JP2004204059A - Preparation process of polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a preparation process of a polymer which prevents gelling and gives uniform polymers of stable quality. <P>SOLUTION: The preparation process requires a monomer component and a polymerization initiator as necessary source materials and comprises performing polymerization by casting the materials into a reaction vessel from separate nozzles for each material installed on the vessel. The straight distance between the casting nozzle for the monomer and the nozzle for the polymerization initiator is not less than the half of the diameter of the reaction vessel. The process is characterized by direct dropping of the monomer component onto the reaction solution in the reaction vessel. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００３０】
で表される化合物であることが好ましい。
上記一般式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、同一若しくは異なって、水素原子又はメチル基を表す。Ｒ^４は、水素原子又は炭素数１〜２０の炭化水素基を表す。Ｒ^５は、同一又は異なって、炭素数２〜１８のアルキレン基を表す。ｍは、Ｒ^５Ｏで表されるオキシアルキレン基の平均付加モル数を表し、１〜３００の数である。Ｙは、炭素数０〜５のアルキル基又は−ＣＯ−を表す。Ｙが−ＣＯ−の場合、一般式（１）はポリアルキレングリコールエステル系単量体を表わし、Ｙが炭素数０〜５のアルキル基の場合、一般式（１）はポリアルキレングリコールエーテル系単量体を表わす。
【００３１】
上記一般式（１）における−（Ｒ^５Ｏ）−で表されるオキシアルキレン基は、炭素数２〜１８のアルキレンオキシド付加物であるが、このようなアルキレンオキシド付加物の構造は、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等のアルキレンオキシドの１種又は２種以上により形成される構造であり、２種類以上により形成される場合、ランダム付加、ブロック付加、交互付加等のいずれの付加形態であってもよい。
【００３２】
上記Ｒ^５Ｏで表されるオキシアルキレン基の平均付加モル数であるｍは、１〜３００の数であるが、ｍが３００を超えると、単量体の重合性が低下するおそれがある。ｍの好ましい範囲としては、２以上であり、より好ましくは、４〜２５０であり、更に好ましくは、１０〜１５０である。なお、平均付加モル数とは、単量体１モル中において付加している当該有機基のモル数の平均値を意味する。
【００３３】
上記Ｒ^４は、水素原子又は炭素数１〜２０の炭化水素基であるが、炭素数が２０を超えると、得られるポリカルボン酸系重合体の疎水性が強くなりすぎるために、良好な分散性を得られないおそれがある。Ｒ^４としては、分散性の点から、より好ましくは、炭素数１〜１０、更に好ましくは、炭素数１〜３、特に好ましくは、炭素数１〜２の炭化水素基である。
【００３４】
上記ポリアルキレングリコールエステル系単量体としては、不飽和カルボン酸ポリアルキレングリコールエステル系化合物が挙げられるが、（アルコキシ）ポリアルキレングリコールモノ（メタ）アクリル酸エステルが好適であり、中でも、以下に示す（アルコキシ）ポリエチレングリコール（ポリ）（炭素数２〜４のアルキレングリコール）（メタ）アクリル酸エステル類が好ましい。
メトキシポリエチレングリコールモノ（メタ）アクリレート、メトキシ｛ポリエチレングリコール（ポリ）プロピレングリコール｝モノ（メタ）アクリレート、エトキシポリエチレングリコールモノ（メタ）アクリレート、ブトキシポリエチレングリコールモノ（メタ）アクリレート等。
【００３５】
上記ポリアルキレングリコールエステル系単量体としては、上述した単量体の他にも、以下に例示のもの等を用いることができる。
（アルコキシ）ポリアルキレングリコールモノマレイン酸エステル、（アルコキシ）ポリアルキレングリコールジマレイン酸エステル等の、炭素数１〜２２個のアルコールや炭素数１〜２２のアミンに炭素数２〜４のオキシアルキレンを１〜３００モル付加させたアルキルポリアルキレングリコールと上記不飽和ジカルボン酸系単量体とのハーフエステル、ジエステル；上記不飽和ジカルボン酸系単量体と炭素数２〜４のグリコールの平均付加モル数２〜３００のポリアルキレングリコールとのハーフエステル、ジエステル；トリエチレングリコールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、（ポリ）エチレングリコール（ポリ）プロピレングリコールジ（メタ）アクリレート等の（ポリ）アルキレングリコールジ（メタ）アクリレート類；トリエチレングリコールジマレート、ポリエチレングリコールジマレート等の（ポリ）アルキレングリコールジマレート類等。
【００３６】
上記ポリアルキレングリコールエーテル系単量体としては、（メタ）アリルアルコールアルキレンオキシド付加物、３−ブテン−１−オールアルキレンオキシド付加物、イソプレンアルコール（３−メチル−３−ブテン−１−オール）アルキレンオキシド付加物、３−メチル−２−ブテン−１−オールアルキレンオキシド付加物等が好適である。
【００３７】
上記ポリアルキレングリコールエーテル系単量体としてはまた、ポリエチレングリコールモノアリルエーテル、ポリエチレングリコールモノ（２−メチル−２−プロペニル）エーテル、ポリエチレングリコールモノ（３−メチル−３−ブテニル）エーテル、ポリエチレングリコールモノ（３−メチル−２−ブテニル）エーテル、ポリエチレングリコールモノ（１，１−ジメチル−２−プロペニル）エーテル、ポリエチレンポリプロピレングリコールモノ（３−メチル−３−ブテニル）エーテル、メトキシポリエチレングリコールモノ（３−メチル−３−ブテニル）エーテル、メトキシポリエチレングリコールモノアリルエーテル等を用いることもできる。
【００３８】
上記その他の不飽和化合物としては、以下に例示する化合物等が好適である。
スチレン、ブロモスチレン、クロロスチレン、メチルスチレン等のスチレン類；１，３−ブタジエン、イソプレン、イソブチレン等のジエン類；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル等の（メタ）アクリル酸エステル類；ヘキセン、ヘプテン、デセン等のα−オレフィン類；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のアルキルビニルエーテル類；酢酸ビニル等のビニルエステル類；酢酸アリル等のアリルエステル類；ヘキサンジオールジ（メタ）アクリレート等の二官能（メタ）アクリレート類；ビニルスルホネート、（メタ）アリルスルホネート、スチレンスルホン酸等の不飽和スルホン酸類、並びに、それらの一価金属塩、二価金属塩、アンモニウム塩及び有機アミン塩。
【００３９】
（メタ）アクリルアミド等の不飽和アミド類；アリルアルコール等のアリル類；ジメチルアミノエチル（メタ）アクリレート等の不飽和アミノ化合物類；メトキシポリエチレングリコールモノビニルエーテル、ポリエチレングリコールモノビニルエーテル、メトキシポリエチレングリコールモノ（メタ）アリルエーテル、ポリエチレングリコールモノ（メタ）アリルエーテル等のビニルエーテル又はアリルエーテル類；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチルエチル（メタ）アクリレート、メトキシプロピル（メタ）アクリレート等の（メタ）アクリレート化合物類。
【００４０】
上記ポリカルボン酸系重合体において、ポリアルキレングリコール鎖を有する不飽和単量体／不飽和カルボン酸／その他の不飽和化合物の組成比（質量比）としては、１〜９９／１〜９９／０〜６０であることが好適である。好ましくは、３５〜９９／１〜５０／０〜４０であり、より好ましくは、５０〜９９／２〜４０／０〜２５である。
【００４１】
上記ポリカルボン酸系重合体の重量平均分子量としては、以下のような条件において測定したゲルパーミエーションクロマトグラフィー（以下「ＧＰＣ」と呼ぶ）によるポリエチレングリコール換算で１，０００〜５００，０００が好適である。重量平均分子量が１，０００未満であっても、５００，０００を越えても、分散性能が低下するおそれがある。好ましくは、３，０００〜３００，０００であり、より好ましくは、５，０００〜１００，０００であり、更に好ましくは、７，０００〜８０，０００である。
【００４２】
＜重量平均分子量測定条件＞

【００４３】
