JP3840347B2 - Method for producing a novel polyhydroxyurethane - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、コーティング剤、接着剤等の各種の用途に有用な新規なポリヒドロキシウレタンの製造方法に関するものである。
【０００２】
【従来の技術】
ポリヒドロキシウレタン類は、ジアミン化合物と５員環の二官能カーボナート化合物からの合成方法が報告されている〔例えば、米国特許 3,072,613号公報、或いはJ. Polym. Sci., Part A, Vol.31, 2765-2773 （1993）〕。しかし、これらの方法により調製されるポリヒドロキシウレタンは、あるものは、硬すぎて皮膜形成性に劣り、あるものは、柔らか過ぎて皮膜としての強度が極めて低く、コーティング剤、接着剤等の各種の用途に使用するのが困難であった。
【０００３】
【発明が解決しようとする課題】
本発明は、上述した如き問題点を解消し、皮膜形成性と皮膜強度に優れる、新規なポリヒドロキシウレタンの製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明者らは、上述した課題を解決するべく鋭意研究を重ねた結果、特定のジアミン化合物と二官能の５員環カーボナート化合物を反応せしめる事により得られるポリヒドロキシウレタンが、上記課題を解決するのに適したものである事を見いだし、本発明を完成させるに至った。即ち本発明は、
【０００５】
１．一般式（１）で示されるジアミン化合物（Ａ）を必須成分として含むジアミン化合物と、一般式（２）で示される二官能の５員環カーボナート化合物（Ｂ）を反応せしめる事を特徴とする、一般式（３）で示される構造を必須の構成単位として含有するポリヒドロキシウレタンの製造方法、
【０００６】
【化９】
【０００７】
〔但し、式中、Ｙは−ＣＨ２Ｏ−で示される結合の少なくとも１個を含有する二価の有機基を表すものとする。〕
【０００８】
【化１０】
【０００９】
〔但し、式中、Ｘは芳香環を含有する二価の有機基し、Ｒは水素原子またはメチル基を表すものとする。〕
【００１０】
【化１１】
【００１１】
〔但し、式中、Ｘは芳香環を含有する二価の有機基を表し、Ｙは−ＣＨ２Ｏ−で示される結合の少なくとも１個を含有する二価の有機基を表し、Ｚ１は式（４）または式（５）で示される二価の基のいずれか一種であり、Ｚ２は式（６）または式（７）で示される二価の基のいずれか一種であるものとする。〕
【００１２】
【化１２】
【００１３】
〔但し、式中、Ｒは水素原子またはメチル基であるものとする。〕
【００１４】
【化１３】
【００１５】
〔但し、式中、Ｒは水素原子またはメチル基であるものとする。〕
【００１６】
【化１４】
【００１７】
〔但し、式中、Ｒは水素原子またはメチル基であるものとする〕
【００１８】
【化１５】
【００１９】
２．前記した、カーボナート化合物（Ｂ）含有される芳香環を有する二価の有機基であるＸが、アルキレン基、シクロアルキレン基、アリールアルキレン基、アリーレン基またはアルキレン基で分断されたアリーレン基である、上記１に記載の製造方法、
【００２０】
３．前記した、ジアミン化合物（Ａ）に含有される二価の有機基であるＹが、−ＣＨ２Ｏ−で示される結合を少なくとも２個を含有し、且つ、芳香環を含有しないものである、上記１または２に記載の製造方法、
【００２１】
４．前記した、カーボナート化合物（Ｂ）に含有される二価の有機基であるＸが、式（８）に示す構造である、上記１、２または３に記載の製造方法、
【００２２】
【化１６】
【００２３】
５．前記した、ジアミン化合物（Ａ）に含有される二価の有機基であるＹが、-(CH２)３O(CH２)２O(CH２)３-、-(CH２)３O(CH２)４O(CH２)３-、-(CH２)３O(CH２)２O(CH２)２O(CH２)３-、-(CH２)２-O(CH２CH２O)ｍCH２CH２-（但し、ｍは、１〜２０の整数を表す。）で示されるポリオキシエチレン基、または、-(CH２)４-O(CH２CH２CH２CH２O)ｎ(CH２)４-（但し、ｎは、１〜２０程度の整数を表す。）を含有する二価の有機基である、請求項１、２または３に記載の製造方法、
【００２４】
６．前記した、ジアミン化合物（Ａ）が、４，７−ジオキサデカン−１，１０−ジアミン、４，９−ジオキサドデカン−１，１２−ジアミンおよび４，７，１０−トリオキサトリデカン−１，１３−ジアミンよりなる群から選ばれる少くなくとも一種である、上記１、２または３に記載の製造方法、を提供するものである。
【００２５】
上述した本発明のポリヒドロキシウレタンの製造方法では、下記の一般式（１）で示される−ＣＨ２Ｏ−で示される結合の少なくとも１個を含有するジアミン化合物（Ａ）を必須成分として含むジアミン化合物と、下記一般式（２）で示される二官能の５員環カーボナート化合物（Ｂ）を反応せしめることによりポリヒドロキシウレタンを調製することが出来る。
【００２６】
【化１７】
【００２７】
〔但し、式中、Ｙは−ＣＨ２Ｏ−で示される結合の少なくとも１個を含有する二価の有機基を表すものとする。〕
【００２８】
【化１８】
【００２９】
〔但し、式中、Ｘは芳香環を含有する二価の有機基を表し、Ｒは水素原子またはメチル基を表すものとする。〕
【００３０】
