JP2004018543A - Manufacturing method of polymer polyol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop an effective manufacturing method of a polymer polyol capable of reducing a content of an ethylenic unsaturated compound to below that of the prior art. <P>SOLUTION: The polymer polyol is manufactured by reacting an un-reacted ethylenic unsaturated compound (b) in a base polymer polyol (A) obtained by polymerizing the ethylenic unsaturated compound (b) with a compound (B) having addition reactivity selected from electrophilic addition reactivity, Michael type addition reactivity and hydriding reactivity in a polyol (a), if necessary, in the presence of an alcohol (C). <P>COPYRIGHT: (C)2004,JPO

Description

【００４７】
［式中、Ｚはｈ価の（ｄ）の残基（ただしｈは２以上の整数）；Ｔは（ｃ）の残基（ただし、重合性不飽和基を有する。）；Ａ_１　はｑ_１　価のポリオール〔（ａ’）、または（ａ’）と（ｄ）からのＯＨプレポリマー〕の残基、Ａ_２　はｑ_２価のポリオール〔（ａ’）、または（ａ’）と（ｄ）からのＯＨプレポリマー〕の残

；Ｔ’はＨまたは炭素数１〜１２のアルキル基；ｇは１またはそれ以上の整数；ｊは１以上の整数である。ただしｑ_１　−ｇ≧０、ｈ−ｊ−１≧０である。なお、ＯＨ基の合計は２以上である。］
【００４８】
すなわち、１個の（ａ’）と１個の（ｃ）が１個の（ｄ）を介して結合したもの、複数の（ｃ）が各々１個の（ｄ）を介して１個の（ａ’）と結合したもの、複数の（ｄ）を介して合計３個以上の（ａ’）および（ｃ）が結合したものなどを含有する。また、これら以外の副生物として、（ａ’）同志が（ｄ）を介して結合したもの（不飽和基を持たない含窒素結合含有ポリオール）、（ｃ）同志が（ｄ）を介して結合したもの（水酸基を持たない含窒素結合含有不飽和化合物）が形成されることがあり、未反応の（ａ’）や（ｃ）を含むこともある。
この混合物はそのまま分散剤として使用し得るが、不飽和基を持たない含窒素結合含有ポリオールや水酸基を持たない含窒素結合含有不飽和化合物の含量が少ないものが好ましく、さらに除去しうるこれらの不純物を除去した後に適用することもできる。
また、（Ｄ１）中の不飽和基は、ポリオールの分子鎖の末端または末端近傍に位置しているため、モノマーと共重合しやすい。
【００４９】
（Ｄ１）は、下記式（４）によって求められる、１分子中の（ｄ）のＮＣＯ基に由来する含窒素結合に対する不飽和基数の比の平均値：Ｋが０．１〜０．４となるような割合で、（ａ’）、（ｃ）および（ｄ）を反応させたものが好ましい。

Ｋの値は、さらに好ましくは０．１〜０．３であり、とくに好ましくは０．２〜０．３である。Ｋの値が上記範囲内であると、重合体ポリオールの分散安定性がとくに良好となる。
【００５０】
重合体ポリオール作成時のポリオール（ａ）と反応性分散剤（Ｄ１）の構成比は、好ましくは、（ａ）１００質量部に対して（Ｄ１）を０．５〜５０質量部使用する。下限は、さらに好ましくは０．８質量部、とくに好ましくは１質量部であり、上限は、さらに好ましくは１５質量部、とくに好ましくは１０質量部である。（Ｄ１）が５０質量部以下であると重合体ポリオールの粘度が上昇せず、０．５質量部以上であると分散性が良好である。
【００５１】
反応性分散剤（Ｄ１）は、それを用いて得られる重合体ポリオールの分散安定性が極めて良好となる。とくにエチレン性不飽和化合物（ｂ）として、（ｂ４）を用いる高濃度（例えば重合体含量４０〜７５質量％）重合体ポリオールの製造に好適に用いられ、より低粘度の重合体ポリオールを得ることができる。
【００５２】
次に、（ｂ）の重合に用いる重合開始剤としては、遊離基を生成して重合を開始させるものが使用でき、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−アルボニトリル）、２，２’−アゾビス（２，４，４−トリメチルペンタン）、ジメチル２，２’−アゾビス（２−メチルプロピオネイト）、２，２’−アゾビス［２−（ヒドロキシメチル）プロピオニトリル］及び１，１’−アゾビス（１−アセトキシ−１−フェニルエタン）等のアゾ化合物；ジベンゾイルパーオキサイド、ジクミルパーオキサイド、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ベンゾイルパーオキサイド、ラウロイルパーオキサイド及び過コハク酸等の有機過酸化物；過硫酸塩及び過ホウ酸塩等の無機過酸化物等が挙げられる。なお、これらは２種以上を併用することができる。
【００５３】
重合開始剤の使用量は、（ｂ）の質量に基づいて、通常０．０５〜２０質量％、好ましくは０．１〜１５質量％、とくに好ましくは０．２〜１０質量％である。重合開始剤の使用量が０．０５〜２０質量％の範囲で重合体ポリオール中の（ｂ）の重合率が十分高くなり、また、分子量も大きくなるため、ウレタンフォームにした際に十分なフォーム圧縮硬さが得られる面で優れている。
【００５４】
ラジカル重合に用いる希釈剤（Ｅ）としては、例えば、トルエン、キシレンなどの芳香族炭化水素系溶剤；ヘキサン、ヘプタンなどの炭素数５〜１５の飽和脂肪族炭化水素系溶剤；ヘキセン、ノネンなどの炭素数５〜１５の不飽和脂肪族炭化水素系溶剤；などが挙げられる。
希釈剤の使用量は、（ｂ）の使用量に基づいて、好ましくは５０質量％以下、さらに好ましくは４０質量％以下である。用いた（Ｅ）は、重合反応後に減圧ストリッピング等により除去するのが好ましい。
【００５５】
また（Ｅ）を、必要により本発明の製法で得られる重合体ポリオールに添加して、重合体ポリオールをさらに低粘度とすることもできる。重合体ポリオール中に含有させる（Ｅ）としては、上記不飽和脂肪族炭化水素系溶剤；芳香族炭化水素系溶剤；および低粘度（１００ｍＰａ・ｓ／２５℃以下）の難燃剤、例えばトリス（クロロエチル）ホスフェート、トリス（クロロプロピル）ホスフェート；などを挙げることができる。
ベース重合体ポリオール（Ａ）中の（Ｅ）の含有量は、好ましくは２質量％以下、さらに好ましくは１質量％以下である。
【００５６】
また、連鎖移動剤としては、例えば、ドデシルメルカプタンおよびメルカプトエタノール等のアルキルメルカプタン類；等が挙げられる。
連鎖移動剤の使用量は、（ｂ）の使用量に基づいて、通常２質量％以下、好ましくは０．１質量％以下である。
【００５７】
（Ａ）中の未反応の（ｂ）と反応させる、付加反応性を有する化合物（Ｂ）としては、有機化合物、無機化合物のいずれでもよく、親電子付加反応するもの（Ｂ１）、マイケル型付加反応するもの（Ｂ２）、および水素添加反応するもの（Ｂ３）が挙げられ、２種以上を併用してもよい。
（Ｂ１）としては、例えば、ルイス酸〔フッ化ホウ素、塩化アルミニウム、塩化銀、硝酸鉄（ＩＩＩ）　など〕、臭素、次亜塩素酸、塩酸、および硫酸が挙げられる。
【００５８】
（Ｂ２）としては硫黄原子を含有するものが好ましく、例えば、亜硫酸塩（Ｂ２１）、次亜硫酸塩（Ｂ２２）、およびチオール（Ｂ２３）が挙げられる。
（Ｂ２１）としては、例えば、アルカリ金属塩（亜硫酸ナトリウム、亜硫酸カリウムなど）、およびアルカリ土類金属塩（亜硫酸カルシウム、亜硫酸マグネシウムなど）が挙げられる。（Ｂ２２）としては、例えば、アルカリ金属塩（次亜硫酸ナトリウム、次亜硫酸カリウムなど）、およびアルカリ土類金属塩（次亜硫酸カルシウム、次亜硫酸マグネシウムなど）が挙げられる。
（Ｂ２３）としては、例えば、アルキルメルカプタンおよびアルキレンジチオグリコール（炭素数１〜２０）（Ｂ２３１）、並びにポリアルキレングリコール（アルキレン基の炭素数が２〜８）の片末端あるいは両末端の水酸基がチオール基に置換した化合物〔総炭素数４〜２０〕（Ｂ２３２）が挙げられる。（Ｂ２３１）としては、例えば、エチルメルカプタン、プロピルメルカプタン、ブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、エチレンジチオグリコール、プロピレンジチオグリコール、ブチレンジチオグリコール、オクチレンジチオグリコール、およびドデシレンジチオグリコールが挙げられる。（Ｂ２３１）の中で好ましいものは、エチレン性不飽和基との反応性の点から、沸点が４０℃〜１５０℃のものであり、例えば、ブチルメルカプタンが挙げられる。（Ｂ２３２）としては、例えば、１，８−ジメルカプト−３，６−ジオキサオクタン（以下、ＤＭＤＯと略記する）が挙げられる。
【００５９】
（Ｂ３）としては水素が挙げられ、水素添加反応時に用いられる触媒としては、ニッケル、白金、パラジウムなどが挙げられる。
これら（Ｂ）のうち好ましいものは（Ｂ２１）、（Ｂ２２）および（Ｂ２３）であり、さらに好ましいものは亜硫酸ナトリウムおよびＤＭＤＯであり、とくに好ましいものは亜硫酸ナトリウムである。
【００６０】
（Ｂ）の使用量は、エチレン性不飽和基１当量に対して、好ましくは１〜１０当量である。下限はさらに好ましくは２当量であり、上限はさらに好ましくは８当量、とくに好ましくは６当量である。（Ｂ）の量が１当量以上ではエチレン性不飽和基が残存せず、１０当量以下では未反応の（Ｂ）が重合体ポリオールを用いるポリウレタン樹脂の性能に影響を及ぼさない。
【００６１】
本発明の製造方法は、必要により、アルコール（Ｃ）の存在下に行うことができる。（Ｃ）を含有させることにより、（ｂ）と（Ｂ）が混ざりやすくなり反応性が向上する。
（Ｃ）としては炭素数が２０以下の低分子アルコールが好ましく、例えば、炭素数１〜８のアルコール（Ｃ１）、および炭素数１〜８のアルコールの（ポリ）オキシアルキレンエーテル（アルキレン基の炭素数が２〜８）（Ｃ２）が挙げられ、２種以上を併用してもよい。