本発明の製造方法において、ポリカルボン酸系重合体を製造する場合、反応槽中で上述した単量体成分と重合開始剤とを必須の製造原料として重合を行う重合工程を含んでなることになるが、その他の工程を含んでいてもよい。
上記重合工程における重合方法としては、溶媒中での重合方法や塊状重合方法等が好適である。溶媒中での重合方法としては、回分式でも連続式でもよい。使用される溶媒としては、水；メチルアルコール、エチルアルコール、２−プロパノール等の低級アルコール；ベンゼン、トルエン、キシレン、シクロヘキサン、ｎ−ヘキサン等の芳香族又は脂肪族炭化水素；酢酸エチル等のエステル化合物；アセトン、メチルエチルケトン等のケトン化合物等が好適である。これらの中でも、単量体成分及び得られるポリカルボン酸系重合体の溶解性並びにこの重合体の使用時の取扱い性の点から、水及びメチルアルコール、エチルアルコール、２−プロパノール等を用いることが好ましい。
【００４４】
上記溶媒中での重合方法において、水媒体中で重合を行う場合に、重合開始剤としては、アンモニウム又はアルカリ金属の過硫酸塩、若しくは、過酸化水素等の水溶性の重合開始剤を用いることが好適である。この際、亜硫酸水素ナトリウム、モール塩、アスコルビン酸（塩）、ロンガリット等の促進剤を併用することもできる。また、低級アルコール、芳香族炭化水素、脂肪族炭化水素、エステル化合物又はケトン化合物を溶媒とする重合には、ベンゾイルパーオキシドやラウロイルパーオキシド等のパーオキシド；クメンハイドロパーオキシド等のハイドロパーオキシド；アゾビスイソブチロニトリル等のアゾ化合物等を重合開始剤として用いることが好ましい。この際、アミン化合物等の促進剤を併用することもできる。更に、重合溶媒として、水−低級アルコール混合溶剤を用いる場合には、上記の種々の重合開始剤又は重合開始剤と促進剤との組み合わせの中から適宜選択して用いることができる。
【００４５】
上記重合条件において重合温度としては、用いる溶媒や重合開始剤により適宜設定すればよいが、０〜１２０℃が好ましい。より好ましくは、２０〜１００℃であり、更に好ましくは、４０〜１００℃である。重合時間としては、１０〜１０００分が好ましい。より好ましくは、２０〜５００分であり、更に好ましくは、３０〜３００分である。
【００４６】
上記塊状重合方法において用いられる重合開始剤としては、ベンゾイルパーオキシドやラウロイルパーオキシド等のパーオキシド；クメンハイドロパーオキシド等のハイドロパーオキシド；アゾビスイソブチロニトリル等のアゾ化合物等が好適である。
上記重合条件における重合温度としては、０〜２００℃の温度範囲内で行うことが好ましい。より好ましくは、２０〜１５０℃であり、更に好ましくは、４０〜１００℃である。重合時間としては、１０〜１０００分が好ましい。より好ましくは、２０〜５００分であり、更に好ましくは、３０〜３００分である。
【００４７】
上記重合工程においてはまた、得られるポリカルボン酸系重合体の分子量調節のために、次亜リン酸（塩）やチオール系連鎖移動剤を併用することもできる。
上記チオール系連鎖移動剤としては、メルカプトエタノール、チオグリセロール、チオグリコール酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオリンゴ酸、チオグリコール酸オクチル、３−メルカプトプロピオン酸オクチル、オクチルメルカプタン、ドデシルメルカプタン等が好適であり、これらの１種又は２種以上を用いることができる。更に、分子量調整のためには、単量体成分として（メタ）アリルスルホン酸（塩）類等の連鎖移動性の高い単量体を用いることもできる。
【００４８】
本発明の製造方法においては得られるポリカルボン酸系重合体は、セメント混和剤用として用いられるものであることが好ましい。このようなポリカルボン酸系重合体は、そのままでもセメント混和剤として用いることができるが、水に対する溶解性が不足する様な場合には、水に対する溶解性を向上させて有機溶媒を含まない水溶液の形で取り扱うために、更に一価金属及び二価金属の水酸化物、塩化物並びに炭素塩等の無機物；アンモニア；有機アミン等（好ましくは水酸化ナトリウム、水酸化カリウム等の一価金属の水酸化物）のアルカリ性物質で中和して得られる重合体塩をセメント混和剤として用いるのが好ましい。
【００４９】
上記ポリカルボン酸系重合体は、水溶液の形態でそのままセメント混和剤の主成分として使用することができるが、カルシウム、マグネシウム等の二価金属の水酸化物で中和して多価金属塩とした後に乾燥させたり、シリカ系微粉末等の無機粉体に担持して乾燥させたりすることにより粉体化して使用してもよい。
【００５０】
上記ポリカルボン酸系重合体は、他の公知のセメント混和剤と組み合わせて使用してもよい。このような公知のセメント混和剤としては、例えば従来のセメント分散剤、空気連行剤、セメント湿潤剤、膨張材、防水剤、遅延剤、急結剤、水溶性高分子物質、分離低減剤、増粘剤、凝集剤、乾燥収縮低減剤、強度増進剤、セルフレベリング剤、防錆剤、着色剤、防カビ剤、硬化促進剤、消泡剤等を挙げることができる。
【００５１】
上記ポリカルボン酸系重合体をセメント混和剤として用いる場合には、各種水硬性材料、すなわち、セメント及び石膏等のセメント以外の水硬性材料に混和剤として用いることができる。本発明によるセメント混和剤を用いた組成物としては、本発明によるセメント混和剤と水硬性材料と水とを含有し、更に必要に応じて細骨材（砂等）や粗骨材（砕石等）を含む水硬性組成物が好適であり、セメントペースト、モルタル、コンクリート、プラスター等が好ましい。
【００５２】
上記水硬性組成物としては、水硬性材料としてセメントを使用し、本発明によるセメント混和剤とセメント及び水を少なくとも含有するセメント組成物が最も一般的であるが、使用するセメントとしては、ポルトランドセメント（普通、早強、超早強、中庸熱、耐硫酸塩及びそれぞれの低アルカリ形）、各種混合セメント（高炉セメント、シリカセメント、フライアッシュセメント）、白色ポルトランドセメント、アルミナセメント、超速硬セメント（１クリンカー速硬性セメント、２クリンカー速硬性セメント、リン酸マグネシウムセメント）、グラウト用セメント、油井セメント、低発熱セメント（低発熱型高炉セメント、フライアッシュ混合低発熱型高炉セメント、ビーライト高含有セメント）、超高強度セメント、セメント系固化材、エコセメント（都市ごみ焼却灰、下水汚泥焼却灰の一種以上を原料として製造されたセメント）等が好適である。
【００５３】
上記水硬性組成物には、更に、高炉スラグ、フライアッシュ、シンダーアッシュ、クリンカーアッシュ、ハスクアッシュ、シリカヒューム、シリカ粉末、石灰石粉末等の微粉体や石膏を添加してもよい。また、骨材として、砂利、砕石、水砕スラグ、再生骨材等以外に、珪石質、粘土質、ジルコン質、ハイアルミナ質、炭化珪素質、黒鉛質、クロム質、クロマグ質、マグネシア質等の耐火骨材を用いることができる。
【００５４】
上記セメント組成物において、その１ｍ^３あたりの単位水量、セメント使用量及び水／セメント比としては、単位水量１００〜１８５ｋｇ／ｍ^３、使用セメント量２５０〜１１００ｋｇ／ｍ^３、水／セメント比（質量比）＝０．１〜０．７であることが好ましく、単位水量１２０〜１７５ｋｇ／ｍ^３、使用セメント量２７０〜８００ｋｇ／ｍ^３、水／セメント比（質量比）＝０．２〜０．６５であることがより好ましく、貧配合〜富配合まで幅広く用いることができ、単位セメント量の多い高強度コンクリート、単位セメント量が３００ｋｇ／ｍ^３以下の貧配合コンクリートのいずれにも用いることができる。
【００５５】
上記セメント組成物におけるセメント混和剤の配合割合としては、水硬セメントを用いるモルタルやコンクリート等に使用する場合には、好ましくは、セメント質量の０．０１〜５．０％、より好ましくは０．０２〜２．０％、更に好ましくは０．０５〜１．０％となる比率の量を添加すればよい。この添加により、単位水量の低減、強度の増大、耐久性の向上等の各種の好ましい諸効果がもたらされることとなる。上記配合割合が０．０１％未満では性能的に充分とならないおそれがあり、５．０％を超えても、その効果は実質上頭打ちとなるおそれがあり、経済性の面からも不利となるおそれがある。
【００５６】
上記セメント混和剤は、コンクリート２次製品用のコンクリート、遠心成形用コンクリート、振動締め固め用コンクリート、蒸気養生コンクリート、吹付けコンクリート等に好適に用いることができ、更に、高流動コンクリート、自己充填性コンクリート、セルフレベリング材等の高い流動性を要求されるモルタルやコンクリートにも好適に用いられるものである。
【００５７】
【実施例】
以下に実施例を掲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。なお、特に断りのない限り、「部」は「重量部」を、「％」は「質量％」を意味するものとする。
【００５８】
実施例１
温度計、攪拌翼（住友重機工業社製「マックスブレンド翼」）、攪拌機、滴下装置、窒素導入管及び還流冷却管を備えたガラス製反応装置に、３−メチル−３−ブテン−１−オールのエチレンオキシド５０モル付加物５５２０ｋｇと水３７８０ｋｇを仕込んだ。攪拌下に反応装置内を窒素置換し、窒素雰囲気下で６０℃まで昇温後、過酸化水素水の６．１％水溶液２４５ｋｇを加えた。このときマックスブレンド翼は図５（ｂ）に示すように反応液の水面より上に存在していた。そこへ、アクリル酸３４３ｋｇを、３時間で図５（ａ）に示す位置にあるモノマーノズルＡ（ノズル直径１２ｍｍ、流速１６．８ｍ／ｍｉｎ）より投入し、メルカプトプロピオン酸１５．２ｋｇ、Ｌ−アスコルビン酸６ｋｇ、水１１６０ｋｇを混合した水溶液を、３．５時間で図５（ａ）に示す位置にある開始剤ノズルＢより投入した。各ノズルの鉛直方向は反応溶液水面であり攪拌翼等のインターナルは存在していない。また、ノズルＡ及びＢからの投入溶液は直接、反応槽内部の反応溶液面に到達し、途中攪拌翼、反応槽側面壁等に接触することはなかった。
