JP3707669B2 - Method for producing water-in-oil polymer emulsion - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、油中水型水溶性高分子エマルジョンの製造方法に関するものであり、詳しくは水溶性カチオン性単量体または前記水溶性カチオン性単量体を含有する単量体混合物の水溶液を不連続相とし、油溶性乳化剤を含有する液状炭化水素を連続相とする油中水型エマルジョンを形成させ重合するに際し、過酸化水素のみを添加して重合することを特徴とする油中水型高分子エマルジョンの製造方法に関する。
【０００２】
【従来の技術】
油中水型水溶性高分子エマルジョンは、水溶性高分子を高濃度の製品形態に保存可能で、しかも分散液の粘性が非常に低いので高分子凝集剤などの高分子量を要する用途に適した液状製品である。例えば特公昭５４−３７９８６号公報には、単量対水溶液３０〜７０重量％と疎水性有機液体７０〜３０重量％を界面活性剤をもちいて乳化分散させ油中水型高分子エマルジョンを製造する方法が開示されている。また、重合持、単量体あるいは単量体混合物中にＮ、Ｎ−メチレンビスアクリルアミドのような多官能性単量体を共存させ架橋性あるいは枝分かれした重合体を製造する方法が開示されている。例えば特許第２９７５６１８号公報には、油中水型エマルジョン重合において、連鎖移動剤存在下で上記のような多官能性単量体を共存させ、せん断がかけられていない状態の撹拌条件で溶解比が３０％以上の分岐した陽イオン性重合体を製造する方法が開示され、この重合体は汚泥の脱水などに好適であることが記載されている。また、特公平８−１６４号公報には、同様に油中水型エマルジョン重合を用い、せん断を掛けない状態では、水不溶性の粒子からなる油中水型エマルジョンを合成しているが、使用している架橋形成剤はやはり前記のようなＮ、Ｎ−メチレンビスアクリルアミド型の架橋剤である。その他重合体の架橋方法あるいは分岐方法としては、ペルオクソニ硫酸塩やＮ、Ｎ−ジメチルアクリルアミドを用いる方法などが知られているが、油中水型エマルジョン重合法を用いて過酸化水素などを重合開始剤と架橋剤を兼ねた使用法は知られていない。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、重合体の架橋方法あるいは分岐方法として従来のように多官能性単量体、Ｎ、Ｎ−ジメチルアクリルアミド型架橋剤あるいはペルオクソ二硫酸塩を用いず、容易に架橋あるいは分岐した重合体を油中水型エマルジョン重合法により水溶性高分子エマルジョンを製造することである。
【０００４】
【課題を解決するための手段】
上記課題を解決するため鋭意研究を重ねた結果、以下のような発明に達した。即ち、本発明の請求項１の発明は、水溶性カチオン性単量体を含有する単量体混合物の水溶液を不連続相とし、油溶性乳化剤を含有する液状炭化水素を連続相とする油中水型エマルジョンを形成させ重合するに際し、過酸化水素のみを添加して重合する方法において、０〜４５℃で重合を開始しその後５０〜９０℃に昇温させ、熱処理を行うことにより架橋反応を促進させることを特徴とする油中水型高分子エマルジョンの製造方法である。
【０００５】
請求項２の発明は、前記水溶性カチオン性単量体を含有する単量体混合物が下記一般式（１）で表わされるカチオン性単量体５〜１００モル％とアクリルアミドを０〜９５モル％と下記一般式（２）で表わされるアニオン性単量体０〜４０モル％からなることを特徴とする請求項１に記載の油中水型高分子エマルジョンの製造方法である。
【化３】
【化４】
【０００６】
請求項３の発明は、前記過酸化水素の単量体あるいは単量体混合物に対する添加量が、０．００５〜５重量％であることを特徴とする請求項１あるいは２に記載の油中水型高分子エマルジョンの製造方法である。
【０００７】
【発明の実施の形態】
本発明の油中水型高分子エマルジョンの製造方法としては、前記カチオン性単量体と共重合可能な単量体からなる単量体混合物を水、少なくとも水と非混和性の炭化水素からなる油状物質、油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤を混合し、強撹拌し、油中水型エマルジョンを形成させた後、重合することにより合成する。この時、開始剤として過酸化水素のみを添加して重合を開始させる。重合は過酸化水素単独で開始させる。過酸化水素としての添加量は対単量体０．０１〜２．０重量％、好ましくは０．０５〜１．０重量％、さらに好ましくは０．１〜０．５重量％である。本発明の重合体の架橋方法は、酸化性雰囲気中で主に重合体中のα−位の水素を引き抜き分子中にラジカルを発生させ、架橋点を生成させ架橋、分岐を作ることにある。
【０００８】
本発明で使用するカチオン性単量体の例としては、三級アミノ基含有単量体として、（メタ）アクリル酸ジメチルアミノエチルやジメチルアミノプロピル（メタ）アクリルアミドなどであり、四級アンモニウム基含有単量体の例としては、前記三級アミノ基含有単量体の（メタ）の塩化メチルや塩化ベンジルによる四級化物である（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルジメチルベンジルアンモニウム塩化物などがあげられる。
【０００９】
共重合する水溶性の単量体の中で非イオン性の化合物としてあげられるのは、メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、酢酸ビニル、アクリロニトリル、アクリル酸メチル、（メタ）アクリル酸２−ヒドロキシエチル、ジアセトンアクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミドなどである。また、アニオン性の単量体も共重合して両性重合体を製造することもできる。そのような単量体の例として、アクリル酸、メタアクリル酸、イタコン酸、マレイン酸、フマル酸、ビニルスルフォン酸、ビニルベンゼンスルフォン酸あるいはアクリルアミド２−メチルプロパンスルフォン酸などがあげられる。最も好ましい単量体の例はアクリル酸とアクリルアミドである。
【００１０】
これら単量体の共重合モル比としては、カチオン性ビニル単量体５〜１００モル％とアクリルアミド０〜９５モル％であり、好ましくは、カチオン性ビニル単量体３０〜１００モル％、アクリルアミド０〜７０モル％である。またアニオン性ビニル単量体は、０〜５０モル％であり、好ましくは０〜３０モル％である。
【００１１】
分散媒として使用する炭化水素からなる油状物質の例としては、パラフィン類あるいは灯油、軽油、中油などの鉱油、あるいはこれらと実質的に同じ範囲の沸点や粘度などの特性を有する炭化水素系合成油、あるいはこれらの混合物があげられる。
【００１２】
油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤の例としては、ＨＬＢ３〜１１のノニオン性界面活性剤であり、その具体例としては、ソルビタンモノオレ−ト、ソルビタンモノステアレ−ト、ソルビタンモノパルミテ−トなどがあげられる。これら界面活性剤の添加量としては、油中水型エマルジョン全量に対して０．５〜１０重量％であり、好ましくは１〜５重量％である。
【００１３】
三級アミノ基含有単量体を使用する場合は、単量体を酸により中和した後、アクリルアミドなどと混合し、溶液ｐＨを２〜６に調製する。その後、界面活性剤を油状物質に溶解した溶解液を添加し、乳化機などにより油中水型エマルジョンを形成させた後、窒素置換を行い、一定の重合温度に油中水型エマルジョンを設定した後、ラジカル重合開始剤によって重合を開始させる。開始剤は、過酸化水素を使用する。
