるようにすることが好ましい。また、上記化合物以外の他の化合物を適宜重合させてもよい。更に、水溶液における化合物の濃度としては特に限定されず、例えば、仕込時の水溶液濃度は取扱の上で３０〜８０重量％とすることが好ましいが、重合開始前又は重合中に脱水操作により更に濃縮してもよい。
【００４０】
上記媒体として用いられる水不溶性有機溶剤としては特に限定されず、例えば、トルエン、キシレン、ベンゼン、ｎ−ヘキサン、シクロヘキサン、オクタン、鉱酸、ミネラルスピリット、ケロシンや、１，１，１−トリクロロエタン、１，２−ジクロロプロパン、テトラクロロエタン、トリクロロプロパン、テトラクロロメタン等の臭素化及び／又は塩素化された炭化水素等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、トルエン、キシレンを用いることが工業的に好適である。
【００４１】
上記媒体は、流動パラフィン及び／又はシリコーンオイル等の粘性流体を含んでいてもよい。これにより、生成する球状粒子の凝集性を抑制したり、球状粒子どうしの粘着を抑制したりして有機高分子架橋体の塊状化を抑制することが可能となる。このような粘性流体の媒体中の含有量としては、例えば、０．１〜５０重量％とすることが好ましい。より好ましくは、１〜４０重量％であり、更に好ましくは、５〜３０重量％である。また、粘性流体を含む媒体の粘度は、粘性流体の添加前後で粘度が上がりさえすればよい。
【００４２】
上記共重合における重合条件、すなわち重合温度、重合時間、攪拌条件や、使用する重合開始剤、添加剤等は、生成する球状粒子の大きさや性能、品質等により適宜設定すればよく、特に限定されるものではない。例えば、重合温度は、２０〜１５０℃とすることが好ましい。より好ましくは、５０〜１２０℃である。また、常圧又は減圧系で共沸脱水を併用してもよい。重合時間は、他の条件により適宜設定すればよく、４〜５０時間とすることが好ましい。攪拌条件は、通常の重合における攪拌速度とすればよい。使用する重合開始剤としては水溶性、油溶性を問わず、ペルオキシド系やアゾ系の一般的な開始剤を用いることができる。添加剤としては特に限定されず、例えば、グリセロールパルミテート、エチルセルロース、ソルビタンモノパルミテート、ソルビタンモノラウレート、ソルビタンモノステアレート等の一般的な分散安定剤等を用いることができる。その他の重合条件は、特に限定されるものではない。
【００４３】
上記有機高分子架橋体の製造方法の代表例として、ジアリルジメチルアンモニウム塩及びＮ，Ｎ，Ｎ′，Ｎ′−テトラアリルジピペリジルプロパニウムジクロライドの水溶液と重合開始剤の水溶液とをトルエンと流動パラフィンとを混合し、分散安定剤を添加した媒体中に滴下し、逆相懸濁重合又は逆相乳化重合を行う場合を下記反応式に示す。
【００４４】
【化３】

【００４５】
上記反応式中、Ｙ⁻は、カウンターアニオンの塩化物イオンを表す。ｍ及びｎは、モル数を表す。
上記逆相懸濁重合又は逆相乳化重合により得られる粒状粒子の平均粒径は、例えば、０．０５〜５ｍｍとなるように設定することが好ましい。
【００４６】
本発明のグリコール類の製造方法では、オキシラン化合物と水とを高分子触媒の存在下で反応させて行うことになるが、高分子触媒の耐熱性が優れることから、触媒活性が安定的に保持されて無着色で高品質のグリコール類を生産性よく製造することができ、しかも、モノグリコール類を選択性と生産性とを両立させて製造することができることになる。また、高分子触媒を上述したように粒状粒子とすると、生成物から高分子触媒を分離することが容易となることから、工業的な製造方法として好適となる。また、上記高分子触媒を用いた反応は、攪拌回分式反応器又は固定床若しくは流動床反応器等を用いて行うことができ、反応方式もバッチ式及び連続式の如何を問わない。更に、触媒反応とその反応で得られた反応物の精製を効率的に行う反応蒸留にも使用可能であり、プロセスによってその使用方法を何ら制限されるものではない。
【００４７】
【実施例】
以下に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。尚、特に断りのない限り、「％」は「重量％」を意味する。
【００４８】
触媒調製方法１
攪拌機、還流冷却管、温度計、窒素ガス導入管及び滴下ロートを備えた１Ｌのセパラブルフラスコに、トルエン３５０ｍＬと流動パラフィン５０ｍＬとを入れ、分散安定剤としてソルビタンモノパルミテート０．６ｇ及びエチルセルロース０．２ｇを添加して４０℃で溶解させた。このとき、窒素ガスを吹き込んで溶存酸素を追い出した。
【００４９】
別に、１００ｍＬのビーカーで６５％ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡＣ）水溶液３３．６１ｇとＮ，Ｎ，Ｎ′，Ｎ′−テトラアリルジピペリジルプロパニウムジクロライド（ＴＡＤＰＰＣ）３．１５ｇ及び水１３．２４ｇを混合溶解し（ＤＡＤＭＡＣ／ＴＡＤＰＰＣ＝９５／５ｍｏｌ％）、更に重合開始剤２，２′−アゾビス（２−アミジノプロパン）ジクロリド（商品名「Ｖ−５０」、和光純薬工業社製）０．４ｇと水３ｇとを混合した溶液を添加した。この混合溶液を３０℃で反応容器中に３０分かけて滴下し、滴下終了後５５℃で４時間、更に昇温し、７５℃で２時間反応させた。
【００５０】
所定時間反応後、冷却し生成樹脂を減圧濾過により分離した。濾別した樹脂をメタノール８００ｍＬで３０分間、３回洗浄し、６０℃で一晩減圧乾燥させ、乾燥樹脂を得た。
得られたカウンターアニオンが塩化物イオンの架橋体２０．０ｇを水で膨潤させ、３％炭酸水素ナトリウム水溶液１５Ｌを用いてカラム方式によりカウンターアニオンを塩化物イオンから炭酸水素イオンに置換した。その後、同量の水量で洗浄することにより、有機高分子架橋体を得た。