投入終了後、更に２時間引き続いて６０℃を維持し、重合反応を完結させた。降温後、水酸化ナトリウム水溶液で中和し、重量平均分子量２７，２００のポリカルボン酸系ポリマー（１）を得た。反応装置内の攪拌翼へのゲル物の付着について、目視による確認を行ったが、確認できなかった。ストレーナーに付着したゲル物を回収すると、その量は４００ｇであった。結果を表１に示す。
なお、実施例及び比較例における図５〜９において、（ａ）は、反応槽を上から見た概念図であり、ノズルと攪拌翼との位置関係を示すためのものである。また、（ｂ）は、反応槽を横から見た概念図であり、攪拌翼と反応液の液面との関係を示すためのものである。
【００５９】
実施例２〜６
翼の形状、モノマー組成比を表１に示すように変更し、分子量が約３万になるようにメルカプトプロピオン酸量を調整のうえ、実施例１と同様に合成を行い、ポリカルボン酸系ポリマー（２）〜（６）を得た。結果を表１に示す。
【００６０】
実施例７
温度計、攪拌翼（住友重機工業社製「マックスブレンド翼」）、攪拌機、滴下装置、窒素導入管及び還流冷却管を備えたガラス製反応装置に、水３３６０ｋｇを仕込み、攪拌下に反応装置内を窒素置換し、窒素雰囲気下で８０℃まで昇温した。このときマックスブレンド翼は図５（ｂ）に示すように反応液の水面より上に存在していた。メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２５モル）３６２４ｋｇ、メタクリル酸７２２ｋｇ、メルカプトプロピオン酸３９ｋｇ、水１３２６ｋｇを混合した水溶液を、４時間で図５（ａ）に示す位置にあるモノマーノズルＡ（ノズル直径２４ｍｍ、流速５２．６ｍ／ｍｉｎ）より投入し、過硫酸アンモニウム５０ｋｇと水４００ｋｇを混合した水溶液を、５時間で図５（ａ）に示す開始剤ノズルＢより投入した。各ノズルの鉛直方向は反応溶液水面であり攪拌翼等のインターナルは存在していない。また、ノズルＡ及びＢからの投入溶液は直接、反応槽内部の反応溶液面に到達し、途中攪拌翼、反応槽側面壁等に接触することはなかった。投入終了後、更に１時間引き続いて８０℃を維持し、重合反応を完結させた。降温後、水酸化ナトリウム水溶液で中和し、重量平均分子量２０，８００のポリカルボン酸系ポリマー（７）を得た。反応装置内、攪拌翼にゲル物の付着は目視では確認できなかった。ストレーナーに付着したゲル物を回収すると、その量は９００ｇあった。結果を表１に示す。
【００６１】
実施例８
翼の形状を表１に示すように変更し、実施例７と同様に合成を行い、ポリカルボン酸系ポリマー（８）を得た。このとき、モノマーノズルＡ及び開始剤ノズルＢは、図６（ａ）に示すような位置にあった。モノマーノズルＡ、開始剤ノズルＢからの投入開始直前の時点で、ファウドラー翼は図６（ｂ）に示すように反応液の水面より下に存在していた。結果を表１に示す。
【００６２】
実施例９
モノマーノズルＡの位置、ノズル径、流速を表１及び図７（ａ）に示すようにそれぞれ変更し、実施例１と同様に合成を行い、ポリカルボン酸系ポリマー（９）を得た。このときマックスブレンド翼は図７（ｂ）に示すように反応液の水面より上に存在していた。結果を表１に示す。
【００６３】
比較例１
モノマーノズルＡの位置、ノズル径、流速を表１及び図８（ａ）に示すように変更し、実施例１と同様に合成を行い、共重合体（１）を得た。このときマックスブレンド翼は図８（ｂ）に示すように反応液の水面より上に存在していた。反応装置内、攪拌翼にゲル物の付着が目視で確認できた。ストレーナーに付着したゲル物を回収すると、その量は８５００ｇあった。結果を表１に示す。
【００６４】
比較例２
モノマーノズルＡの位置を図８（ａ）に示すように変更し、実施例７と同様に合成を行い、共重合体（２）を得た。このときマックスブレンド翼は図８（ｂ）に示すように反応液の水面より上に存在していた。反応装置内、攪拌翼にゲル物の付着が目視で確認できた。ストレーナーに付着したゲル物を回収すると、その量は１２０００ｇあった。結果を表１に示す。
【００６５】
比較例３
モノマーノズルＡの位置、ノズル径、流速を表１及び図９（ａ）に示すように変更し、実施例１と同様に合成を行い、共重合体（３）を得た。このときマックスブレンド翼は図９（ｂ）に示すように反応液の水面より上に存在していた。結果を表１に示す。
【００６６】
モルタル試験
（１）モルタル調製方法
太平洋普通ポルトランドセメント（商品名、太平洋セメント社製）６００ｇ、豊浦標準砂６００ｇをモルタルミキサー（商品名：Ｎ−５０、テスコ社製）により低速回転で３０秒間空練りした。次いで、実施例で製造したポリカルボン酸系共重合体（１）〜（９）又は比較例で製造した共重合体（１）〜（３）を配合した水２２０ｇを空練りしたセメントと砂との混合物に投入して、高速回転で３分間混練してモルタルを調製した。
（２）フロー値の測定
調製したモルタルを注水後５分後に、ステンレス板上に置いた直径５５ｍｍ、高さ５０ｍｍの中空円筒の容器に詰めた。次いで、この中空円筒の容器を垂直に持ち上げた後、ステンレス板上に広がったモルタルの直径を縦横２方向について測定し、この平均値をフロー値（ｍｍ）とした。
表１にセメントに対する固形分換算の添加量とフロー値を示した。
【００６７】
【表１】

【００６８】
表１について以下に説明する。
「ＩＰＮ−５０」は、３−メチル−３−ブテン−１−オール−エチレンオキシド５０モル付加物であり、「ＩＰＮ−１５」は、３−メチル−３−ブテン−１−オール−エチレンオキシド１５モル付加物であり、「ＭＡＬ−５０」は、２−メチル−２−プロペン−１−オール−エチレンオキシド５０モル付加物であり、「ＰＥＡ−１５０」は、２−プロペン−１−オール−エチレンオキシド１５０モル付加物であり、「ＰＧＭ−２５Ｅ」は、メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２５モル）である。「ＡＡ」は、アクリル酸であり、「ＭＡＡ」は、メタクリル酸である。
また、「ＭＢ」は、住友重機械工業社製のマックスブレンド翼であり、「ＦＺ」は、神鋼パンテック社製のフルゾーン翼であり、「ＴＮ」は、住友重機械工業社製のトルネード翼であり、「ＦＤ」は、ファウドラー翼である。
更に、図１０に示すように、攪拌翼の回転軸をＯ、モノマーノズル位置をＡ、開始剤ノズル位置をＢとし、∠ＡＯＢをθとして２つのノズルの距離ＡＢ（＝ｘ）を示した。
【００６９】
以上より、実施例１〜８においては、単量体成分投入ノズルと重合開始剤投入ノズルとの直線距離を反応槽の半径の１／２の長さ以上とし、単量体成分投入ノズルの位置を単量体成分が反応液に直接滴下されるような位置とし、また、単量体成分投入ノズルの吐出口における単量体成分の流速を５．０ｍ／ｍｉｎ以上としたことから、単量体の反応率が高く、また、ゲルが装置に付着することがなく、ゲルのストレーナーへの付着量も少なかった。更に、製造された重合体をセメント混和剤として用いてモルタル試験を実施したところ、実施例１〜８により製造された重合体は、セメントへの添加量が少なくてもモルタルのフロー値を充分に高めることができ、セメント混和剤としての性能が高いものであった。実施例９においては、単量体成分投入ノズルの吐出口における単量体成分の流速を５．０ｍ／ｍｉｎ以上とはしなかったが、比較例１〜３に比べて、ゲルのストレーナーへの付着量は少なくなった。
一方、比較例１〜３においては、ゲルの発生が多く、かつ、セメント混和剤としての性能が高いものではなかった。
【００７０】
【発明の効果】
本発明の重合体の製造方法は、上述したような構成よりなり、これにより、ゲルの発生を防止し、均一な重合体が得られ、品質的に安定に、セメント混和剤等の各種の重合体を工業的に簡便に量産することができる。
【図面の簡単な説明】
【図１】図１は、本発明の実施の一形態である反応槽１を示す概念図である。
【図２】図２は、本発明の実施の一形態である反応槽７を示す概念図である。
【図３】図３は、本発明の実施の一形態である単量体成分投入ノズルの断面模式図である。
【図４】図４（ａ）は、住友重機械工業社製「トルネード翼」を示す模式図であり、図４（ｂ）は、神鋼パンテック社製「フルゾーン翼」を示す模式図であり、図４（ｃ）は、住友重機械工業社製「マックスブレンド翼」を示す模式図であり、図４（ｄ）は、「ファウドラー翼」を示す模式図である。
【図５】図５は、実施例１〜７で用いた反応槽の模式図である。
【図６】図６は、実施例８で用いた反応槽の模式図である。
【図７】図７は、実施例９で用いた反応槽の模式図である。
【図８】図８は、比較例１〜２で用いた反応槽の模式図である。
【図９】図９は、比較例３で用いた反応槽の模式図である。
【図１０】図１０は、実施例及び比較例で用いた反応槽におけるノズルＡ及びＢの距離ｘ、攪拌翼径ｄ及び反応槽内径Ｄを示した模式図である。
【符号の説明】
１、７ 反応槽
２、１０ 単量体成分投入ノズル
３ 重合開始剤投入ノズル
４、１１ 攪拌翼
５、１２ 回転軸
６ ジャケット
８ バッフル
９ 温度センサー[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a polymer. More specifically, the present invention relates to a method for producing a polycarboxylic acid polymer suitable in the field of cement admixture and the like.