（Ｃ１）としては、例えば、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、およびｎ−ブタノールが挙げられる。（Ｃ２）は、通常（Ｃ１）に炭素数２〜８のアルキレンオキサイドを付加して得られ、アルキレンオキサイドとしては、ＥＯ、ＰＯ、ＢＯ、ＳＯ等が挙げられる。
これら（Ｃ）のうち好ましいものは（Ｃ１）であり、さらに好ましくはメタノール、エタノール、およびイソプロパノールであり、とくに好ましくはメタノールである。
【００６２】
（Ｃ）の使用量は、（Ａ）１００質量部に対して、好ましくは１００質量部以下である。下限は好ましくは１質量部、さらに好ましくは２質量部であり、上限はさらに好ましくは８０質量部、とくに好ましくは５０質量部である。（Ｃ）の量が１００質量部以下であると、反応終了後の（Ｃ）の除去が容易になる。
【００６３】
本発明の製造方法においては、必要により、さらに界面活性剤（Ｆ）の存在下に行うことができる。（Ｆ）を含有させることにより、（ｂ）と（Ｂ）が混ざりやすくなり反応性が向上する。
（Ｆ）の種類にとくに限定はなく、アニオン界面活性剤（炭素数８〜２２のカルボン酸塩、スルホン酸塩、燐酸エステル塩など）、カチオン界面活性剤（第４級アンモニウム塩型界面活性剤、アミン塩型界面活性剤など）、非イオン界面活性剤（高級アルコールのＥＯ付加物、多価アルコールエステルのＥＯ付加物、多価アルコール脂肪酸エステルなど）、および両性界面活性剤（ベタイン型界面活性剤など）から選ばれる１種以上を使用することができる。
（Ｆ）の添加量は、（Ａ）１００質量部に対して、好ましくは２０質量部以下である。
【００６４】
（Ａ）中の未反応の（ｂ）と（Ｂ）とを、必要により（Ｃ）等の存在下に反応させる方法としては、付加反応が起こる条件であれば特に限定されないが、例えば、（ｂ）を含む（Ａ）に、（Ｂ）と必要により（Ｃ）等を添加して、５０〜１５０℃（好ましくは６０〜１３０℃）に加熱し、攪拌混合する方法が挙げられる。
また、（Ｃ）を用いる場合の（Ｃ）は、（ｂ）と（Ｂ）との反応後に減圧留去するのが好ましい。（Ｃ）を減圧留去する条件としては、留去するのに有効な条件であれば特に限定されないが、例えば、温度１１０℃〜１５０℃で１〜１００（好ましくは２〜５０）ｔｏｒｒの減圧下、１〜１０時間ストリッピングする方法が挙げられる。
【００６５】
本発明の方法により、（ｂ）の含量の低い重合体ポリオールを得ることができるが、（ｂ）がスチレンおよび／またはアクリロニトリルからなるとき、得られる重合体ポリオール中の、スチレン、アクリロニトリルの含量（ガスクロマトグラフ法による）は、重合体ポリオールを用いてポリウレタンフォームを成形する際の作業環境の点から、アクリロニトリル含量が５０ｐｐｍ以下、スチレン含量が３００ｐｐｍ以下であることが好ましい。アクリロニトリル含量は、さらに好ましくは３０ｐｐｍ以下、とくに好ましくは５ｐｐｍ以下であり、スチレン含量は、さらに好ましくは２５０ｐｐｍ以下、とくに好ましくは１００ｐｐｍ以下である。なお、ガスクロマトグラフ法の詳細は後述の実施例の方法による。
【００６６】
本発明の方法により得られる重合体ポリオールは、ポリオール成分とポリイソシアネート成分を発泡剤の存在下または不存在下に反応させて、発泡または非発泡ポリウレタン樹脂を製造する際のポリオール成分の少なくとも一部として、好適に用いることができる。
【００６７】
ポリオール成分としては、本発明の製法により得られた重合体ポリオール（Ｉ）以外に、必要により公知の他の活性水素原子含有化合物を併用することができる。他の活性水素原子含有化合物としては、ポリウレタンの製造に普通に用いられている他の高分子ポリオール（Ｔ）、低分子活性水素原子含有化合物（Ｕ）、および国際公開ＷＯ９８／４４０１６号公報に記載の末端ラジカル重合性官能基含有活性水素化合物（モノオールも含む）が使用できる。
【００６８】
他の高分子ポリオール（Ｔ）としては、例えば、前記のポリオール（ａ）として例示した（ａ１）および（ａ２）、本発明の方法以外で得られた重合体ポリオール、並びにこれらの混合物が使用できる。
【００６９】
これらのポリオール（Ｔ）は、通常２〜８個、好ましくは３〜８個の水酸基と、好ましくは２００〜４０００、さらに好ましくは４００〜３０００の水酸基当量を有している。
（Ｔ）として好ましいものは（ａ１）である。
【００７０】
（Ｕ）としては、少なくとも２個（好ましくは２〜３個、とくに好ましくは２個）の活性水素原子（水酸基、アミノ基、メルカプト基など、好ましくは水酸基）を有する分子量５００以下（好ましくは６０〜４００）の化合物、たとえば低分子ポリオール、アミノアルコールが挙げられる。（Ｕ）の活性水素原子１個当たりの当量は、好ましくは２００未満、さらに好ましくは３０〜１８０である。低分子ポリオールとしては、前記の多価アルコール；低分子量（たとえば分子量２００〜４００）の多価アルコールアルキレンオキサイド付加物（ポリエチレングリコール、ポリプロピレングリコールなど）；環構造を有する低分子ジオール類、例えばビスフェノールＡのプロピレンオキサイド付加物；等が挙げられる。
アミノアルコールとしては、モノ−またはジアルカノールアミン類（モノエタノールアミン、ジエタノールアミン、モノプロパノールアミンなど）が挙げられる。
これらのうちで好ましいのは、低分子ポリオール、特にジオールであり、具体的にはエチレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオールおよびこれらの２種以上の混合物である。
【００７１】
ポリオール成分中の重合体ポリオール（Ｉ）の量は、好ましくは５質量％以上、より好ましくは１０質量％以上、とくに好ましくは２０質量％以上である。５質量％以上であると、ポリウレタンフォームとした場合のフォームの圧縮硬さが十分に得られる。
また、ポリオール成分中の重合体の含量は、好ましくは５〜７５質量％、さらに好ましくは７〜５５質量％である。上記範囲内では、フォームの硬さと液流れ性が共に良好である。
【００７２】
また、（Ｔ）の含量は、好ましくは９５質量％以下、より好ましくは８０質量％以下である。（Ｔ）が９５質量％以下であると、ポリウレタンの硬度がでやすい。（Ｕ）および末端ラジカル重合性官能基含有活性水素化合物の含量は、好ましくは３０質量％以下、さらに好ましくは１０質量％以下である。
（Ｕ）が３０質量％以下であると、反応時の発熱温度が高くなりすぎず、スコーチが発生する恐れがない。
【００７３】
ポリウレタン樹脂を製造する際にポリイソシアネート成分として使用される有機ポリイソシアネートとしては、従来からポリウレタン樹脂の製造に使用されている公知のものが使用できる。
このようなポリイソシアネートとしては、前記（ｄ）として例示したもの等が挙げられる。
【００７４】
ポリウレタン樹脂の製造に際してのイソシアネート指数［（ＮＣＯ基／活性水素原子含有基）の当量比×１００］は、好ましくは８０〜１４０、さらに好ましくは８５〜１２０、とくに好ましくは９５〜１１５である。またイソシアネート指数を上記範囲より大幅に高くして（たとえば３００〜１０００）ポリウレタン中にポリイソシアヌレート基を導入することもできる。
【００７５】
ポリウレタン樹脂の製造に際しては、反応を促進させるため、ポリウレタン反応に通常使用される触媒を使用してもよい。たとえばアミン系触媒〔トリエチレンアミン、Ｎ−エチルモルホリンなどの３級アミン；１，８−ジアザ−ビシクロ［５．４．０］ウンデセン−７（サンアプロ社製、登録商標名：ＤＢＵ）；等〕、錫系触媒（オクチル酸第１スズ、ジブチルチンジラウレートなど）、その他の金属触媒（オクチル酸鉛など）および米国特許４，２９９，９２４号明細書に記載のイソシアヌレート化触媒が挙げられる。これらの中では、アミン系触媒および／または錫系触媒が好ましい。
触媒を用いる場合の使用量は、反応混合物の質量に基づいて、好ましくは０．００１〜５質量％である。
【００７６】
本発明のポリウレタン樹脂の製造方法においては、必要によりポリウレタン反応に通常使用される発泡剤を使用し、ポリウレタンフォーム（好ましくは発泡倍率が５〜１００倍）とすることができる。発泡剤としては水、水素原子含有ハロゲン化炭化水素、低沸点炭化水素などが挙げられる。
水を用いる場合の使用量は、ポリオール成分１００質量部あたり、好ましくは０．５〜１０質量部、さらに好ましくは０．８〜８質量部である。０．５質量部以上では、反応熱の発生が大きいために成形品を得る時間が短縮され、１０質量部以下であると、良好な発泡体が得られる。
【００７７】
水素原子含有ハロゲン化炭化水素系発泡剤の具体例としては、ＨＣＦＣ（ハイドロクロロフルオロカーボン）タイプのもの（例えばＨＣＦＣ−１２３、ＨＣＦＣ−１４１ｂ、ＨＣＦＣ−２２およびＨＣＦＣ−１４２ｂ）；ＨＦＣ（ハイドロフルオロカーボン）タイプのもの（例えばＨＦＣ−１３４ａ、ＨＦＣ−１５２ａ、ＨＦＣ−３５６ｍｆｆ、ＨＦＣ−２３６ｅａ、ＨＦＣ−２４５ｃａ、ＨＦＣ−２４５ｆａおよびＨＦＣ−３６５ｍｆｃ）などが挙げられる。
これらのうち好ましいものは、ＨＣＦＣ−１４１ｂ、ＨＦＣ−１３４ａ、ＨＦＣ−３５６ｍｆｆ、ＨＦＣ−２３６ｅａ、ＨＦＣ−２４５ｃａ、ＨＦＣ−２４５ｆａ、ＨＦＣ−３６５ｍｆｃおよびこれらの２種以上の混合物である。
水素原子含有ハロゲン化炭化水素を用いる場合の使用量は、ポリオール成分１００質量部あたり、好ましくは０〜５０質量部、さらに好ましくは０〜４５質量部である。
【００７８】
低沸点炭化水素は、通常沸点が−５〜５０℃の炭化水素であり、その具体例としては、ブタン、ペンタン、シクロペンタンおよびこれらの混合物が挙げられる。
低沸点炭化水素を用いる場合の使用量は、ポリオール成分１００質量部あたり、好ましくは０〜４０質量部、さらに好ましくは０〜３０質量部である。
【００７９】
本発明の製法においては、必要により、さらに整泡剤などの通常用いられる添加剤も使用することができる
整泡剤としては、通常のポリウレタンフォームの製造に用いられるものはすべて使用でき、例として、ジメチルシロキサン系整泡剤［例えば、トーレダウコーニングシリコーン（株）製の「ＳＲＸ−２５３」、信越化学工業（株）製の「Ｆ−１２２」］、ポリエーテル変性ジメチルシロキサン系整泡剤［例えば、日本ユニカー（株）製の「Ｌ−５３０９」、「Ｌ−３６０１」、「ＳＺ−１３１１」、信越化学工業（株）製の「Ｆ−２４２Ｔ」］等のシリコーン整泡剤が挙げられる。
整泡剤の使用量は、ポリオール成分１００質量部に対して、好ましくは１０質量部以下、さらに好ましくは０．２〜５質量部である。
【００８０】