本発明の製造方法において使用される上述したジアミン化合物（Ａ）は、−ＣＨ２Ｏ−で示される結合を含有する二価の有機基Ｙに２個のアミノ基が結合したものであり、有機基Ｙの代表的なものとしては、オキシビスエチレン基、オキシビストリメチレン基、オキシビステトラメチレン基、の如き−ＣＨ２Ｏ−で示される結合の１個を含有する基；-(CH2)3O(CH2)2O(CH2)3-、-(CH2)3O(CH2)4O(CH2)3-、-(CH2)3O(CH2)2O(CH2)2O(CH2)3-、-(CH2)2-O(CH2CH2O)mCH2CH2-（但し、ｍは、１〜２０程度の整数を表す。）で示されるポリオキシエチレン基、-(CH2)4-O(CH2CH2CH2CH2O)n(CH2)4-（但し、ｎは、１〜２０程度の整数を表す。）で示されるポリオキシテトラメチレン基、の如き−ＣＨ２Ｏ−で示される結合の少なくとも２個を含有する基等が挙げられる。
【００３１】
上掲したジアミン化合物（Ａ）のうちで、Ｙが、−ＣＨ２Ｏ−で示される結合の少なくとも２個を含有し、且つ、芳香環を含有しない二価の有機基であるものが好ましいものの一つとして挙げられる。そして、かかる好ましいジアミン化合物（Ａ）として特に好ましいものは、Ｙの分子量が１０００程度以下のものである。
【００３２】
また、本発明の製造方法において使用される上述したカーボナート化合物（Ｂ）は、芳香環を含有する二価の有機基であるＸに２個の５員環カーボナート基が結合したものであり、有機基Ｘの代表的なものとしては、１，２−シクロブチレン基、１，４−シクロブチレン基、１，２−シクロペンチレン基、１，３−シクロペンチレン基、１，２−シクロヘキシレン基、１，３−シクロヘキシレン基、１，４−シクロヘキシレン基の如きシクロアルキレン基；
【００３３】
シクロペンタン−１，２−ビスメチレン基、シクロヘキサン−１，４−ビスメチレン基の如きシクロアルカンビスアルキレン基；１，２−フェニレン基、１，３−フェニレン基、１，４−フェニレン基、１，５−ナフチレン基の如きアリーレン基；オルトキシリレン基、メタキシリレン基、パラキシリレン基の如きアリールアルキレン基；メチレン−４，４’−ビスフェニレン基、イソプロピリデン−４，４’−ビスフェニレン基の如きアルキレン基で分断されたアリーレン基、の如き−ＣＨ２Ｏ−で示される結合を含有する有機基等が挙げられる。
【００３４】
さらに、上述した好ましいカーボナート化合物（Ｂ）のうちで特に好ましいものとしては、Ｘが、下記式（８）で示される構造である化合物が挙げられ、上述した好ましいジアミン化合物（Ａ）のなかで特に好ましいものとしては、４，７−ジオキサデカン−１，１０−ジアミン、４，９−ジオキサドデカン−１，１２−ジアミンおよび４，７，１０−トリオキサトリデカン−１，１３−ジアミンが挙げられる。
【００３５】
【化１９】
【００３６】
上述した各種のジアミン化合物（Ａ）とカーボナート化合物（Ｂ）は、それぞれ１種類を使用してもよいし、２種類以上を併用してもよい。また、ジアミン化合物としては、本発明の特徴を損なわない範囲内で、ジアミン化合物（Ａ）以外の各種のジアミン化合物をも併用することができる。
【００３７】
かかるジアミン化合物（Ａ）と併用することが出来るジアミン化合物の代表的なものとしては、エチレンジアミン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，６−ジアミノヘキサン、１，８−ジアミノオクタンの如き脂肪族ジアミン類；オルトキシリレンジアミン、メタキシリレンジアミン、パラキシリレンジアミンの如きアラルキレンジアミン類等が挙げられる。
【００３８】
本発明の製造方法でポリヒドロキシウレタンを調製するに際し、ジアミン化合物（Ａ）を必須成分として含むジアミン化合物と、二官能の５員環カーボナート化合物（Ｂ）との使用比率は、目的とするポリヒドロキシウレタンの分子量および導入しようとする末端基の種類により、適宜決めることができる。即ち、数平均分子量が、２０，０００を超えるような分子量の高いポリヒドロキシウレタンを調製する際には、ジアミン化合物とシクロカーボナート化合物（Ｂ）のモル比が１：１となるように両成分を反応させればよいし、末端に、官能基として、５員環カーボナート基を含有するポリヒドロキシウレタンを調製するには、カーボナート化合物（Ｂ）の使用モル数が、ジアミン化合物のモル数よりも多くなるような比率で両成分を反応させればよい。また、末端に、官能基として、１級アミノ基を含有するポリヒドロキシウレタンを調製するには、カーボナート化合物（Ｂ）の使用モル数が、ジアミン化合物のモル数よりも少なくなるような比率で両成分を反応させればよい。
【００３９】
上述した、ジアミン化合物（Ａ）を必須成分として含むジアミン化合物と、カーボナート化合物（Ｂ）から、ポリヒドロキシウレタンを調製するに際し、無溶剤系での反応や有機溶剤中での反応等各種の反応系を選択することができる。これらのうち、有機溶剤中で反応を行う場合には、ジアミン化合物もしくはカーボナート化合物（Ｂ）と反応しない各種の有機溶剤を使用することができる。
【００４０】
かかる有機溶剤の代表的なものとしては、ベンゼン、トルエン、キシレン、ｎ−ヘキサン、ｎ−オクタン等の炭化水素系化合物；塩化メチレン、クロロホルム、四塩化炭素等のハロゲン化炭化水素類；酢酸メチル、酢酸エチル、酢酸ｎ−ブチル等のエステル系化合物；ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系化合物；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等のアミド系化合物等の各種の化合物が挙げられる。これらの内、生成するポリヒドロキシウレタンの溶解性等の点から、エーテル系化合物もしくはアミド系化合物が特に好ましい。
【００４１】