[0002]
[Prior art]
The method of producing a polymer from a monomer component is adapted to various industrial fields, and in order to industrially efficiently and mass-produce, for example, using a reaction tank, the production raw material provided in the reaction tank It is performed by introducing a raw material into a reaction tank through a charging nozzle and reacting in a reaction solution. In such a production method, stable production in quality is required in the production of various polymers. For example, cement admixtures, builders for powder or liquid detergents, pigment dispersants such as calcium carbonate, carbon black, inks, scale inhibitors, dispersants for gypsum / water slurries, dispersants for coal / water slurries (CWM), In the production of polymers used for dispersants such as thickeners and other chemical products, stable production of uniform polymers is required.
[0003]
In such a polymerization reaction, a gel may be generated, and when the generated gel is mixed into the reaction system, it becomes difficult to produce a polymer of stable quality suitable for various industrial fields, In the transporting step of the produced polymer or the like, the clogging of the gel causes troubles in the production equipment such as stoppage of the pump, and it is difficult to perform stable production even by such troubles. Therefore, in a method for producing a polymer which is widely used industrially, it is important to prevent the generation of a gel and to stably produce the polymer in quality.
[0004]
As a conventional method for producing a polymer from a monomer component, by adding a chain transfer agent before and / or after the addition of the monomer component, an excellent polycarboxylic acid-based cement additive can be reproducibly obtained. In addition, it is disclosed that industrial mass production can be stably performed (for example, see Patent Document 1). However, in a method for producing a polymer that can be easily mass-produced industrially, there is room for devising so that the polymer can be stably produced in quality without considering the timing of adding a chain transfer agent.
[0005]
[Patent Document 1]
JP-A-2000-159555 (page 1-2)
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, and a method for producing a polymer capable of preventing the generation of a gel, obtaining a uniform polymer, and stably producing the same in quality is industrially easily mass-produced. It is intended to be provided by a method that can be used.
[0007]
[Means for Solving the Problems]
The present inventors have studied various methods for producing a polymer from a monomer component, and when a polymer is produced using a reaction tank equipped with a production material input nozzle, it may be used in various industrial fields. The resulting polymer can be easily and industrially mass-produced. However, a gel is generated in a portion (monomer pool) where monomer components supplied (feed) into the reaction tank by the raw material input nozzle are accumulated. It has been found that it becomes difficult to produce a more uniform and quality stable polymer. Then, a monomer component injection nozzle (monomer feed nozzle) and a polymerization initiator injection nozzle are provided, and when the polymerization initiator, the reducing agent, and the chain transfer agent are injected from the polymerization initiator injection nozzle, these two types of injection are performed. When the linear distance (= x) of the nozzle has a certain length or more, the polymerization initiator, the reducing agent, and the chain transfer agent do not come into contact with the fed monomer pool, and the monomer component concentration is reduced. Was found to be able to suppress the start of polymerization in a non-uniform state, so that a uniform copolymer could be obtained and the product could be stably produced in terms of quality. For example, in the case of producing a polyalkylene glycol monoalkenyl ether / acrylic acid-based copolymer, the generation of polyacrylic acid can be suppressed by contact of the initiator with the monomer pool of acrylic acid.
Also, when the monomer component was introduced into the reaction vessel from the monomer feed nozzle and dropped, the reaction was provided in the reaction vessel side wall, stirring blades, and internal (reaction vessel such as coil, baffle, temperature sensor, etc.). It has also been found that even by dropping directly into the reaction solution without contacting the apparatus, gel formation can be prevented and the product can be produced stably in terms of quality. In this case, the monomer component supplied from the monomer feed nozzle into the reaction tank is directly reacted by, for example, placing the monomer feed nozzle at a certain distance from the side wall of the reaction tank, the stirring blade, and the internal. It is possible to drip into the liquid.
Further, regarding the flow rate of the monomer component fed from the monomer feed nozzle, if the flow rate is low, the liquid of the monomer component is dropped while traveling down the nozzle wall, so that the liquid is diffused from the nozzle and the liquid is diffused from the reaction tank wall and It will scatter and adhere to the stirring blades and the like, but if it is a specific flow rate or more, the scattering of the liquid will be suppressed and the generation of gel will be prevented, and the effect of the present invention will be more fully exhibited. The present inventors have also found that the above-mentioned problems can be successfully solved by these manufacturing methods, and have completed the present invention.
[0008]
That is, in the present invention, a monomer component and a polymerization initiator are used as essential production raw materials, and the production raw material is introduced into the reaction tank by a monomer component introduction nozzle and a polymerization initiator introduction nozzle provided in the reaction tank. And reacting in a reaction solution to produce a polymer, wherein the linear distance between the monomer component introduction nozzle and the polymerization initiator introduction nozzle is １ ／ of the radius of the reaction vessel. The above is a method for producing a polymer.
[0009]
In the present invention, a monomer component and a polymerization initiator are used as essential production raw materials, and the production raw material is charged into the reaction tank by a monomer component charging nozzle provided in the reaction tank, and the reaction is performed in the reaction solution. This is a method for producing a polymer by causing the monomer component introduced from the monomer component introduction nozzle to drop directly into a reaction solution in a reaction tank.
Hereinafter, the present invention will be described in detail.
[0010]
In the method for producing a polymer according to the present invention, a raw material containing a monomer component and a polymerization initiator as essential components is charged into a reaction vessel and reacted in a reaction solution to produce a polymer. ) The linear distance between the monomer component introduction nozzle and the polymerization initiator introduction nozzle is set to be equal to or longer than １ ／ of the radius of the reaction tank, or (2) the monomer component introduction nozzle is introduced. It is performed by directly dropping the monomer component into the reaction solution in the reaction tank. In the case of (1), the monomer component is charged into the reaction tank by the monomer component charging nozzle, and the polymerization initiator is charged into the reaction tank by the polymerization initiator charging nozzle. In the case of (2), the method of charging the monomer component into the reaction tank by the monomer component charging nozzle and charging the other production raw materials into the reaction tank is not particularly limited. It is preferable to charge the polymerization initiator into the reaction tank by the polymerization initiator charging nozzle as in (1). In the present invention, the present invention is carried out in any one of the modes (1) and (2). When a reducing agent or a chain transfer agent is used in the polymerization initiator charging nozzle, these may be charged into the reaction tank together with the polymerization initiator or separately.
[0011]
The order in which the production raw materials are charged into the reaction tank may be appropriately set depending on the types of the monomer components and the polymerization initiator, the reaction mode, and the like. In the polymerization using a solvent, a method in which a solvent is usually charged in a reaction vessel in advance and a monomer component is dropped therein is preferable. Further, a method is also suitable in which a part of the monomer component is previously charged together with the solvent into the reaction tank, and the remaining monomer component is dropped therein. The timing of charging the polymerization initiator is preferably after the solvent and a part of the monomer component are charged in the reaction tank in advance, and before the dropping of the monomer component, and the same as the timing of dropping the monomer component. It may be introduced at the appropriate time.
[0012]
In the present invention, the method is applied from the time when the polymerization is started, that is, from the time when the polymerization initiator is charged into the reaction tank, in order to suppress the start of the polymerization in a state where the monomer component concentration is uneven. Will be done. For example, in the case of the above (2), after the solvent and a part of the monomer component are charged into the reaction tank in advance, the polymerization initiator is charged, and when the monomer component is dropped therein, the polymerization initiator is added. Is dropped directly into the reaction solution in the reaction tank after the addition of That is, before charging the polymerization initiator, in the stage of previously charging the solvent and a part of the monomer component into the reaction tank in advance, the solvent and the monomer component charged into the reaction tank are It does not have to be dropped directly into the reaction solution when it is collected in the lower part, but after the polymerization initiator is charged, it is dropped directly into the reaction solution in the reaction tank.
[0013]
In the case of the above (1), the reaction vessel in the production method of the present invention should be one provided with a monomer component introduction nozzle and a polymerization initiator introduction nozzle as essential components. In the case of (2), a nozzle provided with a monomer component injection nozzle as an essential component is used. These nozzles are usually provided at the upper part of the reaction tank so that the raw material to be supplied is dropped without hitting the reaction tank wall.