本発明の製法においては、さらに、酸化防止剤（ヒンダードフェノール系、ヒンダードアミン系など）や紫外線吸収剤（トリアゾール系、ベンゾフェノン系など）のような老化防止剤；無機塩（炭酸カルシウム、硫酸バリウムなど）、無機繊維（ガラス繊維、炭素繊維など）、ウイスカー（チタン酸カリウムウイスカーなど）のような無機充填材；合成短繊維、熱可塑性もしくは熱硬化性樹脂からなる中空微小球のような有機充填剤；難燃剤（リン酸エステル類、ハロゲン化リン酸エステル類など）；可塑剤（フタル酸エステル、アジピン酸エステルなど）；接着剤（変性ポリカプロラクトンポリオールなど）；着色剤（染料、顔料、カーボンブラックなど）；抗菌剤；抗カビ剤等の、通常の添加剤および助剤を必要に応じて使用することができる。
【００８１】
ポリオール成分１００質量部に対するこれらの添加剤の使用量に関しては、老化防止剤は、好ましくは１質量部以下、さらに好ましくは０．０１〜０．５質量部である。無機充填剤は、好ましくは５０質量部以下、さらに好ましくは３０質量部以下である。有機充填剤は、好ましくは５０質量部以下、さらに好ましくは３０質量部以下である。難燃剤は、好ましくは２０質量部以下、さらに好ましくは１〜１５質量部である。可塑剤は、好ましくは１０質量部以下、さらに好ましくは５質量部以下である。これら以外の上記添加剤は、好ましくは１質量部以下である。
【００８２】
ポリウレタン樹脂の製造は、通常の公知の方法で行うことができ、例えば、ワンショット法、セミプレポリマー法、プレポリマー法等が挙げられる。
ポリウレタン樹脂の製造は、通常用いられている公知の製造装置を用いることができ、溶媒を使用しない場合は、例えば、ニーダーやエクストルーダーのような装置を用いることができる。また、閉鎖モールドまたは開放モールド内で各種の非発泡または発泡のポリウレタン樹脂の製造を行うことができる。閉鎖モールドを用い発泡ポリウレタン樹脂を製造する場合のパック率〔（モールド発泡時の密度／フリー発泡時の密度）×１００〕は、好ましくは１１０〜２００％である。
ポリウレタン樹脂の製造は、通常、低圧または高圧の機械装置を用いて原料を混合反応させることにより行われる、さらには、原料混合前後（特に原料混合前）、原料中の溶存空気または混合時に混入した空気等のガスを真空法により除去することによりポリウレタン樹脂の製造を行うこともできる。
本発明の製造方法は、軟質モールドフォーム及びスラブフォームの製造に特に有用である。また、ＲＩＭ（反応射出成形）法による成形にも適用できる。
【００８３】
本発明の製法により得られた重合体ポリオールを用いて製造されたポリウレタン樹脂は、経時的な変色が少なく、例えば、ポリウレタンフォームとして、自動車の内装部品や、家具等の室内調度に用いられる。また、シーラントや合成皮革の材料としても用いられる。
【００８４】
【実施例】
以下に本発明を実施例によりさらに具体的に説明するが、本発明はこれに限定されるものではない。なお、以下において、部および％比は、それぞれ質量部および質量％を示す。
【００８５】
製造例、実施例及び比較例に使用した原料の組成、記号等は次の通りである。
（１）ポリオール
ポリオールａ１：グリセリンにＰＯを平均４６モル付加し、次いでＥＯを平均６モル付加させて得られた、数平均分子量３０００、水酸基当量１０００のポリオール。
ポリオールａ２：ペンタエリスリトールにＰＯを平均１０４モル付加し、次いでＥＯを平均１９モル付加させて得られた数平均分子量７０００、水酸基当量１７５０のポリオール。
（２）エチレン性不飽和化合物
ＡＣＮ　：アクリロニトリル
Ｓｔ　　：スチレン
（３）重合開始剤
ＡＩＢＮ　：２，２’−アゾビスイソブチロニトリル
（４）重合性不飽和基を有する単官能活性水素化合物
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
（５）触媒
ＴＢＴ　　：テトラブチルチタネート〔ナカライテスク（株）製〕
（６）ポリイソシアネート
ＴＤＩ　　：コロネートＴ−８０〔日本ポリウレタン（株）製〕
【００８６】
また、重合体ポリオール中のエチレン性不飽和化合物の含量は、以下のように測定した。
＜アクリロニトリル、スチレン含量測定法＞
ガスクロマトグラフ　：ＧＣ−１４Ｂ（島津製作所製）
カラム　　　　　　　：内径４ｍｍφ、長さ１．６ｍ、ガラス製
カラム充填剤　　　　：ポリエチレングリコール２０Ｍ〔信和化工（株）製〕２０％保持
内部標準物質　　　　：トルエン（スペクトル用）〔ナカライテスク（株）製〕
希釈溶媒　　　　　　：ジプロピレングリコールモノメチルエーテル　１級〔和光純薬（株）製〕（５０％溶液とする。）
インジェクション温度：２００℃
カラム初期温度　　　：１１０℃
昇温速度　　　　　　：５℃／ｍｉｎ．
カラムファイナル温度：２００℃
試料注入量　　　　　：１μｌ
【００８７】
＜製造例１＞反応性分散剤（Ｄ１）の製造
温度調節器、バキューム撹拌翼、滴下ロートを備えた四つ口フラスコに、ＴＤＩを２８部、ＴＢＴを０．０１部入れ、３０℃に冷却し、続いてＨＥＭＡ９部を２時間で滴下した。その間反応温度を４０〜５０℃に保った。その反応液を温度調節器、撹拌翼、滴下ロートを備えた四つ口フラスコにあらかじめ入れておいたポリオールａ２、９６３部中に入れ、反応温度８０〜９０℃で４時間撹拌した。赤外吸収スペクトルにおいて未反応のイソシアネート基が存在しないことを確認して、反応性分散剤（Ｄ１）を得た。
（Ｄ１）の水酸基価は２０、粘度は２００００ｍＰａ・ｓ／２５℃、不飽和基数／含窒素結合の数、の比は０．２２であった。
【００８８】
＜製造例２＞ベース重合体ポリオールの製造
温度調節器、バキューム撹拌翼、滴下ポンプ、減圧装置、ジムロート冷却管、窒素流入口および流出口を備えた４口フラスコに、ａ１：３０部、キシレン：７部およびＤ１：１部を投入し、窒素置換後、窒素雰囲気下（重合終了まで）で撹拌しながら１３０℃に昇温した。次いで、ＡＣＮ：１６部、Ｓｔ：３７部、ａ１：１３部を予め混合した原料、並びに、予め、ａ１：８部およびＡＩＢＮ：０．５部を混合した原料を、各々同時に滴下ポンプを用いて３時間かけて連続的に滴下し、１３０℃で重合させた。さらに同温度で未反応モノマーとキシレンを２０〜３０ｔｏｒｒで２時間減圧下ストリッピングして、ポリマー粒子含量５０％、粘度９６００ｍＰａ・ｓ（２５℃）のベース重合体ポリオールを得た。
ガスクロマトグラフ法により測定した、得られたベース重合体ポリオールのアクリロニトリル含量は３００ｐｐｍ、スチレン含量は１０００ｐｐｍであった。
【００８９】
実施例１
温度調節器、バキューム撹拌翼、ジムロート冷却管、減圧装置、窒素流入および流出口を備えた四つ口フラスコに、製造例２で得たベース重合体ポリオールを入れ、６０℃まで昇温させた。攪拌しながら、飽和亜硫酸ナトリウム水溶液をエチレン性不飽和化合物１当量に対し４．６当量添加した後、メタノールをベース重合体ポリオール１００部に対し２０部加え、１２０℃まで昇温した後、２時間加熱攪拌した。反応終了後、減圧度３０ｔｏｒｒ、温度１３０℃で２時間メタノールと水を除去し、重合体ポリオールを得た。
ガスクロマトグラフ法により測定した、得られた重合体ポリオール中のアクリロニトリル含量は１ｐｐｍ、スチレン含量は２５０ｐｐｍであった。
【００９０】
実施例２
実施例１の飽和亜硫酸ナトリウム水溶液をＤＭＤＯに換え、メタノールを加えないこと以外は、実施例１と同様に加熱および減圧操作を行い、重合体ポリオールを得た。
ガスクロマトグラフ法により測定した、得られた重合体ポリオール中のアクリロニトリル含量は１ｐｐｍ、スチレン含量は９３ｐｐｍであった。
【００９１】
比較例１
実施例１の飽和亜硫酸ナトリウム水溶液、およびメタノールを使用しないこと以外は、実施例１と同様に加熱および減圧操作を行い、重合体ポリオールを得た。
ガスクロマトグラフ法により測定した、得られた重合体ポリオール中のアクリロニトリル含量は５８ｐｐｍ、スチレン含量は７６０ｐｐｍであった。
【００９２】
比較例２
温度調節器、バキューム撹拌翼、ジムロート冷却管、減圧装置、窒素流入および流出口を備えた四つ口フラスコに、製造例２で得たベース重合体ポリオールを入れ、１３０℃まで昇温させた。攪拌しながら、ＡＩＢＮをエチレン性不飽和化合物１当量に対し０．００２５当量添加した後、同温度で２時間加熱攪拌し、重合体ポリオールを得た。
ガスクロマトグラフ法により測定した、得られた重合体ポリオール中のアクリロニトリル含量は２８０ｐｐｍ、スチレン含量は９００ｐｐｍであった。
【００９３】
比較例３
比較例２のＡＩＢＮを、エチレン性不飽和化合物１当量に対し４．６当量添加すること以外は、比較例２と同様に加熱および減圧操作を行い、重合体ポリオールを得た。
ガスクロマトグラフ法により測定した、得られた重合体ポリオール中のアクリロニトリル含量は２５０ｐｐｍ、スチレン含量は７２０ｐｐｍであった。
【００９４】
上記の結果から、エチレン性不飽和基への付加反応性を有する化合物（Ｂ）を用いた実施例１および２では、比較例に比べて、得られた重合体ポリオール中の、アクリロニトリルとスチレンの含量が大幅に減少していることがわかる。
【００９５】
【発明の効果】
本発明の重合体ポリオールの製造方法によれば、得られる重合体ポリオール中の、未反応のエチレン性不飽和化合物の濃度が大幅に減少する。したがって、重合体ポリオールの臭気を著しく低下させることができ、重合体ポリオールを用いるポリウレタン樹脂製造時の作業環境を改善することができる。また、得られるポリウレタンフォームの経時による着色を防止することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a polymer polyol. More specifically, the present invention relates to a method for producing a polymer polyol having a reduced content of unreacted ethylenically unsaturated compounds.
[0002]
[Prior art]
Conventionally, as a method of reducing the unreacted ethylenically unsaturated compound in the polymer polyol, a method of distilling under reduced pressure at a high temperature or a method of adding a radical polymerization initiator after polymerization to increase the polymerization rate is known. I have.