【００１４】
重合濃度は、一般的に１０〜６０重量％であるが、好ましくは２０〜５０重量％が重合反応を制御し易く、また製造の効率も良い。また、本発明による架橋法は、温度が一定以上高いと架橋反応が起き易いため、比較的低温で重合を開始させ、一定時間後反応温度を上昇させるほうが好ましい。そのため開始温度は０〜４５℃、好ましくは１５〜３５℃で１〜３時間反応させた後、５０〜９０℃、好ましくは５５〜８０℃で１〜３時間昇温させ、熱処理を行うことにより架橋反応を促進させる。
【００１５】
本発明の油中水型エマルジョンは重合後、転相剤と呼ばれる親水性界面化成剤を添加して油の膜で被われたエマルジョン粒子が水になじみ易くし、中の水溶性高分子が溶解しやすくする処理を行い、水で希釈しそれぞれの用途に用いる。親水性界面化成剤の例としては、カチオン性界面化成剤やＨＬＢ９〜１５のノニオン性界面化成剤であり、ポリオキシエチレンアルキルエ−テル系などである。
【００１６】
本発明の油中水型エマルジョンからなる水溶性高分子は、製紙工業におけるパルプスラッジの脱水、その他食品工業、金属、石油精製の各排水処理、また建材関係の砂利洗浄排水の処理などに適用可能である。特に有効な対象物として下水、し尿あるいは一般産業排水処理で生じる有機性汚泥及び凝集汚泥を含む混合汚泥などである。これら汚泥は、本発明の油中水型エマルジョンからなるカチオン性水溶性高分子を添加し、凝集させた後、ベルトプレス、フィルタ−プレス、デカンタ−あるいはスクリリュ−プレスなどの脱水機により脱水する。添加量としては、排水の種類、懸濁物濃度などのよって変化するものであるが、液量に対して０．１〜１０００ｐｐｍ程度である。また、汚泥に対しては、汚泥ｓｓに対して０．１〜３重量％である。
【００１７】
【実施例】
以下、実施例および比較例によって本発明をさらに詳しく説明するが、本発明はその要旨を超えない限り、以下の実施例に制約されるものではない。
【００１８】
（実施例１）
攪拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水６０．０ｇおよびアクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液２５７．４ｇ、アクリルアミド５０（以下ＡＡＭと略記）％水溶液３７．８ｇを混合し（単量体のモル比はＤＭＱ：ＡＡＭ＝８：２）溶液のｐＨを３．７２に調節し油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１０％水溶液０．４ｇ（対単量体０．２重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の２０％水溶液２．３ｇ（対単量体０．２重量％）を加え、重合反応を開始させ、３時間反応させた後、６０℃に昇温しそのまま３０分間保ち、反応を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１１．０ｇ（対液２．２重量％）を添加混合して試験に供する試料（試料−１）（本発明の凝集剤）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００１９】
（実施例２）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水６０．０ｇおよびアクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液１８２．６ｇ、アクリルアミド５０％水溶液１０７．２ｇ（単量体のモル比はＤＭＱ：ＡＡＭ＝５０：５０）混合しｐＨを３．５４に調節し、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１．６８ｇ（対単量体０．０２重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の２０％水溶液１．２ｇ（対単量体０．１２重量％）を加え、重合反応を開始させ、３時間反応させた後、６０℃に昇温しそのまま３０分間保ち、反応を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１２．０ｇ（対液２．４重量％）を添加混合して試験に供する試料（試料−２）（本発明の凝集剤）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００２０】
（実施例３）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水７５．０ｇおよびアクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液１１７．６ｇ、アクリルアミド５０％水溶液１６１．０ｇ（単量体のモル比はＤＭＱ：ＡＡＭ＝３０：７０）混合しｐＨを３．３７に調節し、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコールの１０％水溶液０．９ｇ（対単量体０．０５重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の２０％水溶液１．３ｇ（対単量体０．１５重量％）を加え、重合反応を開始させ、３時間反応させた後、６０℃に昇温しそのまま３０分間保ち、反応を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１２．５ｇ（対液２．５重量％）を添加混合して試験に供する試料（試料−３）（本発明の凝集剤）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００２１】
（実施例４）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水８０．０ｇ、アクリル酸の８０％水溶液１４．６ｇ（以下ＡＡＣと略記）、アクリルアミド５０％水溶液１３８．０ｇ混合し水酸化ナトリウムで８５当量％中和したの後、アクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液１１５．５ｇを中和した溶液に添加した（単量体のモル比はＤＭＱ：ＡＡＣ：ＡＡＭ＝３０：１０：６０）。その後、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１０％水溶液０．８ｇ（対単量体０．０５重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の１０％水溶液２．３ｇ（対単量体０．１重量％）を加え、重合反応を開始させ、３時間反応させた後、６０℃に昇温しそのまま３０分間保ち、反応を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１２．５ｇ（対液２．５重量％）を添加混合して試験に供する試料（試料−４）（本発明の凝集剤）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００２２】