[0014]
In the case of the above (2), the monomer component introduction nozzle is located at the upper part of the reaction tank, and the monomer component introduced from the monomer component introduction nozzle is located on the side wall of the reaction vessel and inside the reaction vessel. It is preferable to be installed at a position where it does not hit a certain device. That is, before charging the polymerization initiator, the monomer component charged from the monomer component charging nozzle is provided in a reaction tank such as a side wall or a stirring blade of the reaction tank, a coil, a baffle, or a temperature sensor. However, after the polymerization initiator is charged, the monomer component is charged so that the monomer component does not hit the side wall of the reaction tank and the equipment in the reaction tank. Preferably, a nozzle is provided. In this case, when the liquid level of the reaction solution is higher than the stirring blade or the internal device, which is a device in the reaction tank, after the polymerization initiator is charged and before the monomer component is dropped. A monomer component introduction nozzle can be installed at an upper part of the tank and at a position other than the place where the rotation axis of the stirring blade is installed. However, the stirring is a device in which the liquid level of the reaction solution is in the reaction tank. When there is no internal in the reaction tank, for example, when there is no internal in the reaction tank, the starting point is the rotation axis of the stirring blade of the reaction tank. A monomer component injection nozzle is installed at a position longer than half the blade diameter (= d) (= d / 2) and shorter than the radius (= D / 2) of the inner diameter (= D) of the reaction tank. Will be done. Further, when an internal is provided in the reaction tank, a half of the blade diameter (= d) of the stirring blade at the upper part of the reaction tank and starting from the rotation axis of the stirring blade of the reaction tank. A position longer than the length (= d / 2) and shorter than the radius of the reaction vessel (= D / 2) and at a position other than the upper part of the internal, that is, the monomer component to be dropped is a stirring blade and an The nozzle for introducing the monomer component is installed at a position where it does not hit the null.
[0015]
The cases (1) and (2) will be described with reference to the drawings.
The present invention is not limited to a cylindrical reactor, but is also applicable to a case where a polymer is produced using a reactor having a different shape.
FIG. 1A is a conceptual diagram when the reaction tank 1 is viewed from above, and shows a positional relationship between a monomer component input nozzle 2 and a polymerization initiator input nozzle 3. In FIG. 1 (a), the linear distance between the monomer component input nozzle 2 and the polymerization initiator input nozzle 3 is equal to or longer than の 長 of the radius of the reaction tank 1, 5, the positions of the monomer component input nozzle 2 and the polymerization initiator input nozzle 3 are in a 90 ° relationship. Such a form is one of preferred embodiments of the present invention.
In the present invention, the linear distance between the monomer component input nozzle 2 and the polymerization initiator input nozzle 3 differs depending on the size of the reaction tank 1, and by setting as described above, the monomer component concentration becomes non-uniform. The effect of the present invention is that the initiation of polymerization in a stable state can be suppressed.
In addition, the position of the nozzle means the position of the material input port of the nozzle, and does not mean the mounting position of the device including the nozzle.
[0016]
FIG. 1B is a conceptual view of a cross section taken along line AA ′ of the reaction tank 1 shown in FIG. 1A viewed from the direction B, and shows the installation of the stirring blade 4 and the monomer component introduction nozzle 2. It shows the position. The reaction tank 1 is provided with a jacket 6 for adjusting the temperature of the reaction solution outside the reaction tank. In FIG. 1B, a single circle is defined between two circles centered on the rotation axis 5 of the stirring blade 4, that is, a circle drawn on the side surface of the reaction vessel 1 and a circle drawn by the trajectory when the stirring blade 4 is rotated. Assuming that the diameter of the stirring blade is d and the inner diameter of the reaction tank is D, the installation position of the monomer component injection nozzle 2 in the upper part of the reaction tank is as follows. The position that satisfies the following relationship is represented by the distance from the rotation axis 5 of the second.
d / 2 <(distance of the monomer component injection nozzle 2 from the rotation axis 5) <D / 2
As described above, since the monomer component introduction nozzle 2 is installed at a position where the monomer component introduced therefrom does not hit the side wall of the reaction tank 1 or the stirring blade 4, the monomer component introduction nozzle 2 is provided. Is directly dropped on the reaction solution in the reaction tank 1. The same applies to the position of the polymerization initiator injection nozzle 3 not shown.
[0017]
FIG. 2 is a conceptual diagram when the reaction tank 7 is viewed from above. FIG. 2A is a positional relationship between a baffle 8 (baffle plate) and a monomer component introduction nozzle 10 in which a temperature sensor 9 is installed. It is shown. FIG. 2B shows the positional relationship between the position of a circle drawn by the trajectory of the baffle 8, the temperature sensor 9, and the stirring blade 11 when the stirring blade 11 is rotated, and the monomer component introduction nozzle 10. is there. In FIG. 2B, the monomer component introduction nozzle 10 is located at a position that does not overlap with the position of the circle drawn by the trajectory when the baffle 8, the temperature sensor 9, and the stirring blade 11 are rotated. The monomer component supplied from the monomer component supply nozzle 10 is directly dropped into the reaction solution without coming into contact with the side wall of the reaction vessel 7, the stirring blade 11, and the internals in the reaction vessel 7.
[0018]
In such a case, the installation position of the monomer component introduction nozzle 10 in the upper part of the reaction tank is a position other than the upper part where each internal is located, in addition to the above relationship. When the monomer component introduction nozzle 10 is installed on a straight line connecting the rotation shaft 12 and the internal, the internal and the circle drawn by the trajectory when the stirring blade 11 is rotated when the stirring blade 11 is rotated. The monomer component input nozzle 10 will be installed. That is, assuming that the distance from the rotation axis 12 to the internal is d ′, the installation position of the monomer component introduction nozzle 10 in the upper part of the reaction tank is represented by the distance of the monomer component introduction nozzle 10 from the rotation axis 12. And a position satisfying the following relationship.
d / 2 <(distance from the rotation axis 12 of the monomer component introduction nozzle 10) <d ′
[0019]
FIG. 3 is a schematic cross-sectional view showing the shape of the monomer component introduction nozzle, and is for explaining the relationship between the nozzle inner diameter and the flow rate. In such a monomer component injection nozzle, if the flow rate is low, the liquid is dropped while traveling down the nozzle wall, and is diffused from the nozzle, and the liquid is supplied to the reaction tank wall, the stirring blade, and the device in the reaction tank. It may scatter and adhere. In the present invention, the flow rate of the monomer component at the discharge port of the monomer component supply nozzle is preferably 5.0 m / min or more. More preferably, it is 8.0 m / min or more, and still more preferably 10.0 m / min or more. The inner diameter of the nozzle may be appropriately set depending on the flow rate, the capacity of the reaction tank, and the like, but is preferably 10 mm or more and 500 mm or less on an industrial scale. More preferably, it is 20 mm or more and 300 mm or less. More preferably, it is 50 mm or more and 200 mm or less. Particularly preferably, it is 100 mm or more.
[0020]
In the present invention, the method of adjusting the flow rate can be performed by adjusting the inner diameter of the nozzle, but when the flow rate of the monomer component is small, it is possible to secure the flow rate by reducing the inner diameter of the nozzle. it can.
[0021]
The reaction vessel used in the present invention may be any vessel that can be used in the same meaning as a reaction vessel, a reactor, a reaction vessel, and the like, and is capable of performing a polymerization reaction. The shape of the reaction tank may be polygonal, cylindrical, or the like, but a cylindrical shape is preferred in terms of stirring efficiency, handleability, versatility, and the like.
[0022]
The volume of the reaction tank is 1 m in the case of production on a normal industrial scale. ³ Or more, and 50 m ³ The following is preferred. More preferably, 5m ³ It is more than 40m ³ It is as follows. The material inside the reaction tank is preferably made of SUS, preferably SUS304, SUS316, SUS316L, more preferably SUS316, SUS316L, from the viewpoint of corrosion resistance. Such a reaction tank may be inert to reaction raw materials and products by subjecting the inside thereof to glass lining or the like.
[0023]
The above-mentioned reaction tank is usually provided with a stirrer composed of an electric motor, a shaft, a stirring blade and the like in order to carry out the polymerization reaction uniformly and efficiently. The reaction tank may have an internal part other than the stirrer, and examples thereof include a baffle (baffle plate), a coil, and a temperature sensor. The term “internal” means devices other than the stirrer that are installed in the reaction tank.
[0024]
As the stirring blade, a plurality of flat plates are opposed to a plane having a plurality of openings at a position of 180 degrees, such as a “Tornado blade” manufactured by Sumitomo Heavy Industries, Ltd. shown in FIG. FIG. 4 (c) shows a state in which a plurality of flat blades are provided at small intervals in the vertical direction, such as a mounted one, such as a "full zone wing" manufactured by Shinko Pantech shown in FIG. 4 (b). As shown in FIG. 4D, a flat plate having an opening portion, such as a “Max Blend Wing” manufactured by Sumitomo Heavy Industries, Ltd., and a horizontal and vertical torsion such as a “Faudler Wing” shown in FIG. Are preferred.
[0025]
The production method of the present invention can be suitably applied in fields where stable production of a uniform polymer is required, for example, cement admixtures, powder or liquid detergent builders, calcium carbonate, Pigment dispersants such as carbon black and inks, scale inhibitors, dispersants for gypsum / water slurries, dispersants for coal / water slurries (CWM), dispersants such as thickeners, and polymers used in other chemical products It can be applied to the manufacture of Among them, the production method of the present invention is applied to the production of a polycarboxylic acid-based polymer, which is a polymer particularly required to prevent the generation of a gel and to be able to produce a stable product in quality. Is preferred. That is, the polymer produced in the present invention is preferably a polycarboxylic acid polymer.
