JP3933790B2 - Polyoxyalkylene polyol and polymer-dispersed polyol - Google Patents

Description

〔化学式（１）中、ａ、ｂ、ｃおよびｄは、それぞれ０〜３の正の整数であるが、ａ、ｂ、ｃおよびｄの全てが同時に０ではない。Ｒは同種または異種の炭素数１〜１０個の炭化水素基であり、同一窒素原子上の２個のＲが互いに結合して環構造を形成する場合もある。ｒは１〜３の整数であってホスファゼニウムカチオンの数を表し、Ｔ^r-は価数ｒの無機アニオンを表す〕、または、化学式（２）〔化２〕
【００３２】
【化２】

〔化学式（２）中、ａ、ｂ、ｃおよびｄは、それぞれ０〜３の正の整数であるが、ａ、ｂ、ｃおよびｄの全てが同時に０ではない。Ｒは同種または異種の炭素数１〜１０個の炭化水素基であり、同一窒素原子上の２個のＲが互いに結合して環構造を形成する場合もある。Ｑ^-はヒドロキシアニオン、アルコキシアニオン、アリールオキシアニオンまたはカルボキシアニオンを表す〕で表されるものを用いる。
【００３３】
本発明における化学式（１）及び化学式（２）で表されるホスファゼニウムカチオン中のａ、ｂ、ｃおよびｄは、それぞれ０〜３の正の整数である。ただし、全てが同時に０ではない。好ましくは０〜２の整数である。より好ましくはａ、ｂ、ｃおよびｄの順序に関わらず、（２，１，１，１）、（１，１，１，１）、（０，１，１，１）、（０，０，１，１）または（０，０，０，１）の組み合わせ中の数である。さらに好ましくは、（１，１，１，１）、（０，１，１，１）、（０，０，１，１）または（０，０，０，１）の組み合わせ中の数である。
【００３４】
本発明における化学式（１）及び化学式（２）で表される塩のホスファゼニウムカチオン中のＲは同種または異種の、炭素数１〜１０個の炭化水素基であり、具体的には、このＲは、例えばメチル、エチル、ｎ−プロピル、イソプロピル、アリル、ｎ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、２−ブテニル、１−ペンチル、２−ペンチル、３−ペンチル、２−メチル−１−ブチル、イソペンチル、ｔｅｒｔ−ペンチル、３−メチル−２−ブチル、ネオペンチル、ｎ−ヘキシル、４−メチル−２−ペンチル、シクロペンチル、シクロヘキシル、１−ヘプチル、３−ヘプチル、１−オクチル、２−オクチル、２−エチル−１−ヘキシル、１，１−ジメチル−３，３−ジメチルブチル（ｔｅｒｔ−オクチル）、ノニル、デシル、フェニル、４−トルイル、ベンジル、１−フェニルエチルまたは２−フェニルエチル等の脂肪族または芳香族の炭化水素基から選ばれる。
これらのうち、メチル、エチル、ｎ−プロピル、イソプロピル、ｔｅｒｔ−ブチル、ｔｅｒｔ−ペンチル、ｔｅｒｔ−オクチル等の炭素数１〜１０個の脂肪族炭化水素基が好ましく、メチル基またはエチル基がより好ましい。
【００３５】
また、ホスファゼニウムカチオン中の同一窒素原子上の２個のＲが結合して環構造を形成する場合の該窒素原子上の２価の炭化水素基は、４〜６個の炭素原子からなる主鎖を有する２価の炭化水素基であり（環は窒素原子を含んだ５〜７員環となる）、好ましくは、例えば、テトラメチレン、ペンタメチレンまたはヘキサメチレン等であり、また、それらの主鎖にメチルまたはエチル等のアルキル基が置換したものである。より好ましくは、テトラメチレンまたはペンタメチレン基である。ホスファゼニウムカチオン中の、可能な全ての窒素原子についてこのような環構造をとっていても構わず、一部であってもよい。
【００３６】
本発明における化学式（１）中のＴ^r-は価数ｒの無機アニオンを表す。そして、ｒは１〜３の整数である。このような無機アニオンとしては、例えば、ホウ酸、テトラフルオロ酸、シアン化水素酸、チオシアン酸、フッ化水素酸、塩酸またはシュウ化水素酸などのハロゲン化水素酸、硝酸、硫酸、リン酸、亜リン酸、ヘキサフルオロリン酸、炭酸、ヘキサフルオロアンチモン酸、ヘキサフルオロタリウム酸、および過塩素酸などの無機アニオンが挙げられる。また、無機アニオンとしてＨＳＯ₄ ^-、ＨＣＯ₃ ^-もある。
これらの無機アニオンはイオン交換反応により互いに交換することができる。これらの無機アニオンのうち、ホウ酸、テトラフルオロホウ酸、ハロゲン化水素酸、リン酸、ヘキサフルオロリン酸および過塩素酸等の無機酸のアニオンが好ましく、塩素アニオンがより好ましい。
【００３７】
化学式（１）のホスファゼニウム化合物を触媒として使用する場合には、活性水素化合物のアルカリ金属もしくはアルカリ土類金属の塩を予め調製することが好ましい。該化合物の調製方法は従来公知の方法でよい。化学式（１）とともに共存させる活性水素化合物のアルカリ金属もしくはアルカリ土類金属の塩とは、活性水素化合物の活性水素が水素イオンとして解離してアルカリ金属もしくはアルカリ土類金属イオンと置き換わった形の塩である。
【００３８】
そのような塩を与える活性水素化合物としては、アルコール類、フェノール化合物、ポリアミン、アルカノールアミンなどがある。例えば、水、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−プロパンジオール、１，４−シクロヘキサンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジオール等の２価アルコール類、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアルカノールアミン類、グリセリン、ジグリセリン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ポリグリセロール等の多価アルコール類、グルコース、ソルビトール、デキストロース、フラクトース、蔗糖、メチルグルコシド、ヒドロキシエチルグルコキシド等の糖類またはその誘導体、エチレンジアミン、ジ（２−アミノエチル）アミン、ヘキサメチレンジアミン等の脂肪酸アミン類、トルイレンジアミン、ジフェニルメタンジアミン等の芳香族アミン類、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ノボラック、レゾール、レゾルシン、ハイドロキノン、マンニッヒ化合物等のフェノール化合物等が挙げられる。これらの活性水素化合物は２種以上併用して使用することもできる。さらに、これらの活性水素化合物に従来公知の方法で活性水素基１当量に対して、６モル以下のエポキサイド化合物を付加重合して得られる化合物も使用できる。
【００３９】
通常、これらの活性水素化合物からそれらのアルカリ金属塩、またはアルカリ土類金属塩を得るには、該活性水素化合物と、アルカリ金属類、アルカリ土類金属類、塩基性アルカリ金属、またはアルカリ土類金属化合物とを反応させる方法が用いられる。
【００４０】
化学式（１）で表されるホスファゼニウムカチオンと無機アニオンとの塩、及び、活性水素化合物のアルカリ金属塩またはアルカリ土類金属塩の存在下に、エポキサイド化合物を付加重合させる。この際、アルカリ金属のカチオンまたはアルカリ土類金属のカチオンと無機アニオンとの塩が副生するが、この副生塩が重合反応を阻害する場合は、重合反応に先立ちこれを濾過等の方法で除去しておくこともできる。また、化学式（１）で表される塩と活性水素化合物のアルカリ金属塩またはアルカリ土類金属塩から導かれれる活性水素化合物のホスファゼニウム塩を予め単離し、これの存在下にエポキサイド化合物を重合させることもできる。
【００４１】
本発明のポリオキシアルキレンポリオールの他の製造方法は、化学式（２）で表されるホスファゼニウム化合物と活性水素化合物の存在下、エポキサイド化合物を付加重合する方法である。化学式（２）で表されるホスファゼニウム化合物中のＱ^-は、ヒドロキシアニオン、アルコキシアニオン、アリールオキシアニオンおよびカルボキシアニオンよりなる群から選ばれるアニオンである。
【００４２】
これらのＱ^-の内、好ましくは、ヒドロキシアニオンであり、例えば、メタノール、エタノール、ｎ−プロパノール、イソプロパノール等の脂肪族アルコール類から導かれるアルコキシアニオンである。例えば、フェノール、クレゾール等の芳香族ヒドロキシ化合物から導かれるアリールオキシアニオンである。例えば、ギ酸、酢酸、プロピオン酸等から導かれるカルボキシアニオンである。
【００４３】
これらのうち、より好ましくは、ヒドロキシアニオン、例えば、メタノール、エタノール、ｎ−プロパノールなどの低沸点アルキルアルコールから導かれるアルコキシアニオン、または、ギ酸、酢酸等のカルボン酸から導かれるカルボキシアニオンである。さらに好ましくは、ヒドロキシアニオン、メトキシアニオン、エトキシアニオンおよび酢酸アニオンである。これらのホスファゼニウム化合物は、単独で用いても２種以上を混合して用いてもよい。
【００４４】
化学式（２）と共存させる活性水素化合物は、活性水素化合物のアルカリ金属塩またはアルカリ土類金属塩を与える活性水素化合物として先に詳細に述べたものと同一である。
【００４５】
化学式（２）で表されるホスファゼニウム化合物と活性水素化合物の存在下、エポキサイド化合物を付加重合させる本発明の方法においては、通常過剰に用いられる活性水素化合物の過剰分はそのまま残存する。この他に、水、アルコール、芳香族ヒドロキシ化合物またはカルボン酸は、ホスファゼニウム化合物の種類に応じて副生する。これらの副生物、特に低分子量のモノアルコール化合物は、エポキサイド化合物の付加重合反応の前に除去することが好ましい。除去する方法としては、例えば、不活性ガスによるバブリング操作下、８０〜１３０℃、１３３０〜２６６０Ｐａ以下の条件で加熱、減圧処理する方法、吸着剤を用いる方法等が挙げられる。該副生物の残存量は１０００ｐｐｍ以下、好ましくは８００ｐｐｍ以下、最も好ましくは４００ｐｐｍ以下が好適である。
【００４６】
次に、本発明のポリオキシアルキレンポリオール製造用触媒として用いられるホスファゼニウム化合物とアルカリ金属化合物との混合物について説明する。比較的安価なアルカリ金属化合物をホスファゼニウム化合物と併用することにより、ポリオキシアルキレンポリオールの製造コストが低減する。しかし、前述したようにアルカリ金属化合物の過度の使用は、ポリオキシアルキレンポリオールの総不飽和度の上昇につながる。
【００４７】
ホスファゼニウム化合物とアルカリ金属化合物との混合物を触媒として使用する場合には、混合物１モルに対して、アルカリ金属化合物が５〜５０モル％、好ましくは６〜４０モル％、最も好ましくは８〜３０モル％の範囲である。アルカリ金属化合物の使用量が５モル％未満であるとポリオキシアルキレンポリオールの製造コストの低減効果は低い。一方、アルカリ金属化合物の使用量が５０モル％を超えると総不飽和度（モノオール含有量）が増加し、本発明の目的である水酸基価と総不飽和度との前記数式（１）の関係を満たし難い。
【００４８】
前記アルカリ金属化合物としては、ナトリウム、カリウム、ナトリウム、ルビジウム及びセシウム化合物等が挙げられる。アニオンの形態としては、ヒドロキシアニオン、メトキシ、エトキシ基等のアルコキシアニオン、ＣＯ_３ ^2-、ＨＣＯ₃ ^-等が挙げられる。アルコキシ、ヒドロキシアニオンを有するアルカリ金属化合物が好ましい。また、アルカリ金属化合物としてはセシウム化合物が好ましく、本出願人が先に出願した特開平７−２７８２８９号公報記載の水酸化セシウムが好ましい。
【００４９】
ホスファゼニウム化合物、またはホスファゼニウム化合物とアルカリ金属化合物との混合物の存在下、活性水素化合物へ付加重合させるエポキサイド化合物としては、プロピレンオキサイド、エチレンオキサイド、１，２−ブチレンオキサイド、２，３−ブチレンオキサイド、スチレンオキサイド、シクロヘキセンオキサイド、エピクロロヒドリン、エピブロモヒドリン、メチルグリシジルエーテル、アリルグリシジルエーテル、トリフルオロプロピレンオキサイドなどが挙げられる。これらは２種以上併用してもよい。これらのうち、好ましくはプロピレンオキサイド、エチレンオキサイド及び１，２−ブチレンオキサイドである。
【００５０】
エポキサイド化合物の付加重合方法としては、プロピレンオキサイドを含むエポキサイド化合物を付加重合し、次いで、エチレンオキサイドを付加重合する。具体的には、プロピレンオキサイドを含むエポキサイド化合物を付加重合した後、エチレンオキサイドをブロック共重合するエチレンオキサイドキャップ反応が挙げられる。また、プロピレンオキサイド及びエチレンオキサイドを含むエポキサイド化合物をランダムに共重合し、次いで、エチレンオキサイドを共重合するエチレンオキサイドキャップ反応が挙げられる。
【００５１】
いずれの方法においても、プロピレンオキサイドを含むエポキサイド化合物には、プロピレンオキサイドを少なくとも５０モル％含ませることが好ましい。エチレンオキサイドキャップ反応はいずれの方法においても必須である。
【００５２】
本発明のポリオキシアルキレンポリオールの分子末端一級水酸基化率を少なくとも４０モル％とするためには、分子末端オキシエチレン基含有量が、５〜３０重量％となるような量のエチレンオキサイドをキャップ反応する。
【００５３】
