JP4226179B2 - Novel decomposable reactive emulsifier and polymer modification method using the same - Google Patents

Description

【００１５】
［但し、式中Ｒ₁、Ｒ₂は同一または異なる炭素数１〜２０のアルキル基もしくはアルケニル基または水素原子であり（但し、Ｒ₁、Ｒ₂が共に水素原子であることはない）、Ｒ₃は水素原子またはメチル基である。Ａは炭素数２〜４のアルキレン基または置換アルキレン基、ｍおよびｎは０または１〜５０の整数であり、ｍおよびｎが２以上の場合、（ＡＯ）ｍおよび（ＡＯ）ｎは下式（ｉ）で示される、１種の繰り返し単位からなるホモポリマーであってもよく、下式（ｉｉ）および（ｉｉｉ）で示される、異なる置換基Ａ（Ａ¹、Ａ²、…）を有する２種以上の繰返し単位からなるブロックポリマー又はランダムポリマーであってもよい。またＭは水素原子、アルカリ金属、アンモニウムまたはアルカノールアミン残基である。］
−（ＡＯ）−（ＡＯ）−（ＡＯ）− （ｉ）
−（Ａ¹Ｏ）ｍ₁−（Ａ²Ｏ）ｍ₂−……（ｉｉ）
（但し、ｍ₁＋ｍ₂＋……＝ｍ）
−（Ａ¹Ｏ）ｎ₁−（Ａ²Ｏ）ｎ₂−……（ｉｉｉ）
（但し、ｎ₁＋ｎ₂＋……＝ｎ）
【００１６】
（３）置換基
上記一般式（Ｉ）および（ＩＩ）の化合物において、置換基Ｒ₁、Ｒ₂は同一または異なる炭素数１〜２０のアルキル基もしくはアルケニル基または水素原子であり、例えば、アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、等が挙げられる。
【００１７】
また、アルケニル基として好ましくは、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリドセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基、イコセニル基、等が挙げられる。
【００１８】
以上のアルキル基及びアルケニル基は、一般式（Ｉ）および（ＩＩ）の化合物中に混在していてもよい。
【００１９】
なお、Ｒ₁，Ｒ₂が炭素数２０を超える炭化水素基である場合、酸析法によりポリマーを回収する際、乳化剤の分解生成物が水または温水、アルコール類に難溶もしくは不溶となり、またポリマーへ吸着しやすくなる可能性があるといった問題が生じる。
【００２０】
Ｒ₃は水素原子またはメチル基である。
【００２１】
Ａは炭素数２〜４のアルキレン基または置換アルキレン基であり、例えば、エチレン基、プロピレン基、ブチレン基、イソブチレン基等である。
【００２２】
ｍおよびｎは、０または１〜５０の整数である。前記ｍおよびｎが２以上の場合、一般式（Ｉ）及び（ＩＩ）における（ＡＯ）ｍおよび（ＡＯ）ｎは、１種の繰り返し単位からなるホモポリマー（前式（ｉ）参照）であってもよいし、異なる置換基Ａ（Ａ¹、Ａ²、……）を有する２種以上の繰り返し単位からなるブロックポリマーまたはランダムポリマー（前式（ｉｉ）、（ｉｉｉ）参照）であってもよい。また、ｍおよびｎが２以上の場合、（ＡＯ）ｍおよび（ＡＯ）ｎがホモポリマー、ブロックポリマーあるいはランダムポリマーである化合物の混合物であっても良い。
【００２３】
（４）合成
本発明の分解型反応性乳化剤は以下のようにして得ることができるが、その反応条件は特に限定されるものではない。まず、長鎖アルキル基を有する１，３−ジオキソラン化合物（下記一般式（ＩＩＩ））は、例えば、長鎖アルデヒド類または長鎖ケトン類とグリセリンとを酸触媒の存在下、脱水縮合反応させて得ることができる。またα、β−アルキリデングリセリンのような環状アセタール、例えば１，２−イソプロピリデングリセリンをアセチル化し、ついで長鎖アルデヒド類または長鎖ケトン類と酸触媒の存在下、アセタール交換反応させた後、加水分解して得ることもできる。
【００２４】
また必要に応じて１，３−ジオキソラン化合物（一般式（ＩＩＩ））にアルキレンオキサイドを公知の触媒を用い、常法にて付加して下記一般式（ＩＶ）の１，３−ジオキソラン化合物のアルキレンオキサイド付加物を得ることができる。
【００２５】
【化３】

【００２６】
【化４】

【００２７】
ついで、無水マレイン酸とアリルアルコールまたはアリルアルコールのアルキレンオキサイド付加物とを、必要に応じて適当な触媒の存在下、１００℃以下の温度で反応させて得られるマレイン酸モノエステル化物と、一般式（ＩＩＩ）または一般式（ＩＶ）の化合物とを必要に応じて適当な触媒の存在下、１００℃以上の温度で反応させてマレイン酸ジエステル化物を得ることができる。
【００２８】
続いて、マレイン酸ジエステル化物と亜硫酸塩類を、必要に応じて水あるいは適当な溶剤の存在下、７０〜１５０℃の温度で常圧または加圧条件下で反応させて目的の本発明の分解型反応性乳化剤を得る事ができる。
【００２９】
上記反応はアリルアルコールまたはアリルアルコールのアルキレンオキサイド付加物の代わりにメタリルアルコールおよびメタリルアルコールのアルキレンオキサイド付加物を使用した場合にも適用する事ができる。なお上記スルホン化反応で使用する亜硫酸塩類としては、たとえば酸性亜硫酸ナトリウム、酸性亜硫酸カリウム、酸性亜硫酸アンモニウム、亜硫酸ナトリウム、亜硫酸アンモニウム、他の公知の亜硫酸塩類を使用する事ができ、それらを単独または混合して使用する事ができる。また有機アミン類および有機第四級アンモニウム化合物と亜硫酸ガスとの反応により得られる亜硫酸塩類を使用する事もできる。
【００３０】
また、上記反応工程中で重合性の不飽和結合の重合抑制および好ましくない副反応を抑制する目的でハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール等の他、含イオウ系化合物、含リン系化合物等の一般的に使用される重合抑制剤を反応系に少量添加する事ができる。
【００３１】
（５）乳化重合用モノマー
本発明の分解型反応性乳化剤を用いた乳化重合に適用され得るモノマーとしては各種のものを挙げることができ、例えば、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、アクリロニトリル、アクリルアミド、アクリル酸ヒドロキシエステル等のアクリル系モノマー、スチレン、ジビニルベンゼン等の芳香族モノマー、酢酸ビニル等のビニルエステル系モノマー、塩化ビニル、塩化ビニリデン等のハロゲン化オレフィンモノマー、ブタジエン、イソプレン、クロロプレン等の共役系ジオレフィン系モノマー等の他、エチレン、無水マレイン酸、マレイン酸メチル等がある。なお、使用されるモノマーは上記に限定されるものではない。
【００３２】
本発明の分解型反応性乳化剤は、上記モノマーの１種または２種以上の乳化重合または懸濁重合に利用できる。
【００３３】
（６）重合条件
本発明の分解型反応性乳化剤を使用した乳化重合反応では、重合開始剤は従来公知のものが使用できる。しかしながら、本発明の分解型反応性乳化剤は、酸性条件下で分解するため、乳化重合系のｐＨは、重合中終始、ｐＨ４以上に維持する必要があり、一般的な乳化重合用の重合開始剤である過硫酸アンモニウムや過硫酸カリウム等の過硫酸塩を重合開始剤として使用する場合にはｐＨ調整剤を使用して乳化重合系のｐＨを好適な条件に維持する必要がある。そこで、本発明の分解型反応性乳化剤を使用した乳化重合反応では、重合開始剤として、重合中のｐＨ変化が小さく、ｐＨコントロールが容易なレドックス系の重合開始剤が好適である。レドックス系重合開始剤として、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、過酸化水素、等が使用できる。
【００３４】
また、ｐＨ調整剤としては、一般的に用いられる炭酸水素ナトリウム、リン酸水素二ナトリウム、炭酸ナトリウム、水酸化ナトリウム、水酸化カリウム等が使用し得る。
【００３５】
なお、重合促進剤としては、一般的に用いられるピロ重亜硫酸ナトリウム、亜硫酸水素ナトリウム、硫酸第一鉄、グルコース、ホルムアルデヒドナトリウムスルホキシレート、アスコルビン酸およびそのナトリウム塩、等が使用できる。
【００３６】
本発明の分解型反応性乳化剤の乳化重合系での使用量としては、特に制限はないが、通常、全モノマー１００重量部に対して０．１〜２０重量部が適当であり、より好ましくは、０．２〜８．０重量部が適当である。なお、本発明の分解型反応性乳化剤をポリマー改質の目的に使用する場合には、モノマーの種類、改質の目的、要求される性能に応じて、使用量を決定することが可能であり、使用量は上記の範囲に限定されるものではない。
【００３７】
また、必要に応じて、他種乳化剤または保護コロイド剤、連鎖移動剤、電解質、等を併用してもよい。
【００３８】
また、モノマーおよび重合開始剤の重合系への添加方法は、何れも特に限定されるものではなく、従来の乳化重合で適用されている方法、例えば、一括添加法、連続添加法、分割添加法、等の方法、条件を適宜選択できる。
【００３９】
（作用）
本発明の分解型反応性乳化剤は、その分子内に、酸性条件下で容易に分解する１，３−ジオキソラン環と、共重合性の不飽和基を合わせ持つことを特徴とする新規な乳化重合用乳化剤である。
【００４０】
本発明の分解型反応性乳化剤の使用により、乳化重合系では、本質的に乳化剤として、重合を円滑にかつ安定に進行させ、また、同時にその分子中の共重合性の不飽和基がモノマーと反応して、ポリマー中に組み込まれ、得られたポリマーエマルションの泡立ち、機械安定性、貯蔵安定性、等が著しく改善される。
【００４１】
また、得られたポリマーエマルションから作成した塗膜中においては、遊離した状態で存在する乳化剤量が著しく減少し、塗膜の耐水性、接着性、耐熱性、耐候性、等の塗膜物性の向上に極めて優れた効果を発揮する。
【００４２】
また、乳化重合後、ポリマーエマルションに有機酸または無機酸を添加して、ｐＨを下げることにより、本発明の分解型反応性乳化剤分子内の１，３−ジオキソラン環が分解し、乳化剤としての性能を消失し、容易にポリマーを分離、回収することができる。
【００４３】
本発明の分解型反応性乳化剤を使用して得られたポリマーエマルションは、任意の時点で、容易にポリマーエマルションの分散状態を破壊することが可能であり、また、ポリマーの回収、洗浄後の工程排水中に排出される有機物質の総量を低減できる点において、非常に有効である。
【００４４】
更に、本発明の分解型反応性乳化剤をポリマーの改質を目的として使用する場合には、乳化剤としてモノマーとの相溶性を良好にし得、乳化重合後、酸処理することで、乳化剤分子中の１，３−ジオキソラン環が分解して、ポリマーに親水性部位のみを付与でき、ポリマーに対して、親水性付与、帯電防止性付与、防曇性付与、濡れ性付与、またポリマーアロイの為の相溶性付与、等、ポリマー改質の効果を有し、且つ、性能が長期間維持できる点において非常に有効である。
【００４５】
また、ポリマー中に結合した分解型反応性乳化剤分子中の１，３−ジオキソラン環が酸分解することにより、該分解部位にグリセリン由来のジオールが生成し、これはポリマーの変性、修飾および架橋反応に利用できる点において非常に有効である。
【００４６】
【実施例】
以下、実施例および比較例により本発明の実施様態および効果につき述べるが、例示は単に説明用のものであって、発明思想の限定または制限を意図したものではない。なお、文中「％」および「部」とあるのはそれぞれ重量基準を意味する。
【００４７】
（製造例１）
攪拌装置、還流冷却器、温度計、窒素ガス導入管を備えた反応器に、２−トリデカノン２９７ｇとグリセリン１６６ｇ、溶媒としてトルエンを加え、更に触媒としてパラトルエンスルホン酸３ｇを加えて、還流条件下で２４時間脱水縮合反応させ、次いで、得られた反応粗製物を炭酸カリウム水溶液にて洗浄し、更に蒸留水にて３回洗浄した後、減圧蒸留して、２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランを得た。
【００４８】
また、攪拌装置、還流冷却器、温度計、窒素ガス導入管を備えた別の反応器に、無水マレイン酸９８ｇ、アリルアルコ−ル５８ｇを加え、徐々に昇温し、６０℃で４時間反応させてマレイン酸モノエステル化物を得た後、２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランの２７２ｇを仕込み、触媒としてパラトルエンスルホン酸３ｇ、ハイドロキノン３ｇを加え、窒素ガスを通気しながら１３０℃で６時間反応させてマレイン酸ジエステル化物を得た。
【００４９】
続いて、得られたマレイン酸ジエステル化物に酸性亜硫酸ナトリウム１０４ｇを水５００ｇに溶解して加え、次いでイソプロピルアルコ−ル５００ｇを加え、８０℃で６時間反応させた。
【００５０】
反応終了後、水およびイソプロピルアルコールを減圧留去した後、水を加えて反応粗製物を再溶解し、次いで、ジエチルエ−テルを加えて油性未反応物を抽出除去した後、水層を取り出し、ついでエチルアルコールを加えて減圧下で濃縮した。続いて再度エチルアルコ−ルを加えて攪拌、溶解し、系中の不溶解物を濾過により除去した後、エチルアルコ−ルを減圧留去して得られる反応組成物を本発明分解型反応性乳化剤［Ａ］（化学式を下記化５に示した。）とした。
【００５１】
【化５】