[0026]
The polycarboxylic acid-based polymer is obtained by polymerizing a monomer component containing an unsaturated carboxylic acid. In addition to the unsaturated carboxylic acid, an unsaturated monomer having a polyalkylene glycol chain is used. It is preferably obtained by polymerizing a monomer component containing a monomer. Such a monomer component may contain another unsaturated compound. These monomer components can be used alone or in combination of two or more.
[0027]
The unsaturated carboxylic acid is not particularly limited as long as it is a monomer having an unsaturated group and a group capable of forming a carbanion. Unsaturated monocarboxylic acid monomer, unsaturated dicarboxylic acid monomer A body or the like is preferred.
As the unsaturated monocarboxylic acid monomer, for example, acrylic acid, methacrylic acid, crotonic acid and the like; monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like are preferable.
The unsaturated dicarboxylic acid-based monomer is not particularly limited as long as it has one unsaturated group and two groups capable of forming a carbanion in the molecule. Examples thereof include maleic acid and itacone. Preferred are acids, citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., and their anhydrides.
Examples of the unsaturated carboxylic acid include half esters of unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms, unsaturated dicarboxylic acids (unsaturated dicarboxylic acid monomers), and the like. A half amide of an amine having 1 to 22 carbon atoms, a half ester of an unsaturated dicarboxylic acid monomer and a glycol of 2 to 4 carbon atoms, a half amide of maleamic acid and a glycol of 2 to 4 carbon atoms, or the like is used. be able to.
[0028]
The unsaturated monomer having a polyalkylene glycol chain may be a monomer having an unsaturated group and a polyalkylene glycol chain, and may be a polyalkylene glycol ester monomer or a polyalkylene glycol ether monomer. And the like.
In the unsaturated monomer having a polyalkylene glycol chain, the polyalkylene glycol ester-based monomer may be a monomer having a structure in which an unsaturated group and a polyalkylene glycol chain are bonded via an ester bond. The polyalkylene glycol ether-based monomer may be any compound having a structure in which a polyalkylene glycol chain is added to an alcohol having an unsaturated group, and may be represented by the following general formula (1):
[0029]
Embedded image

[0030]
It is preferable that the compound is represented by
In the above general formula (1), R ¹ , R ² And R ³ Represents the same or different and represents a hydrogen atom or a methyl group. R ⁴ Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ Represents the same or different and represents an alkylene group having 2 to 18 carbon atoms. m is R ⁵ It represents the average number of added moles of the oxyalkylene group represented by O, and is a number from 1 to 300. Y represents an alkyl group having 0 to 5 carbon atoms or -CO-. When Y is -CO-, the general formula (1) represents a polyalkylene glycol ester-based monomer, and when Y is an alkyl group having 0 to 5 carbon atoms, the general formula (1) represents a polyalkylene glycol ether-based monomer. Represents a monomer.
[0031]
In the above general formula (1),-(R ⁵ The oxyalkylene group represented by O)-is an alkylene oxide adduct having 2 to 18 carbon atoms. The structure of such an alkylene oxide adduct is, for example, an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide. The structure is formed by one or two or more kinds, and when formed by two or more kinds, any addition form such as random addition, block addition, and alternate addition may be used.
[0032]
R above ⁵ M, which is the average number of added moles of the oxyalkylene group represented by O, is a number of 1 to 300. If m exceeds 300, the polymerizability of the monomer may be reduced. The preferable range of m is 2 or more, more preferably 4 to 250, and still more preferably 10 to 150. In addition, the average number of moles added means an average value of the number of moles of the organic group added in one mole of the monomer.
[0033]
R above ⁴ Is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When the number of carbon atoms exceeds 20, the resulting polycarboxylic acid-based polymer becomes too strong in hydrophobicity, so that good dispersibility is obtained. May not be possible. R ⁴ From the viewpoint of dispersibility, more preferably a hydrocarbon group having 1 to 10 carbon atoms, further preferably 1 to 3 carbon atoms, particularly preferably 1 to 2 carbon atoms.
[0034]
Examples of the polyalkylene glycol ester-based monomer include an unsaturated carboxylic acid polyalkylene glycol ester-based compound, and an (alkoxy) polyalkylene glycol mono (meth) acrylate is preferred. (Alkoxy) polyethylene glycol (poly) (alkylene glycol having 2 to 4 carbon atoms) (meth) acrylates are preferred.
Methoxy polyethylene glycol mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, butoxy polyethylene glycol mono (meth) acrylate, and the like.
[0035]
As the polyalkylene glycol ester-based monomer, other than the above-mentioned monomers, those exemplified below can be used.
C1 to C22 alcohols and C1 to C22 amines such as (alkoxy) polyalkylene glycol monomaleate and (alkoxy) polyalkylene glycol dimaleate, Half ester or diester of the alkyl polyalkylene glycol added with 1 to 300 moles and the unsaturated dicarboxylic acid monomer; average addition mole number of the unsaturated dicarboxylic acid monomer and glycol having 2 to 4 carbon atoms Half-esters and diesters with 2 to 300 polyalkylene glycols; triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) Propylene glyco Distearate (meth) acrylate of (poly) alkylene glycol di (meth) acrylate; triethylene glycol dimaleate, such as polyethylene glycol dimaleate (poly) alkylene glycol dimaleate and the like.
[0036]
Examples of the polyalkylene glycol ether-based monomer include (meth) allyl alcohol alkylene oxide adduct, 3-buten-1-ol alkylene oxide adduct, isoprene alcohol (3-methyl-3-buten-1-ol) alkylene Oxide adducts, 3-methyl-2-buten-1-ol alkylene oxide adducts and the like are preferred.
[0037]
Examples of the polyalkylene glycol ether-based monomers include polyethylene glycol monoallyl ether, polyethylene glycol mono (2-methyl-2-propenyl) ether, polyethylene glycol mono (3-methyl-3-butenyl) ether, and polyethylene glycol mono. (3-methyl-2-butenyl) ether, polyethylene glycol mono (1,1-dimethyl-2-propenyl) ether, polyethylene polypropylene glycol mono (3-methyl-3-butenyl) ether, methoxypolyethylene glycol mono (3-methyl -3-butenyl) ether, methoxypolyethylene glycol monoallyl ether and the like can also be used.
[0038]
As the other unsaturated compounds, the compounds exemplified below are suitable.
Styrenes such as styrene, bromostyrene, chlorostyrene, and methylstyrene; dienes such as 1,3-butadiene, isoprene, and isobutylene; methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; (Meth) acrylates such as pentyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate; α-olefins such as hexene, heptene, and decene; methyl Alkyl vinyl ethers such as vinyl ether, ethyl vinyl ether and butyl vinyl ether; vinyl esters such as vinyl acetate; allyl esters such as allyl acetate; bifunctional (meth) acrylates such as hexanediol di (meth) acrylate; vinyl sulfonate; (Meth) allyl sulf Sulfonates, unsaturated sulfonic acids such as styrenesulfonic acid, and their monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.
[0039]
Unsaturated amides such as (meth) acrylamide; allyls such as allyl alcohol; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meta) ) Vinyl ethers or allyl ethers such as allyl ether and polyethylene glycol mono (meth) allyl ether; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (Meth) acrylate compounds such as ethyl (meth) acrylate and methoxypropyl (meth) acrylate.
[0040]
In the above-mentioned polycarboxylic acid polymer, the composition ratio (mass ratio) of unsaturated monomer having a polyalkylene glycol chain / unsaturated carboxylic acid / other unsaturated compound is 1 to 99/1 to 99/0. It is preferably from 60 to 60. It is preferably from 35 to 99/1 to 50/0 to 40, and more preferably from 50 to 99/2 to 40/0 to 25.
[0041]
The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 500,000 in terms of polyethylene glycol by gel permeation chromatography (hereinafter referred to as "GPC") measured under the following conditions. is there. If the weight average molecular weight is less than 1,000 or exceeds 500,000, the dispersion performance may be reduced. It is preferably from 3,000 to 300,000, more preferably from 5,000 to 100,000, and still more preferably from 7,000 to 80,000.
[0042]
<Weight average molecular weight measurement conditions>

[0043]
In the production method of the present invention, when producing a polycarboxylic acid-based polymer, it comprises a polymerization step of conducting polymerization using the above-mentioned monomer component and polymerization initiator as essential production raw materials in a reaction vessel. However, other steps may be included.
As the polymerization method in the polymerization step, a polymerization method in a solvent, a bulk polymerization method, and the like are suitable. The polymerization method in a solvent may be a batch system or a continuous system. Examples of the solvent used include water; lower alcohols such as methyl alcohol, ethyl alcohol, and 2-propanol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; and ester compounds such as ethyl acetate. Preferred are ketone compounds such as acetone and methyl ethyl ketone. Among these, water and methyl alcohol, ethyl alcohol, 2-propanol, etc. are preferably used in view of the solubility of the monomer component and the obtained polycarboxylic acid polymer and the handleability of the polymer when used. preferable.