[0003]
[Problems to be solved by the invention]
However, the concentration of the ethylenically unsaturated compound cannot be sufficiently reduced by distillation under reduced pressure or addition of a radical polymerization initiator. In recent years, the amount of ethylenically unsaturated compounds remaining in the polymer polyol has been strictly regulated from the environmental and working environment aspects, and the efficiency of the ethylenically unsaturated compounds has been reduced. There is a need to develop methods that can reduce the concentration. Further, a polyurethane foam obtained by using a conventional polymer polyol has a problem that coloring is likely to occur over time.
[0004]
[Means for Solving the Problems]
The present inventors have intensively studied to solve these problems, and as a result, have reached the present invention.
[0005]
That is, the present invention relates to an unreacted (b) in a base polymer polyol (A) obtained by polymerizing an ethylenically unsaturated compound (b) in a polyol (a), an electrophilic addition reaction, a Michael type addition. A process for producing a polymer polyol, which comprises reacting a compound (B) having an addition reactivity selected from a reaction and a hydrogenation reaction, if necessary, in the presence of an alcohol (C); In a method for producing a foamed or non-foamed polyurethane resin by reacting an isocyanate component in the presence or absence of a foaming agent, using the polymer polyol obtained by the production method as at least a part of the polyol component. This is a method for producing a polyurethane resin.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, as the polyol (a), a known polyol usually used for producing a polymer polyol can be used. For example, a compound having a structure in which an alkylene oxide is added to a compound containing at least 2 (preferably 2 to 8) active hydrogens (polyhydric alcohol, polyhydric phenol, amines, polycarboxylic acid, phosphoric acid, etc.) (Polyether polyol) (a1) and mixtures thereof.
Of these, preferred are compounds having a structure in which an alkylene oxide is added to a polyhydric alcohol.
[0007]
Examples of the polyhydric alcohol include dihydric alcohols having 2 to 20 carbon atoms (eg, aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol). Alkylene glycols such as cycloaliphatic diols such as cyclohexanediol and cyclohexanedimethanol), and trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylolpropane, and trimethylol). Alkanetriols such as ethane and hexanetriol); polyhydric alcohols having 4 to 8 or more carbon atoms having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglyceride) Emissions, alkane polyols and their intramolecular or intermolecular dehydration products, such as dipentaerythritol; and sucrose, glucose, mannose, fructose, sugars and their derivatives such as methyl glucoside) and the like.
[0008]
Examples of polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A, bisphenol F, and bisphenol sulfone; condensates of phenol and formaldehyde (novolak).
[0009]
Examples of the amines include ammonia; and examples of the aliphatic amines include alkanolamines having 2 to 20 carbon atoms (eg, monoethanolamine, diethanolamine, isopropanolamine, and aminoethylethanolamine), and alkylamines having 1 to 20 carbon atoms (eg, n -Butylamine and octylamine), alkylene diamines having 2 to 6 carbon atoms (e.g., ethylene diamine, propylene diamine and hexamethylene diamine), polyalkylene polyamines (dialkylene triamine having 2 to 6 carbon atoms in the alkylene group to hexaalkylene heptamine) , For example, diethylenetriamine and triethylenetetramine).
An aromatic mono- or polyamine having 6 to 20 carbon atoms (for example, aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); an alicyclic having 4 to 20 carbon atoms Amines (isophorone diamine, cyclohexylene diamine and dicyclohexyl methane diamine); and heterocyclic amines having 4 to 20 carbon atoms (eg, aminoethylpiperazine) and the like.
[0010]
Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid, Isophthalic acid), and mixtures of two or more of these.
[0011]
The alkylene oxide to be added to the active hydrogen-containing compound is preferably one having 2 to 8 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), and 1,2-. , 1,3-, 1,4- and 2,3-butylene oxide (hereinafter abbreviated as BO), styrene oxide (hereinafter abbreviated as SO) and the like, and combinations of two or more of these (block and And / or random addition). Preferably, it is PO or a combination of PO and EO (EO content is 25% by mass or less).
[0012]
Specific examples of the polyol include those obtained by adding PO to the active hydrogen-containing compound and those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO), preferably EO in the following manner. Or esterified products of these additional compounds with polycarboxylic acid or phosphoric acid.
(1) Blocks added in PO-AO order (tiped)
(2) PO-AO-PO-AO blocks added in order (balanced)
(3) Blocks added in the order of AO-PO-AO
{Circle around (4)} Blocks added in the order of PO-AO-PO (active secondary)
{Circle around (5)} Random admixture of PO and AO mixed and added
(6) Random or block added in the order described in US Pat. No. 4,226,756
Further, the hydroxyl equivalent of (a1) is preferably from 200 to 4,000, more preferably from 400 to 3,000. It is also preferable that two or more (a1) are used in combination and the hydroxyl equivalent is within this range.
[0013]
As the polyol (a), another polyol (a2) can be used in combination with the compound (a1) having a structure in which an alkylene oxide is added to the active hydrogen-containing compound. In this case, the use ratio (mass ratio) of (a1) / (a2) is preferably 100/0 to 80/20.
Examples of the other polyol (a2) include polymer polyols such as polyester polyols and diene-based polyols, and mixtures thereof.
[0014]
Examples of the polyester polyol include the above-mentioned polyhydric alcohols and / or polyether polyols [ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like. Polyhydric alcohols or mixtures of these with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane, and adducts of these polyhydric alcohols with low moles (1 to 10 moles) of alkylene oxides] Or an anhydride thereof, an ester-forming derivative such as a lower alkyl (alkyl group having 1 to 4 carbon atoms) ester (eg, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.); Carboxylic anhydride Reaction product of an alkylene oxide (EO, PO, etc.) with a polylactone polyol, for example, ring-opening polymerization of a lactone (ε-caprolactone, etc.) using the above polyhydric alcohol as an initiator. And polycarbonate polyols, for example, a reaction product of the above-mentioned polyhydric alcohol and alkylene carbonate; and the like.
[0015]
Further examples include diene-based polyols such as polybutadiene polyols and hydrogenated products thereof; hydroxyl-containing vinyl polymers such as acrylic polyols; natural oil-based polyols such as castor oil; and modified products of natural oil-based polyols.
These polyols (a2) usually have 2 to 8, preferably 3 to 8, hydroxyl groups and usually 200 to 4,000, preferably 400 to 3,000, hydroxyl equivalents.
The number average molecular weight of the polyol (a) [based on gel permeation chromatography (GPC), the same applies to the following number average molecular weight unless otherwise specified] is usually 500 or more, preferably 500 to 20,000, particularly preferably 1 to 20,000. , 200 to 15,000, most preferably 2,000 to 9,000. When the number average molecular weight is 500 or more, it is preferable in terms of foaming properties of the polyurethane foam, and when it is 20,000 or less, the viscosity becomes low, which is preferable in terms of the handleability of the polymer polyol. The hydroxyl equivalent of (a) is preferably from 200 to 4,000, more preferably from 400 to 3,000.
[0016]
Examples of the ethylenically unsaturated compound (b) used in the production of the base polymer polyol (A) include an aromatic hydrocarbon monomer (b1), an unsaturated nitrile (b2), and a (meth) acrylate. (B3), the number average molecular weight is 160 to 490, and the SP value is 9.5 to 13 [(cal / cm³)^1/2And the same shall apply hereinafter), a terminal ethylenically unsaturated group-containing compound (b4), another ethylenically unsaturated compound (b5), and a mixture of two or more of these compounds.
(B1) includes styrene, α-methylstyrene, hydroxystyrene, chlorostyrene and the like.
Examples of (b2) include acrylonitrile and methacrylonitrile. As (b3), methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) ) Acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, and other alkyl (meth) acrylates (where the alkyl group has 1 carbon atom) -24); hydroxypolyoxyalkylene (alkylene group having 2 to 8 carbon atoms) mono (meth) acrylates and the like.
[0017]
In particular, when it is desired to obtain a base polymer polyol having a low viscosity even though the polymer content is high, it is preferable to contain (b4). The lower limit of the number average molecular weight of (b4) is preferably 170, more preferably 180, particularly preferably 182, most preferably 185, and the upper limit is preferably 480, more preferably 450, particularly preferably 420, Most preferably, it is 400. When the number average molecular weight is 160 or more, the viscosity of the polymer polyol is low, which is preferable in terms of handleability, and the hardness of the polyurethane foam obtained therefrom is also good. When the number average molecular weight of (b4) is 490 or less, the hardness of the polyurethane foam obtained by using the same is good.
[0018]
The number of ethylenically unsaturated groups in (b4) may be one or more on average. The number is preferably from 1 to 10, more preferably from 1 to 2, and particularly preferably 1. When the number of ethylenically unsaturated groups is less than one on average, not only the amount of the soluble component of the polyol increases, the viscosity of the resulting polymer polyol increases, but also the physical properties of the polyurethane resin produced by using these remarkably increase. Inferior. As long as the ethylenically unsaturated group of (b4) has at least one (average) terminal, the remaining unsaturated group may be present at a terminal or at a position other than the terminal. Is also good.
Specific examples of the above ethylenically unsaturated groups include (meth) acryloyl groups and α-alkenyl groups such as allyl groups.
[0019]
Further, the molecular weight (X) per single double bond of (b4) is preferably 490 or less. The lower limit is preferably 160, more preferably 180, particularly preferably 185, and the upper limit is more preferably 480, particularly preferably 450, most preferably 400. If it is 490 or less, the effect of lowering the viscosity of the polymer polyol produced by using them is large.
Here, the molecular weight (X) per one double bond in (b4) is defined by the following formula.
X = 1000 / N
N: the degree of unsaturation of (b4) measured by the measurement method specified in JIS K-1557 (1970 edition)
[0020]
The solubility parameter SP value of (b4) is usually 9.5 to 13. The lower limit is preferably 9.8, more preferably 10.0. The upper limit is preferably 12.5, more preferably 12.2. When the SP value of (b1) is 9.5 or more, the viscosity of the polymer polyol produced by using them becomes low. Further, the hardness of a polyurethane foam obtained by using a polymer polyol having an SP of 13 or less increases.
The SP value is represented by the square root of the ratio between the cohesive energy density and the molecular volume as shown below.
[SP value] = (△ E / V)^1/2
Here, ΔE represents the cohesive energy density. V represents a molecular volume, and the value is represented by Robert EF. Calculations by Robert F. Fedors et al., For example, are described in Polymer Engineering and Science, Vol. 14, pp. 147-154.
[0021]
As a specific example of (b4), the following (b41) to (b45) are preferable because two or more of them are used because the viscosity of the polymer polyol decreases and the hardness of the obtained polyurethane foam increases. May be.
(B41): (poly) oxyalkylene (alkylene group having 2 to 8 carbon atoms) ether of terminally unsaturated alcohol (having 3 to 24 carbon atoms)
(B42): a compound represented by the following general formula [1]
(B43): a compound represented by the following general formula [2]
(B44): a compound represented by the following general formula [3]
(B45): a compound represented by the following general formula [4]
CH₂= CRCOO (AO)_kCOCH₂COCH₃[1]
CH₂= CRCOO (AO)_k[CO (CH₂)_sO]_m(AO)_nH [2]
CH₂= CRCO [O (CH₂)_sCO]_mO (AO)_nH [3]
CH₂= CRCOO (AO)_k[QO (AO)_p]_r(QO)_tH [4]
[Wherein R is a hydrogen atom or a methyl group; A is an alkylene group having 2 to 8 carbon atoms; Q is a residue obtained by removing two OH from dicarboxylic acid; k is a number average molecular weight not exceeding 490 An integer of 1 or more, n and p are 0 or an integer of 1 or more whose number average molecular weight does not exceed 490, s is an integer of 3 to 7, m and r are an integer of 1 or more whose number average molecular weight does not exceed 490, t Is 0 or 1]
Here, the number average molecular weight of "the number average molecular weight does not exceed 490" indicates the number average molecular weight of the compound.