【００５２】
（製造例２）
製造例１と同様にして、２−トリデカノンとグリセリンを反応させて得た２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソラン２７２ｇをオートクレーブに移し、水酸化カリウムを触媒として、圧力２Ｋｇ／ｃｍ^２、１３５℃の条件下でエチレンオキシド２２０ｇ（５モル）を付加した。続いて、水５ｇおよび触媒として使用した水酸化カリウムの１０倍量のアルカリ吸着剤と濾過助剤を加え、触媒を吸着処理した後、減圧脱水濾過して２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランのエチレンオキシド５モル付加体を得た。
【００５３】
次いで、攪拌装置、還流冷却器、温度計、窒素ガス導入管を備えた別の反応器に、無水マレイン酸９８ｇ、アリルアルコール５８ｇを加え、徐々に昇温し、８０℃で２時間反応させてマレイン酸モノエステル化物を得た後、２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランのエチレンオキシド５モル付加体の４９２ｇを仕込み、触媒としてパラトルエンスルホン酸３ｇ、ハイドロキノン３ｇを加え、窒素ガスを通気しながら１３０℃で６時間反応させてマレイン酸ジエステル化物を得た。
【００５４】
続いて、得られたマレイン酸ジエステル化物に酸性亜硫酸ナトリウム１０４ｇを水５００ｇに溶解して加え、次いでイソプロピルアルコ−ル５００ｇを加え、８０℃で６時間反応させた後、製造例１と同様の方法にて精製して得られる反応組成物を本発明分解型反応性乳化剤［Ｂ］（化学式を下記化６に示した。）とした。
【００５５】
【化６】

【００５６】
また、２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランのエチレンオキシド５モル付加体の代わりに２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランのエチレンオキシド４０モル付加体を用いて、同様の操作にて得られた反応組成物を本発明分解型反応性乳化剤［Ｃ］（化学式を下記化７に示した。）とした。
【００５７】
【化７】

【００５８】
（製造例３）
製造例２に準じて、無水マレイン酸と公知の方法で得たアリルアルコ−ルのエチレンオキシド５モル付加体を反応させてマレイン酸モノエステル化物を得、次いで、２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランのエチレンオキシド５モル付加体を反応させてマレイン酸ジエステル化物を得た。
【００５９】
続いて、得られたマレイン酸ジエステル化物に亜硫酸ナトリウムにてスルホン化した後、製造例１と同様の方法にて精製して得られる反応組成物を本発明分解型反応性乳化剤［Ｄ］（化学式を下記化８に示した。）とした。
【００６０】
【化８】

【００６１】
（製造例４）
製造例２に準じて、無水マレイン酸と公知の方法で得たアリルアルコ−ルのブチレンオキサイド３モル付加体を反応させてマレイン酸モノエステル化物を得、次いで、２−メチル−２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランを反応させてマレイン酸ジエステル化物を得た。
【００６２】
続いて、得られたマレイン酸ジエステル化物を酸性亜硫酸ナトリウムにてスルホン化した後、製造例１と同様の方法にて精製して得られる反応組成物を本発明分解型反応性乳化剤［Ｅ］（化学式を下記化９に示した。）とした。
【００６３】
【化９】

【００６４】
（製造例５）
攪拌装置、還流冷却器、温度計、窒素ガス導入管を備えた反応器に、１、２−イソプロピリデングリセリン１９８ｇと無水酢酸２３０ｇ、触媒としてピリジンを加え、還流条件下で１時間反応させてアセチル化した後、減圧蒸留して、アセチル−１、２−イソプロピリデングリセリンを得た。
【００６５】
次に、アセチル−１、２−イソプロピリデングリセリン２２６ｇとｎ−ドデカナ−ル２２１ｇ、溶媒としてトルエンを加え、更に触媒としてパラトルエンスルホン酸３ｇを加えて、還流条件下でアセタ−ル交換反応させた。次いで、水酸化ナトリウムのエタノ−ル溶液を加えて還流条件下でエステル部位を分解した後、エタノ−ルを減圧留去して得られた反応粗製物をジエチルエーテルで抽出し、更に蒸留水にて３回洗浄した。続いて、ジエチルエーテル層を炭酸カリウムで乾燥した後、ジエチルエーテルを減圧留去し、更に、２−ウンデシル−４−ヒドロキシメチル−１，３−ジオキソランを得た。
【００６６】
また、攪拌装置、還流冷却器、温度計、窒素ガス導入管を備えた別の反応器に、無水マレイン酸９８ｇ、アリルアルコ−ル５８ｇを加え、徐々に昇温し、６０℃で２時間反応させた後、２−ウンデシル−４−ヒドロキシメチル−１、３−ジオキソラン２５８ｇを仕込み、触媒としてパラトルエンスルホン酸３ｇ、ハイドロキノン３ｇを加え、窒素ガスを通気しながら１３０℃で６時間反応させてマレイン酸ジエステル化物を得た。
【００６７】
続いて、得られたマレイン酸ジエステル化物をオートクレ−ブに移し、酸性亜硫酸アンモニウム９８ｇを水４００ｇに溶解して加え、次いでメチルアルコ−ル４００ｇを加え、加圧下で攪拌しながら１００℃で４時間反応させた後、製造例１と同様の方法にて精製して得られる反応組成物を本発明分解型反応性乳化剤［Ｆ］（化学式を下記化１０に示した。）とした。
【００６８】
【化１０】

【００６９】
（製造例６）
製造例１に準じて、無水マレイン酸と、メタリルアルコ−ルを反応させて、マレイン酸モノエステル化物を得、次いで、７−トリデカノンとグリセリンを反応させて得た２、２−ジヘキシル−４−ヒドロキシメチル−１、３−ジオキソランを反応させてマレイン酸ジエステル化物を得た。
【００７０】
続いて、得られたマレイン酸ジエステル化物を酸性亜硫酸ナトリウム、亜硫酸ナトリウム１：１混合物（重量比）にてスルホン化した後、製造例１と同様の方法にて精製して得られる反応組成物を本発明分解型反応性乳化剤［Ｇ］（化学式を下記化１１に示した。）とした。
【００７１】
【化１１】

【００７２】
（製造例７）
製造例２に準じて、無水マレイン酸と公知の方法で得たアリルアルコ−ルのブチレンオキシド２モル、プロピレンオキシド３モルのランダム付加物を反応させてマレイン酸モノエステル化物を得、次いで、ｎ−オクタデカナールとグリセリンから得た２−ヘプタデシル−４−ヒドロキシメチル−１、３−ジオキソランを反応させてマレイン酸ジエステル化物を得た。
【００７３】
続いて、得られた反応させてマレイン酸ジエステル化物を酸性亜硫酸アンモニウムにてスルホン化した後、製造例１と同様の方法にて精製して得られる反応組成物を本発明分解型反応性乳化剤［Ｈ］（化学式を下記化１２に示した。）とした。
【００７４】
【化１２】