[0044]
In the polymerization method in the above solvent, when performing polymerization in an aqueous medium, a water-soluble polymerization initiator such as ammonium or an alkali metal persulfate, or hydrogen peroxide is used as the polymerization initiator. Is preferred. At this time, an accelerator such as sodium bisulfite, Mohr's salt, ascorbic acid (salt), or Rongalit can be used in combination. For polymerization using a lower alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester compound or a ketone compound as a solvent, a peroxide such as benzoyl peroxide or lauroyl peroxide; a hydroperoxide such as cumene hydroperoxide; It is preferable to use an azo compound such as bisisobutyronitrile as a polymerization initiator. In this case, an accelerator such as an amine compound may be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used as the polymerization solvent, it can be appropriately selected from the above-mentioned various polymerization initiators or a combination of the polymerization initiator and the accelerator.
[0045]
The polymerization temperature under the above polymerization conditions may be appropriately set depending on the solvent and the polymerization initiator used, but is preferably from 0 to 120 ° C. More preferably, it is 20-100 degreeC, Still more preferably, it is 40-100 degreeC. The polymerization time is preferably from 10 to 1000 minutes. More preferably, it is 20 to 500 minutes, and still more preferably, it is 30 to 300 minutes.
[0046]
As the polymerization initiator used in the bulk polymerization method, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azo compounds such as azobisisobutyronitrile are preferable.
The polymerization temperature under the above polymerization conditions is preferably performed within a temperature range of 0 to 200 ° C. The temperature is more preferably from 20 to 150 ° C, and still more preferably from 40 to 100 ° C. The polymerization time is preferably from 10 to 1000 minutes. More preferably, it is 20 to 500 minutes, and still more preferably, it is 30 to 300 minutes.
[0047]
In the above polymerization step, hypophosphorous acid (salt) or a thiol chain transfer agent can also be used in combination for controlling the molecular weight of the obtained polycarboxylic acid polymer.
Examples of the thiol-based chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, octylmercaptan, and dodecyl. Mercaptan and the like are suitable, and one or more of these can be used. Further, in order to adjust the molecular weight, a monomer having a high chain transfer property such as (meth) allylsulfonic acid (salt) may be used as a monomer component.
[0048]
In the production method of the present invention, the obtained polycarboxylic acid-based polymer is preferably used for a cement admixture. Such a polycarboxylic acid polymer can be used as it is as a cement admixture, but when the solubility in water is insufficient, an aqueous solution containing no organic solvent by improving the solubility in water. In order to handle in the form of inorganic materials such as hydroxides, chlorides and carbon salts of monovalent metals and divalent metals; ammonia; organic amines and the like (preferably monovalent metals such as sodium hydroxide and potassium hydroxide) It is preferable to use a polymer salt obtained by neutralization with an alkaline substance (hydroxide) as a cement admixture.
[0049]
The polycarboxylic acid-based polymer can be used as a main component of the cement admixture in the form of an aqueous solution as it is, but is neutralized with a hydroxide of a divalent metal such as calcium and magnesium to form a polyvalent metal salt. After drying, the powder may be used in the form of a powder by drying by carrying on an inorganic powder such as a silica-based fine powder.
[0050]
The polycarboxylic acid-based polymer may be used in combination with other known cement admixtures. Such known cement admixtures include, for example, conventional cement dispersants, air entrainers, cement wetting agents, swelling agents, waterproofing agents, retarders, quick-setting agents, water-soluble polymeric substances, separation reducers, Examples include a tackifier, a coagulant, a drying shrinkage reducing agent, a strength enhancer, a self-leveling agent, a rust inhibitor, a colorant, a fungicide, a curing accelerator, and an antifoaming agent.
[0051]
When the polycarboxylic acid polymer is used as a cement admixture, it can be used as an admixture for various hydraulic materials, that is, hydraulic materials other than cement such as cement and gypsum. The composition using the cement admixture according to the present invention includes the cement admixture according to the present invention, a hydraulic material, and water, and further, if necessary, fine aggregates (sand, etc.) and coarse aggregates (crushed stones, etc.). Is preferred, and cement paste, mortar, concrete, plaster and the like are preferred.
[0052]
As the hydraulic composition, cement is used as a hydraulic material, and a cement composition containing at least a cement admixture, cement and water according to the present invention is the most common, but the cement used is Portland cement. (Ordinary, fast, super fast, moderate heat, sulfate resistant and low alkali type of each), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, ultra fast hardening cement ( 1 Clinker fast-setting cement, 2 clinker fast-setting cement, magnesium phosphate cement), grout cement, oil well cement, low heat generating cement (low heat generating blast furnace cement, fly ash mixed low heat generating blast furnace cement, high belite cement) , Ultra-high strength cement, cement-based solidifying material Ecocement (municipal refuse incineration ash, cement one or more produced as a raw material for sewage sludge incineration ash) and the like.
[0053]
Fine powder or gypsum such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder and the like may be further added to the hydraulic composition. In addition, as aggregates, besides gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium, magnesia, etc. Can be used.
[0054]
In the above cement composition, 1 m ³ The amount of water per unit, the amount of cement used, and the water / cement ratio are 100 to 185 kg / m ³ , Amount of cement used 250-1100kg / m ³ , Water / cement ratio (mass ratio) = 0.1-0.7, unit water amount 120-175 kg / m ³ , Used cement amount 270-800kg / m ³ , Water / cement ratio (mass ratio) = 0.2 to 0.65 is more preferable, and it can be used widely from poor to rich blends, high-strength concrete with a large unit cement amount, unit cement amount of 300 kg / M ³ It can be used for any of the following poorly-mixed concretes.
[0055]
The mixing ratio of the cement admixture in the cement composition is preferably 0.01 to 5.0%, more preferably 0.1 to 5.0% of the cement mass when used in mortar or concrete using hydraulic cement. What is necessary is just to add the amount of the ratio which becomes 02-2.0%, More preferably, it becomes 0.05-1.0%. By this addition, various preferable effects such as reduction of unit water amount, increase of strength, improvement of durability and the like are brought. If the mixing ratio is less than 0.01%, the performance may not be sufficient. If the mixing ratio is more than 5.0%, the effect may be substantially flattened, which is disadvantageous in terms of economy. There is a risk.
[0056]
The above cement admixture can be suitably used in concrete for secondary concrete products, concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, and the like. It is also suitably used for mortar and concrete requiring high fluidity such as concrete and self-leveling material.
[0057]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. Unless otherwise specified, “parts” means “parts by weight” and “%” means “% by mass”.
[0058]
Example 1
A 3-methyl-3-buten-1-ol was added to a glass reactor equipped with a thermometer, a stirring blade ("Max Blend Blade" manufactured by Sumitomo Heavy Industries, Ltd.), a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling tube. 5520 kg of an ethylene oxide 50 mol adduct and 3780 kg of water were charged. The inside of the reactor was replaced with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 245 kg of a 6.1% aqueous solution of hydrogen peroxide was added. At this time, the Max Blend blade was present above the water surface of the reaction solution as shown in FIG. To this, 343 kg of acrylic acid was introduced from the monomer nozzle A (nozzle diameter 12 mm, flow rate 16.8 m / min) at the position shown in FIG. 5A for 3 hours, and 15.2 kg of mercaptopropionic acid and L-ascorbin were added. An aqueous solution obtained by mixing 6 kg of acid and 1160 kg of water was introduced from the initiator nozzle B at the position shown in FIG. The vertical direction of each nozzle is the reaction solution water surface, and there is no internal such as a stirring blade. The solutions supplied from the nozzles A and B directly reached the surface of the reaction solution inside the reaction tank, and did not come into contact with the stirring blade, the side wall of the reaction tank, etc. in the middle.
After completion of the charging, the temperature was kept at 60 ° C. for further 2 hours to complete the polymerization reaction. After cooling, the mixture was neutralized with an aqueous sodium hydroxide solution to obtain a polycarboxylic acid polymer (1) having a weight average molecular weight of 27,200. The adhesion of the gel substance to the stirring blade in the reactor was visually confirmed, but could not be confirmed. When the gel attached to the strainer was recovered, the amount was 400 g. Table 1 shows the results.
5A to 9 in the examples and comparative examples, FIG. 5A is a conceptual diagram of the reaction tank viewed from above, and shows the positional relationship between the nozzle and the stirring blade. (B) is a conceptual diagram of the reaction tank viewed from the side, and shows the relationship between the stirring blade and the level of the reaction solution.
[0059]
Examples 2 to 6
The shape of the blades and the monomer composition ratio were changed as shown in Table 1, and the amount of mercaptopropionic acid was adjusted so that the molecular weight became about 30,000. (2) to (6) were obtained. Table 1 shows the results.