[0022]
Examples of the terminal unsaturated alcohol having 3 to 24 carbon atoms in the above (b41) include allyl alcohol and 1-hexen-3-ol. The number of oxyalkylene units of (b41) is usually 1 to 9, preferably 1 to 5, and more preferably 1 to 3.
In the above general formulas [1] to [4], A is an alkylene group having 2 to 8 carbon atoms, and the AO unit is usually formed by addition of an alkylene oxide having 2 to 8 carbon atoms, and k, n and p Each corresponds to the number of moles of alkylene oxide added. In addition, the (poly) oxyalkylene unit having 2 to 8 carbon atoms of the alkylene group (b41) is usually formed by addition of an alkylene oxide having 2 to 8 carbon atoms.
Examples of the alkylene oxide include the same alkylene oxides as those exemplified as the alkylene oxide added to the active hydrogen-containing compound in the above-mentioned section of the polyol (a). Preferably, it is PO and / or EO.
k is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1. n is preferably 0 or 1 to 7, more preferably 0 or 1 to 5, and particularly preferably 0. p is preferably 0 or 1 to 6.
[0023]
Examples of Q include a residue obtained by removing two OH from a dicarboxylic acid. As the dicarboxylic acid, those having 4 to 10 carbon atoms are preferable, and specific examples include phthalic acid (including isophthalic acid and terephthalic acid), maleic acid, fumaric acid, and succinic acid. Preferred are phthalic acid and succinic acid.
[CO (CH₂) SO] and [O (CH₂) SCO] units are usually formed by the addition of lactones. s is preferably 4 to 6, and more preferably 5. m is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2.
R is preferably 1 to 5, more preferably 1 or 2, particularly preferably 1.
Among these (b41) to (b45), more preferred are (b41) and (b42), and particularly preferred is (b41).
[0024]
As specific examples of (b41) to (b45), for example, (b41) includes 1 to 5 mole addition products of PO and / or EO of allyl alcohol.
Examples of (b42) include acetoacetic esters of compounds obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid.
As (b43), a compound obtained by adding 1 to 5 moles of ε-caprolactone to a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid, and 1 mole to 1 mole of the compound And compounds to which ５5 mol of PO and / or EO are added.
Examples of (b44) include a compound in which 1 to 5 mol of ε-caprolactone is added to 1 mol of (meth) acrylic acid, and a compound in which 1 to 5 mol of PO and / or EO is further added to 1 mol of this compound. Is mentioned.
(B45) includes a monoester of a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid and an equimolar amount of succinic acid, and 1 mole of (meth) acrylic acid contains PO and / or Or a monoester of maleic acid or fumaric acid in an equimolar amount with a compound obtained by adding 1 to 5 moles of EO, and an equimolar amount of a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid And 1 to 5 moles of EO and / or PO further added to 1 mole of the monoester with phthalic acid, and a monoester of this compound with an equimolar amount of phthalic acid.
[0025]
Other ethylenically unsaturated compounds (b5) other than the above include (meth) acrylamide; vinyl group-containing carboxylic acids such as (meth) acrylic acid and derivatives thereof; aliphatic hydrocarbon monomers such as ethylene and propylene; Fluorine-containing vinyl monomers such as perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate; other nitrogen-containing vinyl monomers such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicon; cyclic such as norbornene, cyclopentadiene and norbornadiene Olefin compounds; and the like.
[0026]
Further, the dispersion stability of the polymer polyol can be further improved by using a bifunctional or higher polyfunctional monomer as at least a part (preferably 0.05 to 1% by mass) of (b). Examples of the polyfunctional monomer include divinylbenzene, ethylene di (meth) acrylate, polyalkylene oxide glycol di (meth) acrylate, pentaerythritol triallyl ether, and trimethylolpropane tri (meth) acrylate.
[0027]
As (b), those comprising (b1), (b2) and if necessary (b4) are preferred, and those comprising acrylonitrile and / or styrene and optionally (b4) are more preferred. The total amount of acrylonitrile and styrene in (b) is preferably at least 50% by mass. The lower limit is more preferably 60% by mass, particularly preferably 80% by mass, and the upper limit is preferably 98% by mass, more preferably 95% by mass.
[0028]
The radical polymerization for obtaining the base polymer polyol (A) can be carried out in the same manner as the polymerization in the conventional polymer polyol. For example, a method of polymerizing an ethylenically unsaturated compound (b) in the presence of a polymerization initiator in a polyol (a) containing a dispersant (D) (a method described in US Pat. No. 3,383,351) is known. No.
The polymerization can be carried out in a batch system or a continuous system, and can be carried out under normal pressure, under pressure or under reduced pressure. If necessary, a diluent (E), a chain transfer agent and the like can be used.
Hereinafter, each component used for radical polymerization will be described sequentially.
[0029]
The dispersant (D) is not particularly limited, and a usual dispersant or the like used in a polymer polyol can be used.
For example, (1) a macromer-type dispersant obtained by reacting a polyol such as an ethylenically unsaturated group-containing modified polyether polyol (for example, JP-A-08-333508) with an ethylenically unsaturated compound; Two or more polyol affinity segments having a solubility parameter difference of 1.0 or less as side chains, and a polymer affinity segment having a solubility parameter difference of 2.0 or less from a polymer derived from a vinyl monomer as a main chain. A graft-type dispersant in which a polyol and an oligomer such as a graft-type polymer (for example, JP-A-05-051134) are combined; and (3) methylene dihalide and / or ethylene dihalide Modified polyols having a high molecular weight by reacting with a halide (see, for example, JP-A-07-196749) (4) a vinyl oligomer having a weight-average molecular weight of 1,000 to 30,000, at least a part of which is soluble in a polyol, and the oligomer and the ethylenically unsaturated compound of the above (1) Oligomer-type dispersants such as a dispersant which uses a group-containing modified polyether polyol in combination (for example, JP-A-09-77968); and the like.
Of these, the types (1) and (4) are preferred. In each case, the number average molecular weight is preferably 1,000 to 10,000.
In addition, when these ordinary dispersants are used as (D), the amount used is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 0.1 to 10% by mass, based on the mass of (b). 8% by mass.
[0030]
As (D), a reactive dispersant (D1) described below can be used in addition to these ordinary dispersants, and it is particularly preferable.
The reactive dispersant (D1) binds a monofunctional active hydrogen compound (c) having at least one polymerizable unsaturated group to a substantially saturated polyol (a ') via a polyisocyanate (d). A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol. Here, “substantially saturated” means that the degree of unsaturation measured by a measurement method specified in JISK-1557 (1970 edition) is 0.2 meq / g or less (preferably 0.08 meq / g or less). means.
[0031]
As (a ') constituting the reactive dispersant (D1), the same ones as those exemplified as the above (a) can be used. (A ') and (a) may be the same or different.
The number of hydroxyl groups in one molecule of (a ′) is at least 2, preferably 2 to 8, more preferably 3 to 4, and the hydroxyl equivalent of (a ′) is preferably 1,000 to It is 3,000, more preferably 1,500 to 2,500.
[0032]
(C) used to obtain (D1) is a compound having one active hydrogen-containing group and at least one polymerizable unsaturated group. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, an imino group, a carboxyl group, and an SH group, and a hydroxyl group is particularly preferable.
The polymerizable unsaturated group of (c) is preferably a polymerizable double bond, and the number of polymerizable unsaturated groups in one molecule is preferably from 1 to 3, particularly preferably 1. That is, an unsaturated monohydroxy compound having one polymerizable double bond is preferable as (c).
Examples of the unsaturated monohydroxy compound include a monohydroxy-substituted unsaturated hydrocarbon, a monoester of an unsaturated monocarboxylic acid and a dihydric alcohol, a monoester of an unsaturated dihydric alcohol and a monocarboxylic acid, and an alkenyl side chain. Phenol having a group, unsaturated polyether monol, and the like.
[0033]
Examples of the monohydroxy-substituted unsaturated hydrocarbon include alkenols having 3 to 6 carbon atoms, such as (meth) allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, and 3-buten-1-ol; Alkynol, for example, propargyl alcohol and the like.
Examples of the monoester of an unsaturated monocarboxylic acid and a dihydric alcohol include, for example, an unsaturated monocarboxylic acid having 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; And monohydric alcohols having 2 to 12 carbon atoms, such as glycol, propylene glycol, and butylene glycol. Specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate. , 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and the like.
[0034]
Examples of the monoester of an unsaturated dihydric alcohol and a monocarboxylic acid include monoesters of an unsaturated dihydric alcohol having 3 to 8 carbon atoms and a monocarboxylic acid having 2 to 12 carbon atoms, such as acetic acid monoester of butenediol. Is mentioned.
Examples of the phenol having an alkenyl side chain group include a phenol having an alkenyl side chain group having 2 to 8 carbon atoms of an alkenyl group such as oxystyrene and hydroxy α-methylstyrene.
Examples of the unsaturated polyether monool include 1 to 50 moles of the above-mentioned monohydroxy-substituted unsaturated hydrocarbon or alkylene oxide (2 to 8 carbon atoms) of phenol having an alkenyl side chain group [for example, polyoxyethylene (polymerization degree 2 to 10) monoallyl ether].
[0035]
Examples of (c) other than the unsaturated monohydroxy compound include the following.
Examples of (c) having an amino group or an imino group include mono- and di- (meth) allylamine, aminoalkyl (2 to 4 carbon atoms) (meth) acrylate (such as aminoethyl (meth) acrylate), monoalkyl (carbon (Number 1 to 12) aminoalkyl (2 to 4 carbon atoms) (meth) acrylate [such as monomethylaminoethyl-methacrylate]; (c) having a carboxyl group includes the unsaturated monocarboxylic acid described above; )) Includes compounds corresponding to the unsaturated monohydroxy compounds (OH is replaced by SH).
Examples of (c) having two or more polymerizable double bonds include poly (meth) allyl ether of the above-mentioned trivalent, 4- to 8-valent or more polyhydric alcohol or polyester with the above unsaturated carboxylic acid. [For example, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin di (meth) acrylate, etc.].
[0036]
Among these compounds, preferred are alkenol having 3 to 6 carbon atoms, monoester of an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and a dihydric alcohol having 2 to 12 carbon atoms, and phenol having an alkenyl side chain group. And more preferably a monoester of (meth) acrylic acid with ethylene glycol, propylene glycol or butylene glycol; allyl alcohol; and hydroxy α-methylstyrene, and particularly preferably 2-hydroxyethyl (meth) acrylate.
The molecular weight of (c) is not particularly limited, but is preferably 1,000 or less, particularly preferably 500 or less.