前記１）〜４）の特性を有するポリオキシアルキレンポリオールを製造する場合、以下の条件を選んで行うことが好ましい。すなわち、活性水素化合物１モルに対する化学式（１）または化学式（２）で表されるホスファゼニウム化合物は５×１０^-5〜５モル、好ましくは１×１０^-4〜５×１０^-1モル、より好ましくは１×１０^-3〜１×１０^-2モルの範囲である。ポリオキシアルキレンポリオールを高分子量化する際には、活性水素化合物に対するホスファゼニウム化合物の濃度を上記範囲内で高めることが好ましい。活性水素化合物１モルに対して、化学式（１）または化学式（２）で表されるホスファゼニウム化合物が５×１０^-5モル未満である場合には、アルキレンオキサイドの重合速度が低下し、ポリオキシアルキレンポリオールの製造時間が長くなる。活性水素化合物１モルに対して、化学式（１）または化学式（２）で表されるホスファゼニウム化合物が５モルを超えると、製造コストに占めるホスファゼニウム化合物の割合が高くなる。
【００５４】
ホスファゼニウム化合物とアルカリ金属化合物との混合物を触媒とする際には、化学式（２）で表されるホスファゼニウム化合物を使用することが好ましい。活性水素化合物１モルに対して、該混合物は５×１０^-5〜１モル、好ましくは１×１０^-4〜５×１０^-2モル、より好ましくは１×１０^-3〜１×１０^-2モルの範囲である。
【００５５】
プロピレンオキサイドを主成分とするエポキサイド化合物の付加重合反応温度は１５〜１３０℃、好ましくは４０〜１２０℃、さらに好ましくは５０〜１１０℃の範囲である。反応温度が１５℃より低い場合には、プロピレンオキサイドの重合速度が低下し、ポリオキシアルキレンポリオールの製造時間が長くなる。反応温度が１３０℃を超えると、ポリオキシアルキレンポリオールの高分子量化に伴い、総不飽和度が高くなる。
【００５６】
一方、エチレンオキサイドの付加重合温度は、１５〜１７０℃、好ましくは４０〜１５０℃、さらに好ましくは９０〜１５０℃の範囲である。反応温度が１５℃より低い場合には、エポキサイド化合物の重合速度が低下し、ポリオキシアルキレンポリオールの製造時間が長くなる。反応温度が１７０℃を越えると、ポリオキシアルキレンポリオールが着色する傾向にある。エポキサイド化合物の反応温度を上記範囲内で低い温度で行う場合は、活性水素化合物に対する触媒濃度を先に述べた範囲内で高めることが好ましい。耐圧反応機に仕込んだ触媒と活性水素化合物へのエポキサイド化合物の供給方法は、必要量のエポキサイド化合物の一部を一括して供給する方法、または連続的もしくは間欠的にエポキサイド化合物を供給する方法が用いられる。必要量のエポキサイド化合物の一部を一括して供給する方法においては、エポキサイド化合物の重合反応初期の反応温度は上記範囲内でより低温側とし、エポキサイド化合物の一部を装入した後、次第に反応温度を上昇する方法が好ましい。
【００５７】
エポキサイド化合物の反応時の最大圧力は８８２ｋＰａが好適である。通常、耐圧反応機によりエポキサイド化合物の反応が行われる。エポキサイド化合物の反応は減圧状態から開始しても、大気圧の状態から開始してもよい。大気圧状態から反応を開始する場合には、窒素またはヘリウム等の不活性気体存在下で行うことが望ましい。エポキサイド化合物の最大反応圧力が８８２ｋＰａを超えると副生モノオール量が増加する。最大反応圧力は、好ましくは６８６ｋＰａ、より好ましくは４９０ｋＰａである。エポキサイド化合物として、プロピレンオキサイドを用いる場合には、最大反応圧力は４９０ｋＰａが好ましい。
【００５８】
エポキサイド化合物の付加重合反応に際して、溶媒を使用することもできる。溶媒としては、例えば、ペンタン、ヘキサン、ペプタン等の脂肪族炭化水素類、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類またはジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミド等の非プロトン性極性溶媒等である。溶媒を使用する場合には、ポリオキシアルキレンポリオールの製造コストを上げないためにも、製造後に溶媒を回収し再利用する方法が望ましい。
【００５９】
上記化合物を触媒として、活性水素化合物にエポキサイド化合物を付加重合し、得られた粗製ポリオキシアルキレンポリオールの精製方法について述べる。
ａ）粗製ポリオキシアルキレンポリオール１００重量部に対して、水を１〜２０重量部加えた後、気相の酸素濃度が２％以下の条件下で、粗製ポリオキシアルキレンポリオール中のホスファゼニム化合物１モルに対して、無機酸、無機酸酸性塩及び有機酸から選ばれる少なくとも１種の中和剤を０．５〜８モル使用して、５０〜１３０℃でホスファゼニウム化合物を中和する。その後、粗製ポリオキシアルキレンポリオールに対して、１００〜４０００ｐｐｍの酸化防止剤を添加し、減圧処理を行い、水を留去し、ポリオキシアルキレンポリオールを回収する。
【００６０】
ｂ）粗製ポリオキシアルキレンポリオール１００重量部に対して、ポリオキシアルキレンポリオールに不活性な有機溶剤および水を１〜４０重量部加えた後、気相の酸素濃度が２％以下の条件下で、粗製ポリオキシアルキレンポリオール中のホスファゼニウム化合物１モルに対して、無機酸、無機酸酸性塩及び有機酸から選ばれる少なくとも１種の中和剤を０．５〜８モル使用して５０〜１３０℃でホスファゼニウム化合物を中和する。その後、粗製ポリオキシアルキレンポリオールに対して、１００〜４０００ｐｐｍの酸化防止剤を添加し、減圧処理を行い、水および有機溶剤を留去し、ポリオキシアルキレンポリオールを回収する。
【００６１】
尚、ホスファゼニウム化合物とアルカリ金属化合物の混合物を用いた場合は、前記ａ）〜ｂ）と同様な操作により、ポリオキシアルキレンポリオールの精製処理を行う。この際、使用する中和剤はホスファゼニウム化合物とアルカリ金属化合物との混合物１モルを基準として使用する。
【００６２】
粗製ポリオキシアルキレンポリオールの精製の際の気相の酸素濃度は２％以下である。好ましくは１．５％以下、最も好ましくは１％以下である。気相中の酸素濃度が２％を超えると、水、または水と有機溶剤の混合物を加熱減圧除去する際に、過酸化物またはアルデヒド化合物が副生し易い。該化合物は臭気の原因物質となる上、ポリオキシアルキレンポリオールの経時安定性を悪化させる。
【００６３】
気相中の酸素濃度の制御は、窒素、ヘリウム、アルゴン等の不活性ガスによる置換操作が好ましい。気相中の酸素濃度を低減することにより、粗製ポリオキシアルキレンポリオール（液相）中の酸素濃度も低減するため、過酸化物、アルデヒド化合物等の副生を抑制することができる。
【００６４】
通常、粗製ポリオキシアルキレンポリオールの精製操作は撹拌装置を装着した反応機で実施する。反応機内を不活性ガスで数回、加圧置換する操作、あるいは、反応機内を減圧状態、例えば、６６５０Ｐａ以下の状態とし、しばらく放置した後、不活性ガスで加圧置換する操作を数回繰り返すことにより、気相中の酸素濃度を２％以下にする。その際、微量酸素分析計にて、気相中の酸素濃度を測定する。特に、反応機内を減圧状態とし、次いで、不活性ガスによる加圧置換操作を行うことにより、液相中の酸素濃度は著しく低減する。このような操作を行った後の液相中の酸素濃度は１．３ｐｐｍ以下が好ましい。
【００６５】
ａ）法は水単独で、ｂ）法は水とポリオキシアルキレンポリオールに不活性な有機溶剤を併用する方法である。中和の際には、水（ａ法）またはポリオキシアルキレンポリオールに不活性な有機溶剤と水の混合物（ｂ法）を１〜２０重量部用いる。好ましくは１〜１５重量部、より好ましくは１．２〜１０重量部である。水は必須成分であり、ポリオキシアルキレンポリオールに不活性な有機溶剤および水を用いる際にも該混合溶媒中の水は少なくとも２０重量％は必要である。１重量部未満の場合は、製品中のホスファゼニウム化合物濃度が多くなる。
【００６６】
ポリオキシアルキレンポリオールに不活性な有機溶剤とは、炭化水素系溶剤の中でトルエン、ヘキサン類、ペンタン類、ヘプタン類、ブタン類、低級アルコール類、シクロヘキサン、シクロペンタン、キシレン類などが挙げられる。ポリオキシアルキレンポリオールからこれらの有機溶剤を留去する方法は、加熱減圧操作が好ましい。その際の温度は１００〜１４０℃、減圧度は１３３０Ｐａ以下が好ましい。
【００６７】
ホスファゼニウム化合物、あるいはホスファゼニウム化合物とアルカリ金属化合物との混合物を中和する際の酸として、無機酸、無機酸酸性塩及び有機酸から選ばれる少なくとも１種の中和剤を使用する。無機酸としては、例えば、リン酸、亜リン酸、次亜リン酸、ピロリン酸、塩酸、硫酸、亜硫酸およびそれらの水溶液が挙げられる。無機酸酸性塩としては、例えば、リン酸二リチウム、リン酸二水素ナトリウム、リン酸二水素カリウム、リン酸一水素リチウム、リン酸一水素ナトリウム、リン酸一水素カリウム、硫酸水素リチウム、硫酸水素ナトリウム、硫酸水素カリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、酸性ピロリン酸ナトリウム（例えば、ピロリン酸水素ナトリウム）等が挙げられる。有機酸としては、例えば、ギ酸、シュウ酸、コハク酸、酢酸、マレイン酸、安息香酸、パラトルエンスルホン酸およびそれらの水溶液が挙げられる。特に、好ましくはリン酸、硫酸、塩酸、マレイン酸、シュウ酸であり、水溶液の形態で用いることが良い。
【００６８】
これらの酸は、粗製ポリオキシアルキレンポリオール中に含まれるホスファゼニウム化合物、あるいはホスファゼニウム化合物とアルカリ金属化合物との混合物１モルに対して、０．５〜８モル使用する。好ましくは、０．７〜６モル、より好ましくは１．２〜５モルである。中和は５０〜１３０℃の範囲で実施する。特に好ましくは７０〜９５℃である。中和時間は反応スケールにもよるが、０．５〜３時間である。ホスファゼニウム化合物１モルに対して酸の量が８モルに近いときは酸吸着剤を併用することが好ましい。０．５モル未満であると、ポリオキシアルキレンポリオール中のホスファゼニウム化合物及び／またはアルカリ金属濃度が高くなる傾向にある。
【００６９】
中和反応終了後、粗製ポリオキシアルキレンポリオールに対して、１００〜４０００ｐｐｍの酸化防止剤を使用する。好ましくは、１５０〜３０００ｐｐｍ、最も好ましくは、２００〜１８００ｐｐｍである。酸化防止剤が１００ｐｐｍ未満であると、過酸化物あるいはアルデヒド化合物が副生し易い。４０００ｐｐｍより多くなると、ポリオールのコストに占める酸化防止剤のコストが大きくなる。酸化防止剤としては、通常、ポリウレタン分野に使用されているフェノール系化合物、アミン系化合物、亜リン酸エステル系化合物、ケイ皮酸エステル類が例示できる。
【００７０】
酸化防止剤と共に、吸着剤を使用することが好ましい。吸着剤の装入時期は、中和反応後、もしくは減圧脱水過程のどちらでもよい。粗製ポリオキシアルキレンポリオール１００重量部に対して酸およびアルカリ成分を吸着する吸着剤を０．００５〜２．５重量部添加する。好ましくは、０．０２〜１．５重量部、より好ましくは０．０３〜１．１重量部である。吸着剤としては、例えば合成ケイ酸マグネシウム、合成ケイ酸アルミニウム、活性白土、ゼオライト、酸性白土、合成ケイ酸アルミニウム・マグネシウム等が用いられる。吸着剤を製造する工程で水酸化ナトリウムによる処理を行っていることから、ナトリウム溶出分が少ない吸着剤が好ましい。具体的な吸着剤としては、トミックスシリーズ、例えば、トミックスＡＤ−１００、トミックスＡＤ−２００、トミックスＡＤ−３００、トミックスＡＤ−４００、トミックスＡＤ−５００、トミックスＡＤ−６００、トミックスＡＤ−７００、トミックスＡＤ−８００、トミックスＡＤ−９００〔富田製薬（株）製〕、キョーワードシリーズ、例えば、キョーワード２００、キョーワード３００、キョーワード４００、キョーワード５００、キョーワード６００、キョーワード７００、キョーワード１０００、キョーワード２０００〔協和化学工業（株）製〕、ＭＡＧＮＥＳＯＬ（ＤＡＬＬＡＳ社製）等各種の商品名で市販されている。これらの吸着剤は単独、もしくは２種類以上併用しても構わない。
【００７１】
吸着剤装入後は、水、または水と有機溶剤とを減圧条件下で留去する。反応スケールにもよるが、１００〜１４０℃、１３３０Ｐａの条件で３〜１２時間行うことが好ましい。特に、低分子量のアルデヒド化合物を除去するため、酸化防止剤を添加した後、７０〜１６０℃、３９．９ｋＰａ、好ましくは、２６．６ｋＰａ、より好ましくは、１３．３ｋＰａ以下の条件で、窒素、ヘリウム、アルゴン等の不活性ガスを導入することが好ましい。減圧処理操作は、真空ポンプによる方法、あるいは薄膜蒸発方法等が挙げられる。その際、強制循環式撹拌膜型の蒸発器、あるいは流下膜式分子蒸留装置などを用いることができる。
【００７２】
ａ）〜ｂ）の操作を行った後、ろ過操作により、ポリオキシアルキレンポリオールの回収を行う。その際に、けいそう土、セライトなどのろ過助剤を用いても良い。
【００７３】
上記操作により、ポリオキシアルキレンポリオール中のホスファゼニウム化合物触媒の残存量を１５０ｐｐｍ以下に制御することができる。該化合物触媒のポリオール中の濃度は、１００ｐｐｍ以下が好ましく、更には７０ｐｐｍ以下が最も好ましい。ポリオキシアルキレンポリオール中の該化合物触媒の残存量が１５０ｐｐｍを超えると、レジン液の貯蔵安定性が低下する傾向にある。また、ホスファゼニム化合物とアルカリ金属化合物との混合物を使用した場合、ホスファゼニウム化合物触媒の残存量は１５０ｐｐｍ以下で、且つ、アルカリ金属の残存量は５ｐｐｍ以下である。好ましくは、アルカリ金属の残存量は３ｐｐｍ以下であり、最も好ましくは２ｐｐｍ以下である。アルカリ金属の残存量が５ｐｐｍを超えるとレジン液の貯蔵安定性が低下する。