【００７５】
（製造例８）
製造例２に準じて、無水マレイン酸とアリルアルコ−ルを反応させてマレイン酸モノエステル化物を得、次いで、ｎ−オクタナールとグリセリンから得た２−ヘプチル−４−ヒドロキシメチル−１、３−ジオキソランのブチレンオキシド３モル、エチレンオキシド５モルのブロック付加物を反応させてマレイン酸ジエステル化物を得た。
【００７６】
続いて、得られたマレイン酸ジエステル化物を酸性亜硫酸ナトリウムにてスルホン化した後、製造例１と同様の方法にて精製して得られる反応組成物を本発明分解型反応性乳化剤［Ｉ］（化学式を下記化１３に示した。）とした。
【００７７】
【化１３】

【００７８】
（使用例１）
攪拌機、還流冷却器、温度計および滴下ロートを備えた反応器に、イオン交換水２９０g、炭酸水素ナトリウム０．５ｇを仕込み、７０℃まで昇温させ、窒素ガスを通気して水中の溶存酸素を除去した。次に、酢酸ビニル１４０ｇ、アクリル酸ブチル６０ｇに表１に示す本発明の分解型反応性乳化剤１０ｇを溶解させ、その内の２０％に相当する４１ｇを反応器に仕込み、次いで過硫酸アンモニウム０．５ｇを加えて先行重合させた。続いて、重合開始１０分後より３時間かけて、残りのモノマーと乳化剤の混合液１６５ｇを滴下して重合させた。更に続けて、重合温度にて２時間熟成した後、冷却し、エマルションを取り出し、供試サンプルとした。この乳化重合時の凝集物量、得られたエマルションの固形分、機械安定性、起泡性、乳化剤反応率およびこのエマルションより作成したポリマーフィルムの耐水性の各試験結果を表１に示した。
【００７９】
また、比較として、炭酸水素ナトリウム無添加で実施した乳化重合の結果を表１に示した。更に、表１に示す従来の乳化剤についても、同様の試験を実施した。
【００８０】
【表１】

【００８１】
（注）固形分：エマルション２ｇを１０５℃、２時間乾燥後、重量測定し、秤取したエマルション重量に対して％表示した。
凝集物量：エマルションを１５０メッシュ金網で濾過し、残渣を水洗後、乾燥して得た凝集物重量を仕込みモノマー重量に対して％表示した。
機械安定性：エマルション５０ｇをマーロン型試験器にて荷重１０Ｋｇ、回転数１０００ｒｐｍで５分間攪拌し、生成した凝集物を１５０メッシュ金網で濾過し、残渣を水洗後、乾燥し、その重量をエマルションの固形分に対して％表示した。
起泡性：エマルションをイオン交換水で2倍稀釈し、１００ｍｌネスラー管に３０ｍｌ入れ、１分間振とうした後、静置５分後における泡の量を測定した。
乳化剤反応率：エマルションにメタノールを加えて、ポリマーを凝固し、遠心分離処理後、その上済みを用い、ＨＰＬＣにて未反応の乳化剤量を測定して、乳化剤の反応率を算出した。
耐水性試験：ガラス板上に０．５ｍｍ厚のポリマーフィルムを作製し、これを水中に浸漬し、前記フィルムを透して４．５ポイント文字が読めなくなるまでの時間を測定した。
【００８２】
（使用例２）
アクリル酸ブチル１００ｇ、アクリル酸−２−エチルヘキシル１００ｇ、イオン交換水１９４ｇおよび表２に示す本発明の分解型反応性乳化剤６ｇをホモディスパーにより混合してモノマー乳濁液を調製した。次に、攪拌機、還流冷却器、温度計および滴下ロートを備えた反応器に、イオン交換水１００ｇ、炭酸水素ナトリウム０．５ｇを仕込み、８０℃まで昇温させ、窒素ガスを通気して水中の溶存酸素を除去した。続いて、上記モノマー乳濁液の内、８０ｇを攪拌しながら反応器に加え、更に過硫酸アンモニウム０．５ｇを加えて先行重合させた。そして、重合開始１０分後より３時間かけて、残りのモノマー乳濁液３２０ｇを滴下して重合させた。更に続けて、重合温度８０℃を維持して２時間熟成した後、冷却し、エマルションを取り出し、試供サンプルとした。
【００８３】
この乳化重合時の凝集物量、得られたエマルションの固形分、機械安定性、起泡性、接着性およびこのエマルションより作成したポリマーフィルムの耐熱着色性の各試験結果を表２に示した。
【００８４】
また、比較として、炭酸水素ナトリウム無添加で実施した乳化重合の結果を表２に示した。更に、表２に示す従来の乳化剤についても、同様の試験を実施した。
【００８５】
【表２】

【００８６】
（注）固形分：エマルション２ｇを１０５℃、２時間乾燥後、重量測定し、秤取したエマルション重量に対して％表示した。
凝集物量：エマルションを１５０メッシュ金網で濾過し、残渣を水洗後、乾燥して得た凝集物重量を仕込みモノマー重量に対して％表示した。
機械安定性：エマルション５０ｇをマーロン型試験器にて荷重１０Ｋｇ、回転数１０００ｒｐｍで５分間攪拌し、生成した凝集物を１５０メッシュ金網で濾過し、残渣を水洗後、乾燥し、その重量をエマルションの固形分に対して％表示した。
起泡性：エマルションをイオン交換水で2倍稀釈し、１００ｍｌネスラー 管に３０ｍｌ入れ、１分間振とうした後、静置５分後における泡の量を測定した。
接着力：ＰＥＴフィルムにエマルションを０．１ｍｍ厚で塗工し、１０５℃で１０分間熱処理した後、塗膜上にＰＥＴフィルムを置き、ローラ圧着したサンプル片（１インチ幅）の２５℃における１８０°剥離強度を測定した。
耐熱着色性試験：ガラス板上に０．５ｍｍ厚の塗膜を作製し、２００℃に保持した熱風乾燥器内で３０分間熱処理して、塗膜の着色を調べた。
（評価基準）◎：全く着色が認められない
○：極僅かに着色が認められる
△：淡い黄色に着色している。
×：濃い褐色に着色している
【００８７】
（使用例３）
反応器として、耐圧性を有するガラス瓶、具体的には炭酸飲料用の空き瓶にイオン交換水６０ｇを仕込み、窒素ガスを通気して溶存酸素を除去した。次にガラス瓶を氷水浴中で冷却した後、表３に示す本発明の分解型反応性乳化剤１．２ｇ、ナフタレンスルホン酸ホルマリン縮合物０．１２ｇ、ドデシルメルカプタン０．１２ｇ、スチレン２０ｇ、パラメンタンヒドロペルオキシド０．０３ｇ、硫酸第一鉄７水和物０．０２ｇ、ナトリウムホルムアルデヒドスルホキシド０．０１ｇを仕込んだ。次いでメタノールドライアイス浴中の目盛付き試料採取管にボンベからブタジエンを導入し、液化させて計量したブタジエン２２ｇをストップコック付きのシリンジを用いてガラス瓶に仕込んだ後、静置して２ｇ分のブタジエンを気化させて空気を追い出した後、直ちに打栓、振とうして、ガラス瓶中の内容液を乳濁状態とした。
【００８８】
次に、水温５℃に調整した回転式重合槽内のホルダーにガラス瓶をセットし、回転数５０ｒｐｍにて５時間重合させた。重合反応終了後、ガラス瓶を開栓し、Ｎ、Ｎ−ジエチルヒドロキシルアミンを添加して重合を停止させ、続いて減圧下で残存モノマーを留去して得られたポリブタジエンラテックスを供試サンプルとした。
【００８９】
この乳化重合時の凝集物量、得られたラテックスの固形分、機械安定性、起泡性、ポリマーフィルムの吸水率、耐熱着色性の各試験結果を表３に示した。
【００９０】
また、得られたポリマーラテックスについて、１％硫酸を添加してｐＨを２以下としたところ、ラテックスが破壊され、直ちにポリマーが析出した。更に、引き続き攪拌しながら６０℃に昇温した後、静置してポリマーを浮上させ、これを回収して温水で3回洗浄した後、ポリマーを脱水し、６０℃で減圧乾燥した。この時の得られた乾燥ポリマーの回収率を表３に示した。
【００９１】
なお、比較として従来の乳化剤についても同様の試験を実施し、表３にその試験結果を示した。
【００９２】
【表３】