本発明の方法によりポリヒドロキシウレタンを調製するに際し、ジアミン化合物（Ａ）を必須成分として含むジアミン化合物と、カーボナート化合物（Ｂ）との反応方法としては、両成分を、無溶剤下で、あるいは前記有機溶剤に溶解して、混合する等の各種の方法を適用すればよい。その際の反応温度に関しては特に制限はない。有機溶剤を使用する場合には、その融点以上で沸点以下の温度で反応を行えばよい。ポリヒドロキシウレタンとして好ましい数平均分子量が５００以上のポリマーを実用的な反応時間で得るには、反応温度として、０℃〜２００℃が好ましく、５０℃〜１５０℃が特に好ましい。また、反応時間に関しては、ジアミン化合物やカーボナート化合物（Ｂ）の種類、有機溶剤使用の有無、反応温度等に応じて適宜最適な時間を設定すればよいが、概ね２〜５０時間程度でよい。
【００４２】
かくして得られる本発明の新規なポリヒドロキシウレタンは、原料成分として使用するエーテル結合を含有するジアミン化合物（Ａ）に由来する優れた皮膜形成性、フィルムの柔軟性、溶剤に対する優れた溶解性等を有し、各種コーティング剤、接着剤、成形材料等の各種の用途に有効に利用できるものである。
【００４３】
【実施例】
実施例１ 温度計、還流冷却管、塩化カルシウム管、撹拌装置を装着したガラス製フラスコに、乾燥したＮ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）の２０ミリリットルを仕込んだ。次いで、下記式（９）に示す化合物〔以下、化合物（Ｂ−１）と略称する〕の８．１グラム（０．０１９モル）と、４，９−ジオキサドデカン−１，１２−ジアミン〔以下、化合物（Ａ−１）と略称する〕の３．９グラム（０．０１９モル）を添加して、撹拌しながら１００℃へ昇温し、同温度で２４時間の撹拌を継続した。反応混合物を室温まで冷却し、ジエチルエーテルに滴下して生成したポリマーを析出させ、次いで、濾別により単離したポリマーを減圧で乾燥して、数平均分子量（Ｍｎ）が４２，０００で重量平均分子量（Ｍｗ）が８４，０００なる目的とするポリヒドロキシウレタンを得た。収率は、９８％であった。得られたポリヒドロキシウレタンをＰ−１と略称する。
【００４４】
【化２０】
【００４５】
実施例２ 実施例１と同様のフラスコに、乾燥したＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）の２０ミリリットルを仕込んだ。次いで、化合物（Ｂ−１）の８．６グラム（０．０２モル）と、４，７，１０−トリオキサトリデカン−１，１３-ジアミン〔以下、化合物（Ａ−２）と略称する〕の４．４グラム（０．０２モル）を添加して、撹拌しながら１００℃へ昇温し、同温度で２４時間のあいだ撹拌を継続した。反応混合物を室温まで冷却し、ジエチルエーテルに滴下してポリマーを析出させ、次いで、濾別により単離したポリマーを減圧で乾燥して、Ｍｎが４３，０００で、Ｍｗが８１，７００なる目的のポリヒドロキシウレタンを得た。収率は９９％であった。得られたポリヒドロキシウレタンをＰ−２と略称する。
【００４６】
実施例３ 実施例１と同様のフラスコに、乾燥ＤＭＦの８０ミリリットルを仕込んだ。次いで、下記式（１０）に示す化合物〔以下、化合物（Ｂ−２）と略称する〕の２９．３グラム（０．０８モル）と、化合物（Ａ−１）の１６．３グラム（０．０８モル）を仕込んで、撹拌しながら１００℃へ昇温し、同温度で２４時間のあいだ撹拌を継続した。反応混合物を室温まで冷却し、ジエチルエーテルに滴下してポリマーを析出させ、次いで、濾別により単離したポリマーを減圧で乾燥して、Ｍｎが３２，０００で、Ｍｗが６５，０００なる目的のポリヒドロキシウレタンを得た。収率は９９％であった。得られたポリヒドロキシウレタンをＰ−３と略称する。
【００４７】
【化２１】
【００４８】
実施例４ 実施例１と同様のフラスコに、乾燥ＤＭＡＣの８０ミリリットルを仕込んだ。化合物（Ｂ−２）の２９．３グラム（０．０８モル）と、化合物（Ａ−２）の１７．６グラム（０．０８モル）を添加して、撹拌しながら１００℃へ昇温し、同温度で２４時間のあいだ撹拌を継続した。反応混合物を室温まで冷却し、ジエチルエーテルに滴下してポリマーを析出させ、次いで、濾別により単離したポリマーを減圧で乾燥して、Ｍｎが３８，０００で、Ｍｗが７２，０００なる目的のポリヒドロキシウレタンを得た。収率は９９％であった。得られたポリヒドロキシウレタンをＰ−４と略称する。
【００４９】
実施例５ 実施例１と同様のフラスコに、乾燥ＤＭＡＣの１０ミリリットルを仕込んだ。次いで、化合物（Ｂ−１）の４．３グラム（０．０１モル）、ヘキサメチレンジアミンの０．６グラム（０．００５モル）、および化合物（Ａ−１）の１．０グラム（０．００５モル）を添加して、撹拌しながら１００℃へ昇温し、同温度で24時間のあいだ撹拌を継続した。反応混合物を室温まで冷却し、ジエチルエーテルに滴下してポリマーを析出させ、次いで、濾別により単離したポリマーを減圧で乾燥して、Ｍｎが３０，０００で、Ｍｗが５３，０００なる目的のポリヒドロキシウレタンを得た。収率は９８％であった。得られたポリヒドロキシウレタンをＰ−５と略称する。
【００５０】
実施例６ 実施例１と同様のフラスコに、乾燥ＤＭＦの１０ミリリットルを仕込んだ。次いで、化合物（Ｂ−１）の４．３グラム（０．０１モル）、ｍ−キシリレンジアミンの０．７グラム（０．００５モル）、および化合物（Ａ−２）の１．１グラム（０．００５モル）を添加して、撹拌しながら１００℃へ昇温し、同温度で24時間のあいだ撹拌を継続した。反応混合物を室温まで冷却し、ジエチルエーテルに滴下してポリマーを析出させ、次いで、濾別により単離したポリマーを減圧で乾燥して、Ｍｎが２１，０００で、Ｍｗが３２，０００なる目的のポリヒドロキシウレタンを得た。収率は９９％であった。得られたポリヒドロキシウレタンをＰ−６と略称する。