【００７４】
また、上記操作により得られたポリオキシアルキレンポリオールのＣＰＲ（ポリオール中の塩基性物質の量を示す値）は５以下である。好ましくは、ＣＰＲは３以下、最も好ましくはＣＰＲは０である。ポリオキシアルキレンポリオールのＣＰＲが５より大きくなると、レジン液の貯蔵安定性が低下する。
【００７５】
換言すると、本発明のポリオキシアルキレンポリオールは、ホスファゼニウム化合物触媒の残存量が１５０ｐｐｍ以下、アルカリ金属の残存量が５ｐｐｍ以下であり、且つ、ＣＰＲが５以下であることから、これを用いてポリウレタン製造用組成物であるレジン液を調製したとき、その貯蔵安定性が良好である。
【００７６】
また、上記操作により得られるポリオキシアルキレンポリオール中の過酸化物濃度は０．２８ｍｍｏｌ／ｋｇ以下、好ましくは、０．２０ｍｍｏｌ／ｋｇ以下、最も好ましくは、０．１５ｍｍｏｌ／ｋｇ以下である。過酸化物濃度が０．２８ｍｍｏｌ／ｋｇを超えると、ポリイソシアネート化合物との反応に際して、錫系触媒を使用する場合、過酸化物により錫系触媒の活性が低下するため、ポリウレタンフォームの成形性、力学物性が低下する。また、過酸化物濃度が０．２８ｍｍｏｌ／ｋｇを超えるポリオキシアルキレンポリオールを空気中で放置していると、過酸化物が酸性化合物となり、ポリオキシアルキレンポリオール中の酸価が増加する。酸価が高くなると、ポリイソシアネート化合物との反応性が低下し、得られるポリウレタンフォームの物性が悪化、あるいは臭気が強くなる。レジン液の貯蔵安定性を向上させるため、過酸化物濃度は０．２８ｍｍｏｌ／ｋｇ以下であると共に、ポリオール中の酸化防止剤濃度は１００〜４０００ｐｐｍであることが好ましい。また、このような操作により得られたポリオキシアルキレンポリオールの酸価は０．０５ｍｇＫＯＨ／ｇ以下が好ましい。
【００７７】
次に、本発明に係るポリマー分散ポリオールについて説明する。ポリマー分散ポリオールの分散媒であるポリオキシアルキレンポリオールには、前述した本発明のポリオキシアルキレンポリオールを使用する。
【００７８】
本発明のポリマー分散ポリオールは、前記ポリオキシアルキレンポリオールを分散媒として用い、その中にビニルポリマーの微粒子を分散させることにより製造される。ビニルポリマーは、前記ポリオキシアルキレンポリオールを分散媒として、ビニルモノマーを重合してビニルポリマーの微粒子を分散させてもよいし、また、他の分散系でビニルモノマーを重合し、得られたポリマー粒子を前記ポリオキシアルキレンポリオール中に添加、分散させてもよい。
【００７９】
ビニルポリマーの製造に用いるビニルモノマーは、重合し得るエチレン性不飽和基を少なくとも１個有するものが適当である。例えば、アクリロニトリル、メタクリロニトリル等のシアノ基含有モノマー、メチルアクリレート、ブチルアクリレート、ステアリルアクリレート、ヒドロキシエチルアクリレート、ジメチルアミノエチルアクリレート、ジメチルアミノプロピルメタクリレート等のメタクリル酸エステル系モノマー、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸等のカルボキシル基含有モノマー、無水マレイン酸、無水イタコン酸等の酸無水物基含有モノマー、ブタジエン、イソプレン、１，４−ペンタジエン等の炭化水素系モノマー、スチレン、α−メチルスチレン、フェニルスチレン、クロルスチレン等の芳香族炭化水素系モノマー、塩化ビニル、塩化ビニリデン等のハロゲン含有モノマー、ビニルエチルエーテル、ビニルブチルエーテル等のビニルエーテル類、ビニルエチルケトン等のビニルケトン類、酢酸ビニル等のビニルエステル類、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、メチレンビスアクリルアミド等のアクリルアミド類、Ｎ，Ｎ−ジメチルメタクロイルアミド等のメタクリルアミド類が挙げられる。
【００８０】
これらは、１種でもよいし、また、２種以上の混合物でもよい。好ましくは、アクリロニトリル単独、アクリロニトリルとスチレンの混合物、アクリロニトリルとスチレンとアクリルアミドの混合物、アクリロニトリルとスチレンとメタクリル酸メチルの混合物である。さらに好ましくは、アクリロニトリル単独、アクリロニトリルとスチレンの混合物、アクリロニトリルとスチレンとアクリルアミドの混合物である。
【００８１】
上記ビニルモノマーの重合開始剤として、通常、ラジカルを発生して重合を開始するラジカル開始剤が用いられる。具体的には、２，２’−アゾビスイソブチロニトリル等のアゾ化合物、ベンゾイルパーオキシド、ｔ−ブチルパーオキシド、ジ−ｔ−ブチルパーオキシド等の過酸化物、パーオキシジスルフィド等が挙げられる。重合開始剤の使用量は、通常、ビニルモノマーに対して０．１〜１０．０重量％、好ましくは０．５〜５．０重量％である。
【００８２】
ビニルモノマーの使用量は、ポリオキシアルキレンポリオールとビニルモノマーの総重量に対して５〜５０重量％、好ましくは１０〜４６重量％である。ビニルモノマーの使用量が５重量％未満では、ポリウレタンの硬度等、ポリマー分散ポリオールを使用したことによる十分な改質効果が得られない。ビニルモノマーの使用量が５０重量％を超えると、得られるポリマー分散ポリオールの粘度の上昇が著しく上昇する。
【００８３】
本発明では、必要に応じて連鎖移動剤を用いることができる。連鎖移動剤として、イソプロパノール等のアルコール類、メルカプタン類、ハロゲン化炭化水素、トリエチルアミン、トリプロピルアミン、トリブチルアミン、Ｎ，Ｎ−ジエチルエタノールアミン等の脂肪族３級アミン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン等のモルホリン類、メタリルスルホン酸ナトリウム、アリルスルホン酸ナトリウム等が挙げられる。好ましくは、トリエチルアミン単独、トリエチルアミンとイソプロパノールの混合物である。連鎖移動剤の使用量は、ポリオキシアルキレンポリオールとビニルモノマーの総重量に対して０．１〜１０．０重量％が好ましい。
【００８４】
更に、ポリマー粒子を安定に分散させる目的で、分散安定化剤の存在下に重合を行うこともできる。このような分散安定化剤として、特公昭４９−４６５５６号公報に記載されているような炭素−炭素不飽和結合を含有するポリエステルポリオールや、アクリル基、メタクリル基、アリル基等を分子末端に有する変性ポリオール等が挙げられる。また、実質的に炭素−炭素不飽和結合を含有しない高分子量ポリオキシアルキレンポリオールやポリエステルポリオールも使用できる。
【００８５】
ポリマー分散ポリオールの製造は、上記ポリオキシアルキレンポリオール、ビニルモノマー、重合開始剤、さらには必要に応じて連鎖移動剤、分散安定化剤を用いて重合反応を行う。重合反応はバッチ式でも、連続式でも行うことができる。重合温度は重合開始剤の種類に応じて決められるが、重合開始剤の分解温度以上、好ましくは６０〜２００℃、さらに好ましくは９０〜１５０℃の範囲で行う。また、重合反応は加圧下でも、大気圧下でも行うことができる。
【００８６】
以上、詳述したポリオキシアルキレンポリオール及びポリマー分散ポリオールを使用して、軟質ポリウレタンフォーム製造用レジン液を調製する。通常、レジン液は、ポリオキシアルキレンポリオール、ポリマー分散ポリオール、フォーム製造用触媒、整泡剤、架橋剤、難燃剤等の助剤及び発泡剤を１０〜６０℃の範囲で均一混合して製造される。発泡剤は、通常、水、液化二酸化炭素等の不活性ガス、及びそれらの混合物が使用される。特に、本発明に係るポリオキシアルキレンポリオール、ポリマー分散ポリオールは、発泡剤として少なくとも水を用いた場合にレジン液の貯蔵安定性を向上し得る。
【００８７】
また、本発明のポリオキシアルキレンポリオール、ポリマー分散ポリオールは、軟質ポリウレタンフォームの他に、塗料、接着剤、床材、防水材、シーリング剤、靴底、弾性補強剤及びローラー、タイミングベルト等の幅広いポリウレタン分野において優れた力学物性を提供できる。。
【００８８】
【実施例】
以下に本発明の実施例を示し、本発明の熊様を明らかにするが、本発明はこれら実施例に限定されるものではない。
尚、実施例に示した、ポリオキシアルキレンポリオールまたはポリマー分散ポリオールの水酸基価（ＯＨＶ）、総不飽和度（Ｃ＝Ｃ）、分子末端一級水酸基化率、ヘッド−トウ−テイル（Ｈｅａｄ−ｔｏ−Ｔａｉｌ）結合選択率、オキシエチレン基含有量、ホスファゼニウム化合物触媒残存量、アルカリ金属残存量、及びポリマー濃度、並びに、軟質ポリウレタンフォームのセトリング、反発弾性コア、硬度２５％ＩＬＤ、及び湿熱時の永久圧縮歪みは、下記方法により測定した。
（１）水酸基価（以下、ＯＨＶと略する：単位ｍｇＫＯＨ／ｇ）及び総不飽和度（以下、Ｃ＝Ｃと略する：単位ｍｅｑ．／ｇ）
ＪＩＳ Ｋ−１５５７記載の方法により求めた。
（２）分子末端一級水酸基化率（単位：モル％）
重水素化アセトンを溶媒とし、核磁気共鳴（ＮＭＲ）装置〔日本電子（株）製、４００ＭＨｚ¹³Ｃ〕を用いて測定した。
（３）ヘッド−トウ−テイル（Ｈｅａｄ−ｔｏ−Ｔａｉｌ）結合選択率（以下、Ｈ−Ｔと略する。単位：モル％）
核磁気共鳴（ＮＭＲ）装置〔日本電子（株）製、４００ＭＨｚ¹³Ｃ〕を用い、重水素化クロロホルムを溶媒として、ポリオキシアルキレンポリオールの^１３Ｃ−ＮＭＲスペクトルをとり、ヘッド−トウ−テイル（Ｈｅａｄ−ｔｏ−Ｔａｉｌ）結合のオキシプロピレンユニットのメチル基のシグナル（１６．９〜１７．４ｐｐｍ）とヘッド−トウ−ヘッド（Ｈｅａｄ−ｔｏ−Ｈｅａｄ）結合のオキシプロピレンユニットのメチル基のシグナル（１７．７〜１８．５ｐｐｍ）の比から求めた。各シグナルの帰属は、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ（第１９巻、１３３７〜１３４３頁、１９８６年発行、Ｆ．Ｃ．Ｓｃｈｉｌｌｉｎｇ、Ａ．Ｅ．Ｔｏｎｅｌｌｉ）の報文に記載された値を参考にした。
【００８９】
（４）オキシエチレン基の含有量が少なくとも８５重量％であるポリエーテル化合物の含有量（単位：ｐｐｍ）
５０℃に加熱したポリオールをステンレススチール製の遠心分離管に秤量し、１６℃に調整する。予め、１６℃に調整した遠心分離機にポリオールを秤量した遠心分離管をセットし、１０，０００ｒ．ｐ．ｍ．の条件で１時間遠心分離を行う。遠心分離管を取り出し、管を逆さまに傾け、室温で１時間デカンテーションを行う。次いで、遠心分離管の底に付着した成分にジエチルエーテルを加え、窒素雰囲気下、上記条件にて遠心分離を行う。再度、ジエチルエーテルを遠心分離管に加えた後、ジエチルエーテル溶液をメンブランフィルター（ｐｏｒｅ ｓｉｚｅ０．４５μｍ）にて減圧ろ過を行い、窒素を通気しながらフィルター上のジエチルエーテルを除去する。その後、フィルターの重量を測定し、その値を予め、秤量しておいたフィルターの重量から差し引いた後、使用したポリオールの重量で割ることにより、オキシエチレン基の含有量が少なくとも８５重量％であるポリエーテル化合物の含有量（以下、ポリエーテル副生物の含有量と略する。単位：ｐｐｍ）を求めた。該ポリエーテル副生物のオキシエチレン基含有量は、前記の日本電子製核磁気共鳴（ＮＭＲ）装置により測定を行った。
【００９０】
（５）ホスファゼニウム化合物触媒残存量（単位：ｐｐｍ）
全自動ＣＩＡシステム（ｗａｔｅｒｓ社製）を用いたキャピラリー電気泳動法により行った。ポリオールに塩酸水溶液を添加し、シェーカーにて塩酸水溶液中にホスファゼニウム化合物の抽出を行う。その後、静置分液を行い、水相を分離し、キャピラリー電気泳動分析装置を用いて、触媒残存量の定量を行った。
（６）アルカリ金属残存量（単位：ｐｐｍ）
原子吸光分析装置（パーキンエルマ社製、形式：５１００ＰＣ型）により定量を行った。
（７）ポリマー分散ポリオール中のポリマー濃度（単位：重量％）
ポリマー分散ポリオールにメタノールを加え、良く分散させた後に、遠心分離してメタノール不溶分の重量を測定して求める。ただし、ビニルモノマーとしてアクリロニトリル（ＡＮ）を単独で用いたポリマー分散ポリオールについては元素分析による窒素分から求める。
【００９１】
（８）軟質ポリウレタンフォームの反発弾性コア（％）、硬度２５％ＩＬＤ（ｋｇｆ／３１４ｃｍ²）、及び湿熱時の永久圧縮歪（％）
ＪＩＳ Ｋ−６３０１及びＪＩＳ Ｋ−６４０１に規定される方法により測定する。
（９）軟質ポリウレタンフォームのセトリング（％）
後述する実施例４または比較例４と同一のレジン液及びポリイソシアネート化合物を、温度２３℃、相対湿度５０％の条件下で混合、撹拌し、フォーム発泡用モールド（内寸：３００ｍｍ×３００ｍｍ×４００ｍｍの木箱）に注入してハンド発泡し、フォームの最大発泡高さ（ａ）及びレジン液及びポリイソシアネート化合物の混合、撹拌を開始してから７分後のフォームの発泡高さ（ｂ）を測定し、数式〔（ａ−ｂ）×１００／ａ〕により求める。
【００９２】
調製例１
＜ホスファゼニウム化合物（以下、Ｐ５ＮＭｅ２ＯＨと略する）の合成＞
実施例のポリオキシアルキレンポリオールの合成において、以下の方法で合成したホスファゼニウム化合物をエポキサイド化合物の触媒として使用した。