【００９３】
（注）固形分：ラテックス２ｇを１０５℃、１時間減圧乾燥後、重量測定し、秤取したラテックス重量に対して％表示した。
凝集物量：ラテックスを１５０メッシュ金網で濾過し、残渣を水洗後、減圧乾燥して得た凝固物重量を仕込みモノマー重量に対して％表示した。
機械安定性：ラテックス５０ｇをマーロン型試験器にて荷重１０Ｋｇ、回転数１０００ｒｐｍで５分間攪拌し、生成した凝集物を１５０メッシュ金網で濾過し、残渣を水洗後、減圧乾燥し、その重量をラテックスの固形分に対して％表示した。
起泡性：ラテックスをイオン交換水で2倍稀釈し、１００ｍｌネスラー管に３０ｍｌ入れ、３０回倒立させてから静置５分後における泡の量を測定した。
吸水率：ガラス状上に０．５ｍｍ厚のポリマーフィルムを作製し、ガラス板からフィルムを注意深く引き剥がし、フィルムを縦１００ｍｍ×横１００ｍｍの大きさに切断して試験片を作成した。これを水中に浸漬し、２４時間後に取り出し、素早く2枚の濾紙間で水分を除去し、重量測定し、重量増加分を浸漬前の重量に対して％表示した。
耐熱着色性：ガラス状上に０．５ｍｍ厚の塗膜を作製し、200℃に保持した熱 風乾燥器内で３０分間熱処理して、塗膜の着色を調べた。
（評価基準） ◎：全く着色が認められない
○：極僅かに着色が認められる
△：淡い黄色に着色している。
×：濃い褐色に着色している
ポリマー回収率：得られた乾燥ポリマーの重量を、ラテックスの固形分値から算出した理論固形分重量に対して％表示した。
【００９４】
（使用例４）
攪拌機、温度計および冷却、加熱装置を備えたオートクレーブに、 イオン交換水 ５００g、表４に示す本発明の分解型反応性乳化剤２５ｇ、ナフタレンスルホン酸ホリマリン縮合物２．５ｇ、炭酸ナトリウム２．５ｇ、ドデシルメルカプタン ２．５ｇを仕込み、更に過硫酸カリウム１．５ｇを加えた後、オートクレーブ内を窒素置換した。続いて、オートクレーブに５℃の冷却水を通水して内容物を冷却した後、ブタジエンボンベからオートクレーブに ブタジエン５００ｇを導入し、攪拌を高速にして内容物を乳濁状態とした。次に、内温を６０℃まで昇温し、３５時間重合させた。重合終了後、冷却し、減圧下で未反応ブタジエンを留去してポリブタジエンラテックスを得た。この乳化重合時の凝集物量および得られたポリマーラテックスの固形分、平均粒子径について表４に示した。
【００９５】
次に、攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、上記操作にて調製したポリブタジエンラテックスを固形分換算で３２０ｇ、イオン交換水１８０ｇ （ただし、ポリマーラテックス固形分に応じて微調整する）を仕込み、 そして、スチレン２２５ｇ、アクリロニトリル ９５ｇ、イオン交換水 ３００ｇ、更に乳化剤としてポリブタジエンラテックス調製時と同一の本発明分解型反応性乳化剤 ９．６ｇをホモディスパーにより混合して得たモノマー乳濁液の内、６５ｇを攪拌しながら反応器に加えた後、窒素置換した。 次いで、反応器を冷却して、内温が１０℃となった時点で、パラメンタンヒドロペルオキシド１．２ｇ、硫酸第一鉄7水和物 ０．６ｇ、ナトリウムホルムアルデヒドスルホキシド ０．３ｇを加えて先行重合させた。次に、重合開始１５分後より３時間かけて、残りのモノマー乳濁液を滴下して重合させた。更に続けて、重合温度を維持して２時間熟成した後、Ｎ，Ｎ−ジエチルヒドロキシルアミンを添加して重合を停止させ、続いて、窒素ガス通気、減圧条件下で残存モノマーを留去して得られたポリマーラテックスを供試サンプルとした。
【００９６】
この乳化重合時の凝集物量および得られたポリマーラテックスの固形分、平均粒子径、乳化剤反応率の各試験結果を表５に示した。
【００９７】
また得られたポリマーラテックス２５０ｇについて、１％硫酸を添加してｐＨを２以下としたところ、ラッテクスが破壊され、直ちにポリマーが析出した。引き続き、攪拌しながら６０℃に昇温した後、静置してポリマーを浮上させ、これを回収して温水で３回洗浄した後、ポリマーを脱水、乾燥した。 この時のポリマーの回収率とポリマー回収時の全排水を回収、濃縮して測定した全有機炭素（ＴＯＣ）量、ポリマー成形時の滞留着色性の測定結果を表５に示した。なお比較として従来の乳化剤についても同様の試験を実施し、表４、表５にその試験結果を示した。
【００９８】
【表４】

【００９９】
（注）固形分：ラテックス2ｇを105℃、１時間減圧乾燥後、重量測定し、秤取したラテックス重量に対して％表示した。
凝集物量：ラテックスを150メッシュ金網で濾過し、残渣を水洗後、減圧乾燥して得た凝固物重量を仕込みモノマー重量に対して％表示した。
平均粒子径：島津レーザー回析式粒度分布測定装置SALD−2000を使用して、ラテックスの平均粒子径を測定した。
【０１００】
【表５】

【０１０１】
（注）固形分：ラテックス2ｇを105℃、2時間減圧乾燥後、重量測定し、ラテックス重量に対して％表示した。
凝集物量：ラテックスを150メッシュ金網で濾過し、残渣を水洗後、減圧乾燥して得た凝固物重量を仕込みモノマー重量に対して％表示した。
平均粒子径：島津製作所製レーザー回析式粒度分布測定装置SALD−2000を使用して、ラテックスの平均粒子径を測定した。
乳化剤反応率：ラテックスにメタノールを加えて、ポリマーを凝固し、遠心分離処理後、その上済みを用い、HPLCにて未反応の乳化剤量を測定して、乳化剤の反応率を算出した。
ポリマー回収率：得られた乾燥ポリマーの重量を、ラテックスの固形分値から算出した理論固形分重量に対して％表示した。
全有機炭素（ＴＯＣ）量：ポリマー回収時の全排水（ポリマー洗浄水を含む）を回収し、250mlまで濃縮した後、その一部を採取して島津製作所製ＴＯC−500を使用して、全有機炭素（ＴＯＣ）量測を定した。
滞留着色性：得られた乾燥ポリマーを成形温度250℃、金型温度50℃で成形し m×横125mm×厚さ3.5mmの参照試験片を作成した。同様に、250℃の成形機内で20分間滞留させて成形した試験片について、参照試験片と比較して着色を調べた。
（評価基準）
◎：全く着色が認められない
○：極わずかに着色が認められる
△：淡い黄色に着色している
×：濃い褐色に着色している
【０１０２】
（使用例５）
使用例３と同様の操作にてポリブタジエンラテックスを調製し、以後、ポリブタジエンラテックス中でスチレン、アクリロニトリルを乳化重合する際に使用する分解型反応性乳化剤量を３２ｇに変更した以外は同様の条件で重合してポリマーラテックスを得た。更に得られたポリマーラテックスからポリマーを回収、乾燥を行った。この時得られたポリマーを成形温度２５０℃、金型温度５０℃で成形し、縦１２５mm×横１２５mm×厚さ３．５mmの試験片を作成した。この試験片について、接触角、表面固有抵抗の測定を行った。その各試験の結果について表６に示した。なお、比較として従来の乳化剤についても同様の試験を実施し、表６にその試験結果を示した。
【０１０３】
【表６】

【０１０４】
（注）接触角：得られた乾燥ポリマーを成形温度250℃、金型温度50℃で成形し、縦125mm×横125mm×厚さ3.5mmの試験片を作成し、接触角測定 器により水滴の接触角を測定した。
表面固有抵抗：得られた乾燥ポリマーを成形温度250℃、金型温度50℃で成形した試験片について、温度20℃、湿度45％の雰囲気中に24時間放置した後、表面固有抵抗値を測定した。
【０１０５】
【発明の効果】
以上説明した通り、本発明により、乳化重合時における安定性および得られたポリマーエマルションの安定性を良好にし得、工程中での泡トラブルを解消し、しかも、ポリマー回収工程におけるポリマーの回収率を向上させ、生産性の向上に著しく寄与し、更に、ポリマーの回収、洗浄工程で排出される有機物量を著しく低減できる新規な乳化重合用の分解型反応性乳化剤を提供したことにある。また、ポリマーエマルションから得られたポリマーおよびポリマー塗膜の耐水性および耐熱性を著しく改善できる新規な乳化重合用の分解型反応性乳化剤を提供したことにある。更に、本発明の新規な乳化重合用の分解型反応性乳化剤を使用することにより、得られたポリマーおよびポリマー塗膜の物性を改良するポリマー改質方法を提供したことにある。これら本発明の効果により、関連産業界の発展および需要者の利益に寄与する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel reactive emulsifier composed of a compound having a 1,3-dioxolane ring that easily decomposes under acidic conditions and a copolymerizable unsaturated group in the same molecule. The present invention relates to a polymer modification method using the novel decomposable reactive emulsifier.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, as an emulsifier for emulsion polymerization, for example, anionic surfactants such as dodecylbenzene sulfonate, alkyl sulfate ester salt, alkyl sulfosuccinate ester salt, polyoxyalkylene alkyl (aryl) ether sulfate ester salt, polyoxyalkylene Nonionic surfactants such as alkyl (aryl) ethers and polyoxyethylene polyoxypropylene block copolymers, and soaps such as higher fatty acid soaps and rosin soaps are used alone or in combination. The stability of the film, the properties of the coating film and polymer obtained from the emulsion are not always satisfactory, and many problems to be solved remain. That is, there are problems in polymerization stability of emulsion, foam trouble during the process, mechanical stability, chemical stability, freeze-thaw stability, pigment miscibility, storage stability, etc. of the obtained emulsion. When the film is formed, the used emulsifier remains in the coating film in a free state, which causes problems such as poor water resistance, adhesion, heat resistance, weather resistance, and the like of the coating film.
[0003]
In addition, when the emulsion is destroyed by means such as salting out, aciding out, and the polymer is taken out, if the emulsifier remains in the polymer, the water resistance and heat resistance of the obtained polymer, weather resistance, polymer strength, etc. Various polymer physical properties are deteriorated. Therefore, in order to sufficiently remove the emulsifier in the polymer, a large amount of washing water is required. Furthermore, since a large amount of emulsifier is contained in the wastewater, which causes river pollution, There was a problem that labor was required.
[0004]
As measures against these problems, attempts have been made to reduce the amount of emulsifier used during emulsion polymerization, and to reduce the amount of surfactants added in other processes, but these are fundamental to various problems. There is no solution, and sufficient solution has not yet been achieved in terms of polymerization stability during emulsion polymerization, stability of the obtained emulsion, and various physical properties of the coating film and polymer.
[0005]
From this point of view, many reactive emulsifiers having a copolymerizable unsaturated group have been proposed in order to improve the problems of conventional emulsifiers. For example, JP-B-46-12472, JP-A-54-14431, JP-B-46-34894, JP-B-54-29657, JP-A-51-30285, JP-B-49-46291, and JP-A-56. JP-A No. 127697 describes anionic reactive surfactants, and JP-A Nos. 56-28208 and 50-98484 describe non-ionic reactive surfactants. Emulsion polymerization of various monomers has been attempted.
[0006]
However, when these reactive emulsifiers are used alone as an emulsifier, the stability during emulsion polymerization is insufficient, and in use, polymerization often does not proceed smoothly unless used in combination with conventional emulsifiers. In fact, the coating film obtained from the emulsion has not yet been sufficiently satisfactory in terms of water resistance, adhesion, heat resistance and weather resistance.
[0007]
In addition, reactive emulsifiers have been tried to reduce drainage load when breaking the emulsion and taking out the polymer, but conventional reactive emulsifiers break the emulsion by salting out or aciding out methods. When the polymer is recovered, the precipitation and separation of the polymer are incomplete, the polymer cannot be easily removed, and the polymer recovery rate is often reduced. As a result, the unreacted emulsifier flows into the waste water, and the problem of drainage load has not been sufficiently solved.
[0008]
As a measure for improving these problems, a technique has been proposed in which a degradable surfactant that is easily decomposed by chemical treatment is used as an emulsifier for emulsion polymerization from a viewpoint different from that of a reactive emulsifier. For example, Japanese Patent Application Laid-Open No. 3-281602 discloses a technique in which a decomposable surfactant that is easily decomposed by acid treatment is used as an emulsifier for emulsion polymerization, and a polymer is easily recovered by acid precipitation. However, with degradable emulsifiers, depending on the type of hydrophobic group or hydrophilic group in the emulsifier molecule, the decomposition product after acid treatment may be poorly soluble in water or adsorbed to the polymer. Water is necessary, and the decomposition products remaining in the polymer in a free state after washing the polymer may adversely affect the physical properties of the polymer, and the above problems have not been sufficiently solved.
[0009]
In addition, various surfactants have been used for the purpose of modifying polymers, and various properties such as imparting hydrophilicity, imparting antistatic properties, imparting antifogging properties, imparting wettability, imparting film-forming properties, imparting compatibility, etc. Used for purposes. However, in the conventional surfactant, since the surfactant is present in a free state, the performance deteriorates with time, and the performance is not fully satisfactory. In recent years, in order to improve these problems, attempts have been made to use reactive emulsifiers as polymer modifiers. However, conventional reactive emulsifiers do not necessarily have sufficient copolymerizability with monomers, so performance is improved. The problem of decreasing with time has not been completely solved, and there have been problems such as deterioration of various physical properties of the polymer. In addition, the reactive emulsifier is essentially an emulsifier, and its structure consists of a hydrophobic group site and a hydrophilic group site. For the purpose of polymer modification, for example, imparting hydrophilicity, the hydrophobic group site is always necessary for imparting performance. However, in general, the physical properties of the polymer are often adversely affected, and the above problems have not been sufficiently solved.
[0010]
[Object of invention]
The present invention has been made in view of the above circumstances, and the object thereof is to improve the stability during emulsion polymerization, and to improve the water resistance, adhesiveness, and the coating film obtained from the emulsion. The present invention provides a decomposition-type reactive emulsifier for emulsion polymerization that can remarkably improve heat resistance and weather resistance, and can easily break a polymer emulsion at the time of polymer recovery, and can significantly improve physical properties of the obtained polymer. It is in.
[0011]
[Means for Solving the Problems]
The present invention has been made paying attention to such conventional problems.
[0012]
(1) Progress of invention
As a result of intensive studies, the present inventors have, in the same molecule, a 1.3-dioxolane ring that easily decomposes under acidic conditions and an allyl group or a methallyl group as a copolymerizable unsaturated group. The present inventors have found that the compound is suitable as an emulsifier for emulsion polymerization and have reached the present invention.
[0013]
(2) Summary of the invention
Based on the above knowledge, the present invention is a decomposition-type reactive emulsifier for emulsion polymerization represented by the following general formula (I) and / or the following general formula (II) (hereinafter referred to as “the present invention-decomposable reactive emulsifier” or It is simply referred to as “the emulsifier of the present invention”).
[0014]
[Chemical formula 2]