【００５１】
比較例１ 実施例１と同様のフラスコに、乾燥ＤＭＡＣの１０ミリリットルを仕込んだ。化合物（Ｂ−１）の４．３グラム（０．０１モル）と、ヘキサメチレンジアミンの１．２グラム（０．０１モル）を添加して、撹拌しながら１００℃へ昇温し、同温度で２４時間のあいだ撹拌を継続した。反応混合物を室温へ冷却し、水に滴下してポリマーを析出させ、次いで、濾別により単離したポリマーを減圧で乾燥して、Ｍｎが３２，０００で、Ｍｗが６０，８００なるポリヒドロキシウレタンを得た。収率は
９５％であった。得られたポリヒドロキシウレタンをＲＰ−１と略称する。
【００５２】
比較例２ 乾燥ＤＭＡＣの３ミリリットルを使用し、化合物（Ｂ−１）に替えて化合物（Ｂ−２）の１．１グラム（０．００３モル）を使用し、且つ、ヘキサメチレンジアミンの使用量を０．３グラム（０．００３モル）に変更する以外は、比較例１と同様に反応と単離・乾燥操作を行って、Ｍｎが２８，０００で、Ｍｗが５８，８００なるポリヒドロキシウレタンを得た。収率は９６％であった。得られたポリヒドロキシウレタンをＲＰ−２と略称する。
【００５３】
応用例 上記した実施例及び比較例で調製した各ポリヒドロキシウレタンのＤＭＦ溶液を調製して、ロール オン ナイフ コーターを使用して、ポリプロピレンラミネート離型紙に塗布、７０℃で２分間、その後１５０℃で３分間の乾燥を行って、膜厚が約５０μｍなるフィルムを作製した。得られたそれぞれのフィルムについて、減圧乾燥処理を施した後、テンシロン試験器を使用して引張強度と破断伸度を測定した。結果を第１表に纏めた。
【００５４】
【表１】
第１表（１）
【表２】
第１表（２）
＊１、＊２：皮膜が脆くて亀裂が生じ、強度と伸度の測定が出来なかった。
【００５７】
【発明の効果】
本発明は、皮膜形成性、皮膜強度、皮膜伸長性に優れる新規なポリヒドロキシウレタン、及びその製造方法を提供するものであり、また、本発明の方法により当該ポリヒドロキシウレタンを簡便に収率良く製造する事ができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a novel polyhydroxyurethane useful for various applications such as coating agents and adhesives.
[0002]
[Prior art]
Polyhydroxyurethanes have been reported to be synthesized from a diamine compound and a 5-membered bifunctional carbonate compound [eg, US Pat. No. 3,072,613 or J. Polym. Sci., Part A, Vol. 31, 2765-2773 (1993)]. However, some of the polyhydroxyurethanes prepared by these methods are too hard and inferior in film-forming properties, and some are too soft and have extremely low strength as a film. Various coating agents, adhesives, etc. It was difficult to use for the purpose.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel method for producing a polyhydroxyurethane that solves the above-described problems and is excellent in film-forming properties and film strength.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have solved the above problems by polyhydroxyurethane obtained by reacting a specific diamine compound with a bifunctional five-membered carbonate compound. As a result, the present invention has been found to be suitable. That is, the present invention
[0005]
1. A diamine compound (A) represented by the general formula (1) as an essential component is reacted with a bifunctional 5-membered carbonate compound (B) represented by the general formula (2). A method for producing polyhydroxyurethane containing the structure represented by the general formula (3) as an essential constituent unit;
[0006]
[Chemical 9]
[0007]