温度計、滴下ロートを取り付けた３０００ｍｌの３つ口フラスコに五塩化リン〔純正化学（株）製〕６０．２０ｇを秤取り、５２５ｍｌのオルソジクロロベンゼン〔以下、ＯＤＣＢと略する。三井化学（株）製〕を加えて懸濁液とした。これを３０℃に加熱し、９００ｍｌのＯＤＣＢに、Ａｎｇｅｗ．Ｃｈｅｍ．Ｉｎｔ．Ｅｄ．Ｅｎｇｌ．（１９９３年、第３２巻、１３６１〜１３６３頁、ＲｅｉｎｈａｒｄＳｃｈｗｅｓｉｎｇｅｒ，ｅｔ ａｌ．）記載の方法により合成したトリス（ジメチルアミノ）ホスファゼン｛（Ｍｅ₂Ｎ）₃Ｐ＝ＮＨ｝４３９．２７ｇを溶解させた溶液を１時間かけて滴下した。同温度で３０分間撹拌した後、約３０分間かけて１６０℃まで昇温し、さらに２０時間撹拌した。
生成した不溶物をろ過し、ろ液にイオン交換水を添加し、３回水洗処理を行った。水洗処理後の水不溶層（以下、有機層と略する）１０９１．２ｇに対して、イオン交換水６１９．２６ｇと１規定の塩酸を２８９．５ｍｌ加え、水層を分液し、テトラキス〔トリス（ジメチルアミノ）ホスフォラニリデンアミノ〕ホスホニウムクロライド｛〔（Ｍｅ₂Ｎ）₃Ｐ＝Ｎ〕₄Ｐ⁺Ｃｌ^-｝を得た。さらに、 イオン交換水を加え、２．５重量％水溶液に調製した。
【００９３】
次いで、１Ｎ水酸化ナトリウム水溶液により交換基を水酸基型にしたイオン交換樹脂レバチットＭＰ−５００（バイエル社製）を充填したポリカーボネート製円筒状カラムにテトラキス〔トリス（ジメチルアミノ）ホスフォラニリデンアミノ〕ホスホニウムクロライドの２．５重量％水溶液を２３℃、ＳＶ（ＳｐａｃｅＶｅｌｏｃｉｔｙ）０．５（１／ｈｒ）でカラム底部より上昇流で通液し、テトラキス〔トリス（ジメチルアミノ）ホスフォラニリデンアミノ〕ホスホニウムヒドロキシドにイオン交換を行った。更に、該イオン交換樹脂を充填したカラムにイオン交換水を通液し、カラムに残存しているホスファゼニウム化合物の回収を行った。その後、テトラキス〔トリス（ジメチルアミノ）ホスフォラニリデンアミノ〕ホスホニウムヒドロキシドの水溶液を８０℃、減圧度７９８０Ｐａの条件下で２時間、更に８０℃、１３３Ｐａの条件で７時間減圧脱水処理を行うことにより、粉末のテトラキス〔トリス（ジメチルアミノ）ホスフォラニリデンアミノ〕ホスホニウムヒドロキシド｛〔（Ｍｅ₂Ｎ）₃Ｐ＝Ｎ〕₄Ｐ⁺ＯＨ^-｝（Ｐ５ＮＭｅ２ＯＨ）を得た。
乾燥後の該化合物の重量測定から求めた収率は９８％であった。重水素化ジメチルホルムアミド溶液によるテトラメチルシランを内部標準とした¹Ｈ−ＮＭＲ（日本電子製、形式：４００ＭＨｚＮＭＲ）の化学シフトは２．６ｐｐｍ（ｄ，Ｊ＝９．９Ｈｚ、７２Ｈ）であった。元素分析値はＣ：３８．２８、Ｈ：９．８２、Ｎ：２９．４３、Ｐ：１９．９４（理論値Ｃ：３８．０９、Ｈ：９．７２、Ｎ：２９．６１、Ｐ：２０．４６）であった。該ホスファゼニウム化合物は化学式（２）においてａ、ｂ、ｃ、ｄの順に（１，１，１，１）で、Ｒがメチル基であり、Ｑ^-がＯＨ^-のヒドロキシアニオンである。
【００９４】
調製例２
実施例で用いたアルカリ金属化合物触媒として、水酸化セシウム溶液（ケメタル社製、ピュアーグレード、５０重量％）を使用した。
【００９５】
調製例３
比較例におけるポリオキシアルキレンポリオール製造用触媒として、ＵＳＰ５，１４４，０９３号公報（カラム４、５２行〜カラム５、４行目）に記載されている複金属シアン化物錯体｛Ｚｎ₃〔Ｃｏ（ＣＮ）₆〕₂・２．４８ＤＭＥ・４．６５Ｈ₂０・０．９４ＺｎＣｌ₂；以降、ＤＭＣと略する｝（ＤＭＥとはジメトキシエタンの略号である。）を使用した。
【００９６】
調製例４
ＤＭＣを触媒として得られたポリオキシプロピレンポリオールにエチレンオキサイドの付加重合を行う際のアルカリ金属触媒として、水酸化カリウム〔日本曹達（株）製、純度：９６重量％〕を用いた。
＜ポリオキシアルキレンポリオールの合成装置＞
以下に、ポリオキシアルキレンポリオールの合成について説明する。ポリオキシアルキレンポリオールの合成ならびに精製装置は、攪拌機、温度計、圧力計、窒素装入口、気相中の酸素測定用ラインおよびモノマーであるエポキサイド化合物装入口を装着した内容積２．５Ｌ、６Ｌならびに９Ｌの耐圧製オートクレーブ（日東高圧製）を使用した。以下、該合成装置をオートクレーブと略する。ポリオキシアルキレンポリオールの合成ならびに精製時には、回転数１００〜３５０ｒ．ｐ．ｍ．の条件で撹拌を行った。
【００９７】
実施例１
＜ポリオキシアルキレンポリオールＡ＞
攪拌装置、窒素導入管および温度計を装備した５００ｍｌの４つ口フラスコにグリセリン１モルに対して０．０１２モルのＰ５ＮＭｅ２ＯＨと０．０６モルのトルエン（和光純薬製試薬特級）を加え、窒素をキャピラリー管で導入し、１０５℃、１３３０Ｐａ以下の条件で５時間、減圧脱水、脱トルエン操作を行った（水分含有量９５ｐｐｍ）。その後、フラスコ内容物を窒素雰囲気下でオートクレーブに仕込み、さらに、数回、窒素置換を行った後、大気圧状態から反応温度を７０℃とし、反応時の最大圧力が３９２ｋＰａの条件でＯＨＶが３８．８ｍｇＫＯＨ／ｇになるまでプロピレンオキサイドの多段付加重合を行った。
オートクレーブの内圧の変化が無くなった時点で同温度にて６６５Ｐａ、３０分間減圧処理を行い、次いで、内温を１３０℃に昇温し、同温度にて１３３０Ｐａ以下、１時間の減圧処理を行った。内温１３０℃、最大反応圧力が６１７ｋＰａの条件でＯＨＶが３３ｍｇＫＯＨ／ｇになるまでエチレンオキサイドの付加重合反応を行った。内圧の変化が無くなった時点で同温度にて６６５Ｐａ、３０分間減圧処理を行い、ホスファゼニウム化合物を含んだ状態の粗製ポリオキシアルキレンポリオールを得た（分子末端エチレンオキサイド含有量１５重量％）。以下、該粗製ポリオキシアルキレンポリオールを粗製ポリオールＡと称する。
【００９８】
粗製ポリオールＡを窒素雰囲気下でオートクレーブに仕込み、８０℃に昇温後、同温度でオートクレーブ内を２６６０Ｐａの減圧状態とし、同条件にて、８分間保持した。次いで、窒素により、３９２ｋＰａまで加圧した後、放圧し、大気圧状態とした。次に、粗製ポリオールＡ１００重量部に対して、７重量部のイオン交換水を加え、次いで，粗製ポリオールＡ中のホスファゼニウム化合物１モルに対して３モルのリン酸（７５．１重量％の水溶液の形態）を素早く装入し、８０℃で２時間の中和反応を行った。
中和反応終了後に、粗製ポリオールＡ１００重量部に対して、１２００ｐｐｍの酸化防止剤〔チバガイギー（株）製、商品名：ＩＲＧＡＮＯＸ１０１０〕を装入後、減圧下で脱水を行い、圧力が１３．３ｋＰａの時点で粗製ポリオールＡ１００重量部に対して、２．０重量部の吸着剤ＡＤ−６００〔吉富製薬（株）製〕を素早く装入した。最終的に、液相中に窒素を通気しながら、１０５℃、２６６０Ｐａの条件で４時間、減圧窒素バブリングを行った。窒素により減圧から大気圧状態にした後、セライトを引き詰めたアドバンテック東洋株式会社製の５Ｃろ紙（保持粒径１μ）により減圧ろ過を行い、ポリオキシアルキレンポリオールの精製を行った。
精製操作後のポリオキシアルキレンポリオールの水酸基価（ＯＨＶ）は３３．１ｍｇＫＯＨ／ｇ、総不飽和度（Ｃ＝Ｃ）０．０１０ｍｅｑ．／ｇ、一級水酸基化率は８５．２モル％、Ｈ−Ｔは９６．８モル％であった。また、ポリオキシアルキレンポリオール中のポリエーテル副生物の含有量は２ｐｐｍ、該化合物のオキシエチレン基含有量は９４重量％であった。ポリオール中のホスファゼニウム化合物触媒残存量は１７ｐｐｍであった。
【００９９】
実施例２
＜ポリオキシアルキレンポリオールＢ＞
攪拌装置、窒素導入管および温度計を装備した５００ｍｌの４つ口フラスコにグリセリン１モルに対して０．００９モルのＰ５ＮＭｅ２ＯＨならびに０．００３モルの水酸化セシウム（５０重量％の水溶液の形態）及び０．０９モルのトルエン（和光純薬製試薬特級）を加え、窒素をキャピラリー管で導入し、１０５℃、１３３０Ｐａ以下の条件で７時間、減圧脱水、脱トルエン操作を行った（水分含有量８７ｐｐｍ）。その後、フラスコ内容物を窒素雰囲気下でオートクレーブに仕込み、さらに、数回、窒素置換を行った後、大気圧状態から反応温度を８０℃とし、反応時の最大圧力が３９２ｋＰａの条件でＯＨＶが２８ｍｇＫＯＨ／ｇになるまでプロピレンオキサイドの多段付加重合を行った。
オートクレーブの内圧の変化が無くなった時点で６６５Ｐａ、３０分間減圧処理を行い、次いで、内温を１３０℃に昇温し、同温度にて１３３０Ｐａ以下、１時間の減圧処理を行った。内温１３０℃、最大反応圧力が６１７ｋＰａの条件でＯＨＶが２４ｍｇＫＯＨ／ｇになるまでエチレンオキサイドの付加重合反応を行った。内圧の変化が無くなった時点で同温度にて６６５Ｐａ、３０分間減圧処理を行い、ホスファゼニウム化合物及びセシウム化合物を含んだ状態の粗製ポリオキシアルキレンポリオールを得た（分子末端エチレンオキサイド含有量１５重量％）。以下、該粗製ポリオキシアルキレンポリオールを粗製ポリオールＢと称する。
【０１００】
粗製ポリオールＢを窒素雰囲気下でオートクレーブに仕込み、８０℃に昇温後、同温度でオートクレーブ内を２６６０Ｐａの減圧状態とし、同条件にて、８分間保持した。次いで、窒素により、３９２ｋＰａまで加圧した後、放圧し、大気圧状態とした。次に、粗製ポリオールＢ１００重量部に対して、１０重量部のイオン交換水を加え、次いで粗製ポリオールＢ中のホスファゼニウム化合物及びセシウム化合物の混合物１モルに対して４モルのリン酸（７５．１重量％の水溶液の形態）を素早く装入し、８０℃で２時間の中和反応を行った。
中和反応終了後に、粗製ポリオールＢ１００重量部に対して、１０００ｐｐｍの酸化防止剤〔チバガイギー（株）製、商品名：ＩＲＧＡＮＯＸ１０１０〕を装入後、減圧下で脱水を行い、圧力が１３．３ｋＰａの時点で粗製ポリオールＢ１００重量部に対して、１．８重量部の吸着剤ＡＤ−６００〔吉富製薬（株）製〕を素早く装入した。最終的に、液相中に窒素を通気しながら、１０５℃、２６６０Ｐａの条件で４時間、減圧窒素バブリングを行った。窒素により減圧から大気圧状態にした後、セライトを引き詰めたアドバンテック東洋株式会社製の５Ｃろ紙（保持粒径１μ）により減圧ろ過を行い、ポリオキシアルキレンポリオールの精製を行った。
精製操作後のポリオキシアルキレンポリオールの水酸基価（ＯＨＶ）は２４．２ｍｇＫＯＨ／ｇ、総不飽和度（Ｃ＝Ｃ）０．０１５ｍｅｑ．／ｇ、一級水酸基化率は８６．５モル％、Ｈ−Ｔは９６．３モル％であった。また、ポリオキシアルキレンポリオール中のポリエーテル副生物の含有量は５０ｐｐｍ、該化合物のオキシエチレン基含有量は９５重量％であった。ポリオール中のホスファゼニウム化合物触媒残存量は３５ｐｐｍ、アルカリ金属（セシウム）残存量は０．５ｐｐｍであった。
【０１０１】
比較例１
＜ポリオキシアルキレンポリオールＣ＞
グリセリンにプロピレンオキサイドを付加したポリプロピレンポリオールＭＮ１０００〔三井化学（株）製；ＯＨＶ１６８ｍｇＫＯＨ／ｇ〕１００重量部に対して０．０３重量部のＤＭＣを添加し、１０５℃、１３３０Ｐａ以下で３時間の減圧脱水を行った。次に、オートクレーブに該化合物を仕込み、反応温度７０℃、反応時の最大圧力３９２ｋＰａの条件でＯＨＶ３８．８ｍｇＫＯＨ／ｇになるまでプロピレンオキサイドの付加重合を行い、ＤＭＣを含有している粗製ポリオキシプロピレンポリオールを得た。
該ポリオキシプロピレンポリオール１００重量部に対して２．２２重量部の５０重量％の水酸化カリウム（ＫＯＨ）水溶液を添加し、脱水処理を１０５℃、２６６０Ｐａで１時間行った。その後、水を３重量部とＡＤ−６００〔富田製薬（株）製〕を５重量部加え、９０℃、窒素雰囲気下で２時間撹拌し、アドバンテック東洋株式会社製５Ｃろ紙（保持粒径１μ）を用いて減圧ろ過を行った。ろ過後、１２０℃、１３３０Ｐａ以下で１時間減圧脱水を行い、ＤＭＣの除去処理を行った。エチレンオキサイドの付加重合を行うため、ＤＭＣ除去後のポリオキシプロピレンポリオール１００重量部に２．５重量部の５０重量％のＫＯＨ水溶液を添加し、脱水処理を１０５℃、１３３０Ｐａ以下で１時間行った。オートクレーブに該化合物を仕込み、窒素置換後、反応温度１３０℃、反応時の最大圧力が４９０ｋＰａの条件でＯＨＶが３３．０ｍｇＫＯＨ／ｇになるまでエチレンオキサイドを装入し、反応させた。反応後、減圧処理を行い、粗製ポリオキシアルキレンポリオールを得た（分子末端エチレンオキサイド含有量１５重量％）。
【０１０２】
次いで、粗製ポリオキシアルキレンポリオール中のカリウム１モルに対して１．０５モルのリン酸（７５．１重量％のリン酸水溶液）ならびに粗製ポリエーテルポリオール１００重量部に対して４重量部のイオン交換水を装入し、８０℃、２時間の条件で中和反応を行った。その後、酸化防止剤〔チバガイギー（株）製、商品名：ＩＲＧＡＮＯＸ１０１０〕を１２００ｐｐｍならびに吸着剤ＫＷ−７００ＳＮ〔協和化学工業（株）製〕を８０００ｐｐｍ添加し、減圧下、水を留去しながら最終的に１０５℃、１３３０Ｐａで３時間減圧脱水を行った。
窒素により減圧から大気圧状態にした後、アドバンテック東洋株式会社製の５Ｃろ紙（保持粒径１μ）により減圧ろ過を行い、ポリオキシアルキレンポリオールの回収を行った。カリウム除去操作後のポリオキシアルキレンポリオールの水酸基価（ＯＨＶ）は３３．３ｍｇＫＯＨ／ｇ、総不飽和度（Ｃ＝Ｃ）０．０１１ｍｅｑ．／ｇ、一級水酸基化率は８０．１モル％、Ｈ−Ｔは８７．５モル％であった。また、ポリオキシアルキレンポリオール中のポリエーテル副生物の含有量は１３１０ｐｐｍ、該化合物のオキシエチレン基含有量は９２重量％であった。ポリオール中のアルカリ金属（カリウム）残存量は６．５ｐｐｍであった。
【０１０３】
比較例２
＜ポリオキシアルキレンポリオールＤ＞