【００５１】
実施例１
触媒調製方法１で得られた架橋体の水膨潤体１８２ｍＬ（メスシリンダーで計量後、減圧濾過したｗｅｔ品を使用）、水１４００ｇ及びエチレンオキサイド３５０ｇを５Ｌのオートクレーブに仕込み、窒素雰囲気下、１２０℃で２時間反応させた。尚、水は架橋体中に含有される水の量も含めた全量が１４００ｇとなるように仕込んだ。得られた反応液を分析したところ、エチレンオキサイド転化率９９．９％、モノエチレングリコールの選択率が９４．２ｍｏｌ％であった。
【００５２】
実施例２
触媒調製方法１で得られた架橋体の水膨潤体１６０ｍＬ（メスシリンダーで計量後、減圧濾過したｗｅｔ品を使用）及び水１２３０ｇを５Ｌのオートクレーブに仕込み、窒素雰囲気下、１２０℃でエチレンオキサイド５２７ｇを連続添加しながら２時間反応させた。尚、水は架橋体中に含有される水の量も含めた全量が１２３０ｇとなるように仕込んだ。得られた反応液を分析したところ、モノエチレングリコールの選択率が８９．８ｍｏｌ％であった。
【００５３】
実施例３
触媒調製方法１で得られた架橋体の水膨潤体１６０ｍＬ（メスシリンダーで計量後、減圧濾過したｗｅｔ品を使用）及び水１２３０ｇを５Ｌのオートクレーブに仕込み、窒素雰囲気下、１２０℃でエチレンオキサイド８２０ｇを連続添加しながら２時間反応させた。尚、水は架橋体中に含有される水の量も含めた全量が１２３０ｇとなるように仕込んだ。得られた反応液を分析したところ、モノエチレングリコールの選択率が８５．５ｍｏｌ％であった。
【００５４】
触媒調製方法２
重合アンプル中に６５％ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡＣ）水溶液６．４５ｇ及び７２％Ｎ，Ｎ，Ｎ′，Ｎ′−テトラアリルジアミノブタン２塩酸塩（ＴｅＡＤＡＢ）水溶液１．２９ｇを混合して仕込み（ＤＡＤＭＡＣ／ＴｅＡＤＡＢ＝９０／１０ｍｏｌ％）、更に重合開始剤Ｖ−５０を０．０６４ｇと開始剤を溶解させるための水０．３２ｇとを混合した溶液を添加した。
この混合溶液を５５℃で４時間、更に昇温し、７５℃で２時間反応させた。
所定時間反応後、冷却し生成樹脂を粉砕し、メタノール１６０ｍＬ中で３０分間、３回洗浄し、６０℃で一晩減圧乾燥させ、乾燥樹脂を得た。
得られた架橋体２．０ｇを３％炭酸水素ナトリウム水溶液２００ｇで３回に分けて攪拌洗浄し、その後同量の水量で３回に分けて洗浄することにより、カウンターアニオンを塩化物イオンから炭酸水素イオンに置換した高分子架橋体を得た。
【００５５】
実施例４
触媒調製法２で得られた高分子架橋体の水膨潤体５．２ｍＬ及び水４０．０ｇを１００ｍＬのオートクレーブに仕込み、窒素雰囲気下、１２０℃でエチレンオキサイド４．９ｇを反応系中にフィードし、１時間反応させた。尚、水は架橋体中に含有される水の量も含めた全量が４０．０ｇとなるように仕込んだ。得られた反応液を分析したところ、エチレンオキサイド転化率８５．１％、モノエチレングリコールの選択率が９８．１ｍｏｌ％であった。
【００５６】
実施例５
触媒調製方法１で得られた架橋体の水膨潤体１８２ｍＬ（メスシリンダーで計量後、減圧濾過したｗｅｔ品を使用）、水１４００ｇ及びエチレンオキサイド３５０ｇを５Ｌのオートクレーブに仕込み、二酸化炭素を加えた（オートクレーブ中の水、ＥＯ、ＣＯ２ のうちＣＯ２ 添加量が０．１重量％）。１２０℃で２時間反応させた後、得られた反応液を分析したところ、エチレンオキサイド転化率９９．９％、モノエチレングリコールの選択率が９５．０ｍｏｌ％であった。
【００５７】
実施例６
触媒調製方法１で得られた架橋体の水膨潤体１８２ｍＬ（メスシリンダーで計量後、減圧濾過したｗｅｔ品を使用）、水１４００ｇ及びエチレンオキサイド３５０ｇを５Ｌのオートクレーブに仕込み、二酸化炭素を加えた（オートクレーブ中の水、ＥＯ、ＣＯ_２のうちＣＯ_２添加量が５重量％）。１２０℃で２時間反応させた後、得られた反応液を分析したところ、エチレンオキサイド転化率９９．９％、モノエチレングリコールの選択率が９４．８ｍｏｌ％であった。
【００５８】
実施例７
触媒調製方法１で得られた架橋体の水膨潤体１６０ｍＬ（メスシリンダーで計量後、減圧濾過したｗｅｔ品を使用）、水１２３０ｇを５Ｌのオートクレーブに仕込み、二酸化炭素を加えた（オートクレーブ中の水、投入予定ＥＯ、ＣＯ_２のうちＣＯ_２添加量が０．１重量％）。１２０℃でエチレンオキサイド８２０ｇを連続添加しながら２時間反応させた。得られた反応液を分析したところ、モノエチレングリコールの選択率が８６．２ｍｏｌ％であった。
【００５９】
実施例８
触媒調製方法１で得られた架橋体の水膨潤体１６０ｍＬ（メスシリンダーで計量後、減圧濾過したｗｅｔ品を使用）、水１２３０ｇを５Ｌのオートクレーブに仕込み、二酸化炭素を加えた（オートクレーブ中の水、投入予定ＥＯ、ＣＯ_２のうちＣＯ_２添加量が５重量％）。１２０℃でエチレンオキサイド８２０ｇを連続添加しながら２時間反応させた。得られた反応液を分析したところ、モノエチレングリコールの選択率が８６．０ｍｏｌ％であった。
【００６０】
【発明の効果】
本発明のグリコール類の製造方法は、上述のような構成からなるため、高分子触媒を用いてグリコール類を製造するに際し、高分子触媒の耐熱性が優れることから、触媒活性が安定的に保持されて無着色で高品質のグリコール類を生産性よく製造することができ、しかも、モノグリコール類を選択性と生産性とを両立させて製造することができ、ポリエチレンテレフタレート等のポリエステル原料や不凍液の他、様々な工業製品の原料等として幅広い用途に用いることができるグリコール類を好適に製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing glycols.