（実施例５）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水８５．０ｇ、アクリル酸の８０％水溶液２４．８ｇ（以下ＡＡＣと略記）、アクリルアミド５０％水溶液３９．２ｇ混合し水酸化ナトリウムでアクリル酸の８５当量％中和したの後、アクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液２００．０ｇを中和した溶液に添加した（単量体のモル比はＤＭＱ：ＡＡＣ：ＡＡＭ＝６０：２０：２０）。その後、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１０％水溶液１．４ｇ（対単量体０．０７重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の１０％水溶液２．３ｇ（対単量体０．１重量％）を加え、重合反応を開始させ、３時間反応させた後、６０℃に昇温しそのまま３０分間保ち、反応を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１０．０ｇ（対液２．０重量％）を添加混合して試験に供する試料（試料−５）（本発明の凝集剤）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００２３】
（比較例１）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込みよう明きさせた。別に脱イオン水７０．０ｇおよびアクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＱと略記）８０％水溶液２８１．３ｇを混合し溶解させ、ｐＨを４．１２に調節し、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１０％水溶液１．１ｇ（対単量体０．０５重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の１０％水溶液４．５ｇ（対単量体０．２０重量％）を加え、重合反応を開始させた。反応温度を２５〜２８℃で７時間反応させ重合を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１１．０ｇ（対液２．２重量％）を添加混合して試験に供する試料（比較品−１）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００２４】
（比較例２）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水８５．０ｇ、アクリル酸の８０％水溶液２４．８ｇ（以下ＡＡＣと略記）、アクリルアミド５０％水溶液３９．２ｇ混合し水酸化ナトリウムでアクリル酸の８５当量％中和したの後、アクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液２００．０ｇを中和した溶液に添加した（単量体のモル比はＤＭＱ：ＡＡＣ：ＡＡＭ＝６０：２０：２０）。その後、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１０％水溶液１．４ｇ（対単量体０．０７重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の１０％水溶液２．３ｇ（対単量体０．１重量％）を加え、重合反応を開始させた。反応温度を２５〜２８℃で７時間反応させ重合を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１０．０ｇ（対液２．０重量％）を添加混合して試験に供する試料（比較品−２）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００２５】
（比較例３）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水７０．０ｇおよびアクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＱと略記）８０％水溶液２８１．３ｇを混合し溶解させ、ｐＨを４．０１に調節し、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１０％水溶液１．１ｇ（対単量体０．０５重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、２、２’−アゾビス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕二塩化水素化物、２．２ｇ（対単量体０．１重量％）を加え、７時間反応させ重合を完結させた。生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１１．０ｇ（対液２．２重量％）を添加混合して試験に供する試料（比較品−３）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表２に示す。
【００２６】
（比較例４）
比較例１同様にアクリロイルオキシエチルトリメチルアンモニウム塩化物とアクリルアミドのモル比が５０：５０からなる重合体の油中水型エマルジョン（比較品−４）を合成し、その後、同様の処、測定を行った。結果を表２に示す。
【００２７】
（比較例５）
比較例１同様にアクリロイルオキシエチルトリメチルアンモニウム塩化物とアクリル酸とアクリルアミドのモル比が６０：２０：２０からなる重合体の油中水型エマルジョン（比較品−５）を合成し、その後、同様の処、測定を行った。結果を表２に示す。
【００２８】
（比較例６）
撹拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇおよびソルビタンモノオレート１２．０ｇを仕込み溶解させた。別に脱イオン水８５．０ｇ、アクリル酸の８０％水溶液２４．８ｇ（以下ＡＡＣと略記）、アクリルアミド５０％水溶液３９．２ｇ混合し水酸化ナトリウムでアクリル酸の８５当量％中和したの後、アクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液２００．０ｇ及びＮ、Ｎ−メチレンビスアクリルアミドの１０％水溶液０．６ｇを中和した溶液に添加した（単量体のモル比はＤＭＱ：ＡＡＣ：ＡＡＭ＝６０：２０：２０）。その後、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで６０分間撹拌乳化した。得られたエマルジョンにイソプロピルアルコール１０％水溶液１．４ｇ（対単量体０．０７重量％）を加え、単量体溶液の温度を２５〜２８°Ｃに保ち、窒素置換を３０分行った後、過酸化水素の１０％水溶液２．３ｇ（対単量体０．１重量％）を加え、重合反応を開始させた。反応温度を２５〜２８℃で７時間反応させ重合を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１０．０ｇ（対液２．０重量％）を添加混合して試験に供する試料（比較品−６）とした。また、また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。結果を表１に示す。
【００２９】
（実施例６〜１０）
都市下水余剰汚泥（ｐＨ６．８５、全ｓｓ分１９、４００ｍｇ／Ｌ）２００ｍＬをポリビ−カ−に採取し、塩化第二鉄溶液を見かけで１０００ｐｐｍ添加しビ−カ−移し変え撹拌１０回を行い、表１の試作品−１〜５を対液５００ｐｐｍ添加し、ビ−カ−移し変え撹拌１０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、４５秒後の濾液量を測定した。また濾過した汚泥をプレス圧２Ｋｇ／ｍ2 で１分間脱水する。その後ケ−キ自己支持性（脱水ケ−キの硬さ、含水率と関係）、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）および濾布剥離を測定した。結果を表２に示す。
【００３０】
（比較例７〜１２）
表２の比較合成例の比較品−１〜６を用いた他は、実施例６〜１０と同様な試験操作により行った。結果を表２に示す。
【００３１】
（実施例１１〜１５）