グリセリンにプロピレンオキサイドを付加したポリプロピレンポリオールＭＮ１０００〔三井化学（株）製；ＯＨＶ１６８ｍｇＫＯＨ／ｇ〕１００重量部に対して０．０３重量部のＤＭＣを添加し、１０５℃、１３３０Ｐａ以下で３時間の減圧脱水を行った。次に、オートクレーブに該化合物を仕込み、反応温度８０℃、反応時の最大圧力３９２ｋＰａの条件でＯＨＶ２８．２ｍｇＫＯＨ／ｇになるまでプロピレンオキサイドの付加重合を行い、ＤＭＣを含有している粗製ポリオキシプロピレンポリオールを得た。
該ポリオキシプロピレンポリオール１００重量部に対して２．０重量部の５０重量％の水酸化カリウム（ＫＯＨ）水溶液を添加し、脱水処理を１０５℃、２６６０Ｐａで１時間行った。その後、水を８重量部とＡＤ−６００〔富田製薬（株）製〕を５重量部加え、９０℃、窒素雰囲気下で２時間撹拌し、アドバンテック東洋株式会社製５Ｃろ紙（保持粒径１μ）を用いて減圧ろ過を行った。ろ過後、１２０℃、１３３０Ｐａ以下で１時間減圧脱水を行い、ＤＭＣの除去処理を行った。エチレンオキサイドの付加重合を行うため、ＤＭＣ除去後のポリオキシプロピレンポリオール１００重量部に３．５重量部の５０重量％のＫＯＨ水溶液を添加し、脱水処理を１０５℃、１３３０Ｐａ以下で１時間行った。オートクレーブに該化合物を仕込み、窒素置換後、反応温度１３０℃、反応時の最大圧力が４９０ｋＰａの条件でＯＨＶが２４．０ｍｇＫＯＨ／ｇになるまでエチレンオキサイドを装入し、反応させた。反応後、減圧処理を行い、粗製ポリオキシアルキレンポリオールを得た（分子末端エチレンオキサイド含有量１５重量％）。
【０１０４】
次いで、粗製ポリオキシアルキレンポリオール中のカリウム１モルに対して１．０５モルのリン酸（７５．１重量％のリン酸水溶液）ならびに粗製ポリエーテルポリオール１００重量部に対して８重量部のイオン交換水を装入し、８０℃、２時間の条件で中和反応を行った。その後、酸化防止剤〔チバガイギー（株）製、商品名：ＩＲＧＡＮＯＸ１０１０〕を１０００ｐｐｍならびに吸着剤ＫＷ−７００ＳＮ〔協和化学工業（株）製〕を８０００ｐｐｍ添加し、減圧下、水を留去しながら最終的に１０５℃、１３３０Ｐａで３時間減圧脱水を行った。
窒素により減圧から大気圧状態にした後、アドバンテック東洋株式会社製の５Ｃろ紙（保持粒径１μ）により減圧ろ過を行い、ポリオキシアルキレンポリオールの回収を行った。カリウム除去操作後のポリオキシアルキレンポリオールの水酸基価（ＯＨＶ）は２４．１ｍｇＫＯＨ／ｇ、総不飽和度（Ｃ＝Ｃ）０．０１５ｍｅｑ．／ｇ、一級水酸基化率は８３．２モル％、Ｈ−Ｔは８８．２モル％であった。また、ポリオキシアルキレンポリオール中のポリエーテル副生物の含有量は１５００ｐｐｍ、該化合物のオキシエチレン基含有量は９６重量％であった。ポリオール中のアルカリ金属（カリウム）残存量は８．２ｐｐｍであった。
【０１０５】
実施例１〜２、比較例１〜２で得られたポリオキシアルキレンポリオールの分析結果を〔表１〕に示す。
＜〔表１〕の記号の説明＞
〔表１〕中のポリオールとは、ポリオキシアルキレンポリオールの略号を、ポリオール製造触媒において、実施例で用いたホスファゼニウム化合物をＰＺＮ、水酸化セシウムをＣｓＯＨ、比較例で用いた複金属シアン化物錯体をＤＭＣ、水酸化カリウムはＫＯＨと略した。ＯＨＶ、Ｃ＝Ｃは各々、水酸基価、総不飽和度の略号である。へッド−トウ−テイル（Ｈｅａｄ−ｔｏ−Ｔａｉｌ）結合選択率はＨ−Ｔと略した。また、ポリオキシアルキレンポリオール中のホスファゼニウム化合物触媒の残存量は、ホスファゼニウム化合物触媒残存量という表記にした。アルカリ金属の残存量に関しては、アルカリ金属残存量とした。
【０１０６】
【表１】

次いで、実施例１〜２、比較例１〜２で得られたポリオールを用いて、ポリマー分散ポリオールの製造を行った。
【０１０７】
実施例３
＜ポリマー分散ポリオールＥ＞
温度計、攪拌装置、送液装置付き１リットルオートクレーブにポリオールＡを満液状態に仕込み、攪拌しながら１２０℃まで昇温した。続いて、予めポリオールＡを７７．６重量部、アクリロニトリル〔三井化学（株）製〕を２２．４重量部及びラジカル開始剤であるアゾビスイソブチロニトリル（以下、ＡＩＢＮと略する）０．３５重量部の比率で均一混合した混合液をオートクレーブに連続的に装入し、排出口より連続的にポリマー分散ポリオールを得た。このとき反応圧力は４４４ｋＰａ、滞留時間は５０分間であった。定常状態に達した後、得られた反応液を１２０℃、２６６０Ｐａで４時間減圧吸引処理し、未反応ビニルモノマー等を除去してポリマー分散ポリオールＥを得た。ポリマー分散ポリオールの水酸基価（ＯＨＶ）は２６．１ｍｇＫＯＨ／ｇ、ポリマー濃度は２０．７重量％であった。
【０１０８】
比較例３
＜ポリマー分散ポリオールＦ＞
温度計、攪拌装置、送液装置付き１リットルオートクレーブにポリオールＣを満液状態に仕込み、攪拌しながら１２０℃まで昇温した。続いて、予めポリオールＣを７７．６重量部、アクリロニトリル〔三井化学（株）製〕を２２．４重量部及びラジカル開始剤であるアゾビスイソブチロニトリル（以下、ＡＩＢＮと略する）０．３５重量部の比率で均一混合していた混合液をオートクレーブに連続的に装入し、排出口より連続的にポリマー分散ポリオールを得た。このとき反応圧力は４４４ｋＰａ、滞留時間は５０分であった。定常状態に達した後、得られた反応液を１２０℃、２６６０Ｐａで４時間減圧吸引処理し、未反応ビニルモノマー等を除去してポリマー分散ポリオールＦを得た。ポリマー分散ポリオールの水酸基価（ＯＨＶ）は２６．３ｍｇＫＯＨ／ｇ、ポリマー濃度は２０．５重量％であった。
【０１０９】
実施例４、比較例４
本発明により得られたポリオキシアルキレンポリオール及びポリマー分散ポリオールの効果を明らかにするため、以下にこれらのポリオールを使用した軟質ポリウレタンフォーム用レジン液及びフォームの製造例を示す。実施例４及び比較例４に用いた原料を以下に示す。本発明はこれら実施例に限定されるものではない。
＜レジン液の調製＞
レジン液：実施例４（レジン液Ｇ）、比較例４（レジン液Ｈ）
ポリオキシアルキレンポリオール：実施例４（Ｂ）、比較例４（Ｄ）
ポリマー分散ポリオール：実施例４（Ｅ）、比較例４（Ｆ）
架橋剤：ＤＥＯＡ（三井化学社製、ジエタノールアミン）
発泡剤：イオン交換水
触媒−１：Ｌ−１０２０〔活材ケミカル社製、３級アミン触媒（トリエチレンジアミンの３３重量％ジエチレングリコール溶液）〕
触媒−２：ＴＭＤＡ〔活材ケミカル社製、３級アミン触媒（ビスジメチルアミノエチルエーテルの７０重量％ジエチレングリコール溶液）〕
整泡剤：Ｌ−５３０９；日本ユニカー社製シリコーン整泡剤
【０１１０】
ポリオール６０重量部、ポリマー分散ポリオール４０重量部をポリカップに計量し、次いで、水３．４重量部、ＤＥＯＡ１．１重量部、Ｌ−１０２０を０．７重量部、ＴＭＤＡを０．１重量部、そしてＬ−５３０９を１．０重量部を添加した。内温を２５℃に調製し、同温度にて均一混合を行い、レジン液（実施例４：レジン液Ｇ、比較例４：レジン液Ｈ）を調製した。得られたレジン液を２０℃に冷却し、窒素雰囲気下、金属製容器に密閉し、２０℃の恒温オーブンに入れ１５日間貯蔵した。
【０１１１】
＜軟質ポリウレタンフォームの製造＞
軟質ポリウレタンフォームの製造用ポリイソシアネート化合物：（ポリイソシアネート化合物）コスモネートＴＭ−２０〔三井化学（株）社製、ポリイソシアネート、ＴＤＩ−８０とポリメリックＭＤＩとの８０：２０重量比の混合物〕
２０℃の恒温オーブン中で１５日間貯蔵したレジン液を２５℃に調整した。次に、レジン液の活性水素とイソシアネート基との当量比（ＮＣＯ／Ｈ）が１．００となる量のコスモネートＴＭ−２０を２５℃に調整した。次いで、先に調製したレジン液と６秒間激しく攪拌混合し、予め市販の離型剤を塗布した６０℃のアルミ製テストモールド（内寸４００×４００×１００ｍｍ）に注入後、蓋を閉めクランプにより密閉し、発泡硬化させた。攪拌開始から６分後にテストモールドのクランプを外し、硬化した軟質ポリウレタンフォームを脱型し、ローラーを使って厚みを８０％圧縮して気泡を完全に連通化させた（クラッシング操作）。発泡して２４時間後に軟質ポリウレタンフォームを得た。得られた軟質ポリウレタンフォームの諸物性を上記方法により測定した。評価結果を〔表２〕に示す。
【０１１２】
【表２】

【０１１３】
＜実施例の考察＞
〔表２〕より、実施例のポリエーテル副生物が少なく、且つ、へッド−トウ−テイル（Ｈｅａｄ−ｔｏ−Ｔａｉｌ）結合選択率を９５モル％以上有しているポリオキシアルキレンポリオール、及びそれを分散媒としたポリマー分散ポリオールから調製したレジン液の２０℃、１５日後のフォーム物性は、ポリエーテル副生物が１２００ｐｐｍを超え、且つ、へッド−トウ−テイル（Ｈｅａｄ−ｔｏ−Ｔａｉｌ）結合選択率が９５モル％未満のポリオキシアルキレンポリオール及びポリマー分散ポリオールを用いたレジン液のフォーム物性と比較して、セトリングが低く、反発弾性、硬度が高く、しかも湿熱時の永久圧縮歪みが少ないことがわかる。本発明に係るポリオキシアルキレンポリオール及びそれを分散媒としたポリマー分散ポリオールから、レジン液の貯蔵安定性、及び成形安定性、更には力学物性に優れた軟質ポリウレタンフォームが得られる。
【０１１４】
【発明の効果】
本発明により、プロピレンオキサイド付加重合によるへッド−トウ−テイル（Ｈｅａｄ−ｔｏ−Ｔａｉｌ）結合最低選択率が９５モル％、分子末端一級水酸基化率が少なくとも４０モル％、オキシエチレン基の含有量が少なくとも８５重量％であるポリエーテル化合物の含有量が１２００ｐｐｍ以下、水酸基価が５〜７０ｍｇＫＯＨ／ｇであり、且つ、水酸基価（ＯＨＶ）と総不飽和度（Ｃ＝Ｃ）が前記数式（１）で表される関係にあるポリオキシアルキレンポリオール、並びに、該ポリオキシアルキレンポリオールを分散媒とするポリマー分散ポリオールが提供される。
上記特性を有する本発明のポリオキシアルキレンポリオール及びポリマー分散ポリオールは、ポリイソシアネート化合物との反応性に優れ、また、ポリウレタン樹脂を製造するに際し、発泡剤として水を使用する場合のレジン液の貯蔵安定性に優れる。更に、本発明のポリオキシアルキレンポリオール及びポリマー分散ポリオールを用いることにより、力学物性、及び成形安定性に優れたポリウレタン樹脂が得られる。
そのため、本発明のポリオキシアルキレンポリオール及びポリマー分散ポリオールは、ポリウレタンフォーム、特に高弾性ポリウレタンフォーム、エラストマー、シーリング、接着剤、床材、靴底等の資材として広い分野で使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyoxyalkylene polyol and a polymer-dispersed polyol using the same as a dispersion medium. Specifically, the structure of the oxypropylene group by propylene oxide addition polymerization is limited, the molecular terminal primary hydroxylation rate is high, and the content of the polyether compound having a high oxyethylene group content is below a specific concentration, and The present invention relates to a polyoxyalkylene polyol having a low total unsaturation of an oxyalkylene polyol, which can be suitably used as a polyurethane resin raw material, and a polymer-dispersed polyol using the same as a dispersion medium.
[0002]
[Prior art]
Usually, polyoxyalkylene polyols are produced by anionic polymerization of epoxide compounds using alkali metal hydroxides such as potassium hydroxide (hereinafter abbreviated as KOH) and sodium hydroxide (hereinafter abbreviated as NaOH) as catalysts. Has been. However, in the conventional production method using these compounds as a catalyst, when propylene oxide, which is most widely used as an epoxide compound, is used, a chain transfer reaction of propylene oxide occurs with an increase in the molecular weight of the polyoxyalkylene polyol. A polyoxyalkylene monool having an unsaturated group at the terminal (hereinafter abbreviated as monool) is by-produced.