[0002]
[Prior art]
The method for producing glycols can be industrially performed by reacting an oxirane compound and water. Among glycols produced in this way, monoglycols produced by the reaction of one molecule of oxirane compound and water are industrially useful. In addition to polyester raw materials such as polyethylene terephthalate and antifreeze, It can be used for a wide range of applications as a raw material for products.
[0003]
For example, in the production method of monoethylene glycol which is industrially particularly useful as glycols, by using a large amount of water, by-products such as diethylene glycol and triethylene glycol are suppressed, and the main product, monoethylene glycol. It has been carried out selectively. However, such a production method is industrially unpreferable because it requires a process for removing excess water used in the reaction by using a large amount of energy in the purification step after obtaining the product. Therefore, a method for selectively producing monoethylene glycol even when the amount of water used is suppressed by reacting in the presence of a catalyst has been studied.
[0004]
Japanese Examined Patent Publication No. 5-47528 discloses a method for producing alkylene glycols in which an alkylene oxide and water are reacted in a heterogeneous system involving a metalate-containing solid. In this production method, the metalate-containing solid has a structure in which a styrene-divinylbenzene copolymer or the like is used as a solid support and a metalate anion is associated with an electropositive complexing site thereof. However, in this metalate-containing solid, the electropositive complexing site with which the metalate anion is associated has a structure bonded to the solid support by a single bond, so that it is easily thermally decomposed chemically. Since it is desorbed and decomposed due to this, there is room for improvement in improving the economics of production by improving the heat resistance and stably maintaining the catalytic activity. In addition, since the product is colored when the electropositive complexing site with which the metalate anion is associated is thermally decomposed, when the alkylene glycol as the product is used as a polyester raw material such as polyethylene terephthalate, Since polyethylene terephthalate and the like are required to have quality such as transparency, there has been room for improvement in order to achieve high quality without coloring.
[0005]
JP-A-9-508136 discloses alkylene glycol in the presence of a catalyst composition containing a solid material having one or more electropositive sites coordinated with one or more anions other than metalate and halogen anion. A manufacturing method is disclosed, and it is said that a quaternary ammonium type anion exchange resin is preferable as a solid material and bicarbonate is preferable as an anion. However, even this solid material has a structure in which a quaternary ammonium group having bicarbonate as an anion is bonded to a matrix of the solid material by a single bond, and a device for improving the heat resistance of the quaternary ammonium group has been proposed. Since it was not made, there was room for improvement in improving the heat resistance of the catalyst to produce glycols.
[0006]
JP-A-11-12206 discloses a structure in which a polymer of a vinyl aromatic compound is used as a catalyst as a catalyst and a quaternary ammonium group is bonded to the aromatic group via a linking group having a chain length of 3 atoms or more. A process for producing alkylene glycols using an anion exchange resin having the same is disclosed. In this production method, the anion exchange resin is a styrene-divinylbenzene copolymer or the like, but the heat resistance of the quaternary ammonium group that exhibits catalytic activity is improved by the linking group. However, in the case of producing alkylene glycols at a high temperature in order to improve productivity, the product is colored, so there is room for improvement to make the product uncolored and high quality.
[0007]
Japanese translation of PCT publication No. 2000-500478 discloses a method for producing alkylene glycol in the presence of a catalyst containing a polymeric organosiloxane ammonium salt having a silica-like skeleton. In this production method, the structure of the polymeric organosiloxane ammonium salt includes a unit having a cationized nitrogen atom to which an anion is ionically bonded, and the structure of this unit is not easily thermally decomposed chemically. And the product can be made uncolored and of high quality. However, in the preferred form of this polymeric organosiloxane ammonium salt, the cationized nitrogen atom, which becomes the active site of the catalyst, is bonded to the silica-like skeleton via three or four bonds, so As a result, the ratio of the active points of the lowers. In this case, if the reaction temperature is lowered to improve the selectivity of the monoalkylene glycol, the productivity cannot be maintained, so that the ratio of active sites in the polymer is further increased so that the catalytic activity is sufficiently exhibited. There was room to devise.
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, and in producing glycols using a polymer catalyst, since the heat resistance of the polymer catalyst is excellent, the catalyst activity is stably maintained and no coloring is applied. It is an object of the present invention to provide a method for producing glycols, which can produce high-quality glycols with high productivity and can produce monoglycols with both selectivity and productivity. .
[0009]
[Means for Solving the Problems]
The present invention is a method for producing glycols by reacting an oxirane compound and water in the presence of a polymer catalyst, wherein the polymer catalyst has a hetero atom as an essential component in the main chain and / or cross-linking site. And a process for producing glycols which are organic polymer compounds having no hydrogen atom bonded to a heteroatom.
[0010]
As a result of intensive investigation after careful investigation of the problems relating to the production method of glycols, the present inventors have found that the active site of the polymer catalyst is thermally decomposed in a chemical structure in the production method described above. Since desorption and decomposition due to the difficulty are suppressed, the catalytic activity is stably maintained, the economic efficiency of production is improved, and there is no coloring and high as in the case of no catalyst. It is possible to produce quality glycols and pay attention to the fact that high reactivity is expected when reacted at high temperatures, so that it can be produced with good productivity, and the catalytic activity of the polymer catalyst is excellent. Therefore, while maintaining the productivity of conventional non-catalyst systems (total production of mono-, di-, tri-, etc.), the selectivity of monoglycols such as monoethylene glycol is improved and surplus by-products (Di body, And improving selectivity by reducing the amount of water used and increasing the concentration of oxirane compounds while maintaining selectivity (ratio of mono, di, and tri) In view of the fact that the selectivity and productivity of monoglycols can be made compatible by reducing the amount of steam, the present invention has been achieved.