[Wherein, Y represents a divalent organic group containing at least one bond represented by —CH 2 O—. ]
[0008]
[Chemical Formula 10]
[0009]
[Wherein, X represents a divalent organic group containing an aromatic ring, and R represents a hydrogen atom or a methyl group. ]
[0010]
Embedded image
[0011]
[Wherein, X represents a divalent organic group containing an aromatic ring, Y represents a divalent organic group containing at least one bond represented by —CH 2 O—, and Z 1 represents Any one of the divalent groups represented by formula (4) or formula (5), and Z 2 is any one of the divalent groups represented by formula (6) or formula (7); To do. ]
[0012]
Embedded image
[0013]
[In the formula, R is a hydrogen atom or a methyl group. ]
[0014]
Embedded image
[0015]
[In the formula, R is a hydrogen atom or a methyl group. ]
[0016]
Embedded image
[0017]
[In the formula, R is a hydrogen atom or a methyl group.]
[0018]
Embedded image
[0019]
2. X, which is the divalent organic group having an aromatic ring contained in the carbonate compound (B), is an alkylene group, a cycloalkylene group, an arylalkylene group, an arylene group or an arylene group separated by an alkylene group, The manufacturing method according to 1 above,
[0020]
3. Y, which is a divalent organic group contained in the diamine compound (A), contains at least two bonds represented by —CH 2 O— and does not contain an aromatic ring. The manufacturing method according to 1 or 2 above,
[0021]
4). The production method according to 1, 2 or 3, wherein X, which is the divalent organic group contained in the carbonate compound (B), is a structure represented by the formula (8):
[0022]
Embedded image
[0023]
5). As described above, Y, which is a divalent organic group contained in the diamine compound (A), is — (CH 2 ) 3 O (CH 2 ) 2 O (CH 2 ) 3 —, — (CH 2 ) 3 O ( CH 2 ) 4 O (CH 2 ) 3 -,-(CH 2 ) 3 O (CH 2 ) 2 O (CH 2 ) 2 O (CH 2 ) 3 -,-(CH 2 ) 2 -O (CH 2 CH 2 O) m CH 2 CH 2 — (where m represents an integer of 1 to 20), or — (CH 2 ) 4 —O (CH 2 CH 2 CH 2 CH 2 O) n (CH 2) 4 -. ( where, n is a divalent organic group containing a representative) an integer of 1 to 20, the method of manufacturing according to claim 1, 2 or 3,
[0024]
6). The diamine compound (A) described above is 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, and 4,7,10-trioxatridecane-1,13. -The manufacturing method of said 1, 2 or 3 which is at least 1 type chosen from the group which consists of diamine.