[0037]
The polyisocyanate (d) is a compound having at least two isocyanate groups, and is an aromatic polyisocyanate, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, or a modified product of these polyisocyanates (urethane Group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group or oxazolidone group-containing modified product), and a mixture of two or more of these.
[0038]
Examples of the aromatic polyisocyanate include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the same applies to the following polyisocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, and crude products of these isocyanates And the like. Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4 ' -Diphenylmethane diisocyanate (MDI), crude MDI [condensation product of crude diaminodiphenylmethane formaldehyde and an aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine; Reaction mixture of｝ with phosgene: polyallyl polyisocyanate (PAPI), etc.], naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.
Examples of the aliphatic polyisocyanate include an aliphatic diisocyanate having 2 to 18 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.
[0039]
Examples of the alicyclic polyisocyanate include an alicyclic diisocyanate having 4 to 16 carbon atoms. Specific examples include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic isocyanates include araliphatic diisocyanates having 8 to 15 carbon atoms. Specific examples include xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate. Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
Of these, aromatic diisocyanates are preferred, and 2,4- and / or 2,6-TDI are more preferred.
[0040]
The nitrogen-containing bond of the reactive dispersant (D1) is generated by a reaction between an isocyanate group and an active hydrogen-containing group. When the active hydrogen-containing group is a hydroxyl group, a urethane bond is mainly generated and an amino group is formed. In some cases, mainly urea bonds are formed. An amide bond is formed in the case of a carboxyl group, and a thiourethane bond is formed in the case of an SH group. In addition to these groups, other bonds such as a burette bond and an allophanate bond may be formed.
This nitrogen-containing bond is formed by the reaction between the hydroxyl group of the substantially saturated polyol (a ') and the isocyanate group of the polyisocyanate (d), and the active hydrogen-containing group of the unsaturated monofunctional active hydrogen compound (c). Some are produced by the reaction of (d) with isocyanate groups.
[0041]
In light of the dispersion stability of the polymer polyol, the average value of the number of hydroxyl groups in one molecule of (D1) is usually 2 or more, preferably 2.5 to 10, and more preferably 3 to 7. The average value of the number of unsaturated groups in one molecule of (D1) is preferably 0.8 to 2, and more preferably 0.9 to 1.2.
In addition, from the viewpoint of dispersion stability of the polymer polyol, the hydroxyl equivalent of (D1) is preferably from 500 to 10,000, more preferably from 1,000 to 7000, and particularly preferably from 2,000 to 6,000.
Further, from the viewpoint of the dispersion stability and the ease of handling of the polymer polyol, the number average molecular weight of (D1) (by the terminal group quantification method) is preferably 5,000 to 40,000. The lower limit is more preferably 10,000, particularly preferably 15,500, and the upper limit is more preferably 30,000, particularly preferably 25,000.
The viscosity of (D1) is preferably 10,000 to 50,000 mPa · s / 25 ° C., and more preferably 15,000 to 35,000 mPa · s / 25 ° C. When the viscosity is within the above range, the dispersibility of the polymer is better, and the viscosity of the polymer polyol obtained by using (D1) is low, and the handling is easy.
[0042]
The method for producing the reactive dispersant (D1) using these raw materials is not particularly limited.
A preferred method is to add a polyisocyanate (d) to a mixture of an unsaturated monofunctional active hydrogen compound (c) and a substantially saturated polyol (a '), and react the mixture in the presence of a catalyst if necessary. , (C) and (d), if necessary, in the presence of a catalyst to produce an unsaturated compound having an isocyanate group, and reacting this with (a '). The latter method is the most preferred method because it is a method capable of obtaining a nitrogen-containing bond-containing unsaturated polyol with less generation of by-products such as a compound having no hydroxyl group.
Further, after reacting with (d) using the precursor instead of (c) or (a ′), the precursor portion may be modified to form (D1). [For example, an unsaturated monocarboxylic acid or an ester-forming derivative thereof is reacted after the reaction with an isocyanate to introduce an unsaturated group, and after the reaction with the isocyanate, jumping with an alkylene dihalide, a dicarboxylic acid, or the like to form (D1) Form〕
[0043]
Examples of the catalyst at the time of the above reaction include, for example, a commonly used urethane-forming catalyst, such as a tin-based catalyst (such as dibutyltin dilaurate and Starnas octoate), another metal catalyst (such as tetrabutyl titanate), and an amine-based catalyst ( Triethylenediamine and the like are used. Preferred among these is tetrabutyl titanate.
The amount of the catalyst is preferably 0.0001 to 5% by mass, more preferably 0.001 to 3% by mass, based on the mass of the reaction mixture.
[0044]
The reaction ratio of these three components is preferably the equivalent ratio of the active hydrogen-containing group of (c) and (a ′) to the isocyanate group of (d) based on the total amount used in the reaction, preferably (1.2 to 4). ): 1, more preferably (1.5-3): 1.
The amount of (c) used in the reaction with respect to 100 parts by mass of (a ') is preferably less than 2 parts by mass, and more preferably 0.5 to 1.8 parts by mass.
A mixture of (D1) and (a ') is formed by using a large excess of (a') which reacts with (d), and unreacted (a ') is not separated and polyol A method used as a part of (a) can also be adopted.
[0045]
The reactive dispersant (D1) obtained by the above method may be a single compound, but in many cases, is a mixture of various compounds such as a compound represented by the following general formula [5].
[0046]
Embedded image

[0047]
[Wherein, Z is a residue of (d) having a valency of h (where h is an integer of 2 or more); T is a residue of (c) (which has a polymerizable unsaturated group);₁Is q₁Residue of a trivalent polyol [(a ') or OH prepolymer from (a') and (d)], A₂Is q₂Of polyvalent polyol [(a ') or OH prepolymer from (a') and (d)]

T 'is H or an alkyl group having 1 to 12 carbon atoms; g is an integer of 1 or more; j is an integer of 1 or more; Where q₁−g ≧ 0 and h−j−1 ≧ 0. The total number of OH groups is 2 or more. ]
[0048]
That is, one (a ′) and one (c) are connected via one (d), and a plurality of (c) are each connected via one (d) to one ( a '), and a total of three or more (a') and (c) bonded via a plurality of (d). In addition, as other by-products, (a ′) a compound in which the bonds are bonded via (d) (a polyol containing a nitrogen-containing bond having no unsaturated group), and (c) a bond in which the bonds are bonded via (d). (A nitrogen-containing unsaturated compound having no hydroxyl group) may be formed, and may contain unreacted (a ') or (c).
This mixture can be used as a dispersant as it is, but those containing a small amount of a nitrogen-containing bond-containing polyol having no unsaturated group or a nitrogen-containing bond-containing unsaturated compound having no hydroxyl group are preferable, and these impurities which can be further removed are preferable. Can also be applied after removal.
Further, since the unsaturated group in (D1) is located at or near the terminal of the molecular chain of the polyol, it is easy to copolymerize with the monomer.
[0049]
(D1) is an average value of the ratio of the number of unsaturated groups to the nitrogen-containing bond derived from the NCO group of (d) in one molecule determined by the following formula (4): K is 0.1 to 0.4; It is preferable that (a '), (c) and (d) are reacted at such a ratio.

The value of K is more preferably from 0.1 to 0.3, and particularly preferably from 0.2 to 0.3. When the value of K is within the above range, the dispersion stability of the polymer polyol becomes particularly good.
[0050]
The constituent ratio of the polyol (a) and the reactive dispersant (D1) at the time of preparing the polymer polyol is preferably 0.5 to 50 parts by mass of (D1) based on 100 parts by mass of (a). The lower limit is more preferably 0.8 parts by mass, particularly preferably 1 part by mass, and the upper limit is more preferably 15 parts by mass, particularly preferably 10 parts by mass. When (D1) is 50 parts by mass or less, the viscosity of the polymer polyol does not increase, and when it is 0.5 parts by mass or more, the dispersibility is good.
[0051]
The reactive dispersant (D1) has extremely good dispersion stability of the polymer polyol obtained using the reactive dispersant (D1). Particularly, it is suitably used for the production of a high-concentration (for example, polymer content of 40 to 75% by mass) polymer polyol using (b4) as the ethylenically unsaturated compound (b) to obtain a polymer polyol having a lower viscosity. Can be.
[0052]
Next, as the polymerization initiator used for the polymerization of (b), those which generate free radicals and initiate polymerization can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′- Azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-alkonitrile), 2,2′-azobis (2 4,4-trimethylpentane), dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis [2- (hydroxymethyl) propionitrile] and 1,1′-azobis (1 Azo compounds such as -acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, and benzene Peroxide, organic peroxides such as lauroyl peroxide and peracetic acid; such as persulfates and perborates inorganic peroxides, and the like. In addition, these can use 2 or more types together.
[0053]
The amount of the polymerization initiator to be used is generally 0.05 to 20% by mass, preferably 0.1 to 15% by mass, particularly preferably 0.2 to 10% by mass, based on the mass of (b). When the amount of the polymerization initiator used is in the range of 0.05 to 20% by mass, the polymerization rate of (b) in the polymer polyol becomes sufficiently high, and the molecular weight also becomes large. It is excellent in that compression hardness can be obtained.
[0054]
Examples of the diluent (E) used for radical polymerization include aromatic hydrocarbon solvents such as toluene and xylene; saturated aliphatic hydrocarbon solvents having 5 to 15 carbon atoms such as hexane and heptane; hexene, nonene and the like. An unsaturated aliphatic hydrocarbon solvent having 5 to 15 carbon atoms;
The amount of the diluent used is preferably 50% by mass or less, more preferably 40% by mass or less, based on the amount of (b) used. (E) used is preferably removed by vacuum stripping or the like after the polymerization reaction.
[0055]
Further, (E) can be added to the polymer polyol obtained by the production method of the present invention, if necessary, to further lower the viscosity of the polymer polyol. Examples of (E) to be contained in the polymer polyol include the above-mentioned unsaturated aliphatic hydrocarbon-based solvents; aromatic hydrocarbon-based solvents; and low-viscosity (100 mPa · s / 25 ° C. or less) flame retardants such as tris (chloroethyl). ) Phosphate, tris (chloropropyl) phosphate; and the like.
The content of (E) in the base polymer polyol (A) is preferably 2% by mass or less, more preferably 1% by mass or less.
[0056]
Examples of the chain transfer agent include alkyl mercaptans such as dodecyl mercaptan and mercaptoethanol; and the like.
The amount of the chain transfer agent to be used is generally 2% by mass or less, preferably 0.1% by mass or less, based on the amount of (b) used.
[0057]
The compound (B) having addition reactivity, which reacts with the unreacted (b) in (A), may be any of an organic compound and an inorganic compound, a compound which undergoes an electrophilic addition reaction (B1), a Michael type addition A reaction (B2) and a hydrogenation reaction (B3) may be mentioned, and two or more kinds may be used in combination.
Examples of (B1) include Lewis acids (such as boron fluoride, aluminum chloride, silver chloride, iron (III) nitrate), bromine, hypochlorous acid, hydrochloric acid, and sulfuric acid.
[0058]
(B2) is preferably a compound containing a sulfur atom, and examples thereof include a sulfite (B21), a hyposulfite (B22), and a thiol (B23).