The present invention is described in detail below.
[0011]
The method for producing glycols of the present invention is a method for producing glycols by reacting an oxirane compound and water in the presence of a polymer catalyst.
The oxirane compound is not particularly limited as long as it is an epoxy group-containing compound, and examples thereof include fats such as ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and pentylene oxide. Aromatic alkylene oxides such as styrene oxide; cyclohexene oxide and the like. These may be used alone or in combination of two or more. Among these, C2-C3 aliphatic alkylene oxides, that is, ethylene oxide and propylene oxide are preferable. More preferably, it is ethylene oxide. Therefore, the method for producing glycols of the present invention is most suitably applied when ethylene glycol is produced by reacting ethylene oxide and water.
[0012]
In this invention, it does not specifically limit as a ratio of the oxirane compound used as a reaction raw material, and water, For example, it is preferable that the molar ratio of water / oxirane compound shall be 1/1-20/1. When the molar ratio of water to the oxirane compound is less than 1, the production amount of by-products such as diglycols and triglycols increases when monoglycols are produced with good selectivity. Selectivity may be reduced. When the molar ratio of water to the oxirane compound exceeds 20, a process for removing excess water used in the reaction with a great deal of energy is required in the purification step after obtaining the product, so utility reduction effect Cannot be expected, and may be unfavorable in terms of process. More preferably 1/1 to 10/1, more preferably 1/1 to 7/1, more preferably 5/1 to 20/1, and more preferably 7/1 for highly selective monoglycols. ~ 20/1.
[0013]
The polymer catalyst used in the method for producing glycols of the present invention is an organic polymer compound that has a hetero atom as an essential component in the main chain and / or a crosslinking site and does not have a hydrogen atom bonded to the hetero atom. Such an organic polymer compound may be used alone or in combination of two or more.
[0014]
The organic polymer compound has a main chain as an essential component, and preferably has a main chain and a crosslinking site as essential components. In the case where the main chain and the crosslinking site are essential, the organic polymer compound is also referred to as an organic polymer crosslinked body. The organic polymer compound has a structure in which a hetero atom is incorporated into one or both of the main chain and the crosslinking site. That is, having a hetero atom as an essential component in a main chain and / or a crosslinking site means having a hetero atom incorporated in the structure of the main chain and / or the crosslinking site as an essential component. It does not mean that a group having a hetero atom is bonded like a side chain. When the organic polymer compound has such a structure, the heat resistance is improved unlike the case where the active site is in the side chain, the chemical deterioration is suppressed, and the catalyst is in the reaction solution during the production of glycols. Elution is difficult.
[0015]
In the organic polymer compound, the cross-linked site means a site where main chains are bonded to each other, and the cross-linked site is a combination of a part constituting the main chain and a cross-linked structure connecting them. It is structured by structure. Such a main chain and a crosslinked structure are usually bonded by a covalent bond. By having a crosslinking site, the mechanical strength of the polymer catalyst is increased.
[0016]
When the organic polymer compound has a cross-linked site, the structure of the cross-linked site is not particularly limited, and the number thereof is not particularly limited, and one or two in one molecule of the organic polymer compound. There will be more than one. When two or more cross-linked sites are present in one molecule of the organic polymer compound, the structures of the cross-linked sites may all be the same or different. The structure of the organic polymer compound having such a crosslinking site is usually a network structure formed of a main chain and a crosslinking site, and the average number of main chains of one molecule of the organic polymer compound is 2 If it is above, it will not specifically limit.
[0017]
The crosslinking density of the organic polymer compound having the crosslinking site is not particularly limited. For example, the monomer (crosslinking agent) that forms a crosslinked structure with respect to the total number of moles of the monomer that forms the organic polymer compound. ) Is preferably 0.1 to 80 mol%. If the amount is less than 0.1 mol%, the mechanical strength of the polymer catalyst may be reduced. If the amount exceeds 80 mol%, the liquid permeability of the reaction solution passing through the polymer catalyst in the production of glycols. May decrease, and the catalytic activity may not be sufficiently exhibited. More preferably, it is 0.5-50 mol%, More preferably, it is 1-20 mol%.
[0018]
The hetero atom present in the main chain and / or the crosslinking site of the organic polymer compound can be an active site that exhibits catalytic ability in the reaction of producing glycols from the oxirane compound and water. As described above, since the active site of the organic polymer compound constituting the polymer catalyst is incorporated in the structure of the main chain and / or the cross-linked site, it is difficult to thermally decompose in terms of chemical structure. Compared with the catalyst, the active site is less likely to be detached or decomposed due to the influence of heat or the like during the reaction, and the polymer catalyst has excellent heat resistance.
[0019]
The hetero atom is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, an aluminum atom, a boron atom, a zinc atom, a copper atom, a nickel atom, and an iron atom. These may be one type or two or more types. Among these, it is preferable to have a nitrogen atom. In addition, these heteroatoms are preferably ionized because the catalytic activity is improved. More preferably, it is cationized. Therefore, as the most preferable form of the polymer catalyst in the present invention, the organic polymer compound constituting the polymer catalyst has a cationized nitrogen atom in the main chain and / or a crosslinking site, that is, a cationized nitrogen atom is present. It has a structure incorporated in the main chain and / or the crosslinking site. In this specification, such a structure is referred to as an ammonium salt structure. In such an ammonium salt structure, a structure in which a cationized nitrogen atom is incorporated into the main chain by two bonds and / or a positive chain in order to improve the catalytic activity by increasing the proportion of active sites in the polymer catalyst. It is preferable to have a structure in which ionized nitrogen atoms are incorporated into the crosslinking site by three or four bonds.
[0020]
The organic polymer compound constituting the polymer catalyst in the present invention is preferably formed with a main unit of a repeating unit having a quaternary ammonium salt structure in the main chain. In this case, the main chain of the organic polymer compound may or may not additionally have a repeating unit having no quaternary ammonium salt structure. Moreover, it is preferable that the repeating unit having such a quaternary ammonium salt structure is formed by a cyclic amine structure.