[0060]
Example 7
3360 kg of water was charged into a glass reactor equipped with a thermometer, a stirring blade (“Max Blend Blade” manufactured by Sumitomo Heavy Industries, Ltd.), a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling tube, and the inside of the reactor was stirred. Was replaced with nitrogen, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. At this time, the Max Blend blade was present above the water surface of the reaction solution as shown in FIG. An aqueous solution obtained by mixing 3624 kg of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide of 25 mol), 722 kg of methacrylic acid, 39 kg of mercaptopropionic acid, and 1326 kg of water was mixed for 4 hours with the monomer nozzle A at the position shown in FIG. (Nozzle diameter: 24 mm, flow rate: 52.6 m / min), and an aqueous solution obtained by mixing 50 kg of ammonium persulfate and 400 kg of water was introduced from the initiator nozzle B shown in FIG. The vertical direction of each nozzle is the reaction solution water surface, and there is no internal such as a stirring blade. The solutions supplied from the nozzles A and B directly reached the surface of the reaction solution inside the reaction tank, and did not come into contact with the stirring blade, the side wall of the reaction tank, etc. in the middle. After the completion of the charging, the temperature was kept at 80 ° C. for 1 hour to complete the polymerization reaction. After cooling, the mixture was neutralized with an aqueous sodium hydroxide solution to obtain a polycarboxylic acid polymer (7) having a weight average molecular weight of 20,800. The adhesion of the gel substance to the stirring blade in the reactor was not visually confirmed. When the gel substance attached to the strainer was recovered, the amount was 900 g. Table 1 shows the results.
[0061]
Example 8
The shape of the blade was changed as shown in Table 1, and synthesis was carried out in the same manner as in Example 7 to obtain a polycarboxylic acid polymer (8). At this time, the monomer nozzle A and the initiator nozzle B were at positions as shown in FIG. Immediately before the start of charging from the monomer nozzle A and the initiator nozzle B, the Faudler blade was present below the water surface of the reaction solution as shown in FIG. 6B. Table 1 shows the results.
[0062]
Example 9
The position of the monomer nozzle A, the nozzle diameter, and the flow rate were changed as shown in Table 1 and FIG. 7A, and the synthesis was carried out in the same manner as in Example 1 to obtain a polycarboxylic acid polymer (9). At this time, the Max Blend blade was present above the water surface of the reaction solution as shown in FIG. Table 1 shows the results.
[0063]
Comparative Example 1
The position of the monomer nozzle A, the nozzle diameter, and the flow rate were changed as shown in Table 1 and FIG. 8A, and synthesis was performed in the same manner as in Example 1 to obtain a copolymer (1). At this time, the Max Blend blade was present above the water surface of the reaction liquid as shown in FIG. The adhesion of the gel substance to the stirring blade in the reactor was visually confirmed. When the gel attached to the strainer was recovered, the amount was 8,500 g. Table 1 shows the results.
[0064]
Comparative Example 2
The position of the monomer nozzle A was changed as shown in FIG. 8A, and synthesis was performed in the same manner as in Example 7, to obtain a copolymer (2). At this time, the Max Blend blade was present above the water surface of the reaction liquid as shown in FIG. The adhesion of the gel substance to the stirring blade in the reactor was visually confirmed. When the gel attached to the strainer was recovered, the amount was 12000 g. Table 1 shows the results.
[0065]
Comparative Example 3
The position of the monomer nozzle A, the nozzle diameter, and the flow rate were changed as shown in Table 1 and FIG. 9A, and synthesis was performed in the same manner as in Example 1 to obtain a copolymer (3). At this time, the Max Blend blade was present above the water surface of the reaction liquid as shown in FIG. 9 (b). Table 1 shows the results.
[0066]
Mortar test
(1) Mortar preparation method
600 g of Pacific ordinary Portland cement (trade name, manufactured by Taiheiyo Cement Co.) and 600 g of Toyoura standard sand were kneaded with a mortar mixer (trade name: N-50, manufactured by Tesco Corporation) at a low speed for 30 seconds. Then, cement and sand obtained by kneading 220 g of water containing the polycarboxylic acid-based copolymers (1) to (9) produced in the examples or the copolymers (1) to (3) produced in the comparative example were mixed. And kneaded at a high speed for 3 minutes to prepare a mortar.
(2) Measurement of flow value
Five minutes after water injection, the prepared mortar was packed in a hollow cylindrical container having a diameter of 55 mm and a height of 50 mm placed on a stainless steel plate. Next, after this hollow cylindrical container was vertically lifted, the diameter of the mortar spread on the stainless steel plate was measured in two directions, and the average value was defined as a flow value (mm).
Table 1 shows the solid content conversion amount and the flow value with respect to the cement.
[0067]
[Table 1]

[0068]
Table 1 is described below.
“IPN-50” is a 3-methyl-3-buten-1-ol-ethylene oxide 50 mol adduct, and “IPN-15” is 3-methyl-3-buten-1-ol-ethylene oxide 15 mol adduct. "MAL-50" is a 2-methyl-2-propen-1-ol-ethylene oxide 50 mol adduct, and "PEA-150" is 2-propen-1-ol-ethylene oxide 150 mol adduct. "PGM-25E" is methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 25 mol). “AA” is acrylic acid and “MAA” is methacrylic acid.
“MB” is a Max Blend wing manufactured by Sumitomo Heavy Industries, “FZ” is a full zone wing manufactured by Shinko Pantech, and “TN” is a Tornado wing manufactured by Sumitomo Heavy Industries. And “FD” is a Faudler wing.
Further, as shown in FIG. 10, the rotation axis of the stirring blade was O, the monomer nozzle position was A, the initiator nozzle position was B, and ΔAOB was θ, and the distance AB (= x) between the two nozzles was shown.
[0069]
As described above, in Examples 1 to 8, the linear distance between the monomer component input nozzle and the polymerization initiator input nozzle was set to be equal to or longer than １ ／ of the radius of the reaction tank, and the position of the monomer component input nozzle was determined. Is set at a position where the monomer component is directly dropped into the reaction solution, and the flow rate of the monomer component at the discharge port of the monomer component introduction nozzle is set to 5.0 m / min or more. The reaction rate of the body was high, the gel did not adhere to the device, and the amount of the gel adhered to the strainer was small. Furthermore, when a mortar test was carried out using the produced polymer as a cement admixture, the polymers produced according to Examples 1 to 8 had a sufficient mortar flow value even with a small amount of addition to cement. It could be increased, and the performance as a cement admixture was high. In Example 9, the flow rate of the monomer component at the discharge port of the monomer component injection nozzle was not set to 5.0 m / min or more. The amount of adhesion was reduced.
On the other hand, in Comparative Examples 1 to 3, gel was generated frequently and the performance as a cement admixture was not high.
[0070]
【The invention's effect】
The method for producing a polymer of the present invention has the above-described constitution, thereby preventing generation of a gel, obtaining a uniform polymer, and stably maintaining various kinds of weights such as a cement admixture. The united product can be easily mass-produced industrially.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram showing a reaction tank 1 according to one embodiment of the present invention.
FIG. 2 is a conceptual diagram showing a reaction tank 7 according to one embodiment of the present invention.
FIG. 3 is a schematic cross-sectional view of a monomer component introduction nozzle according to an embodiment of the present invention.
FIG. 4A is a schematic view showing “Tornado wing” manufactured by Sumitomo Heavy Industries, Ltd., and FIG. 4B is a schematic view showing “Full zone wing” manufactured by Shinko Pantech Co., Ltd. FIG. 4C is a schematic view showing “Max Blend Wing” manufactured by Sumitomo Heavy Industries, Ltd., and FIG. 4D is a schematic view showing “Faudler Wing”.
FIG. 5 is a schematic view of a reaction tank used in Examples 1 to 7.
FIG. 6 is a schematic diagram of a reaction tank used in Example 8.
FIG. 7 is a schematic view of a reaction tank used in Example 9.
FIG. 8 is a schematic diagram of a reaction tank used in Comparative Examples 1 and 2.
FIG. 9 is a schematic diagram of a reaction tank used in Comparative Example 3.
FIG. 10 is a schematic diagram showing a distance x between nozzles A and B, a stirring blade diameter d, and a reaction tank inner diameter D in the reaction tanks used in Examples and Comparative Examples.
[Explanation of symbols]
1, 7 reactor
2,10 Monomer component injection nozzle
3 polymerization initiator injection nozzle
4, 11 stirring blade
5, 12 rotation axis
6 jacket
8 Baffle
9 Temperature sensor

Claims (6)

A monomer component and a polymerization initiator are used as essential production raw materials, and the production raw materials are introduced into the reaction tank by a monomer component introduction nozzle and a polymerization initiator introduction nozzle provided in the reaction tank, and A method of producing a polymer by reacting
A method for producing a polymer, wherein the linear distance between the monomer component introduction nozzle and the polymerization initiator introduction nozzle is at least half the radius of the reaction tank. The monomer component and the polymerization initiator are used as essential production raw materials, and the production raw material is introduced into the reaction tank by a monomer component introduction nozzle provided in the reaction tank, and reacted in a reaction solution to form a polymer. A method of manufacturing,
A method for producing a polymer, wherein a monomer component introduced from the monomer component introduction nozzle is directly dropped into a reaction solution in a reaction vessel. The monomer component input nozzle is installed at a position above the reaction tank, where the monomer component input from the monomer component input nozzle does not hit the side wall of the reaction tank and an apparatus in the reaction tank. The method for producing a polymer according to claim 2, wherein The method for producing a polymer according to any one of claims 1 to 3, wherein a flow rate of the monomer component at an outlet of the monomer component introduction nozzle is 5.0 m / min or more. The method for producing a polymer according to any one of claims 1 to 4, wherein the polymer is a polycarboxylic acid-based polymer. The method for producing a polymer according to any one of claims 1 to 5, wherein the polycarboxylic acid polymer is used for a cement admixture.

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