[0015]
[However, in the formula, R ₁ , R ₂ Are the same or different alkyl or alkenyl groups having 1 to 20 carbon atoms or hydrogen atoms (provided that R is ₁ , R ₂ Are not hydrogen atoms), R _Three Is a hydrogen atom or a methyl group. A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m and n are 0 or an integer of 1 to 50, and when m and n are 2 or more, (AO) m and (AO) n are It may be a homopolymer consisting of one type of repeating unit represented by (i), and different substituents A (A represented by the following formulas (ii) and (iii): ¹ , A ² , ...) may be a block polymer or a random polymer composed of two or more kinds of repeating units. M is a hydrogen atom, alkali metal, ammonium or alkanolamine residue. ]
-(AO)-(AO)-(AO)-(i)
-(A ¹ O) m ₁ -(A ² O) m ₂ − …… (ii)
(However, m ₁ + M ₂ + …… = m)
-(A ¹ O) n ₁ -(A ² O) n ₂ − …… (iii)
(However, n ₁ + N ₂ + …… = n)
[0016]
(3) Substituent
In the compounds of the above general formulas (I) and (II), the substituent R ₁ , R ₂ Are the same or different alkyl group or alkenyl group having 1 to 20 carbon atoms or a hydrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and the like.
[0017]
The alkenyl group is preferably a propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridosenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, Examples include heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, and the like.
[0018]
The above alkyl group and alkenyl group may be mixed in the compounds of the general formulas (I) and (II).
[0019]
R ₁ , R ₂ When is a hydrocarbon group having more than 20 carbon atoms, when the polymer is recovered by the acid precipitation method, the decomposition product of the emulsifier may become insoluble or insoluble in water, hot water or alcohols, and may be easily adsorbed to the polymer. The problem that there is the nature arises.
[0020]
R _Three Is a hydrogen atom or a methyl group.
[0021]
A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and examples thereof include an ethylene group, a propylene group, a butylene group, and an isobutylene group.
[0022]
m and n are 0 or an integer of 1-50. When m and n are 2 or more, (AO) m and (AO) n in the general formulas (I) and (II) are homopolymers composed of one type of repeating unit (see the above formula (i)). Or different substituents A (A ¹ , A ² ,...) May be a block polymer or a random polymer (see the above formulas (ii) and (iii)) composed of two or more kinds of repeating units. When m and n are 2 or more, a mixture of compounds in which (AO) m and (AO) n are homopolymer, block polymer or random polymer may be used.
[0023]
(4) Synthesis
The decomposable reactive emulsifier of the present invention can be obtained as follows, but the reaction conditions are not particularly limited. First, a 1,3-dioxolane compound having a long-chain alkyl group (the following general formula (III)) is obtained by, for example, subjecting a long-chain aldehyde or long-chain ketone and glycerin to a dehydration condensation reaction in the presence of an acid catalyst. Obtainable. In addition, a cyclic acetal such as α, β-alkylidene glycerol, for example 1,2-isopropylidene glycerol, is acetylated and then subjected to an acetal exchange reaction in the presence of an acid catalyst with a long-chain aldehyde or a long-chain ketone, followed by hydrolysis. It can also be obtained by decomposing.
[0024]
If necessary, alkylene oxide of 1,3-dioxolane compound represented by the following general formula (IV) is added to 1,3-dioxolane compound (general formula (III)) by a conventional method using alkylene oxide. An oxide adduct can be obtained.
[0025]
[Chemical 3]

[0026]
[Formula 4]