Examples of (B21) include alkali metal salts (eg, sodium sulfite, potassium sulfite) and alkaline earth metal salts (eg, calcium sulfite, magnesium sulfite). Examples of (B22) include alkali metal salts (such as sodium hyposulfite and potassium hyposulfite) and alkaline earth metal salts (such as calcium hyposulfite and magnesium hyposulfite).
Examples of (B23) include alkylmercaptan and alkylenedithioglycol (C1-20) (B231), and polyalkyleneglycol (alkylene group having 2 to 8 carbon atoms) in which one or both hydroxyl groups are thiol. And a compound substituted with a group [total carbon number of 4 to 20] (B232). Examples of (B231) include ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, ethylene dithioglycol, propylene dithioglycol, butylene dithio glycol, octylene dithio glycol, and dodecylene dithio glycol. Preferred among (B231) are those having a boiling point of 40 ° C to 150 ° C from the viewpoint of reactivity with the ethylenically unsaturated group, for example, butyl mercaptan. (B232) includes, for example, 1,8-dimercapto-3,6-dioxaoctane (hereinafter abbreviated as DMDO).
[0059]
Examples of (B3) include hydrogen, and examples of the catalyst used in the hydrogenation reaction include nickel, platinum, and palladium.
Among these (B), preferred are (B21), (B22) and (B23), more preferred are sodium sulfite and DMDO, and particularly preferred is sodium sulfite.
[0060]
The amount of (B) used is preferably 1 to 10 equivalents to 1 equivalent of the ethylenically unsaturated group. The lower limit is more preferably 2 equivalents, and the upper limit is more preferably 8 equivalents, particularly preferably 6 equivalents. When the amount of (B) is 1 equivalent or more, the ethylenically unsaturated group does not remain, and when it is 10 equivalents or less, unreacted (B) does not affect the performance of the polyurethane resin using the polymer polyol.
[0061]
The production method of the present invention can be carried out in the presence of an alcohol (C), if necessary. By containing (C), (b) and (B) are easily mixed, and the reactivity is improved.
As (C), a low-molecular alcohol having 20 or less carbon atoms is preferable. For example, an alcohol having 1 to 8 carbon atoms (C1) and a (poly) oxyalkylene ether of an alcohol having 1 to 8 carbon atoms (the carbon atom of the alkylene group) The number is 2 to 8) (C2), and two or more kinds may be used in combination.
(C1) includes, for example, methanol, ethanol, n-propanol, isopropanol, and n-butanol. (C2) is usually obtained by adding an alkylene oxide having 2 to 8 carbon atoms to (C1), and examples of the alkylene oxide include EO, PO, BO, and SO.
Preferred of these (C) is (C1), more preferably methanol, ethanol and isopropanol, particularly preferably methanol.
[0062]
The amount of (C) used is preferably 100 parts by mass or less based on 100 parts by mass of (A). The lower limit is preferably 1 part by mass, more preferably 2 parts by mass, and the upper limit is more preferably 80 parts by mass, particularly preferably 50 parts by mass. When the amount of (C) is 100 parts by mass or less, removal of (C) after completion of the reaction becomes easy.
[0063]
The production method of the present invention can be carried out in the presence of a surfactant (F), if necessary. By containing (F), (b) and (B) are easily mixed and the reactivity is improved.
There is no particular limitation on the type of (F), and anionic surfactants (carboxylates having 8 to 22 carbon atoms, sulfonates, phosphate esters, etc.), cationic surfactants (quaternary ammonium salt type surfactants) , Amine salt type surfactants, etc.), nonionic surfactants (EO adducts of higher alcohols, EO adducts of polyhydric alcohol esters, polyhydric alcohol fatty acid esters, etc.), and amphoteric surfactants (betaine type surfactants) And the like can be used.
The addition amount of (F) is preferably 20 parts by mass or less based on 100 parts by mass of (A).
[0064]
The method of reacting unreacted (b) and (B) in (A) in the presence of (C) or the like, if necessary, is not particularly limited as long as the addition reaction occurs. A method of adding (B) and, if necessary, (C) to (A) containing b), heating to 50 to 150 ° C. (preferably 60 to 130 ° C.), and stirring and mixing.
When (C) is used, it is preferable that (C) be distilled off under reduced pressure after the reaction between (b) and (B). The conditions under which the (C) is distilled off under reduced pressure are not particularly limited as long as the conditions are effective for distilling it off. For example, a reduced pressure of 1 to 100 (preferably 2 to 50) torr at a temperature of 110 to 150 ° C. Below, a method of stripping for 1 to 10 hours may be mentioned.
[0065]
According to the method of the present invention, a polymer polyol having a low content of (b) can be obtained. However, when (b) consists of styrene and / or acrylonitrile, the content of styrene and acrylonitrile in the obtained polymer polyol ( Gas chromatographic method) preferably has an acrylonitrile content of 50 ppm or less and a styrene content of 300 ppm or less from the viewpoint of a working environment when molding a polyurethane foam using a polymer polyol. The acrylonitrile content is more preferably 30 ppm or less, particularly preferably 5 ppm or less, and the styrene content is more preferably 250 ppm or less, particularly preferably 100 ppm or less. The details of the gas chromatography method are based on the method described in Examples below.
[0066]
The polymer polyol obtained by the method of the present invention is obtained by reacting a polyol component and a polyisocyanate component in the presence or absence of a foaming agent, and at least a part of the polyol component when producing a foamed or non-foamed polyurethane resin. Can be suitably used.
[0067]
As the polyol component, in addition to the polymer polyol (I) obtained by the production method of the present invention, other known active hydrogen atom-containing compounds can be used in combination, if necessary. As other active hydrogen atom-containing compounds, other high molecular polyols (T) commonly used in the production of polyurethane, low molecular weight active hydrogen atom-containing compounds (U), and WO 98/44016 are described. The active hydrogen compound having a terminal radical polymerizable functional group (including monool) can be used.
[0068]
As the other polymer polyol (T), for example, (a1) and (a2) exemplified as the above-mentioned polyol (a), polymer polyols obtained by methods other than the method of the present invention, and mixtures thereof can be used. .
[0069]
These polyols (T) generally have 2 to 8, preferably 3 to 8 hydroxyl groups, and preferably have a hydroxyl equivalent of 200 to 4000, more preferably 400 to 3000.
Preferred as (T) is (a1).
[0070]
(U) has a molecular weight of 500 or less (preferably 60) having at least 2 (preferably 2 to 3, particularly preferably 2) active hydrogen atoms (hydroxyl group, amino group, mercapto group and the like, preferably hydroxyl group). To 400), for example, low molecular polyols and amino alcohols. The equivalent per active hydrogen atom of (U) is preferably less than 200, more preferably 30 to 180. Examples of the low-molecular polyol include the above-mentioned polyhydric alcohols; low-molecular-weight (for example, 200 to 400) polyhydric alcohol alkylene oxide adducts (polyethylene glycol, polypropylene glycol, and the like); low-molecular diols having a ring structure, for example, bisphenol A And a propylene oxide adduct of
Amino alcohols include mono- or dialkanolamines (such as monoethanolamine, diethanolamine, monopropanolamine).
Preferred among these are low molecular weight polyols, especially diols, specifically ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and mixtures of two or more of these. is there.
[0071]
The amount of the polymer polyol (I) in the polyol component is preferably at least 5% by mass, more preferably at least 10% by mass, particularly preferably at least 20% by mass. When the content is 5% by mass or more, a sufficient compression hardness of the polyurethane foam can be obtained.
The content of the polymer in the polyol component is preferably 5 to 75% by mass, and more preferably 7 to 55% by mass. Within the above range, both foam hardness and liquid flowability are good.
[0072]
Further, the content of (T) is preferably 95% by mass or less, more preferably 80% by mass or less. When (T) is 95% by mass or less, the hardness of the polyurethane tends to be high. The content of (U) and the active hydrogen compound having a terminal radical polymerizable functional group is preferably 30% by mass or less, more preferably 10% by mass or less.
When (U) is 30% by mass or less, the exothermic temperature during the reaction does not become too high, and there is no possibility that scorch is generated.
[0073]
As the organic polyisocyanate used as a polyisocyanate component when producing a polyurethane resin, known organic polyisocyanates conventionally used for producing a polyurethane resin can be used.
Examples of such a polyisocyanate include those exemplified above in (d).
[0074]
The isocyanate index [equivalent ratio of (NCO group / active hydrogen atom-containing group) × 100] in the production of the polyurethane resin is preferably 80 to 140, more preferably 85 to 120, and particularly preferably 95 to 115. The polyisocyanurate group can also be introduced into the polyurethane by setting the isocyanate index significantly higher than the above range (for example, 300 to 1000).
[0075]
In producing the polyurethane resin, a catalyst generally used for a polyurethane reaction may be used to accelerate the reaction. For example, amine catalysts [tertiary amines such as triethyleneamine and N-ethylmorpholine; 1,8-diaza-bicyclo [5.4.0] undecene-7 (manufactured by San-Apro Co., registered trademark: DBU); etc.] And tin-based catalysts (such as stannous octylate and dibutyltin dilaurate), other metal catalysts (such as lead octylate), and isocyanuration catalysts described in US Pat. No. 4,299,924. Among them, amine catalysts and / or tin catalysts are preferred.
When a catalyst is used, the amount used is preferably 0.001 to 5% by mass, based on the mass of the reaction mixture.
[0076]
In the method for producing a polyurethane resin of the present invention, a foaming agent usually used for a polyurethane reaction may be used, if necessary, to obtain a polyurethane foam (preferably having an expansion ratio of 5 to 100 times). Examples of the foaming agent include water, hydrogen atom-containing halogenated hydrocarbons, and low-boiling hydrocarbons.
When water is used, the amount used is preferably 0.5 to 10 parts by mass, more preferably 0.8 to 8 parts by mass, per 100 parts by mass of the polyol component. When the amount is 0.5 parts by mass or more, the time for obtaining a molded article is shortened due to the large amount of reaction heat generated, and when the amount is 10 parts by mass or less, a good foam is obtained.
[0077]
Specific examples of the hydrogen atom-containing halogenated hydrocarbon-based blowing agent include those of the HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123, HCFC-141b, HCFC-22 and HCFC-142b); and the HFC (hydrofluorocarbon) type (Eg, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mfc).
Among these, preferred are HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, and a mixture of two or more thereof.
The amount of the hydrogen atom-containing halogenated hydrocarbon used is preferably 0 to 50 parts by mass, more preferably 0 to 45 parts by mass, per 100 parts by mass of the polyol component.
[0078]
The low-boiling hydrocarbon is generally a hydrocarbon having a boiling point of -5 to 50C, and specific examples thereof include butane, pentane, cyclopentane, and a mixture thereof.
When the low boiling point hydrocarbon is used, the amount used is preferably 0 to 40 parts by mass, more preferably 0 to 30 parts by mass, per 100 parts by mass of the polyol component.
[0079]
In the production method of the present invention, if necessary, commonly used additives such as a foam stabilizer can also be used.