[0021]
Since the cyclic amine structure is less susceptible to oxidative decomposition than the aliphatic amine structure, the thermal decomposition resistance of the polymer catalyst is more excellent. Examples of such a cyclic amine structure include a 5-membered ring and a 6-membered ring, and a 5-membered ring is preferable. Moreover, since it becomes easy to form a principal chain with a repeating unit having a quaternary ammonium salt structure as a main component, it is preferably formed of a diallyldimethylammonium salt.
[0022]
The polymer catalyst in the present invention must be an organic polymer compound that does not have a hydrogen atom bonded to a heteroatom, and the organic polymer compound has a main chain that is a skeleton formed mainly of hydrocarbons. Means a polymer compound. In the present specification, the term “polymer compound” is used as a generic term for a polymer or a compound having a molecular weight distribution, and does not mean that the molecular weight is higher than a specific molecular weight.
[0023]
When the organic polymer compound has a hydrogen atom bonded to a heteroatom, the polymer catalyst expands as the reaction of the oxirane compound and water proceeds, for example, because the hydrogen reacts with the oxirane compound. As a result, the reaction efficiency is lowered and the polymer catalyst is repeatedly used. Examples of the hydrogen atom bonded to the heteroatom include —OH group, —NH group, —NH₂This is a hydrogen atom that is directly and covalently bonded to a hetero atom such as a group, —SH group, —COOH group, etc., and is not limited to this. Further, the hydrogen atom bonded to the hetero atom contained in the polymerization initiator, suspending agent, precipitation inhibitor and the like is not limited to this.
[0024]
The organic polymer compound preferably also has a counter anion.
The counter anion means, for example, an anion coordinated to a cationized hetero atom present in a main chain and / or a crosslinking site as a cationized site in an organic polymer compound. The number of counter anions in one molecule of the organic polymer compound is not particularly limited.
[0025]
The counter anion is not particularly limited, and examples thereof include halide ions, hydroxide ions, organic acid anions, inorganic acid anions, and the like. Examples of the halogen atom in the halide ion include fluorine, chlorine, bromine, iodine and the like. An anion of an organic acid or an anion of an inorganic acid means one in which at least one hydrogen ion has been eliminated from the organic acid or the inorganic acid. For example, the anion of the inorganic acid includes sulfate ion, phosphonate ion (phosphorous acid). Acid ion), borate ion, cyanide ion, carbonate ion, hydrogen carbonate ion, thiocyanate ion, thiosulfate ion, sulfite ion, hydrogen sulfite ion, nitrate ion, cyanate ion, phosphate ion, hydrogen phosphate ion, Metalate ion (eg, molybdate ion, tungstate ion, metavanadate ion, pyrovanadate ion, hydrogen pyrovanadate ion, niobate ion, tantalate ion, perrhenate ion, etc.), tetrafluoroaluminate ion, tetrafluoro Borate ion, hexafluorophosphate ion, La chloro-aluminate ion, Al₂Cl₇ ⁻Examples of organic acid anions include sulfonate ions, formate ions, oxalate ions, acetate ions, (meth) acrylate ions, trifluoroacetate ions, trifluoromethanesulfonate ions, and bis (trifluoromethanesulfonate acids). ) Amide ion, (CF₃SO₂)₃C⁻Etc. These counter anions may be one kind or two or more kinds in the organic polymer compound. Among these, hydrogen carbonate ion, hydrogen sulfite ion, formate ion and metalate ion are preferable. More preferred are bicarbonate ions, formate ions, and most preferred are bicarbonate ions. Therefore, in the present invention, it is preferable that the counter anion requires a hydrogen carbonate ion. Thereby, catalyst activity improves more and the selectivity of monoglycols improves more.
[0026]
As a method for producing the organic polymer compound, for example, when having a cross-linked site, the formation of the main chain and the cross-linked site may be performed stepwise or simultaneously, and is not particularly limited. The polymerization can be carried out by polymerizing a monomer component containing a monomer that forms a main chain and a monomer that forms a crosslinking site. A method of cross-linking an active site in a linear polymer with a cross-linking agent such as a method of cross-linking a linear polymer containing a group with a compound having a reactive group such as dihalogen as a cross-linking agent can also be performed. The polymerization conditions, polycondensation conditions, crosslinking conditions and the like in such a production method are not particularly limited. As the method for preparing the polymer catalyst in the present invention, after the production of the organic polymer compound, operations such as washing and drying may be performed as necessary, or a composition containing other components may be used. When is solid, processing such as pulverization may be performed.
[0027]
The form of the polymer catalyst in the present invention is not particularly limited. For example, the polymer catalyst is preferably in the form of powder or solid because separation from the reaction solution is facilitated after the reaction between the oxirane compound and water.
[0028]
In the method for producing glycols of the present invention, the amount of the polymer catalyst used, the method of supplying it to the reaction apparatus, and the method of separating the polymer catalyst from the reaction solution after the reaction include the form in which the method of the present invention is carried out It may be set as appropriate in accordance with this, and is not particularly limited. Moreover, it does not specifically limit as reaction conditions, For example, it is preferable that reaction temperature is 80-200 degreeC. If it is lower than 80 ° C., the reaction rate becomes slow and the yield per unit time may be lowered. When it exceeds 200 ° C., the selectivity of monoglycols may be lowered. More preferably, it is 80-160 degreeC, More preferably, it is 90-140 degreeC. The reaction pressure is preferably 0.1 to 5 MPa. More preferably, it is 0.15-3 MPa, More preferably, it is 0.2-2 MPa.