実施例６〜１０と同種の都市下水余剰汚泥（ｐＨ６．８５、全ｓｓ分１９、４００ｍｇ／Ｌ）を用い試験を行った。汚泥２００ｍＬをポリビ−カ−に採取し、表１の試作品−１〜５を対液５００ｐｐｍ添加し、ビ−カ−移し変え撹拌１０回行った後、アニオン性凝集剤（Ｖ−３２０、アニオン化度２０モル％、分子量１２００万、ハイモ社製）の０．１％水溶液を２００ｐｐｍ添加しビ−カ−移し変え撹拌１０回を行いＴ−１１７９Ｌの濾布（ナイロン製）により濾過し、４５秒後の濾液量を測定した。また濾過した汚泥をプレス圧２Ｋｇ／ｍ2 で１分間脱水する。その後ケ−キ自己支持性（脱水ケ−キの硬さ、含水率と関係）、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）および濾布剥離を測定した。結果を表３に示す。
【００３２】
（比較例１３〜１８）
表２の比較合成例の比較品−１〜６を用いた他は、実施例１１〜１５と同様な試験操作により行った。結果を表３に示す。
【００３３】
（実施例１６〜２０）
化学工場余剰汚泥（ｐＨ７．００、全ｓｓ分２６、５００ｍｇ／Ｌ）２００ｍＬをポリビ−カ−に採取し、表１の試作品−１〜５を対液５５０ｐｐｍ添加し、ビ−カ−移し変え撹拌１０回行った後、アニオン性凝集剤０．１％水溶液（ハイモロックＶ−３１０、アニオン化度１０モル％、分子量１２００万、ハイモ社製）をそれぞれ対液を２５０ｐｐｍ添加し、ビ−カ−移し変え撹拌１０回を行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、４５秒後の濾液量を測定した。また濾過した汚泥をプレス圧２Ｋｇ／ｍ2 で１分間脱水する。その後ケ−キ自己支持性（脱水ケ−キの硬さ、含水率と関係）、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）および濾布剥離を測定した。結果を表４に示す。
【００３４】
（比較例１９〜２４）
表２の比較合成例の比較品−１〜６を用いた他は、実施例１６〜２０と同様な試験操作により行った。結果を表４に示す。
【００３５】
【表１】
【表２】
【表３】
【表４】
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a water-in-oil type water-soluble polymer emulsion. Specifically, an aqueous solution of a water-soluble cationic monomer or a monomer mixture containing the water-soluble cationic monomer is not used. A water-in-oil type, characterized by adding only hydrogen peroxide to form a water-in-oil emulsion with a continuous phase and a liquid hydrocarbon containing an oil-soluble emulsifier as a continuous phase. The present invention relates to a method for producing a molecular emulsion.
[0002]
[Prior art]
Water-in-oil water-soluble polymer emulsions are suitable for applications that require high molecular weight such as polymer flocculants because the water-soluble polymer can be stored in high concentration product form and the viscosity of the dispersion is very low. It is a liquid product. For example, in Japanese Patent Publication No. 54-37986, a water-in-oil type polymer emulsion is prepared by emulsifying and dispersing a single amount of 30 to 70% by weight of an aqueous solution and 70 to 30% by weight of a hydrophobic organic liquid using a surfactant. A method is disclosed. Also disclosed is a method for producing a cross-linkable or branched polymer by allowing a polyfunctional monomer such as N, N-methylenebisacrylamide to coexist in a monomer or monomer mixture. . For example, in Japanese Patent No. 2975618, in water-in-oil emulsion polymerization, a polyfunctional monomer as described above is coexistent in the presence of a chain transfer agent, and a dissolution ratio is obtained under stirring conditions in which no shear is applied. Discloses a method for producing a branched cationic polymer of 30% or more, and it is described that this polymer is suitable for sludge dehydration and the like. In Japanese Patent Publication No. 8-164, a water-in-oil emulsion polymerization comprising water-insoluble particles is synthesized in a state where water-in-oil emulsion polymerization is similarly applied and no shear is applied. The cross-linking agent is an N, N-methylenebisacrylamide type cross-linking agent as described above. Other known methods for crosslinking or branching the polymer include methods using peroxonisulfate and N, N-dimethylacrylamide, but use water-in-oil emulsion polymerization to initiate polymerization of hydrogen peroxide and the like. There is no known method of using both an agent and a crosslinking agent.