[0003]
Since this monool has a lower molecular weight than the polyoxyalkylene polyol produced by the main reaction of propylene oxide, the molecular weight distribution of the polyoxyalkylene polyol is broadened and the average number of functional groups is lowered. Therefore, polyurethane resins using polyoxyalkylene polyols with a high monool content, regardless of whether they are foams or elastomers, exhibit undesirable phenomena such as increased hysteresis, decreased hardness, decreased cure, and increased permanent compression strain. Accompany.
[0004]
Japanese Patent No. 2615927 exemplifies a method for producing a polyurethane foam using a polyol having a hydroxyl value of more than 38 and 60 or less and a total unsaturation of 0.03 or less. It has been shown that such polyols are generally obtained by using diethyl zinc, iron chloride, metalloporphyrin, double metal cyanide complex, etc. as a catalyst (column 3, lines 27-29). ).
[0005]
  Furthermore, Japanese Patent Application Laid-Open No. Hei.03No. 244620 adds at least one high molecular weight polyol selected from a polyoxyalkylene polyol having a hydroxyl value of 5 to 38 and a polymer-dispersed polyol having the polyoxyalkylene polyol as a matrix, and a polyisocyanate compound. A method for producing a polyurethane foam in which a low-viscosity compound having a polymerizable unsaturated group, a catalyst, and a foaming agent are reacted is exemplified.
[0006]
In the polyoxyalkylene polyol described in the publication, the hydroxyl value (XmgKOH / g) and the total unsaturation (Ymeq./g) are in a relationship of Y ≦ 0.9 / (X-10), and Y is 0 .07 meq. / G or less, the hydroxyl value (X) is 5-38 mgKOH / g, and the number of hydroxyl groups is 2-8. Such polyoxyalkylene polyol is generally obtained by using a catalyst other than an alkali catalyst, such as diethyl zinc, iron chloride, metal porphyrin, double metal cyanide complex, and the like. In particular, it is described that a good polyoxyalkylene polyol can be obtained by using a double metal cyanide complex (hereinafter abbreviated as DMC) (page 5, right column, lines 1 to 13). ).
[0007]
As a result of synthesizing a polyoxyalkylene polyol by using a double metal cyanide complex that is considered to be particularly preferable, the present inventors have found that a head-to-tail (Head-to-tail) after addition polymerization of propylene oxide. Tail) The bond selectivity is low (82 to 88 mol%), and the viscosity is higher than that of a polyoxyalkylene polyol using a conventional KOH catalyst. When such a polyoxyalkylene polyol is used for a flexible polyurethane foam, there is a problem in terms of molding stability and mixing at the time of foam molding when producing a urethane foam. In addition, the isocyanate group-terminated prepolymer obtained by reacting the polyoxyalkylene polyol and the polyisocyanate compound has problems such as a marked increase in viscosity and a decrease in workability.
[0008]
On the other hand, in the polyurethane field, in order to increase the reactivity with the polyisocyanate compound, polyoxyalkylene polyol in which ethylene oxide is addition-polymerized at the molecular terminal of polyoxypropylene polyol to improve the terminal primary hydroxylation rate is used. . Such polyoxyalkylene polyols are produced by a two-step reaction process. Usually, a method of performing addition polymerization of propylene oxide on an active hydrogen compound using a KOH catalyst and then performing addition polymerization of ethylene oxide is used. This method has an advantage that the same catalyst (KOH) can be used in the propylene oxide addition polymerization step and the ethylene oxide addition polymerization step. However, when the KOH catalyst is used as described above, the monool content in the polyoxyalkylene polyol is contained. There is a disadvantage that the amount increases.
[0009]
Although the above-mentioned DMC has an excellent performance for suppressing side reactions of propylene oxide, it is known that it is impossible to block copolymerize ethylene oxide with propylene oxide using the catalyst. Therefore, when ethylene oxide is copolymerized after polymerization of propylene oxide with a DMC catalyst, the DMC is deactivated by reaction with an oxidizing agent such as oxygen-containing gas, peroxide, or sulfuric acid. The catalyst residue is separated from the polyol, and addition polymerization of ethylene oxide using an alkali metal hydroxide such as KOH or an alkali metal alkoxide is required (US Pat. No. 5,1144,093, USP 5,235). 114).
[0010]
Various methods have been proposed to deactivate the DMC catalyst and to copolymerize ethylene oxide at the molecular ends. However, in any method, the manufacturing process is complicated and poor in economic efficiency, and when ethylene oxide is added to a high molecular weight polyoxypropylene polyol, the solubility of the alkali metal compound as a catalyst in the polyol decreases. There is a problem that polyethylene oxide having the compound as an initiation component is by-produced.
[0011]
As described above in detail, in order to improve the mechanical properties of polyurethane resins and polyurethane foams and the reactivity with polyisocyanate compounds, the primary hydroxyl group at the molecular end is low in monool content and copolymerized with ethylene oxide. Polyoxyalkylene polyols with a high conversion rate are known to be effective, but polyoxyalkylene polyols having such a structure, polymer-dispersed polyols using them as dispersion media, water as blowing agents, catalysts, and regulators. It is not known about the effect on the storage stability practically required for the resin liquid at the time of producing the polyurethane foam obtained from the foaming agent.