[0025]
In the method of manufacturing polyhydroxy urethanes of the present invention described above, the diamine containing the general formula (1) a diamine compound containing at least one bond represented -CH 2 O-in represented by the (A) as an essential component A polyhydroxyurethane can be prepared by reacting a compound with a bifunctional 5-membered carbonate compound (B) represented by the following general formula (2).
[0026]
Embedded image
[0027]
[Wherein, Y represents a divalent organic group containing at least one bond represented by —CH 2 O—. ]
[0028]
Embedded image
[0029]
[Wherein, X represents a divalent organic group containing an aromatic ring, and R represents a hydrogen atom or a methyl group. ]
[0030]
The above-described diamine compound (A) used in the production method of the present invention is a compound in which two amino groups are bonded to a divalent organic group Y containing a bond represented by —CH 2 O—. Typical examples of the group Y include a group containing one of bonds represented by —CH 2 O— such as an oxybisethylene group, an oxybistrimethylene group, and an oxybistetramethylene group; — (CH 2 ) 3 O (CH 2 ) 2 O (CH 2 ) 3 -,-(CH 2 ) 3 O (CH 2 ) 4 O (CH 2 ) 3 -,-(CH 2 ) 3 O (CH 2 ) 2 O (CH 2 ) 2 O (CH 2 ) 3 —, — (CH 2 ) 2 —O (CH 2 CH 2 O) m CH 2 CH 2 — (where m represents an integer of about 1 to 20). A polyoxyethylene group represented by — (CH 2 ) 4 —O (CH 2 CH 2 CH 2 CH 2 O) n (CH 2 ) 4 — (where n represents an integer of about 1 to 20). at least two free bonds polyoxytetramethylene group, represented such -CH 2 O-in the Group which can be mentioned.
[0031]
Of the diamine compounds (A) listed above, those wherein Y is a divalent organic group containing at least two bonds represented by —CH 2 O— and not containing an aromatic ring are preferred. One of them. Particularly preferred as such a preferred diamine compound (A) is one having a molecular weight of Y of about 1000 or less.
[0032]
The carbonate compound (B) used in the production method of the present invention is a compound in which two 5-membered carbonate groups are bonded to X, which is a divalent organic group containing an aromatic ring, Representative examples of the group X include 1,2-cyclobutylene group, 1,4-cyclobutylene group, 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene. A cycloalkylene group such as a group, 1,3-cyclohexylene group, 1,4-cyclohexylene group;
[0033]
Cycloalkanebisalkylene groups such as cyclopentane-1,2-bismethylene group and cyclohexane-1,4-bismethylene group; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,5 An arylene group such as a naphthylene group; an arylalkylene group such as an orthoxylylene group, a metaxylylene group or a paraxylylene group; an alkylene group such as a methylene-4,4′-bisphenylene group or an isopropylidene-4,4′-bisphenylene group And an organic group containing a bond represented by —CH 2 O— such as an arylene group separated by
[0034]
Furthermore, among the preferable carbonate compounds (B) described above, particularly preferable compounds include compounds in which X is a structure represented by the following formula (8), and among the preferable diamine compounds (A) described above, Preferable examples include 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, and 4,7,10-trioxatridecane-1,13-diamine. .
[0035]
Embedded image
[0036]
Each of the various diamine compounds (A) and carbonate compounds (B) described above may be used alone or in combination of two or more. Moreover, as a diamine compound, various diamine compounds other than a diamine compound (A) can also be used together in the range which does not impair the characteristic of this invention.
[0037]
Typical examples of the diamine compound that can be used in combination with the diamine compound (A) include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,8-diamino. Aliphatic diamines such as octane; aralkylenediamines such as orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, and the like.
[0038]
In preparing the polyhydroxyurethane by the production method of the present invention, the ratio of the diamine compound containing the diamine compound (A) as an essential component to the bifunctional 5-membered carbonate compound (B) is the target polyhydroxyurethane. It can be determined appropriately depending on the molecular weight of the urethane and the type of end group to be introduced. That is, when preparing a high molecular weight polyhydroxyurethane having a number average molecular weight exceeding 20,000, both components are adjusted so that the molar ratio of the diamine compound and the cyclocarbonate compound (B) is 1: 1. In order to prepare polyhydroxyurethane containing a 5-membered carbonate group as a functional group at the terminal, the number of moles of the carbonate compound (B) used is more than the number of moles of the diamine compound. What is necessary is just to make both components react by the ratio which increases. In addition, in order to prepare a polyhydroxyurethane containing a primary amino group as a functional group at the terminal, both the molar ratio of the carbonate compound (B) is less than the molar number of the diamine compound. What is necessary is just to make a component react.