[0029]
In the method for producing glycols of the present invention, it can be carried out in the presence of an inert gas such as carbon dioxide, nitrogen, argon, or helium, and the counter anion is hydrogen carbonate ion, hydroxide ion, chlorine ion, bromine ion. In the case of iodine ion, it is preferably carried out in the presence of carbon dioxide. Among these, when hydrogen carbonate ions are used as the counter anion, it is preferable to carry out in the substantial presence of carbon dioxide in consideration of maintaining the catalytic activity during production and loss of the anion. Substantial presence means that carbon dioxide gas is not intentionally removed, carbon dioxide gas is added to the gas phase part or liquid phase part, or bicarbonate or carbonate is used. At this time, the carbon dioxide gas added to the system has a carbon dioxide content of 0.1% by weight or more in a raw material feed from which a catalyst such as an oxirane compound, water, carbon dioxide and the like is removed. Further, the bicarbonate and carbonate added to the system may be in the form of a solid or a solution, and may be brought about by a neutralization reaction between an acid and an alkali in the system. For example, bicarbonate ions and carbonate ions in the aqueous solution are preferably 0.01 to 15% by weight, more preferably 0.2 to 5% by weight. Examples of the bicarbonate and carbonate include salts of potassium and sodium with an alkali metal. In addition, as long as the effects of the present invention are exhibited, as a component other than the oxirane compound and water as a reaction raw material and the polymer catalyst, for example, other catalysts may be added as necessary.
[0030]
The glycols produced according to the present invention are not particularly limited and include various glycols. In the present invention, monoglycols produced by the reaction of one molecule of an oxirane compound and water are selected for selectivity and productivity. It is possible to manufacture in a balanced manner. For example, when ethylene oxide is used as the oxirane compound, it is possible to improve the selectivity of monoethylene glycol by suppressing excess by-products such as diethylene glycol and triethylene glycol, and to suppress the amount of water used. Even if the concentration of ethylene oxide is increased, monoethylene glycol can be produced with good selectivity. The monoglycols produced in this manner may be used as they are or may be subjected to operations such as purification. However, since the monoglycols are excellent in selectivity, they can be used for industrial use as they are.
[0031]
DETAILED DESCRIPTION OF THE INVENTION
Preferable specific examples of the polymer catalyst used in the method for producing glycols of the present invention include an aqueous solution containing an ammonium compound represented by the following general formula and a compound having two or more diallylammonium groups in the molecule as a water-insoluble organic compound. Examples thereof include a crosslinked organic polymer obtained by copolymerization by reverse phase suspension polymerization or reverse phase emulsion polymerization using a solvent as a medium. In such a crosslinked organic polymer, a compound having two or more diallylammonium groups in the molecule forms a crosslinked structure as a crosslinking agent and is produced as spherical particles. In addition, the polymer catalyst in this invention can also be obtained by solution-polymerizing the said aqueous solution, shape | molding in a desired shape, and granulating.
[0032]
[Chemical 1]

[0033]
In the above general formula, R¹And R²Are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group or a halogen atom. R³And R⁴Are the same or different and each represents an alkyl group, an alkoxyalkyl group or an aryl group, or R³-N⁺-R⁴Is R³And R⁴And a piperidine ring or a morpholinium ring. X¹And X²Are the same or different and each represents a hydrogen atom, an alkyl group or a halogen atom. Y⁻Represents a counter anion.
[0034]
The halogen atom is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine.
The alkyl group or alkoxyalkyl group preferably has 1 to 18 carbon atoms in total. Such an alkyl group is not particularly limited, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, Examples include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. More preferably, it has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
The aryl group preferably has 6 to 15 carbon atoms, and more preferably 6 to 12 carbon atoms. Such an aryl group is not particularly limited, and examples thereof include a phenyl group, a tolyl group, and a xylyl group.
In the piperidine ring and the morpholinium ring, one or two or more hydrogen atoms may be substituted with an alkyl group having 1 to 13 carbon atoms.
[0035]
Preferable examples of the ammonium compound represented by the above general formula include diallyldialkylammonium chlorides such as diallyldimethylammonium chloride and diallyldiethylammonium chloride; dimethallyldialkylammonium chlorides such as dimethallyldimethylammonium chloride and the like. These may be used alone or in combination of two or more.
[0036]
Preferable specific examples of the compound having two or more diallylammonium groups in the molecule include compounds represented by the following formulas (1) to (10).
[0037]
[Chemical 2]

[0038]
Among the compounds represented by the above formulas (1) to (10), N, N, N ′, N′-tetraallyldipiperidylpropanium dichloride represented by the formula (10) is more preferable. Examples of the compound having two or more diallylammonium groups in the molecule include N, N′-dimethyl-N, N, N ′, other than the compounds represented by formulas (1) to (10). N'-tetraallyl-2-butene-1,4-diammonium dichloride and compounds having two or more paravinylphenylmethylammonium groups and / or metavinylphenylmethylammonium groups in the molecule include, for example, N, N ' -Di (paravinylphenylmethyl) ethylenediammonium dichloride, N, N'-di (methvinylphenylmethyl) ethylenediammonium dichloride, N, N'-di (paravinylphenylmethyl) propylenediammonium dichloride, N, N ′ -Di (metavinylphenylmethyl) propylenediammonium dichloride It is below. The compounds listed here are representative examples, and besides these, for example, compounds synthesized from phenylenediamine or other diamines and allyl chloride or allyl acetate can be mentioned. These may be used alone or in combination of two or more. In addition, the counter anion which these compounds have is not restricted to a chloride type | system | group, Another thing may be used.
[0039]
In the production of the crosslinked organic polymer, the copolymerization ratio of the ammonium compound and the compound having two or more diallylammonium groups in the molecule is not particularly limited, and for example, 40 to 99.9 / 60 to weight ratio. It is preferable to be 0.1. Moreover, you may polymerize other compounds other than the said compound suitably. Further, the concentration of the compound in the aqueous solution is not particularly limited. For example, the concentration of the aqueous solution at the time of charging is preferably 30 to 80% by weight on handling, but it is further concentrated by dehydration operation before or during the polymerization. May be.
[0040]
The water-insoluble organic solvent used as the medium is not particularly limited. For example, toluene, xylene, benzene, n-hexane, cyclohexane, octane, mineral acid, mineral spirit, kerosene, 1,1,1-trichloroethane, 1 , 2-dichloropropane, tetrachloroethane, trichloropropane, tetrachloromethane and the like brominated and / or chlorinated hydrocarbons. These may be used alone or in combination of two or more. Among these, it is industrially preferable to use toluene and xylene.