[0003]
[Problems to be solved by the invention]
The object of the present invention is to easily crosslink or branch without using a polyfunctional monomer, N, N-dimethylacrylamide type cross-linking agent or peroxodisulfate as a conventional method for crosslinking or branching a polymer. A water-soluble polymer emulsion is produced from a polymer by a water-in-oil emulsion polymerization method.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the following inventions have been achieved. That is, the invention of claim 1 of the present invention is an oil in which an aqueous solution of a monomer mixture containing a water-soluble cationic monomer is a discontinuous phase and a liquid hydrocarbon containing an oil-soluble emulsifier is a continuous phase. In the polymerization method by forming only a water-type emulsion and adding only hydrogen peroxide, the polymerization is started at 0 to 45 ° C., then the temperature is raised to 50 to 90 ° C., and the crosslinking reaction is performed by heat treatment. It is a method for producing a water-in-oil polymer emulsion characterized in that it is promoted.
[0005]
The invention according to claim 2 is characterized in that the monomer mixture containing the water-soluble cationic monomer comprises 5 to 100 mol% of a cationic monomer represented by the following general formula (1) and 0 to 95 mol% of acrylamide. 2. The method for producing a water-in-oil polymer emulsion according to claim 1, comprising 0 to 40 mol% of an anionic monomer represented by the following general formula (2):
[Chemical 3]
[Formula 4]
[0006]
The invention according to claim 3 is characterized in that the amount of hydrogen peroxide added to the monomer or monomer mixture is 0.005 to 5% by weight. Type polymer emulsion.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
As a method for producing water-in-oil polymer emulsion of the present invention, a monomer mixture consisting of the cations on monomer copolymerizable with the monomer from water, at least water-immiscible hydrocarbon By mixing at least one surfactant having an HLB with an amount effective to form an oily substance, a water-in-oil emulsion, and vigorously stirring to form a water-in-oil emulsion and then polymerizing. Synthesize. At this time, only hydrogen peroxide is added as an initiator to initiate polymerization. The polymerization is initiated with hydrogen peroxide alone. The amount added as hydrogen peroxide is 0.01 to 2.0% by weight, preferably 0.05 to 1.0% by weight, more preferably 0.1 to 0.5% by weight, based on the monomer. The polymer cross-linking method of the present invention is to draw hydrogen at the α-position in the polymer mainly in an oxidizing atmosphere to generate radicals in the molecules, to generate cross-linking points and to form cross-links and branches.
[0008]
Examples of cationic monomers used in the present invention include tertiary amino group-containing monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide, which contain quaternary ammonium groups. Examples of the monomer include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy 2 which is a quaternized product of (meth) methyl chloride or benzyl chloride of the tertiary amino group-containing monomer. -Hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride, (meth) acrylic Etc. yl aminopropyl dimethyl benzyl ammonium chloride and the like.
[0009]
Among the water-soluble monomers to be copolymerized, examples of nonionic compounds include meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, and (meth) acrylic acid 2- Hydroxyethyl, diacetone acrylamide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide and the like. An amphoteric polymer can also be produced by copolymerizing an anionic monomer. Examples of such monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl sulfonic acid, vinyl benzene sulfonic acid or acrylamide 2-methylpropane sulfonic acid. Examples of the most preferred monomers are acrylic acid and acrylamide.
[0010]
The copolymerization molar ratio of these monomers is 5 to 100 mol% of the cationic vinyl monomer and 0 to 95 mol% of acrylamide, preferably 30 to 100 mol% of the cationic vinyl monomer, and 0% of acrylamide. -70 mol%. Moreover, an anionic vinyl monomer is 0-50 mol%, Preferably it is 0-30 mol%.
[0011]
Examples of oily substances composed of hydrocarbons used as a dispersion medium include paraffins, mineral oils such as kerosene, light oil, and middle oil, or hydrocarbon-based synthetic oils having characteristics such as boiling point and viscosity substantially in the same range as these. Or a mixture thereof.
[0012]
Examples of at least one surfactant having an amount effective to form a water-in-oil emulsion and HLB are HLB 3-11 nonionic surfactants, specific examples of which include sorbitan monooleate Sorbitan monostearate, sorbitan monopalmitate and the like. The amount of these surfactants to be added is 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the water-in-oil emulsion.
[0013]
When a tertiary amino group-containing monomer is used, the monomer is neutralized with an acid and then mixed with acrylamide or the like to adjust the solution pH to 2-6. After that, a solution obtained by dissolving a surfactant in an oily substance was added, and after forming a water-in-oil emulsion with an emulsifier or the like, nitrogen substitution was performed, and the water-in-oil emulsion was set to a constant polymerization temperature. Thereafter, polymerization is initiated by a radical polymerization initiator. Hydrogen peroxide is used as the initiator.
[0014]
The polymerization concentration is generally 10 to 60% by weight, but preferably 20 to 50% by weight easily controls the polymerization reaction, and the production efficiency is good. In the crosslinking method according to the present invention, since a crosslinking reaction is likely to occur when the temperature is higher than a certain level, it is preferable to start the polymerization at a relatively low temperature and raise the reaction temperature after a certain time. Therefore, after reacting at a starting temperature of 0 to 45 ° C., preferably 15 to 35 ° C. for 1 to 3 hours, the temperature is raised to 50 to 90 ° C., preferably 55 to 80 ° C. for 1 to 3 hours, and heat treatment is performed. Promotes the cross-linking reaction.
[0015]
In the water-in-oil emulsion of the present invention, after the polymerization, a hydrophilic interfacial modifier called a phase inversion agent is added so that the emulsion particles covered with the oil film can easily become familiar with water, and the water-soluble polymer therein dissolves. To make it easier to use, diluted with water and used for each application. Examples of hydrophilic interfacial chemicals include cationic interfacial chemicals and HLB 9-15 nonionic interfacial chemicals, such as polyoxyethylene alkyl ethers.