[0012]
[Problems to be solved by the invention]
In view of the above problems, an object of the present invention is to provide a polyoxyalkylene polyol excellent in reactivity with a polyisocyanate compound. Another object of the present invention is to provide a polyoxyalkylene polyol from which a polyurethane resin excellent in mechanical properties and molding stability can be obtained. It is another object of the present invention to provide a polymer-dispersed polyol using the polyoxyalkylene polyol as a dispersion medium, from which a polyurethane resin having excellent mechanical properties and molding stability can be obtained.
[0013]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have a high head-to-tail bond rate by propylene oxide addition polymerization and a high molecular end primary hydroxylation rate. Furthermore, a polyoxyalkylene polyol having a high content of a polyether compound having a high oxyethylene group content and not more than a specific concentration and having a low total unsaturation degree of the polyoxyalkylene polyol, and the polyoxyalkylene polyol The present inventors have found that a polymer-dispersed polyol used as a dispersion medium can solve the above-mentioned problems.
[0014]
That is, according to the present invention, a polyoxyalkylene polyol obtained by addition polymerization of an epoxide compound containing propylene oxide and ethylene oxide to an active hydrogen compound, which is head-to-tail by propylene oxide addition polymerization. The minimum selectivity of the bond is 95 mol%, the molecular terminal primary hydroxylation rate is at least 40 mol%, the content of the polyether compound having an oxyethylene group content of at least 85 wt% is 1200 ppm or less, and the hydroxyl value is 5 to 70 mgKOH / G, and the hydroxyl value (OHV) and the total degree of unsaturation (C = C) are represented by the formula (1) [Equation 2].
[0015]
[Expression 2]
C = C ≦ 1.2 / OHV (1)
There is provided a polyoxyalkylene polyol characterized by having a relationship represented by:
[0016]
A preferred embodiment of the polyoxyalkylene polyol of the present invention is a polyol produced by addition polymerization of an epoxide compound to an active hydrogen compound using a phosphazenium compound as a catalyst, and a residual amount of the phosphazenium compound catalyst is 150 ppm or less. It is an oxyalkylene polyol. Another preferred embodiment is a polyol produced by addition polymerization of an epoxide compound to an active hydrogen compound using a mixture of a phosphazenium compound and an alkali metal compound as a catalyst, and the residual amount of the phosphazenium compound catalyst is 150 ppm or less, It is a polyoxyalkylene polyol having an alkali metal residual amount of 5 ppm or less. When using a mixture catalyst, it is preferable to use a mixture catalyst containing 5 to 50 mol% of an alkali metal compound. A preferred alkali metal compound is a cesium compound, and more preferably cesium hydroxide.
[0017]
According to another aspect of the present invention, there is provided a polymer-dispersed polyol in which fine particles of vinyl polymer are dispersed in the polyoxyalkylene polyol, wherein the concentration of the vinyl polymer is 5 to 50% by weight. A polymer-dispersed polyol is provided. The vinyl polymer is preferably a polymer of a monomer having at least one ethylenically unsaturated group selected from acrylonitrile, styrene, acrylamide, and methyl methacrylate. More preferred are monomers selected from acrylonitrile, a mixture of acrylonitrile and styrene, and a mixture of acrylonitrile, styrene and acrylamide.
[0018]
The polyoxyalkylene polyol and the polymer-dispersed polyol of the present invention are suitable as raw materials for polyurethane resins and polyurethane foams, particularly high-elastic polyurethane foams, which are excellent in reactivity with polyisocyanate compounds and excellent in mechanical properties and molding stability. It is also suitable as a raw material for polyurethane resins such as elastomers, sealings, flooring materials, and shoe soles.
[0019]
In the present invention, the residual amount of the phosphazenium compound catalyst means the residual amount of the phosphazenium compound and / or the neutralized salt of the compound.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The polyoxyalkylene polyol according to the present invention is produced by addition polymerization of an epoxide compound containing propylene oxide and ethylene oxide to an active hydrogen compound in the presence of a catalyst, and purifying the obtained crude polyoxyalkylene polyol. It is a polyoxyalkylene polyol having the following characteristics 1) to 4).
1) The minimum selectivity of a head-to-tail bond by propylene oxide addition polymerization is 95 mol%. That is, it is 95 mol% or more.
2) The molecular terminal primary hydroxylation rate is at least 40 mol%.
3) The content of the polyether compound having an oxyethylene group content of at least 85% by weight is 1200 ppm or less.
4) The hydroxyl value (hereinafter abbreviated as OHV) and the total degree of unsaturation (hereinafter abbreviated as C = C) are in the relationship represented by the mathematical formula (1).
[0021]
Each of the above items will be described.
1) When the head-to-tail bond selectivity by propylene oxide addition polymerization is less than 95%, the head-to-tail bond selectivity is decreased. The increase in viscosity is significant when the molecular weight of oxyalkylene polyol is increased. When a polyoxyalkylene polyol having a head-to-tail bond selectivity of less than 95% is used as a raw material for a flexible polyurethane foam, the molding stability during mechanical foaming during the production of the foam is stable. There is a problem in that the problem arises in terms of properties and mixing properties, and the mixing properties with auxiliary agents such as foam stabilizers also deteriorate.
[0022]
2) The molecular terminal primary hydroxylation rate of the polyoxyalkylene polyol is at least 40 mol%. Preferably it is 60 mol% or more, Most preferably, it is 80 mol% or more. When the molecular terminal primary hydroxylation rate is less than 40 mol%, the reactivity with the polyisocyanate compound, the moldability of the flexible polyurethane foam, and the mechanical properties of the resulting polyurethane foam are lowered.
The content of terminal oxyethylene groups in the polyoxyalkylene polyol of the present invention is 5 to 30% by weight, preferably 6 to 25% by weight, and most preferably 7 to 20% by weight. When the amount is less than 5% by weight, the molecular terminal primary hydroxylation rate is less than 40% by mole. When it exceeds 30% by weight, the wet heat permanent compression strain of the flexible polyurethane foam increases.
[0023]
3) In order to improve the molecular end primary hydroxylation rate of the polyoxyalkylene polyol, ethylene oxide is copolymerized at the molecular end. The content of the polyether compound in which the oxyethylene group content in the polyoxyalkylene polyol is at least 85% by weight due to this copolymerization is 1200 ppm or less. Preferably, it is 800 ppm or less, and most preferably 400 ppm or less.
When addition polymerization of ethylene oxide at the molecular terminal is carried out, if a large amount of water or a low molecular weight propoxyl compound is present in the polyol, a highly ethoxylated compound is by-produced. In particular, when a double metal cyanide complex (DMC) is propoxylated as a catalyst and an alkali metal compound serving as a catalyst for deactivation of DMC and ethoxylation is used as a catalyst, a polyoxyalkylene polyol having a high molecular weight (several Since an alkali metal compound (especially an alkali metal hydroxide) has a low solubility in an average molecular weight of 4000 or more, an ethoxylated polyether compound using the compound as an initiation component is by-produced.
[0024]
In the case of using a reaction product of an active hydrogen compound and an alkali metal compound, particularly an alkali metal hydroxide, which is an initiator at the time of producing the polyoxyalkylene polyol, moisture and carbonic acid (dissolved carbon dioxide in the air) are removed from the reaction product. If not fully stripped), highly ethoxylated polyether compounds are by-produced. In particular, the water content in the reaction product is 1000 ppm or less, preferably 800 ppm or less, and most preferably 200 ppm or less.
[0025]
According to the knowledge of the present inventors, when the polyether compound having an oxyethylene group content of at least 85% by weight exceeds 1200 ppm, not only the transparency of the polyoxyalkylene polyol is lowered, but also for polyurethane foam. The storage stability of the resin liquid as a raw material is deteriorated. The resin liquid is a raw material for producing polyurethane foam in which polyoxyalkylene polyol, polymer-dispersed polyol, foaming agent, catalyst, foam stabilizer and the like are uniformly mixed.
[0026]
According to Freon regulations, it is common to use water alone, inert gas alone, or a mixture of water and inert gas as a foaming agent. In particular, a resin solution for flexible polyurethane foam using water as a foaming agent. Are often stored for long periods of time. At this time, if a polyether compound having an oxyethylene group content of at least 85% by weight exceeds 1200 ppm in the polyoxyalkylene polyol, a gelled product is generated in the resin liquid. When a flexible polyurethane foam is produced using a resin liquid containing the gelled product, molding failure occurs or physical properties of the foam are lowered.
[0027]
4) The hydroxyl value (OHV) of the polyoxyalkylene polyol is in the range of 5 to 70 mgKOH / g, and the hydroxyl value (OHV) and the total degree of unsaturation (C = C) are represented by the formula (1). There is a relationship. That is, there is a relationship of [C = C ≦ 1.2 / OHV]. When C = C is larger than the above formula, the mechanical properties of the resulting polyurethane foam are lowered, and the object of the present invention is not achieved.
[0028]
The polyoxyalkylene polyol of the present invention having the above characteristics 1) to 4) was obtained by addition polymerization of an epoxide compound containing propylene oxide or an epoxide compound containing ethylene oxide in an active hydrogen compound in the presence of a catalyst. It is produced by purifying crude polyoxyalkylene polyol. The catalyst preferably used is a phosphazenium compound or a mixture of a phosphazenium compound and an alkali metal compound.
[0029]
The phosphazenium compound used in the present invention will be described. As the phosphazenium compound, it is preferable to use a compound shown in EP-A-0791600 filed earlier by the present applicant.
[0030]
Specifically, chemical formula (1) [Chemical Formula 1]
[0031]
[Chemical 1]

[In the chemical formula (1), a, b, c and d are each a positive integer of 0 to 3, but all of a, b, c and d are not 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations;^r-Represents an inorganic anion having a valence of r], or a chemical formula (2)
[0032]
[Chemical 2]

[In the chemical formula (2), a, b, c and d are each a positive integer of 0 to 3, but all of a, b, c and d are not 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. Q^-Represents a hydroxy anion, an alkoxy anion, an aryloxy anion, or a carboxy anion].
[0033]
In the phosphazenium cation represented by the chemical formula (1) and the chemical formula (2) in the present invention, a, b, c and d are each a positive integer of 0 to 3. However, all are not 0 at the same time. Preferably it is an integer of 0-2. More preferably, regardless of the order of a, b, c and d, (2, 1, 1, 1), (1, 1, 1, 1), (0, 1, 1, 1), (0, 0 , 1, 1) or (0, 0, 0, 1) in combination. More preferably, it is a number in a combination of (1, 1, 1, 1), (0, 1, 1, 1), (0, 0, 1, 1) or (0, 0, 0, 1). .
[0034]
R in the phosphazenium cation of the salt represented by the chemical formula (1) and the chemical formula (2) in the present invention is the same or different hydrocarbon group having 1 to 10 carbon atoms, specifically, This R is, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1 -Butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl 2-ethyl-1-hexyl, 1,1-dimethyl-3,3-dimethylbutyl (tert-octyl), nonyl, decyl, phenyl, 4 Toluyl, benzyl, selected from aliphatic or aromatic hydrocarbon groups such as 1-phenylethyl or 2-phenylethyl.
Of these, aliphatic hydrocarbon groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl, and tert-octyl are preferable, and a methyl group or an ethyl group is more preferable. .
[0035]
In addition, when two Rs on the same nitrogen atom in the phosphazenium cation are bonded to form a ring structure, the divalent hydrocarbon group on the nitrogen atom is from 4 to 6 carbon atoms. A divalent hydrocarbon group having a main chain (the ring is a 5- to 7-membered ring containing a nitrogen atom), preferably tetramethylene, pentamethylene or hexamethylene, etc. The main chain is substituted with an alkyl group such as methyl or ethyl. More preferably, it is a tetramethylene or pentamethylene group. Such a ring structure may be taken for all possible nitrogen atoms in the phosphazenium cation, or a part thereof.
[0036]
T in the chemical formula (1) in the present invention^r-Represents an inorganic anion having a valence of r. And r is an integer of 1-3. Examples of such inorganic anions include boric acid, tetrafluoro acid, hydrocyanic acid, thiocyanic acid, hydrofluoric acid, hydrochloric acid or hydrohalic acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, and the like. Inorganic anions such as acid, hexafluorophosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafluorothalamic acid, and perchloric acid. In addition, HSO as an inorganic anion_Four ^-, HCO_Three ^-There is also.
These inorganic anions can be exchanged with each other by an ion exchange reaction. Among these inorganic anions, anions of inorganic acids such as boric acid, tetrafluoroboric acid, hydrohalic acid, phosphoric acid, hexafluorophosphoric acid and perchloric acid are preferable, and a chlorine anion is more preferable.
[0037]
When the phosphazenium compound of the chemical formula (1) is used as a catalyst, it is preferable to prepare an alkali metal or alkaline earth metal salt of an active hydrogen compound in advance. The compound may be prepared by a conventionally known method. The alkali metal or alkaline earth metal salt of the active hydrogen compound coexisting with the chemical formula (1) is a salt in which the active hydrogen of the active hydrogen compound is dissociated as a hydrogen ion and replaced with the alkali metal or alkaline earth metal ion. It is.