[0041]
The medium may contain a viscous fluid such as liquid paraffin and / or silicone oil. Thereby, it becomes possible to suppress agglomeration of the spherical polymer particles, or to suppress the adhesion between the spherical particles, thereby suppressing the agglomeration of the crosslinked organic polymer. As content in the medium of such a viscous fluid, it is preferable to set it as 0.1 to 50 weight%, for example. More preferably, it is 1-40 weight%, More preferably, it is 5-30 weight%. The viscosity of the medium containing the viscous fluid only needs to increase before and after the addition of the viscous fluid.
[0042]
The polymerization conditions in the above copolymerization, i.e., polymerization temperature, polymerization time, stirring conditions, polymerization initiator used, additives, etc. may be appropriately set depending on the size, performance, quality, etc. of the produced spherical particles, and are not particularly limited. It is not something. For example, the polymerization temperature is preferably 20 to 150 ° C. More preferably, it is 50-120 degreeC. Further, azeotropic dehydration may be used in combination at normal pressure or reduced pressure. The polymerization time may be appropriately set depending on other conditions, and is preferably 4 to 50 hours. The stirring condition may be the stirring speed in normal polymerization. As a polymerization initiator to be used, a general peroxide-based or azo-based initiator can be used regardless of whether it is water-soluble or oil-soluble. The additive is not particularly limited, and for example, general dispersion stabilizers such as glycerol palmitate, ethyl cellulose, sorbitan monopalmitate, sorbitan monolaurate, sorbitan monostearate, and the like can be used. Other polymerization conditions are not particularly limited.
[0043]
As a representative example of the method for producing a crosslinked organic polymer, an aqueous solution of diallyldimethylammonium salt and N, N, N ′, N′-tetraallyldipiperidylpropanium dichloride and an aqueous solution of a polymerization initiator are mixed with toluene and liquid paraffin. Is added dropwise to a medium to which a dispersion stabilizer has been added, and the case where reverse phase suspension polymerization or reverse phase emulsion polymerization is performed is shown in the following reaction formula.
[0044]
[Chemical Formula 3]

[0045]
In the above reaction formula, Y⁻Represents the chloride ion of the counter anion. m and n represent the number of moles.
The average particle diameter of the granular particles obtained by the above-described reverse phase suspension polymerization or reverse phase emulsion polymerization is preferably set to be 0.05 to 5 mm, for example.
[0046]
In the method for producing glycols of the present invention, the reaction is carried out by reacting an oxirane compound and water in the presence of a polymer catalyst. However, since the heat resistance of the polymer catalyst is excellent, the catalytic activity is stably maintained. As a result, high-quality glycols without coloring can be produced with good productivity, and monoglycols can be produced with both selectivity and productivity. Further, when the polymer catalyst is formed into granular particles as described above, it is easy to separate the polymer catalyst from the product, which is preferable as an industrial production method. The reaction using the polymer catalyst can be carried out using a stirred batch reactor, a fixed bed or a fluidized bed reactor, and the reaction method is not limited to a batch method or a continuous method. Furthermore, it can be used for reactive distillation which efficiently purifies the catalytic reaction and the reaction product obtained by the reaction, and the method of use is not limited at all by the process.
[0047]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Note that “%” means “% by weight” unless otherwise specified.
[0048]
Catalyst preparation method 1
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet tube and a dropping funnel, 350 mL of toluene and 50 mL of liquid paraffin were placed, and 0.6 g of sorbitan monopalmitate and ethyl cellulose 0 were added as a dispersion stabilizer. .2g was added and dissolved at 40 ° C. At this time, nitrogen gas was blown to drive out dissolved oxygen.
[0049]
Separately, 33.61 g of 65% diallyldimethylammonium chloride (DADMAC) aqueous solution, 3.15 g of N, N, N ′, N′-tetraallyldipiperidylpropanium dichloride (TADPPC) and 13.24 g of water were mixed in a 100 mL beaker. Dissolved (DADMAC / TADPPC = 95/5 mol%), and further polymerization initiator 2,2′-azobis (2-amidinopropane) dichloride (trade name “V-50”, manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g A solution mixed with 3 g of water was added. This mixed solution was added dropwise to the reaction vessel at 30 ° C. over 30 minutes, and after completion of the addition, the temperature was further raised at 55 ° C. for 4 hours, and reacted at 75 ° C. for 2 hours.
[0050]
After reacting for a predetermined time, it was cooled and the resulting resin was separated by vacuum filtration. The resin separated by filtration was washed three times with 800 mL of methanol for 30 minutes and dried under reduced pressure at 60 ° C. overnight to obtain a dry resin.
The obtained counter anion swelled 20.0 g of a crosslinked product of chloride ions with water, and the counter anion was replaced with chloride ions from chloride ions by a column system using 15 L of 3% aqueous sodium hydrogen carbonate solution. Then, the organic polymer crosslinked body was obtained by wash | cleaning with the same amount of water.
[0051]
Example 1
182 mL of a water swelled product of the crosslinked product obtained in Catalyst Preparation Method 1 (weighed with a graduated cylinder and used a wet product filtered under reduced pressure), 1400 g of water and 350 g of ethylene oxide were charged into a 5 L autoclave, and 120 ° C. in a nitrogen atmosphere. For 2 hours. In addition, water was prepared so that the total amount including the amount of water contained in the crosslinked body would be 1400 g. When the obtained reaction liquid was analyzed, the ethylene oxide conversion rate was 99.9% and the selectivity of monoethylene glycol was 94.2 mol%.
[0052]
Example 2
160 mL of the water-swelled product of the crosslinked product obtained by the catalyst preparation method 1 (weighed with a graduated cylinder and used a wet product filtered under reduced pressure) and 1230 g of water were charged into a 5 L autoclave and 527 g of ethylene oxide at 120 ° C. in a nitrogen atmosphere. Was allowed to react for 2 hours with continuous addition. In addition, the water was prepared so that the total amount including the amount of water contained in the crosslinked body would be 1230 g. When the obtained reaction liquid was analyzed, the selectivity of monoethylene glycol was 89.8 mol%.