As the foam stabilizer, any one used in the production of ordinary polyurethane foams can be used. Examples thereof include dimethylsiloxane-based foam stabilizers [for example, “SRX-253” manufactured by Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd. "F-122" manufactured by Kogyo Co., Ltd .; polyether-modified dimethylsiloxane-based foam stabilizer [for example, "L-5309", "L-3601", "SZ-1311" manufactured by Nippon Unicar Co., Ltd .; Silicone foam stabilizers such as "F-242T" manufactured by Shin-Etsu Chemical Co., Ltd.].
The use amount of the foam stabilizer is preferably 10 parts by mass or less, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the polyol component.
[0080]
In the process of the present invention, antioxidants such as antioxidants (hindered phenols, hindered amines, etc.) and ultraviolet absorbers (triazoles, benzophenones, etc.); inorganic salts (calcium carbonate, barium sulfate, etc.) ), Inorganic fillers such as inorganic fibers (glass fibers, carbon fibers, etc.) and whiskers (potassium titanate whiskers, etc.); organic fillers such as synthetic micro fibers, hollow microspheres made of thermoplastic or thermosetting resin. Flame retardants (phosphate esters, halogenated phosphate esters, etc.); plasticizers (phthalate esters, adipate esters, etc.); adhesives (modified polycaprolactone polyol, etc.); coloring agents (dyes, pigments, carbon black) Ordinary additives and auxiliaries, such as antibacterial agents and antifungal agents, can be used as necessary. Kill.
[0081]
With respect to the use amount of these additives with respect to 100 parts by mass of the polyol component, the amount of the antioxidant is preferably 1 part by mass or less, more preferably 0.01 to 0.5 part by mass. The amount of the inorganic filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. The amount of the organic filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. The amount of the flame retardant is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass. The amount of the plasticizer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The above-mentioned additives other than these are preferably 1 part by mass or less.
[0082]
The production of the polyurethane resin can be performed by an ordinary known method, for example, a one-shot method, a semi-prepolymer method, a prepolymer method and the like.
For the production of the polyurethane resin, a commonly used known production apparatus can be used. When a solvent is not used, for example, an apparatus such as a kneader or an extruder can be used. In addition, various non-foamed or foamed polyurethane resins can be produced in a closed mold or an open mold. The pack ratio [(density at the time of mold foaming / density at the time of free foaming) × 100] in the case of producing a foamed polyurethane resin using a closed mold is preferably 110 to 200%.
The production of a polyurethane resin is usually performed by mixing and reacting raw materials using a low-pressure or high-pressure mechanical device. Furthermore, before or after mixing of raw materials (particularly before mixing of raw materials), dissolved air in the raw materials or mixed during mixing. The polyurethane resin can be produced by removing a gas such as air by a vacuum method.
The production method of the present invention is particularly useful for producing a flexible mold foam and a slab foam. Further, the present invention can be applied to molding by RIM (reaction injection molding).
[0083]
The polyurethane resin produced by using the polymer polyol obtained by the production method of the present invention has little discoloration with time, and is used, for example, as a polyurethane foam for interior fittings of automobile interior parts and furniture. It is also used as a material for sealants and synthetic leather.
[0084]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the following, parts and% ratio indicate parts by mass and% by mass, respectively.
[0085]
The compositions, symbols, and the like of the raw materials used in Production Examples, Examples, and Comparative Examples are as follows.
(1) Polyol
Polyol a1: a polyol having a number average molecular weight of 3,000 and a hydroxyl equivalent of 1,000 obtained by adding 46 mol of PO on average to glycerin and then 6 mol of EO on average.
Polyol a2: a polyol having a number average molecular weight of 7000 and a hydroxyl equivalent of 1750 obtained by adding 104 mol of PO on average to pentaerythritol and then adding 19 mol of EO on average.
(2) ethylenically unsaturated compound
ACN: acrylonitrile
St: Styrene
(3) polymerization initiator
AIBN: 2,2'-azobisisobutyronitrile
(4) Monofunctional active hydrogen compound having a polymerizable unsaturated group
HEMA: 2-hydroxyethyl methacrylate
(5) Catalyst
TBT: Tetrabutyl titanate [manufactured by Nakarai Tesque Co., Ltd.]
(6) Polyisocyanate
TDI: Coronate T-80 [manufactured by Nippon Polyurethane Co., Ltd.]
[0086]
The content of the ethylenically unsaturated compound in the polymer polyol was measured as follows.
<Acrylonitrile and styrene content measurement method>
Gas chromatograph II: GC-14B (manufactured by Shimadzu Corporation)
Column I: Inner diameter 4mmφ, length 1.6m, glass
Column packing material: polyethylene glycol 20M [manufactured by Shinwa Kako Co., Ltd.] 20% retention
Internal standard substance I: Toluene (for spectrum) [manufactured by Nacalai Tesque, Inc.]
Diluent solvent: dipropylene glycol monomethyl ether first class [manufactured by Wako Pure Chemical Industries, Ltd.] (50% solution)
Injection temperature: 200 ° C
Column initial temperature: 110 ° C
Heating rate: 5 ° C./min.
Column final temperature: 200 ° C
Sample injection volume: 1 μl
[0087]
<Production Example 1> Production of reactive dispersant (D1)
28 parts of TDI and 0.01 parts of TBT were placed in a four-necked flask equipped with a temperature controller, a vacuum stirring blade, and a dropping funnel, cooled to 30 ° C., and then 9 parts of HEMA was added dropwise over 2 hours. Meanwhile, the reaction temperature was maintained at 40 to 50 ° C. The reaction solution was placed in 963 parts of polyol a2 previously placed in a four-necked flask equipped with a temperature controller, a stirring blade, and a dropping funnel, and stirred at a reaction temperature of 80 to 90 ° C for 4 hours. After confirming that there was no unreacted isocyanate group in the infrared absorption spectrum, a reactive dispersant (D1) was obtained.
The hydroxyl value of (D1) was 20, the viscosity was 20,000 mPa · s / 25 ° C., and the ratio of the number of unsaturated groups / the number of nitrogen-containing bonds was 0.22.
[0088]
<Production Example 2> Production of base polymer polyol
To a four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth condenser, a nitrogen inlet and an outlet, 30 parts of a1, 30 parts of xylene and 1 part of D1, were charged. After purging with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the polymerization was completed). Next, a raw material in which ACN: 16 parts, St: 37 parts, a1: 13 parts was previously mixed, and a raw material in which a1: 8 parts and AIBN: 0.5 part were previously mixed were respectively simultaneously and simultaneously dripped using a dropping pump. The solution was continuously dropped over 3 hours, and polymerized at 130 ° C. At the same temperature, unreacted monomer and xylene were stripped under reduced pressure at 20 to 30 torr for 2 hours to obtain a base polymer polyol having a polymer particle content of 50% and a viscosity of 9600 mPa · s (25 ° C.).
The acrylonitrile content of the obtained base polymer polyol was 300 ppm, and the styrene content was 1000 ppm, as measured by gas chromatography.
[0089]
Example 1
The base polymer polyol obtained in Production Example 2 was placed in a four-necked flask equipped with a temperature controller, a vacuum stirring blade, a Dimroth condenser, a decompression device, a nitrogen inlet and an outlet, and the temperature was raised to 60 ° C. While stirring, 4.6 equivalents of a saturated sodium sulfite aqueous solution was added to 1 equivalent of the ethylenically unsaturated compound, 20 parts of methanol was added to 100 parts of the base polymer polyol, and the temperature was raised to 120 ° C., and then 2 hours. The mixture was heated and stirred. After completion of the reaction, methanol and water were removed at a reduced pressure of 30 torr and a temperature of 130 ° C. for 2 hours to obtain a polymer polyol.
The acrylonitrile content and the styrene content in the obtained polymer polyol measured by gas chromatography were 1 ppm and 250 ppm, respectively.
[0090]
Example 2
A heating and depressurizing operation was performed in the same manner as in Example 1 except that the saturated aqueous solution of sodium sulfite in Example 1 was changed to DMDO and methanol was not added, to obtain a polymer polyol.
The acrylonitrile content and the styrene content in the obtained polymer polyol measured by gas chromatography were 1 ppm and 93 ppm, respectively.
[0091]
Comparative Example 1
A heating and depressurizing operation was performed in the same manner as in Example 1 except that the aqueous saturated sodium sulfite solution of Example 1 and methanol were not used, to obtain a polymer polyol.
The acrylonitrile content and the styrene content in the obtained polymer polyol measured by gas chromatography were 58 ppm and 760 ppm, respectively.
[0092]
Comparative Example 2
The base polymer polyol obtained in Production Example 2 was placed in a four-necked flask equipped with a temperature controller, a vacuum stirring blade, a Dimroth condenser, a pressure reducing device, a nitrogen inlet and an outlet, and the temperature was raised to 130 ° C. After stirring, AIBN was added in an amount of 0.0025 equivalent to 1 equivalent of the ethylenically unsaturated compound, and then heated and stirred at the same temperature for 2 hours to obtain a polymer polyol.
The acrylonitrile content in the obtained polymer polyol was 280 ppm and the styrene content was 900 ppm, as measured by gas chromatography.
[0093]
Comparative Example 3
Except for adding 4.6 equivalents of AIBN of Comparative Example 2 to 1 equivalent of the ethylenically unsaturated compound, the same heating and depressurizing operation was performed as in Comparative Example 2 to obtain a polymer polyol.
The acrylonitrile content in the obtained polymer polyol was 250 ppm and the styrene content was 720 ppm as measured by gas chromatography.
[0094]
From the above results, in Examples 1 and 2 using the compound (B) having addition reactivity to the ethylenically unsaturated group, the acrylonitrile and styrene in the obtained polymer polyol were compared with the comparative example. It can be seen that the content is greatly reduced.
[0095]
【The invention's effect】
According to the method for producing a polymer polyol of the present invention, the concentration of the unreacted ethylenically unsaturated compound in the obtained polymer polyol is greatly reduced. Therefore, the odor of the polymer polyol can be significantly reduced, and the working environment at the time of producing a polyurethane resin using the polymer polyol can be improved. In addition, coloring of the obtained polyurethane foam over time can be prevented.

Claims (5)

Unreacted (b) in a base polymer polyol (A) obtained by polymerizing an ethylenically unsaturated compound (b) in a polyol (a), and an electrophilic addition reaction, a Michael type addition reaction, and hydrogenation A method for producing a polymer polyol, which comprises reacting a compound (B) having addition reactivity selected from the reaction with an alcohol (C) if necessary. The method for producing a polymer polyol according to claim 1, wherein (B) is at least one selected from sulfites, hyposulfites, and thiols. The polymer according to claim 1 or 2, wherein (C) is an alcohol having 1 to 8 carbon atoms and / or a polyoxyalkylene ether of an alcohol having 1 to 8 carbon atoms (the alkylene group has 2 to 8 carbon atoms). A method for producing a polyol. The method for producing a polymer polyol according to any one of claims 1 to 3, wherein (b) comprises styrene and / or acrylonitrile, and the obtained polymer polyol has a styrene content of 300 ppm or less and an acrylonitrile content of 50 ppm or less. A method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component and a polyisocyanate component in the presence or absence of a foaming agent, wherein the production according to any one of claims 1 to 4 as at least a part of the polyol component. PROCESS FOR PRODUCING POLYURETHANE RESIN, USING POLYMER POLYOL OBTAINED BY PROCESS