[0039]
When preparing polyhydroxyurethane from the diamine compound containing the diamine compound (A) as an essential component and the carbonate compound (B), various reaction systems such as a reaction in a solvent-free system and a reaction in an organic solvent are used. Can be selected. Among these, when the reaction is performed in an organic solvent, various organic solvents that do not react with the diamine compound or the carbonate compound (B) can be used.
[0040]
Representative examples of such organic solvents include hydrocarbon compounds such as benzene, toluene, xylene, n-hexane, and n-octane; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; methyl acetate, Ester compounds such as ethyl acetate and n-butyl acetate; ether compounds such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like And various compounds such as amide compounds. Of these, ether compounds or amide compounds are particularly preferred from the viewpoint of the solubility of the resulting polyhydroxyurethane.
[0041]
In preparing the polyhydroxyurethane by the method of the present invention, as a reaction method of the diamine compound containing the diamine compound (A) as an essential component and the carbonate compound (B), both components can be used in the absence of a solvent or the above-mentioned Various methods such as dissolution in an organic solvent and mixing may be applied. There is no restriction | limiting in particular regarding the reaction temperature in that case. When an organic solvent is used, the reaction may be performed at a temperature not lower than the melting point and not higher than the boiling point. In order to obtain a polymer having a number average molecular weight of 500 or more preferable as a polyhydroxyurethane in a practical reaction time, the reaction temperature is preferably 0 ° C to 200 ° C, particularly preferably 50 ° C to 150 ° C. Regarding the reaction time, an optimum time may be appropriately set according to the kind of the diamine compound or the carbonate compound (B), the presence or absence of the organic solvent, the reaction temperature, etc., but it may be about 2 to 50 hours.
[0042]
The novel polyhydroxyurethane of the present invention thus obtained has excellent film forming properties derived from the diamine compound (A) containing an ether bond used as a raw material component, flexibility of the film, excellent solubility in a solvent, and the like. It can be effectively used for various applications such as various coating agents, adhesives and molding materials.
[0043]
【Example】
Example 1 A glass flask equipped with a thermometer, a reflux condenser, a calcium chloride tube, and a stirrer was charged with 20 ml of dried N, N-dimethylacetamide (DMAC). Next, 8.1 g (0.019 mol) of a compound represented by the following formula (9) [hereinafter abbreviated as compound (B-1)] and 4,9-dioxadodecane-1,12-diamine [ Hereinafter, 3.9 g (0.019 mol) of Compound (A-1)] was added, the temperature was raised to 100 ° C. with stirring, and stirring was continued at the same temperature for 24 hours. The reaction mixture was cooled to room temperature and dropped into diethyl ether to precipitate the produced polymer, and then the polymer isolated by filtration was dried under reduced pressure to have a number average molecular weight (Mn) of 42,000 and a weight average. A target polyhydroxyurethane having a molecular weight (Mw) of 84,000 was obtained. The yield was 98%. The obtained polyhydroxyurethane is abbreviated as P-1.
[0044]
Embedded image
[0045]
Example 2 A flask similar to that of Example 1 was charged with 20 ml of dried N, N-dimethylformamide (DMF). Next, 8.6 g (0.02 mol) of compound (B-1) and 4,7,10-trioxatridecane-1,13-diamine [hereinafter abbreviated as compound (A-2)] Of 4.4 g (0.02 mol) was added, the temperature was raised to 100 ° C. with stirring, and stirring was continued at the same temperature for 24 hours. The reaction mixture is cooled to room temperature and added dropwise to diethyl ether to precipitate the polymer, and then the polymer isolated by filtration is dried under reduced pressure to give the desired Mn of 43,000 and Mw of 81,700. Polyhydroxyurethane was obtained. The yield was 99%. The obtained polyhydroxyurethane is abbreviated as P-2.
[0046]
Example 3 A flask similar to that of Example 1 was charged with 80 ml of dry DMF. Subsequently, 29.3 g (0.08 mol) of a compound represented by the following formula (10) [hereinafter abbreviated as compound (B-2)] and 16.3 g (0. 08 mol), the temperature was raised to 100 ° C. with stirring, and stirring was continued for 24 hours at the same temperature. The reaction mixture is cooled to room temperature and added dropwise to diethyl ether to precipitate the polymer, and then the polymer isolated by filtration is dried under reduced pressure to give the desired Mn of 32,000 and Mw of 65,000. Polyhydroxyurethane was obtained. The yield was 99%. The obtained polyhydroxyurethane is abbreviated as P-3.