[0027]
Subsequently, a maleic acid monoester product obtained by reacting maleic anhydride with allyl alcohol or an alkylene oxide adduct of allyl alcohol in the presence of a suitable catalyst as necessary at a temperature of 100 ° C. or lower, and a general formula A maleic acid diesterified product can be obtained by reacting the compound of (III) or the general formula (IV) with a suitable catalyst in the presence of a suitable catalyst at a temperature of 100 ° C. or higher.
[0028]
Subsequently, the maleic acid diesterified product and sulfites are reacted in the presence of water or a suitable solvent, if necessary, at a temperature of 70 to 150 ° C. under normal pressure or pressurized conditions to obtain the desired decomposition type of the present invention. A reactive emulsifier can be obtained.
[0029]
The above reaction can also be applied when methallyl alcohol and an alkylene oxide adduct of methallyl alcohol are used instead of allyl alcohol or an alkylene oxide adduct of allyl alcohol. As the sulfites used in the sulfonation reaction, for example, acidic sodium sulfite, acidic potassium sulfite, acidic ammonium sulfite, sodium sulfite, ammonium sulfite, and other known sulfites can be used alone or in combination. Can be used. In addition, sulfites obtained by reaction of organic amines and organic quaternary ammonium compounds with sulfurous acid gas can also be used.
[0030]
In addition, in addition to hydroquinone, hydroquinone monomethyl ether, catechol, etc., in addition to sulfur-containing compounds, phosphorus-containing compounds, etc., for the purpose of suppressing polymerization of polymerizable unsaturated bonds and suppressing undesirable side reactions in the above reaction step A small amount of the polymerization inhibitor used in the reaction can be added to the reaction system.
[0031]
(5) Monomer for emulsion polymerization
Examples of the monomer that can be applied to emulsion polymerization using the decomposition-type reactive emulsifier of the present invention include various monomers such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-acrylic acid 2- Acrylic monomers such as ethylhexyl, methyl methacrylate, acrylonitrile, acrylamide, and acrylic acid hydroxy ester, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, and halogenated olefin monomers such as vinyl chloride and vinylidene chloride In addition to conjugated diolefin monomers such as butadiene, isoprene and chloroprene, there are ethylene, maleic anhydride, methyl maleate and the like. In addition, the monomer used is not limited to the above.
[0032]
The decomposable reactive emulsifier of the present invention can be used for emulsion polymerization or suspension polymerization of one or more of the above monomers.
[0033]
(6) Polymerization conditions
In the emulsion polymerization reaction using the decomposition-type reactive emulsifier of the present invention, conventionally known polymerization initiators can be used. However, since the decomposition-type reactive emulsifier of the present invention decomposes under acidic conditions, the pH of the emulsion polymerization system needs to be maintained at pH 4 or higher throughout the polymerization, and is a general polymerization initiator for emulsion polymerization. When using a persulfate such as ammonium persulfate or potassium persulfate as a polymerization initiator, it is necessary to maintain the pH of the emulsion polymerization system under suitable conditions using a pH adjuster. Therefore, in the emulsion polymerization reaction using the decomposition-type reactive emulsifier of the present invention, a redox polymerization initiator that is small in pH change during polymerization and easy in pH control is suitable as the polymerization initiator. As the redox polymerization initiator, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, hydrogen peroxide, and the like can be used.
[0034]
Moreover, as a pH adjuster, generally used sodium hydrogen carbonate, disodium hydrogen phosphate, sodium carbonate, sodium hydroxide, potassium hydroxide and the like can be used.
[0035]
As the polymerization accelerator, commonly used sodium pyrobisulfite, sodium hydrogensulfite, ferrous sulfate, glucose, formaldehyde sodium sulfoxylate, ascorbic acid and its sodium salt, and the like can be used.
[0036]
Although there is no restriction | limiting in particular as an usage-amount in the emulsion polymerization system of the decomposition-type reactive emulsifier of this invention, Usually, 0.1-20 weight part is suitable with respect to 100 weight part of all monomers, More preferably 0.2 to 8.0 parts by weight is appropriate. When the decomposition-type reactive emulsifier of the present invention is used for the purpose of polymer modification, the amount used can be determined according to the type of monomer, the purpose of modification, and the required performance. The amount used is not limited to the above range.
[0037]
Moreover, you may use together another type emulsifier or a protective colloid agent, a chain transfer agent, electrolyte, etc. as needed.
[0038]
In addition, the method for adding the monomer and the polymerization initiator to the polymerization system is not particularly limited, and a method applied in conventional emulsion polymerization, for example, a batch addition method, a continuous addition method, a divided addition method, or the like. The method and conditions such as can be selected as appropriate.
[0039]
(Function)
The decomposable reactive emulsifier of the present invention is a novel emulsion polymerization characterized in that the molecule has a 1,3-dioxolane ring that easily decomposes under acidic conditions and a copolymerizable unsaturated group. Emulsifier.
[0040]
By using the decomposable reactive emulsifier of the present invention, in the emulsion polymerization system, the polymerization proceeds smoothly and stably essentially as an emulsifier, and at the same time, a copolymerizable unsaturated group in the molecule is a monomer and Reacting and incorporated into the polymer, the foaming, mechanical stability, storage stability, etc. of the resulting polymer emulsion are significantly improved.
[0041]
In the coating film prepared from the obtained polymer emulsion, the amount of the emulsifier present in the free state is remarkably reduced, and the coating film properties such as water resistance, adhesiveness, heat resistance, weather resistance, etc. of the coating film are reduced. Demonstrates extremely good improvement.
[0042]
Further, after emulsion polymerization, by adding an organic acid or inorganic acid to the polymer emulsion and lowering the pH, the 1,3-dioxolane ring in the decomposition-type reactive emulsifier molecule of the present invention is decomposed, and the performance as an emulsifier The polymer can be easily separated and recovered.
[0043]
The polymer emulsion obtained by using the decomposable reactive emulsifier of the present invention can easily break the dispersion state of the polymer emulsion at any point, and the process after the recovery and washing of the polymer This is very effective in that the total amount of organic substances discharged into the wastewater can be reduced.
[0044]
Furthermore, when the decomposition-type reactive emulsifier of the present invention is used for the purpose of polymer modification, the compatibility with the monomer can be improved as an emulsifier, and after emulsion polymerization, acid treatment can be performed. The 1,3-dioxolane ring can be decomposed to give only a hydrophilic portion to the polymer. For the polymer, hydrophilicity, antistatic property, antifogging property, wettability, and polymer alloy This is very effective in that it has an effect of modifying the polymer such as imparting compatibility and the performance can be maintained for a long time.
[0045]
In addition, the 1,3-dioxolane ring in the decomposable reactive emulsifier molecule bonded in the polymer undergoes acid decomposition to produce a glycerin-derived diol at the decomposition site, which is a modification, modification and crosslinking reaction of the polymer. It is very effective in that it can be used for
[0046]
【Example】
Hereinafter, although an embodiment and an effect of the present invention are described according to an example and a comparative example, illustration is only for explanation and is not intended to limit or limit the inventive idea. In the text, “%” and “part” mean weight basis.
[0047]
(Production Example 1)
To a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, add 297 g of 2-tridecanone and 166 g of glycerin, toluene as a solvent, and further add 3 g of paratoluenesulfonic acid as a catalyst. The reaction crude product thus obtained was washed with an aqueous potassium carbonate solution and further washed three times with distilled water, and then distilled under reduced pressure to give 2-methyl-2-undecyl-4. -Hydroxymethyl-1,3-dioxolane was obtained.
[0048]
Further, 98 g of maleic anhydride and 58 g of allyl alcohol are added to another reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, and the temperature is gradually raised and reacted at 60 ° C. for 4 hours. Then, 272 g of 2-methyl-2-undecyl-4-hydroxymethyl-1,3-dioxolane was added, 3 g of paratoluenesulfonic acid and 3 g of hydroquinone were added as catalysts, and nitrogen gas was added. The reaction was carried out at 130 ° C. for 6 hours with aeration to obtain a maleic acid diesterified product.
[0049]
Subsequently, 104 g of acidic sodium sulfite was dissolved in 500 g of water and added to the resulting maleic acid diesterified product, and then 500 g of isopropyl alcohol was added and reacted at 80 ° C. for 6 hours.
[0050]
After completion of the reaction, water and isopropyl alcohol were distilled off under reduced pressure, water was added to redissolve the reaction crude product, and then diethyl ether was added to extract and remove oily unreacted materials. Then, ethyl alcohol was added and concentrated under reduced pressure. Subsequently, ethyl alcohol is added again, and the mixture is stirred and dissolved. After insoluble materials in the system are removed by filtration, the reaction composition obtained by distilling off ethyl alcohol under reduced pressure is used as the decomposition-type reactive emulsifier of the present invention [ A] (the chemical formula is shown in Chemical Formula 5 below).
[0051]
[Chemical formula 5]

[0052]
(Production Example 2)
In the same manner as in Production Example 1, 272 g of 2-methyl-2-undecyl-4-hydroxymethyl-1,3-dioxolane obtained by reacting 2-tridecanone and glycerin was transferred to an autoclave, and potassium hydroxide was used as a catalyst. Pressure 2Kg / cm ² Then, 220 g (5 mol) of ethylene oxide was added at 135 ° C. Subsequently, 5 g of water and an alkali adsorbent 10 times the amount of potassium hydroxide used as a catalyst and a filter aid were added, and the catalyst was adsorbed, followed by vacuum dehydration filtration and 2-methyl-2-undecyl-4- An ethylene oxide 5-mol adduct of hydroxymethyl-1,3-dioxolane was obtained.
[0053]
Next, 98 g of maleic anhydride and 58 g of allyl alcohol were added to another reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, and the temperature was gradually raised and reacted at 80 ° C. for 2 hours. After obtaining a maleic acid monoester product, 492 g of ethylene oxide 5 mol adduct of 2-methyl-2-undecyl-4-hydroxymethyl-1,3-dioxolane was charged, and 3 g of paratoluenesulfonic acid and 3 g of hydroquinone were used as catalysts. In addition, a maleic acid diesterified product was obtained by reacting at 130 ° C. for 6 hours while supplying nitrogen gas.
[0054]
Subsequently, 104 g of acidic sodium sulfite dissolved in 500 g of water was added to the resulting maleic acid diesterified product, 500 g of isopropyl alcohol was added, and the mixture was reacted at 80 ° C. for 6 hours, and then the same method as in Production Example 1 The reaction composition obtained by purification in step 1 was designated as the decomposition-type reactive emulsifier [B] of the present invention (chemical formula shown in chemical formula 6 below).
[0055]
[Chemical 6]

[0056]
Further, instead of the ethylene oxide 5 mol adduct of 2-methyl-2-undecyl-4-hydroxymethyl-1,3-dioxolane, ethylene oxide 40 of 2-methyl-2-undecyl-4-hydroxymethyl-1,3-dioxolane 40 Using the molar adduct, a reaction composition obtained in the same manner was used as the decomposition-type reactive emulsifier [C] of the present invention (chemical formula is shown in the following chemical formula 7).
[0057]
[Chemical 7]

[0058]
(Production Example 3)
According to Production Example 2, maleic anhydride and an allyl alcohol ethylene oxide 5-mole adduct obtained by a known method are reacted to obtain a maleic acid monoester product, and then 2-methyl-2-undecyl-4- A maleic acid diesterified product was obtained by reacting a 5-methyl adduct of hydroxymethyl-1,3-dioxolane with ethylene oxide.
[0059]
Subsequently, the resulting maleic acid diesterified product is sulfonated with sodium sulfite, and then purified by the same method as in Production Example 1 to obtain a reaction composition obtained by decomposing the present invention reactive reactive emulsifier [D] (chemical formula Is shown in the following chemical formula 8).
[0060]
[Chemical 8]

[0061]
(Production Example 4)
According to Production Example 2, maleic anhydride and a 3-mole adduct of allyl alcohol obtained by a known method were reacted to obtain a maleic acid monoester product, and then 2-methyl-2-undecyl-4 -Hydroxymethyl-1,3-dioxolane was reacted to obtain a maleic acid diesterified product.
[0062]
Subsequently, the obtained maleic acid diesterified product is sulfonated with acidic sodium sulfite, and then purified by the same method as in Production Example 1 to obtain a reaction composition obtained by the present invention decomposition-type reactive emulsifier [E] ( The chemical formula is shown in the following chemical formula 9.).
[0063]
[Chemical 9]

[0064]
(Production Example 5)
To a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube, 198 g of 1,2-isopropylideneglycerin and 230 g of acetic anhydride and pyridine as a catalyst were added and reacted for 1 hour under reflux conditions. And then distilled under reduced pressure to obtain acetyl-1,2-isopropylideneglycerin.
[0065]
Next, 226 g of acetyl-1,2-isopropylideneglycerin and 221 g of n-dodecanal, toluene as a solvent were added, and 3 g of paratoluenesulfonic acid was added as a catalyst, and an acetyl exchange reaction was performed under reflux conditions. . Next, an ethanol solution of sodium hydroxide was added to decompose the ester moiety under reflux conditions, and then the reaction crude product obtained by distilling off ethanol under reduced pressure was extracted with diethyl ether, and further added to distilled water. And washed 3 times. Subsequently, after the diethyl ether layer was dried with potassium carbonate, the diethyl ether was distilled off under reduced pressure to obtain 2-undecyl-4-hydroxymethyl-1,3-dioxolane.
[0066]
Further, 98 g of maleic anhydride and 58 g of allyl alcohol are added to another reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, and the temperature is gradually raised and reacted at 60 ° C. for 2 hours. After that, 258 g of 2-undecyl-4-hydroxymethyl-1,3-dioxolane was added, 3 g of paratoluenesulfonic acid and 3 g of hydroquinone were added as catalysts, and the mixture was reacted at 130 ° C. for 6 hours while bubbling nitrogen gas, to give maleic acid. A diesterified product was obtained.
[0067]
Subsequently, the obtained maleic acid diesterified product was transferred to an autoclave, 98 g of acidic ammonium sulfite dissolved in 400 g of water was added, then 400 g of methyl alcohol was added, and the mixture was stirred at 100 ° C. for 4 hours while stirring under pressure. After the reaction, the reaction composition obtained by purification in the same manner as in Production Example 1 was designated as the present invention decomposition type reactive emulsifier [F] (chemical formula shown in the following chemical formula 10).
[0068]
[Chemical Formula 10]