[0053]
Example 3
160 mL of the water-swelled product of the crosslinked product obtained by the catalyst preparation method 1 (weighed with a graduated cylinder and used a wet product filtered under reduced pressure) and 1230 g of water were charged into a 5 L autoclave and 820 g of ethylene oxide at 120 ° C. in a nitrogen atmosphere. Was allowed to react for 2 hours with continuous addition. In addition, the water was prepared so that the total amount including the amount of water contained in the crosslinked body would be 1230 g. When the obtained reaction liquid was analyzed, the selectivity of monoethylene glycol was 85.5 mol%.
[0054]
Catalyst preparation method 2
A polymer ampoule was mixed with 6.45 g of 65% diallyldimethylammonium chloride (DADMAC) aqueous solution and 1.29 g of 72% N, N, N ′, N′-tetraallyldiaminobutane dihydrochloride (TeADAB) aqueous solution. DADMAC / TeADAB = 90/10 mol%) and 0.064 g of a polymerization initiator V-50 and 0.32 g of water for dissolving the initiator were further added.
The mixed solution was further heated at 55 ° C. for 4 hours and reacted at 75 ° C. for 2 hours.
After reacting for a predetermined time, the product was cooled and the resulting resin was pulverized, washed three times in 160 mL of methanol for 30 minutes, and dried under reduced pressure at 60 ° C. overnight to obtain a dry resin.
2.0 g of the obtained cross-linked product was stirred and washed with 200 g of 3% aqueous sodium hydrogen carbonate in 3 portions, and then washed with 3 portions of the same amount of water, whereby the counter anion was carbonated from chloride ions. A polymer crosslinked product substituted with hydrogen ions was obtained.
[0055]
Example 4
5.2 mL of the water-swelled polymer crosslinked product obtained in Catalyst Preparation Method 2 and 40.0 g of water were charged into a 100 mL autoclave, and 4.9 g of ethylene oxide was fed into the reaction system at 120 ° C. in a nitrogen atmosphere. The reaction was performed for 1 hour. Water was charged so that the total amount including water contained in the crosslinked product was 40.0 g. When the obtained reaction liquid was analyzed, the ethylene oxide conversion was 85.1% and the selectivity for monoethylene glycol was 98.1 mol%.
[0056]
Example 5
182 mL of the water swell of the crosslinked product obtained in Catalyst Preparation Method 1 (wet product weighed in a graduated cylinder and then filtered under reduced pressure), 1400 g of water and 350 g of ethylene oxide were charged into a 5 L autoclave, and carbon dioxide was added ( CO2 addition amount of water, EO and CO2 in the autoclave is 0.1% by weight). After reacting at 120 ° C. for 2 hours, the resulting reaction solution was analyzed. The conversion of ethylene oxide was 99.9% and the selectivity for monoethylene glycol was 95.0 mol%.
[0057]
Example 6
182 mL of the water swell of the crosslinked product obtained in Catalyst Preparation Method 1 (wet product weighed in a graduated cylinder and then filtered under reduced pressure), 1400 g of water and 350 g of ethylene oxide were charged into a 5 L autoclave, and carbon dioxide was added ( Water, EO, CO in autoclave₂CO₂The addition amount is 5% by weight). After reacting at 120 ° C. for 2 hours, the resulting reaction solution was analyzed. The conversion of ethylene oxide was 99.9% and the selectivity for monoethylene glycol was 94.8 mol%.
[0058]
Example 7
160 mL of the water-swelled product of the crosslinked product obtained in Catalyst Preparation Method 1 (wet product weighed with a graduated cylinder and then filtered under reduced pressure), 1230 g of water was charged into a 5 L autoclave, and carbon dioxide was added (water in the autoclave). , EO, CO planned to be introduced₂CO₂The addition amount is 0.1% by weight). While continuously adding 820 g of ethylene oxide at 120 ° C., the reaction was allowed to proceed for 2 hours. When the obtained reaction liquid was analyzed, the selectivity of monoethylene glycol was 86.2 mol%.
[0059]
Example 8
160 mL of the water-swelled product of the crosslinked product obtained in Catalyst Preparation Method 1 (wet product weighed with a graduated cylinder and then filtered under reduced pressure), 1230 g of water was charged into a 5 L autoclave, and carbon dioxide was added (water in the autoclave). , EO, CO planned to be introduced₂CO₂The addition amount is 5% by weight). While continuously adding 820 g of ethylene oxide at 120 ° C., the reaction was allowed to proceed for 2 hours. When the obtained reaction liquid was analyzed, the selectivity of monoethylene glycol was 86.0 mol%.
[0060]
【The invention's effect】
Since the glycols production method of the present invention has the above-described configuration, when the glycols are produced using the polymer catalyst, the heat resistance of the polymer catalyst is excellent, so that the catalytic activity is stably maintained. In addition, it is possible to produce high-quality glycols with no coloration with high productivity, and to produce monoglycols with both selectivity and productivity. Polyester raw materials such as polyethylene terephthalate and antifreeze In addition, glycols that can be used in a wide range of applications as raw materials for various industrial products can be suitably produced.

Claims (4)

A method for producing glycols by reacting an oxirane compound and water in the presence of a polymer catalyst,
The polymer catalyst is composed of an organic polymer compound having a nitrogen atom as an essential component in the main chain and the crosslinking site and not having a hydrogen atom bonded to the nitrogen atom ,
The following general formula:

(In the above general formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group or a halogen atom. R ³ and R ⁴ are the same or different and represent an alkyl group, an alkoxyalkyl group. R ³ —N ⁺ —R ⁴ represents a piperidine ring or a morpholinium ring by bonding R ³ and R ^4, and X ¹ and X ² are the same or different, Represents a hydrogen atom, an alkyl group, or a halogen atom, Y ⁻ represents a counter anion, and an organic compound obtained by copolymerizing an ammonium compound represented by ) and a compound having two or more diallylammonium groups in the molecule. A method for producing glycols, which is a cross-linked molecule .   2. The method for producing glycols according to claim 1, wherein the organic polymer compound has a main chain formed of a repeating unit having a quaternary ammonium salt structure as a main component.   The method for producing glycols according to claim 2, wherein the quaternary ammonium salt structure is formed of diallyldimethylammonium salt. The organic polymer compound has a counter anion,
4. The method for producing glycols according to claim 1, wherein the counter anion essentially comprises hydrogen carbonate ions.