[0016]
The water-soluble polymer comprising the water-in-oil emulsion of the present invention can be applied to pulp sludge dewatering in the paper industry, other wastewater treatment in the food industry, metal and oil refining, and treatment of gravel washing wastewater related to building materials. It is. Particularly effective objects include sewage, human waste, or mixed sludge containing organic sludge and agglomerated sludge generated in general industrial wastewater treatment. These sludges are added with a cationic water-soluble polymer comprising the water-in-oil emulsion of the present invention and agglomerated, and then dehydrated by a dehydrator such as a belt press, a filter press, a decanter, or a screw press. The amount added varies depending on the type of waste water, the concentration of the suspension, etc., but is about 0.1 to 1000 ppm with respect to the liquid amount. Moreover, with respect to sludge, it is 0.1 to 3 weight% with respect to sludge.
[0017]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in more detail with an Example and a comparative example, this invention is not restrict | limited to a following example, unless the summary is exceeded.
[0018]
(Example 1)
In a reaction vessel equipped with a stirrer and a temperature control device, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 60.0 g of deionized water, 257.4 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride, and 37.8 g of 50% aqueous solution of acrylamide 50 (hereinafter abbreviated as AAM) were mixed (the monomer molar ratio was DMQ: AAM = 8: 2) The pH of the solution was adjusted to 3.72, the oil and the aqueous solution were mixed, and the mixture was stirred and emulsified with a homogenizer at 1000 rpm for 60 minutes. After adding 0.4 g of 10% aqueous solution of isopropyl alcohol (0.2% by weight of monomer) to the obtained emulsion, maintaining the temperature of the monomer solution at 25 to 28 ° C., and performing nitrogen substitution for 30 minutes , 20% aqueous solution 2.3 g (vs. monomer 0.2 wt%) of hydrogen peroxide was added, the polymerization reaction is started and, after reacting for 3 hours, kept at 60 ° C. was heated for 30 minutes as it reacted Was completed. After polymerization, 11.0 g of polyoxyethylene tridecyl ether (2.2% by weight with respect to the liquid) is added to the resulting water-in-oil emulsion as a phase inversion agent and mixed to prepare a sample (sample-1) (this) Inventive flocculant). Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0019]
(Example 2)
In a reaction vessel equipped with a stirrer and a temperature controller, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 60.0 g of deionized water and 182.6 g of an 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride and 107.2 g of an aqueous solution of 50% acrylamide (molar ratio of monomers: DMQ: AAM = 50: 50) were mixed to adjust the pH to 3. .54, the oil and the aqueous solution were mixed, and stirred and emulsified with a homogenizer at 1000 rpm for 60 minutes. To the obtained emulsion, 1.68 g of isopropyl alcohol (0.02% by weight of monomer) was added, the temperature of the monomer solution was kept at 25 to 28 ° C., and nitrogen substitution was performed for 30 minutes. was added 20% aqueous solution 1.2 g (vs. monomer 0.12 wt%) of hydrogen, the polymerization reaction is started and, after reacting for 3 hours, kept at 60 ° C. was heated for 30 minutes as it was to complete the reaction It was. After the polymerization, 12.0 g (2.4% by weight of polyoxyethylene tridecyl ether) as a phase inversion agent was added to the resulting water-in-oil emulsion and mixed, and the sample (sample-2) (this sample) was used for the test. Inventive flocculant). Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0020]
(Example 3)
In a reaction vessel equipped with a stirrer and a temperature controller, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 75.0 g of deionized water, 117.6 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride, and 161.0 g of 50% aqueous solution of acrylamide (molar ratio of monomer is DMQ: AAM = 30: 70), and the pH is 3 37, the oil and the aqueous solution were mixed, and the mixture was emulsified with stirring at 1000 rpm with a homogenizer for 60 minutes. To the obtained emulsion, 0.9 g of a 10% aqueous solution of isopropyl alcohol (0.05% by weight of monomer) was added, the temperature of the monomer solution was kept at 25 to 28 ° C., and nitrogen substitution was performed for 30 minutes. after, 20% aqueous solution 1.3 g (vs. monomer 0.15 wt%) of hydrogen peroxide was added, the polymerization reaction is started and, after reacting for 3 hours, kept at 60 ° C. was heated for 30 minutes as it The reaction was completed. After polymerization, 12.5 g of polyoxyethylene tridecyl ether (2.5% by weight of the liquid) as a phase inversion agent was added to and mixed with the resulting water-in-oil emulsion and used for the test (Sample-3) Inventive flocculant). Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0021]
(Example 4)
In a reaction vessel equipped with a stirrer and a temperature controller, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 80.0 g of deionized water, 14.6 g of an 80% aqueous solution of acrylic acid (hereinafter abbreviated as AAC) and 138.0 g of an acrylamide 50% aqueous solution were mixed and neutralized with sodium hydroxide at 85 equivalent percent, and then acryloyloxyethyltrimethyl. 115.5 g of an 80% aqueous solution of ammonium chloride was added to the neutralized solution (monomer molar ratio was DMQ: AAC: AAM = 30: 10: 60). Then, oil and aqueous solution were mixed and emulsified with stirring at 1000 rpm with a homogenizer for 60 minutes. After adding 0.8 g of 10% aqueous solution of isopropyl alcohol (0.05% by weight of monomer) to the obtained emulsion, maintaining the temperature of the monomer solution at 25 to 28 ° C., and performing nitrogen substitution for 30 minutes , a 10% aqueous solution 2.3 g (vs. monomer 0.1 wt%) of hydrogen peroxide was added, the polymerization reaction is started and, after reacting for 3 hours, kept at 60 ° C. was heated for 30 minutes as it reacted Was completed. After polymerization, 12.5 g of polyoxyethylene tridecyl ether (2.5% by weight of the liquid) was added to and mixed with the resulting water-in-oil emulsion as a phase inversion agent and used for the test (Sample-4) Inventive flocculant). Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0022]