[0069]
(Production Example 6)
According to Production Example 1, maleic anhydride and methallyl alcohol were reacted to obtain a maleic acid monoester product, and then 2,2-dihexyl-4-hydroxy obtained by reacting 7-tridecanone and glycerin. Methyl-1,3-dioxolane was reacted to obtain a maleic acid diesterified product.
[0070]
Subsequently, the resulting maleic acid diesterified product is sulfonated with a 1: 1 mixture (weight ratio) of acidic sodium sulfite and sodium sulfite, and then purified by the same method as in Production Example 1 to obtain a reaction composition obtained. The present invention decomposition-type reactive emulsifier [G] (chemical formula is shown in the following chemical formula 11).
[0071]
Embedded image

[0072]
(Production Example 7)
According to Production Example 2, maleic anhydride was reacted with a random adduct of 2 moles of butylene oxide and 3 moles of propylene oxide obtained by a known method to obtain a maleic acid monoester, and then n- Maleic acid diesterified product was obtained by reacting 2-heptadecyl-4-hydroxymethyl-1,3-dioxolane obtained from octadecanal and glycerin.
[0073]
Subsequently, the resulting reaction mixture was sulfonated with maleic acid diesterified product with acidic ammonium sulfite, and then purified by the same method as in Production Example 1 to obtain the reaction composition obtained by decomposing the reactive reactive emulsifier of the present invention [ H] (chemical formula is shown in the following chemical formula 12).
[0074]
Embedded image

[0075]
(Production Example 8)
According to Production Example 2, maleic anhydride and allyl alcohol were reacted to obtain a maleic acid monoester, and then 2-heptyl-4-hydroxymethyl-1,3-dioxolane obtained from n-octanal and glycerin. A block adduct of 3 moles of butylene oxide and 5 moles of ethylene oxide was reacted to obtain a maleic acid diesterified product.
[0076]
Subsequently, the resulting maleic acid diesterified product is sulfonated with acidic sodium sulfite, and then purified by the same method as in Production Example 1 to obtain a reaction composition obtained by decomposing the reactive reactive emulsifier [I] ( The chemical formula is shown in the following chemical formula 13).
[0077]
Embedded image

[0078]
(Usage example 1)
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel is charged with 290 g of ion-exchanged water and 0.5 g of sodium hydrogen carbonate, heated to 70 ° C., and nitrogen gas is passed through to dissolve dissolved oxygen in the water. Removed. Next, 10 g of the decomposition-type reactive emulsifier of the present invention shown in Table 1 is dissolved in 140 g of vinyl acetate and 60 g of butyl acrylate, and 41 g corresponding to 20% is charged into the reactor, and then 0.5 g of ammonium persulfate is added. For prepolymerization. Subsequently, 165 g of the remaining monomer / emulsifier mixed solution was dropped and polymerized over 3 hours from 10 minutes after the start of the polymerization. Subsequently, after aging for 2 hours at the polymerization temperature, the mixture was cooled, the emulsion was taken out, and used as a test sample. Table 1 shows the results of tests on the amount of agglomerates during the emulsion polymerization, the solid content of the obtained emulsion, the mechanical stability, the foaming property, the emulsifier reaction rate, and the water resistance of the polymer film prepared from this emulsion.
[0079]
As a comparison, Table 1 shows the results of emulsion polymerization carried out without addition of sodium bicarbonate. Furthermore, the same test was implemented also about the conventional emulsifier shown in Table 1.
[0080]
[Table 1]

[0081]
(Note) Solid content: 2 g of the emulsion was dried at 105 ° C. for 2 hours, then weighed, and expressed as% relative to the weight of the weighed emulsion.
Aggregate amount: The emulsion was filtered through a 150 mesh wire mesh, the residue was washed with water, and dried.
Mechanical stability: 50 g of emulsion was stirred with a Marlon type tester at a load of 10 kg at a rotation speed of 1000 rpm for 5 minutes, the resulting aggregate was filtered through a 150 mesh wire mesh, the residue was washed with water and dried, and the weight of the emulsion was measured. Expressed as a percentage of solids.
Foaming property: The emulsion was diluted twice with ion-exchanged water, placed in 30 ml in a 100 ml Nessler tube, shaken for 1 minute, and then the amount of foam after standing for 5 minutes was measured.
Emulsifier reaction rate: Methanol was added to the emulsion to coagulate the polymer, and after centrifugation, the amount of unreacted emulsifier was measured using HPLC, and the reaction rate of the emulsifier was calculated.
Water resistance test: A polymer film having a thickness of 0.5 mm was prepared on a glass plate, immersed in water, and measured until 4.5 point characters could not be read through the film.
[0082]
(Usage example 2)
A monomer emulsion was prepared by mixing 100 g of butyl acrylate, 100 g of 2-ethylhexyl acrylate, 194 g of ion-exchanged water, and 6 g of the decomposition-type reactive emulsifier of the present invention shown in Table 2 with a homodisper. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was charged with 100 g of ion-exchanged water and 0.5 g of sodium hydrogen carbonate, the temperature was raised to 80 ° C., nitrogen gas was bubbled into the water. Dissolved oxygen was removed. Subsequently, 80 g of the monomer emulsion was added to the reactor with stirring, and 0.5 g of ammonium persulfate was further added for prepolymerization. Then, 320 g of the remaining monomer emulsion was added dropwise over 3 hours from 10 minutes after the start of polymerization to polymerize. Further, after aging for 2 hours while maintaining the polymerization temperature of 80 ° C., the mixture was cooled, the emulsion was taken out, and used as a sample sample.
[0083]
Table 2 shows the results of tests on the amount of agglomerates during the emulsion polymerization, the solid content of the obtained emulsion, the mechanical stability, the foaming property, the adhesiveness, and the heat resistance coloring property of the polymer film prepared from this emulsion.
[0084]
For comparison, the results of emulsion polymerization carried out without addition of sodium bicarbonate are shown in Table 2. Furthermore, the same test was implemented also about the conventional emulsifier shown in Table 2.
[0085]
[Table 2]

[0086]
(Note) Solid content: 2 g of the emulsion was dried at 105 ° C. for 2 hours, then weighed, and expressed as% relative to the weight of the weighed emulsion.
Aggregate amount: The emulsion was filtered through a 150 mesh wire mesh, the residue was washed with water, and dried.
Mechanical stability: 50 g of emulsion was stirred with a Marlon type tester at a load of 10 kg at a rotation speed of 1000 rpm for 5 minutes, the resulting aggregate was filtered through a 150 mesh wire mesh, the residue was washed with water and dried, and the weight of the emulsion was measured. Expressed as a percentage of solids.
Foaming property: The emulsion was diluted twice with ion-exchanged water, put in 30 ml in a 100 ml Nessler tube, shaken for 1 minute, and then the amount of foam after standing for 5 minutes was measured.
Adhesive strength: The emulsion was applied to a PET film with a thickness of 0.1 mm, heat-treated at 105 ° C. for 10 minutes, placed on the coating film, and roller-pressed sample piece (1 inch width) at 25 ° C. at 180 ° C. ° Peel strength was measured.
Heat resistant colorability test: A 0.5 mm thick coating film was prepared on a glass plate, and heat-treated for 30 minutes in a hot air drier maintained at 200 ° C., and the color of the coating film was examined.
(Evaluation criteria) A: No coloring is observed
○: Slightly colored
Δ: Light yellow
X: Colored dark brown
[0087]
(Usage example 3)
As a reactor, 60 g of ion-exchanged water was charged into a pressure-resistant glass bottle, specifically, an empty bottle for carbonated beverages, and dissolved oxygen was removed by ventilating nitrogen gas. Next, after cooling the glass bottle in an ice water bath, 1.2 g of the decomposition type reactive emulsifier of the present invention shown in Table 3, 0.12 g of naphthalenesulfonic acid formalin condensate, 0.12 g of dodecyl mercaptan, 20 g of styrene, paramentane hydro 0.03 g of peroxide, 0.02 g of ferrous sulfate heptahydrate, and 0.01 g of sodium formaldehyde sulfoxide were charged. Next, butadiene was introduced from a cylinder into a graduated sampling tube in a methanol dry ice bath, and 22 g of butadiene that was liquefied and weighed was charged into a glass bottle using a syringe with a stopcock, and then left to stand for 2 g of butadiene. After evaporating and expelling the air, the contents in the glass bottle were put into an emulsion state by immediately plugging and shaking.
[0088]
Next, a glass bottle was set in a holder in a rotary polymerization tank adjusted to a water temperature of 5 ° C., and polymerized at a rotation speed of 50 rpm for 5 hours. After completion of the polymerization reaction, the glass bottle was opened, N, N-diethylhydroxylamine was added to stop the polymerization, and then the residual monomer was distilled off under reduced pressure to obtain a polybutadiene latex as a test sample. .
[0089]
Table 3 shows the results of tests on the amount of aggregates during the emulsion polymerization, solid content of the obtained latex, mechanical stability, foaming property, water absorption rate of the polymer film, and heat resistance coloring property.
[0090]
Moreover, when 1% sulfuric acid was added to the obtained polymer latex to adjust the pH to 2 or less, the latex was broken and a polymer was immediately deposited. Further, the temperature was raised to 60 ° C. with continued stirring, and the polymer was allowed to stand and floated. The polymer was collected and washed three times with warm water, and then the polymer was dehydrated and dried at 60 ° C. under reduced pressure. Table 3 shows the recovery rate of the obtained dry polymer.
[0091]
For comparison, the same test was conducted for conventional emulsifiers, and Table 3 shows the test results.
[0092]
[Table 3]