[0047]
Embedded image
[0048]
Example 4 A flask similar to Example 1 was charged with 80 ml of dry DMAC. 29.3 g (0.08 mol) of compound (B-2) and 17.6 g (0.08 mol) of compound (A-2) were added, and the temperature was raised to 100 ° C. while stirring. Stirring was continued for 24 hours at the same temperature. The reaction mixture is cooled to room temperature and added dropwise to diethyl ether to precipitate the polymer, then the polymer isolated by filtration is dried under reduced pressure to give the desired Mn of 38,000 and Mw of 72,000. Polyhydroxyurethane was obtained. The yield was 99%. The obtained polyhydroxyurethane is abbreviated as P-4.
[0049]
Example 5 A flask similar to Example 1 was charged with 10 milliliters of dry DMAC. Then 4.3 grams (0.01 moles) of compound (B-1), 0.6 grams (0.005 moles) of hexamethylenediamine, and 1.0 gram (0. 0 moles) of compound (A-1). 005 mol) was added, the temperature was raised to 100 ° C. with stirring, and stirring was continued for 24 hours at the same temperature. The reaction mixture is cooled to room temperature and added dropwise to diethyl ether to precipitate the polymer, and then the polymer isolated by filtration is dried under reduced pressure to give the desired Mn of 30,000 and Mw of 53,000. Polyhydroxyurethane was obtained. The yield was 98%. The obtained polyhydroxyurethane is abbreviated as P-5.
[0050]
Example 6 A flask similar to Example 1 was charged with 10 milliliters of dry DMF. Then 4.3 grams (0.01 mole) of compound (B-1), 0.7 grams (0.005 mole) of m-xylylenediamine, and 1.1 grams of compound (A-2) ( 0.005 mol) was added, the temperature was raised to 100 ° C. with stirring, and stirring was continued for 24 hours at the same temperature. The reaction mixture is cooled to room temperature and added dropwise to diethyl ether to precipitate the polymer, then the polymer isolated by filtration is dried under reduced pressure to give the desired Mn of 21,000 and Mw of 32,000. Polyhydroxyurethane was obtained. The yield was 99%. The obtained polyhydroxyurethane is abbreviated as P-6.
[0051]
Comparative Example 1 A flask similar to Example 1 was charged with 10 ml of dry DMAC. 4.3 g (0.01 mol) of compound (B-1) and 1.2 g (0.01 mol) of hexamethylenediamine were added, and the temperature was raised to 100 ° C. while stirring. And stirring was continued for 24 hours. The reaction mixture is cooled to room temperature, dropped into water to precipitate the polymer, and then the polymer isolated by filtration is dried under reduced pressure to give a polyhydroxyurethane having an Mn of 32,000 and an Mw of 60,800 Got. The yield was 95%. The obtained polyhydroxyurethane is abbreviated as RP-1.
[0052]
Comparative Example 2 3 ml of dry DMAC was used, 1.1 g (0.003 mol) of compound (B-2) was used instead of compound (B-1), and the amount of hexamethylenediamine used Polyhydroxyurethane having Mn of 28,000 and Mw of 58,800 by carrying out the reaction and isolation / drying operation in the same manner as in Comparative Example 1 except that is changed to 0.3 gram (0.003 mol). Got. The yield was 96%. The obtained polyhydroxyurethane is abbreviated as RP-2.
[0053]
Application Examples Prepare DMF solutions of each polyhydroxyurethane prepared in the above Examples and Comparative Examples, and apply to polypropylene laminate release paper using a roll-on-knife coater, at 70 ° C. for 2 minutes, and then at 150 ° C. After drying for 3 minutes, a film having a thickness of about 50 μm was produced. About each obtained film, after giving the vacuum drying process, the tensile strength and breaking elongation were measured using the Tensilon tester. The results are summarized in Table 1.
[0054]
[Table 1]
Table 1 (1)
[Table 2]
Table 1 (2)
* 1, * 2: The film was brittle and cracked, and the strength and elongation could not be measured.
[0057]
【The invention's effect】
The present invention provides a novel polyhydroxyurethane excellent in film formability, film strength, and film extensibility, and a method for producing the same, and the polyhydroxyurethane can be easily obtained in a high yield by the method of the present invention. Can be manufactured.
Claims (6)
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| US9540537B2 (en) | 2011-02-24 | 2017-01-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Coating composition for forming gas barrier layer, gas barrier film, and method for producing gas barrier film |
| WO2012150684A1 (en) | 2011-05-02 | 2012-11-08 | 大日精化工業株式会社 | Polyhydroxyurethane microparticles, and process for producing same |
| US9416227B2 (en) | 2011-05-02 | 2016-08-16 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Polyhydroxyurethane microparticles, and process for producing same |
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