(Example 5)
In a reaction vessel equipped with a stirrer and a temperature controller, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 85.0 g of deionized water, 24.8 g of 80% aqueous solution of acrylic acid (hereinafter abbreviated as AAC) and 39.2 g of 50% aqueous solution of acrylamide were mixed and neutralized with 85 eq% of acrylic acid with sodium hydroxide, and then acryloyl. 200.0 g of 80% aqueous solution of oxyethyltrimethylammonium chloride was added to the neutralized solution (monomer molar ratio was DMQ: AAC: AAM = 60: 20: 20). Then, oil and aqueous solution were mixed and emulsified with stirring at 1000 rpm with a homogenizer for 60 minutes. After adding 1.4 g of 10% aqueous solution of isopropyl alcohol (0.07% by weight of monomer) to the obtained emulsion, maintaining the temperature of the monomer solution at 25 to 28 ° C., and performing nitrogen substitution for 30 minutes , a 10% aqueous solution 2.3 g (vs. monomer 0.1 wt%) of hydrogen peroxide was added, the polymerization reaction is started and, after reacting for 3 hours, kept at 60 ° C. was heated for 30 minutes as it reacted Was completed. After polymerization, 10.0 g of polyoxyethylene tridecyl ether (2.0% by weight with respect to the liquid) was added to the resulting water-in-oil emulsion as a phase inversion agent and mixed, and the sample was used for the test (Sample-5) Inventive flocculant). Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0023]
(Comparative Example 1)
A reactor equipped with a stirrer and a temperature control device was charged with 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate. Separately, 70.0 g of deionized water and 281.3 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DMQ) are mixed and dissolved, the pH is adjusted to 4.12, the oil and the aqueous solution are mixed, and the homogenizer The mixture was emulsified with stirring at 1000 rpm for 60 minutes. After adding 1.1 g of isopropyl alcohol 10% aqueous solution (0.05% by weight of monomer) to the obtained emulsion, keeping the temperature of the monomer solution at 25 to 28 ° C., and performing nitrogen substitution for 30 minutes Then, 4.5 g of a 10% aqueous solution of hydrogen peroxide (0.20% by weight of monomer) was added to initiate the polymerization reaction. The reaction was carried out at a reaction temperature of 25 to 28 ° C. for 7 hours to complete the polymerization. After polymerization, 11.0 g of polyoxyethylene tridecyl ether (2.2% by weight with respect to the liquid) was added and mixed as a phase inversion agent to the resulting water-in-oil emulsion, and a sample for comparison (Comparative product- 1) did. Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0024]
(Comparative Example 2)
In a reaction vessel equipped with a stirrer and a temperature controller, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 85.0 g of deionized water, 24.8 g of 80% aqueous solution of acrylic acid (hereinafter abbreviated as AAC) and 39.2 g of 50% aqueous solution of acrylamide were mixed and neutralized with 85 eq% of acrylic acid with sodium hydroxide, and then acryloyl. 200.0 g of 80% aqueous solution of oxyethyltrimethylammonium chloride was added to the neutralized solution (monomer molar ratio was DMQ: AAC: AAM = 60: 20: 20). Then, oil and aqueous solution were mixed and emulsified with stirring at 1000 rpm with a homogenizer for 60 minutes. After adding 1.4 g of 10% aqueous solution of isopropyl alcohol (0.07% by weight of monomer) to the obtained emulsion, maintaining the temperature of the monomer solution at 25 to 28 ° C., and performing nitrogen substitution for 30 minutes , a 10% aqueous solution 2.3 g (vs. monomer 0.1 wt%) of hydrogen peroxide was added to initiate the polymerization reaction. The reaction was carried out at a reaction temperature of 25 to 28 ° C. for 7 hours to complete the polymerization. After the polymerization, 10.0 g of polyoxyethylene tridecyl ether (2.0% by weight of the liquid) as a phase inversion agent was added to the resulting water-in-oil emulsion and mixed, and the sample for comparison (Comparative product- 2) did. Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0025]
(Comparative Example 3)
In a reaction vessel equipped with a stirrer and a temperature controller, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 70.0 g of deionized water and 281.3 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DMQ) are mixed and dissolved, the pH is adjusted to 4.01, the oil and the aqueous solution are mixed, and the homogenizer The mixture was emulsified with stirring at 1000 rpm for 60 minutes. After adding 1.1 g of isopropyl alcohol 10% aqueous solution (0.05% by weight of monomer) to the obtained emulsion, keeping the temperature of the monomer solution at 25 to 28 ° C., and performing nitrogen substitution for 30 minutes , 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2.2 g of (vs. monomer 0.1 wt%) was added, 7 hours To complete the polymerization. The resulting water-in-oil emulsion was mixed with 11.0 g of polyoxyethylene tridecyl ether (2.2% by weight with respect to the liquid) as a phase inversion agent and used as a sample for comparison (Comparative product-3). Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 2.
[0026]
(Comparative Example 4)
In the same manner as in Comparative Example 1, a polymer water-in-oil emulsion (Comparative product-4) having a molar ratio of acryloyloxyethyltrimethylammonium chloride to acrylamide of 50:50 was synthesized. It was. The results are shown in Table 2.