[0093]
(Note) Solid content: 2 g of latex was dried at 105 ° C. under reduced pressure for 1 hour, then weighed, and expressed as% relative to the weighed latex weight.
Aggregate amount: The latex was filtered through a 150-mesh wire mesh, the residue was washed with water, and dried under reduced pressure.
Mechanical stability: 50 g of latex was stirred with a Marlon type tester at a load of 10 kg at a rotation speed of 1000 rpm for 5 minutes, the resulting agglomerate was filtered through a 150-mesh wire mesh, the residue was washed with water, dried under reduced pressure, and the weight of the latex was latex. % Relative to the solid content.
Foaming property: Latex was diluted twice with ion-exchanged water, 30 ml was put into a 100 ml Nessler tube, and the amount of foam was measured after 5 minutes of standing after being inverted 30 times.
Water absorption: A polymer film having a thickness of 0.5 mm was prepared on a glass, the film was carefully peeled off from the glass plate, and the film was cut into a size of 100 mm length × 100 mm width to prepare a test piece. This was immersed in water, taken out after 24 hours, quickly removed moisture between two filter papers, weighed, and the weight increase was displayed as a percentage of the weight before immersion.
Heat resistant colorability: A 0.5 mm thick coating film was prepared on a glass and heat treated for 30 minutes in a hot air drier maintained at 200 ° C. to examine the color of the coating film.
(Evaluation criteria) A: No coloring is observed
○: Slightly colored
Δ: Light yellow
X: Colored dark brown
Polymer recovery rate: The weight of the obtained dry polymer was expressed in% with respect to the theoretical solid content weight calculated from the solid content value of the latex.
[0094]
(Usage example 4)
In an autoclave equipped with a stirrer, a thermometer and a cooling and heating device, 500 g of ion-exchanged water, 25 g of the decomposition-type reactive emulsifier of the present invention shown in Table 4, 2.5 g of naphthalene sulfonic acid holymarin condensate, 2.5 g of sodium carbonate, After charging 2.5 g of dodecyl mercaptan and further adding 1.5 g of potassium persulfate, the inside of the autoclave was purged with nitrogen. Subsequently, after cooling the contents by passing cooling water at 5 ° C. through the autoclave, 500 g of butadiene was introduced into the autoclave from the butadiene cylinder, and the contents were made into an emulsion state by increasing the stirring speed. Next, the internal temperature was raised to 60 ° C. and polymerized for 35 hours. After completion of the polymerization, the mixture was cooled and unreacted butadiene was distilled off under reduced pressure to obtain a polybutadiene latex. Table 4 shows the amount of aggregate during the emulsion polymerization, the solid content of the obtained polymer latex, and the average particle size.
[0095]
Next, in a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 320 g of polybutadiene latex prepared by the above operation in terms of solid content and 180 g of ion-exchanged water (however, depending on the polymer latex solid content) A monomer obtained by mixing 225 g of styrene, 95 g of acrylonitrile, 300 g of ion-exchanged water, and 9.6 g of the present invention degradable reactive emulsifier as an emulsifier with the homodisper. 65 g of the emulsion was added to the reactor with stirring and purged with nitrogen. Next, the reactor was cooled, and when the internal temperature reached 10 ° C., 1.2 g of paramentane hydroperoxide, 0.6 g of ferrous sulfate heptahydrate and 0.3 g of sodium formaldehyde sulfoxide were added in advance. Polymerized. Next, 15 minutes after the start of polymerization, the remaining monomer emulsion was dropped over 3 hours to polymerize. Further, after aging for 2 hours while maintaining the polymerization temperature, the polymerization was stopped by adding N, N-diethylhydroxylamine, and then the residual monomer was distilled off under nitrogen gas flow and reduced pressure conditions. The obtained polymer latex was used as a test sample.
[0096]
Table 5 shows the amount of agglomerates during the emulsion polymerization and the test results of the solid content, average particle diameter, and emulsifier reaction rate of the obtained polymer latex.
[0097]
Moreover, when 250% of the obtained polymer latex was added with 1% sulfuric acid to adjust the pH to 2 or less, the latex was destroyed and a polymer was immediately deposited. Subsequently, the temperature was raised to 60 ° C. with stirring, and then allowed to stand to float the polymer. The polymer was collected and washed three times with warm water, and then the polymer was dehydrated and dried. Table 5 shows the recovery rate of the polymer at this time, the total organic carbon (TOC) amount measured by collecting and concentrating the total waste water at the time of polymer recovery, and the measurement results of the retention colorability at the time of polymer molding. For comparison, the same test was carried out for conventional emulsifiers, and the test results are shown in Tables 4 and 5.
[0098]
[Table 4]

[0099]
(Note) Solid content: 2 g of latex was dried under reduced pressure at 105 ° C. for 1 hour, then weighed, and expressed as% relative to the weighed latex weight.
Aggregate amount: The latex was filtered through a 150 mesh wire net, the residue was washed with water and dried under reduced pressure, and the weight of the coagulum obtained was expressed as a percentage of the charged monomer weight.
Average particle size: The average particle size of the latex was measured using a Shimadzu laser diffraction particle size distribution analyzer SALD-2000.
[0100]
[Table 5]

[0101]
(Note) Solid content: 2 g of latex was dried under reduced pressure at 105 ° C. for 2 hours, weighed, and expressed as a percentage of the latex weight.
Aggregate amount: The latex was filtered through a 150 mesh wire net, the residue was washed with water and dried under reduced pressure, and the weight of the coagulum obtained was expressed as a percentage of the charged monomer weight.
Average particle diameter: The average particle diameter of latex was measured using a laser diffraction particle size distribution analyzer SALD-2000 manufactured by Shimadzu Corporation.
Emulsifier reaction rate: Methanol was added to the latex to coagulate the polymer, and after centrifugation, the amount of the unreacted emulsifier was measured using HPLC, and the reaction rate of the emulsifier was calculated.
Polymer recovery rate: The weight of the obtained dry polymer was expressed in% with respect to the theoretical solid content weight calculated from the solid content value of the latex.
Total organic carbon (TOC) amount: Collect all drainage (including polymer wash water) at the time of polymer recovery, concentrate to 250 ml, collect a portion of it, and use TOC-500 manufactured by Shimadzu Corporation to An organic carbon (TOC) measurement was determined.
Residual coloring property: The obtained dry polymer was molded at a molding temperature of 250 ° C. and a mold temperature of 50 ° C. to prepare a reference test piece of m × width 125 mm × thickness 3.5 mm. Similarly, the color of a test piece molded by being retained for 20 minutes in a molding machine at 250 ° C. was examined in comparison with a reference test piece.
(Evaluation criteria)
A: No coloring is observed
○: Slightly colored
Δ: Light yellow
X: Colored dark brown
[0102]
(Usage example 5)
A polybutadiene latex was prepared in the same manner as in Use Example 3, and then polymerized under the same conditions except that the amount of the decomposable reactive emulsifier used in emulsion polymerization of styrene and acrylonitrile in the polybutadiene latex was changed to 32 g. Thus, a polymer latex was obtained. Furthermore, the polymer was recovered from the obtained polymer latex and dried. The polymer obtained at this time was molded at a molding temperature of 250 ° C. and a mold temperature of 50 ° C. to prepare test pieces having a length of 125 mm × width of 125 mm × thickness of 3.5 mm. The test piece was measured for contact angle and surface resistivity. The results of each test are shown in Table 6. For comparison, the same test was conducted for conventional emulsifiers, and Table 6 shows the test results.
[0103]
[Table 6]

[0104]
(Note) Contact angle: The resulting dried polymer was molded at a molding temperature of 250 ° C and a mold temperature of 50 ° C, and a test piece measuring 125mm long x 125mm wide x 3.5mm thick was made. The contact angle was measured.
Surface resistivity: Measure the surface resistivity of a test piece obtained by molding the resulting dry polymer at a molding temperature of 250 ° C and a mold temperature of 50 ° C for 24 hours in an atmosphere of 20 ° C and 45% humidity. did.
[0105]
【The invention's effect】
As explained above, according to the present invention, the stability during emulsion polymerization and the stability of the resulting polymer emulsion can be improved, foam troubles in the process can be eliminated, and the polymer recovery rate in the polymer recovery process can be improved. The present invention provides a novel decomposition-type reactive emulsifier for emulsion polymerization that can significantly improve the productivity and contribute to the improvement of productivity, and can significantly reduce the amount of organic matter discharged in the process of polymer recovery and washing. Another object of the present invention is to provide a novel decomposable reactive emulsifier for emulsion polymerization that can remarkably improve the water resistance and heat resistance of a polymer obtained from a polymer emulsion and a polymer coating film. Furthermore, the present invention provides a polymer modification method for improving the physical properties of the obtained polymer and polymer coating film by using the novel decomposition-type reactive emulsifier for emulsion polymerization of the present invention. These effects of the present invention contribute to the development of related industries and the interests of consumers.

Claims (2)

A novel decomposable reactive emulsifier represented by the following general formula (I) and / or the following general formula (II).

[Wherein R ₁ and R ₂ are the same or different alkyl group or alkenyl group having 1 to 20 carbon atoms or a hydrogen atom (provided that R ₁ and R ₂ are not both hydrogen atoms), R ₃ is a hydrogen atom or a methyl group. A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m and n are 0 or an integer of 1 to 50, and when m and n are 2 or more, (AO) m and (AO) n are It may be a homopolymer composed of one type of repeating unit represented by (i), or different substituents A (A ¹ , A ² ,...) Represented by the following formulas (ii) and (iii): It may be a block polymer or a random polymer composed of two or more kinds of repeating units. M is a hydrogen atom, alkali metal, ammonium or alkanolamine residue. ]
-(AO)-(AO)-(AO)-(i)
-(A ¹ O) m _1- (A ² O) m _2- (ii)
(However, m ₁ + m ₂ + …… = m)
-(A ¹ O) n _1- (A ² O) n _2- (iii)
(However, n ₁ + n ₂ + …… = n) In the presence of the decomposable reactive emulsifier according to claim 1, the monomer is emulsion-polymerized, and then the 1,3-dioxolane ring site in the emulsifier molecule copolymerized in the polymer is acid-decomposed. A method for modifying a polymer, which comprises imparting a hydrophilic site to a polymer.