[0027]
(Comparative Example 5)
In the same manner as in Comparative Example 1, a polymer water-in-oil emulsion (Comparative Product-5) having a molar ratio of acryloyloxyethyltrimethylammonium chloride / acrylic acid / acrylamide of 60:20:20 was synthesized. The measurement was performed. The results are shown in Table 2.
[0028]
(Comparative Example 6)
In a reaction vessel equipped with a stirrer and a temperature controller, 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 12.0 g of sorbitan monooleate were charged and dissolved. Separately, 85.0 g of deionized water, 24.8 g of 80% aqueous solution of acrylic acid (hereinafter abbreviated as AAC) and 39.2 g of 50% aqueous solution of acrylamide were mixed and neutralized with 85 eq% of acrylic acid with sodium hydroxide, and then acryloyl. 200.0 g of 80% aqueous solution of oxyethyltrimethylammonium chloride and 0.6 g of 10% aqueous solution of N, N-methylenebisacrylamide were added to the neutralized solution (the molar ratio of monomers was DMQ: AAC: AAM = 60). : 20: 20). Then, oil and aqueous solution were mixed and emulsified with stirring at 1000 rpm with a homogenizer for 60 minutes. After adding 1.4 g of 10% aqueous solution of isopropyl alcohol (0.07% by weight of monomer) to the obtained emulsion, maintaining the temperature of the monomer solution at 25 to 28 ° C., and performing nitrogen substitution for 30 minutes , a 10% aqueous solution 2.3 g (vs. monomer 0.1 wt%) of hydrogen peroxide was added to initiate the polymerization reaction. The reaction was carried out at a reaction temperature of 25 to 28 ° C. for 7 hours to complete the polymerization. After polymerization, 10.0 g of polyoxyethylene tridecyl ether (2.0% by weight with respect to the liquid) was added to the resulting water-in-oil emulsion as a phase inversion agent and mixed to prepare a sample for comparison (Comparative Product- 6). It was. Moreover, the weight average molecular weight was measured with the molecular weight measuring device (Otsuka Electronics DLS-7000) by a static light scattering method. The results are shown in Table 1.
[0029]
(Examples 6 to 10)
Collect 200 mL of municipal wastewater surplus sludge (pH 6.85, total ss 19, 19, 400 mg / L) in a poly beaker, add an apparent 1000 ppm ferric chloride solution, transfer the beaker, and change the beaker 10 times. After adding 500 ppm of the prototypes 1 to 5 in Table 1, transferring the beaker and stirring 10 times, filtering through a T-1179L filter cloth (made of nylon), the amount of filtrate after 45 seconds Was measured. The filtered sludge is dehydrated at a press pressure of 2 kg / m 2 for 1 minute. Thereafter, the cake self-supporting property (related to the hardness and water content of the dewatered cake), the cake water content (dried at 105 ° C. for 20 hours) and the peeling of the filter cloth were measured. The results are shown in Table 2.
[0030]
(Comparative Examples 7-12)
The same test operation as in Examples 6 to 10 was performed except that Comparative products -1 to 6 of Comparative Synthesis Examples in Table 2 were used. The results are shown in Table 2.
[0031]
(Examples 11 to 15)
The tests were conducted using the same type of municipal sewage surplus sludge (pH 6.85, total ss content 19, 400 mg / L) as in Examples 6 to 10. 200 mL of sludge was collected in a poly beaker, prototypes 1 to 5 in Table 1 were added to the solution 500 ppm, the beaker was transferred and stirred 10 times, and then an anionic flocculant (V-320, anion). 200 ppm of a 0.1% aqueous solution having a degree of conversion of 20 mol%, a molecular weight of 12 million, manufactured by Hymo Co., Ltd.), transferred to a beaker, stirred 10 times, filtered through a T-1179L filter cloth (made of nylon), 45 The amount of filtrate after 2 seconds was measured. The filtered sludge is dehydrated at a press pressure of 2 kg / m 2 for 1 minute. Thereafter, the cake self-supporting property (related to the hardness and water content of the dewatered cake), the cake water content (dried at 105 ° C. for 20 hours) and the peeling of the filter cloth were measured. The results are shown in Table 3.
[0032]
(Comparative Examples 13-18)
The same test operations as in Examples 11 to 15 were performed except that Comparative products 1 to 6 of Comparative Synthesis Examples in Table 2 were used. The results are shown in Table 3.
[0033]
(Examples 16 to 20)
Chemical factory surplus sludge (pH 7.00, total ss content 26, 500 mg / L) 200 mL was collected in a poly beaker, prototypes 1 to 5 in Table 1 were added to the liquid 550 ppm, and the beaker was transferred. After 10 times of stirring, 250 ppm of an anionic flocculant 0.1% aqueous solution (Himoloc V-310, anionization degree 10 mol%, molecular weight 12 million, manufactured by Hymo Co., Ltd.) was added to the beaker. The mixture was transferred and stirred 10 times, and then filtered through a T-1179L filter cloth (manufactured by nylon), and the amount of filtrate after 45 seconds was measured. The filtered sludge is dehydrated at a press pressure of 2 kg / m 2 for 1 minute. Thereafter, the cake self-supporting property (related to the hardness and water content of the dewatered cake), the cake water content (dried at 105 ° C. for 20 hours) and the peeling of the filter cloth were measured. The results are shown in Table 4.
[0034]
(Comparative Examples 19-24)
The same test operation as in Examples 16 to 20 was performed except that Comparative products 1 to 6 of Comparative Synthesis Examples in Table 2 were used. The results are shown in Table 4.
[0035]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
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| KR102158398B1 (en) | 2012-08-22 | 2020-09-22 | 엠티 아쿠아포리마 가부시키가이샤 | Polymer-coagulating agent and method for producing same, and method for dehydrating sludge using same |
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