[0038]
Active hydrogen compounds that give such salts include alcohols, phenolic compounds, polyamines, alkanolamines, and the like. For example, water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol , Dihydric alcohols such as 1,4-cyclohexanediol, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, poly Polysaccharides such as glycerol, sugars such as glucose, sorbitol, dextrose, fructose, sucrose, methyl glucoside, hydroxyethyl glucooxide or derivatives thereof Fatty acid amines such as ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine, aromatic amines such as toluylenediamine, diphenylmethanediamine, bisphenol A, bisphenol F, bisphenol S, novolac, resole, resorcin, hydroquinone, And phenolic compounds such as Mannich compounds. Two or more of these active hydrogen compounds can be used in combination. Furthermore, compounds obtained by addition polymerization of 6 mol or less of epoxide compound to 1 equivalent of active hydrogen group by a conventionally known method can be used for these active hydrogen compounds.
[0039]
Usually, in order to obtain an alkali metal salt or alkaline earth metal salt thereof from these active hydrogen compounds, the active hydrogen compound and an alkali metal, alkaline earth metal, basic alkali metal, or alkaline earth A method of reacting with a metal compound is used.
[0040]
The epoxide compound is subjected to addition polymerization in the presence of a salt of a phosphazenium cation represented by the chemical formula (1) and an inorganic anion and an alkali metal salt or alkaline earth metal salt of an active hydrogen compound. At this time, a salt of an alkali metal cation or an alkaline earth metal cation and an inorganic anion is by-produced. When this by-product salt inhibits the polymerization reaction, it is filtered prior to the polymerization reaction. It can also be removed. In addition, the phosphazenium salt of the active hydrogen compound derived from the salt represented by the chemical formula (1) and the alkali metal salt or alkaline earth metal salt of the active hydrogen compound is previously isolated, and the epoxide compound is polymerized in the presence thereof. You can also.
[0041]
Another method for producing the polyoxyalkylene polyol of the present invention is a method in which an epoxide compound is subjected to addition polymerization in the presence of a phosphazenium compound represented by the chemical formula (2) and an active hydrogen compound. Q in the phosphazenium compound represented by the chemical formula (2)^-Is an anion selected from the group consisting of a hydroxy anion, an alkoxy anion, an aryloxy anion and a carboxy anion.
[0042]
These Q^-Of these, hydroxy anions are preferable, and alkoxy anions derived from aliphatic alcohols such as methanol, ethanol, n-propanol, and isopropanol are preferable. For example, an aryloxy anion derived from an aromatic hydroxy compound such as phenol or cresol. For example, a carboxy anion derived from formic acid, acetic acid, propionic acid and the like.
[0043]
Among these, a hydroxy anion, for example, an alkoxy anion derived from a low-boiling alkyl alcohol such as methanol, ethanol or n-propanol, or a carboxy anion derived from a carboxylic acid such as formic acid or acetic acid is more preferable. More preferred are hydroxy anion, methoxy anion, ethoxy anion and acetate anion. These phosphazenium compounds may be used alone or in combination of two or more.
[0044]
The active hydrogen compound coexisting with the chemical formula (2) is the same as that described in detail above as the active hydrogen compound that gives the alkali metal salt or alkaline earth metal salt of the active hydrogen compound.
[0045]
In the method of the present invention in which the epoxide compound is subjected to addition polymerization in the presence of the phosphazenium compound represented by the chemical formula (2) and the active hydrogen compound, the excess of the active hydrogen compound usually used in excess remains as it is. In addition, water, alcohol, aromatic hydroxy compound or carboxylic acid is by-produced depending on the type of phosphazenium compound. These by-products, particularly low molecular weight monoalcohol compounds, are preferably removed before the addition polymerization reaction of the epoxide compound. Examples of the removing method include a method of heating and decompressing under conditions of 80 to 130 ° C. and 1330 to 2660 Pa or less under a bubbling operation with an inert gas, and a method using an adsorbent. The residual amount of the by-product is 1000 ppm or less, preferably 800 ppm or less, and most preferably 400 ppm or less.
[0046]
Next, a mixture of a phosphazenium compound and an alkali metal compound used as a catalyst for producing the polyoxyalkylene polyol of the present invention will be described. By using a relatively inexpensive alkali metal compound in combination with the phosphazenium compound, the production cost of the polyoxyalkylene polyol is reduced. However, as described above, excessive use of the alkali metal compound leads to an increase in the total degree of unsaturation of the polyoxyalkylene polyol.
[0047]
When a mixture of a phosphazenium compound and an alkali metal compound is used as a catalyst, the alkali metal compound is 5 to 50 mol%, preferably 6 to 40 mol%, most preferably 8 to 30 mol, based on 1 mol of the mixture. % Range. When the amount of the alkali metal compound used is less than 5 mol%, the effect of reducing the production cost of the polyoxyalkylene polyol is low. On the other hand, when the amount of the alkali metal compound used exceeds 50 mol%, the total unsaturation (monool content) increases, and the formula (1) of the hydroxyl value and the total unsaturation, which is the object of the present invention, increases. It is difficult to satisfy the relationship.
[0048]
Examples of the alkali metal compound include sodium, potassium, sodium, rubidium and cesium compounds. As anion forms, hydroxy anions, alkoxy anions such as methoxy and ethoxy groups, CO₃ ^2-, HCO_Three ^-Etc. Alkali metal compounds having an alkoxy or hydroxy anion are preferred. Further, as the alkali metal compound, a cesium compound is preferable, and cesium hydroxide described in JP-A-7-278289 filed earlier by the present applicant is preferable.
[0049]
Epoxide compounds that undergo addition polymerization to an active hydrogen compound in the presence of a phosphazenium compound or a mixture of a phosphazenium compound and an alkali metal compound include propylene oxide, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and styrene. Examples thereof include oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, and trifluoropropylene oxide. Two or more of these may be used in combination. Of these, propylene oxide, ethylene oxide and 1,2-butylene oxide are preferred.
[0050]
As an addition polymerization method of an epoxide compound, an epoxide compound containing propylene oxide is subjected to addition polymerization, and then ethylene oxide is subjected to addition polymerization. Specifically, an ethylene oxide cap reaction in which ethylene oxide is block-copolymerized after addition polymerization of an epoxide compound containing propylene oxide can be mentioned. Moreover, the ethylene oxide cap reaction which copolymerizes the epoxide compound containing propylene oxide and ethylene oxide at random, and then copolymerizes ethylene oxide is mentioned.
[0051]
In any method, the epoxide compound containing propylene oxide preferably contains at least 50 mol% of propylene oxide. The ethylene oxide capping reaction is essential in any method.
[0052]
In order to make the molecular end primary hydroxylation rate of the polyoxyalkylene polyol of the present invention at least 40 mol%, cap reaction with ethylene oxide in such an amount that the molecular end oxyethylene group content is 5 to 30% by weight. To do.
[0053]
When producing a polyoxyalkylene polyol having the characteristics 1) to 4), the following conditions are preferably selected. That is, the phosphazenium compound represented by the chemical formula (1) or the chemical formula (2) with respect to 1 mol of the active hydrogen compound is 5 × 10 5.^-Five~ 5 mol, preferably 1 x 10^-Four~ 5x10^-1Mole, more preferably 1 × 10^-3~ 1x10^-2The range of moles. When increasing the molecular weight of the polyoxyalkylene polyol, it is preferable to increase the concentration of the phosphazenium compound relative to the active hydrogen compound within the above range. The phosphazenium compound represented by the chemical formula (1) or the chemical formula (2) is 5 × 10 5 to 1 mol of the active hydrogen compound.^-FiveWhen it is less than the mole, the polymerization rate of the alkylene oxide is lowered, and the production time of the polyoxyalkylene polyol is prolonged. When the amount of the phosphazenium compound represented by the chemical formula (1) or the chemical formula (2) exceeds 5 moles relative to 1 mole of the active hydrogen compound, the proportion of the phosphazenium compound in the production cost increases.
[0054]
When a mixture of a phosphazenium compound and an alkali metal compound is used as a catalyst, it is preferable to use a phosphazenium compound represented by the chemical formula (2). For one mole of active hydrogen compound, the mixture is 5 × 10^-Five~ 1 mole, preferably 1 x 10^-Four~ 5x10^-2Mole, more preferably 1 × 10^-3~ 1x10^-2The range of moles.
[0055]
The addition polymerization reaction temperature of the epoxide compound containing propylene oxide as the main component is 15 to 130 ° C, preferably 40 to 120 ° C, more preferably 50 to 110 ° C. When the reaction temperature is lower than 15 ° C., the polymerization rate of propylene oxide decreases and the production time of the polyoxyalkylene polyol becomes longer. When the reaction temperature exceeds 130 ° C., the total degree of unsaturation increases as the polyoxyalkylene polyol increases in molecular weight.
[0056]
On the other hand, the addition polymerization temperature of ethylene oxide is 15 to 170 ° C, preferably 40 to 150 ° C, more preferably 90 to 150 ° C. When the reaction temperature is lower than 15 ° C., the polymerization rate of the epoxide compound decreases, and the production time of the polyoxyalkylene polyol becomes longer. When the reaction temperature exceeds 170 ° C., the polyoxyalkylene polyol tends to be colored. When the reaction temperature of the epoxide compound is carried out at a low temperature within the above range, it is preferable to increase the catalyst concentration relative to the active hydrogen compound within the above-described range. The supply method of the epoxide compound to the catalyst and the active hydrogen compound charged in the pressure-resistant reactor includes a method of supplying a part of the required amount of the epoxide compound at once, or a method of supplying the epoxide compound continuously or intermittently. Used. In the method of supplying a part of the required amount of the epoxide compound in a batch, the reaction temperature at the initial stage of the polymerization reaction of the epoxide compound is set to a lower temperature within the above range, and after the epoxide compound is partially charged, the reaction is gradually performed. A method of increasing the temperature is preferred.
[0057]
The maximum pressure during the reaction of the epoxide compound is preferably 882 kPa. Usually, the reaction of an epoxide compound is performed by a pressure resistant reactor. The reaction of the epoxide compound may be started from a reduced pressure state or an atmospheric pressure state. When starting the reaction from an atmospheric pressure state, it is desirable to carry out in the presence of an inert gas such as nitrogen or helium. When the maximum reaction pressure of the epoxide compound exceeds 882 kPa, the amount of by-product monool increases. The maximum reaction pressure is preferably 686 kPa, more preferably 490 kPa. When propylene oxide is used as the epoxide compound, the maximum reaction pressure is preferably 490 kPa.
[0058]
A solvent can also be used in the addition polymerization reaction of the epoxide compound. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane and peptane, ethers such as diethyl ether, tetrahydrofuran and dioxane, or aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide. When a solvent is used, a method of recovering and reusing the solvent after production is desirable in order not to increase the production cost of the polyoxyalkylene polyol.
[0059]
A method for purifying a crude polyoxyalkylene polyol obtained by addition polymerization of an epoxide compound to an active hydrogen compound using the above compound as a catalyst will be described.
a) After adding 1 to 20 parts by weight of water to 100 parts by weight of the crude polyoxyalkylene polyol, 1 mol of the phosphazenim compound in the crude polyoxyalkylene polyol is obtained under a condition where the oxygen concentration in the gas phase is 2% or less. On the other hand, the phosphazenium compound is neutralized at 50 to 130 ° C. using 0.5 to 8 mol of at least one neutralizing agent selected from inorganic acids, inorganic acid acidic salts and organic acids. Thereafter, 100 to 4000 ppm of an antioxidant is added to the crude polyoxyalkylene polyol, a reduced pressure treatment is performed, water is distilled off, and the polyoxyalkylene polyol is recovered.
[0060]
b) After adding 1 to 40 parts by weight of an inert organic solvent and water to 100 parts by weight of the crude polyoxyalkylene polyol, the oxygen concentration in the gas phase is 2% or less, At 50 to 130 ° C., 0.5 to 8 mol of at least one neutralizing agent selected from inorganic acids, inorganic acid acidic salts and organic acids is used per 1 mol of phosphazenium compound in the crude polyoxyalkylene polyol. Neutralizes phosphazenium compounds. Thereafter, 100 to 4000 ppm of antioxidant is added to the crude polyoxyalkylene polyol, a reduced pressure treatment is performed, water and the organic solvent are distilled off, and the polyoxyalkylene polyol is recovered.
[0061]
In addition, when the mixture of a phosphazenium compound and an alkali metal compound is used, the refinement | purification process of a polyoxyalkylene polyol is performed by operation similar to said a) -b). At this time, the neutralizing agent to be used is used on the basis of 1 mol of a mixture of a phosphazenium compound and an alkali metal compound.
[0062]
The oxygen concentration in the gas phase during the purification of the crude polyoxyalkylene polyol is 2% or less. Preferably it is 1.5% or less, Most preferably, it is 1% or less. When the oxygen concentration in the gas phase exceeds 2%, a peroxide or an aldehyde compound is easily produced as a by-product when water or a mixture of water and an organic solvent is removed by heating under reduced pressure. This compound becomes a causative substance of odor and deteriorates the temporal stability of the polyoxyalkylene polyol.
[0063]
The control of the oxygen concentration in the gas phase is preferably a replacement operation with an inert gas such as nitrogen, helium, or argon. By reducing the oxygen concentration in the gas phase, the oxygen concentration in the crude polyoxyalkylene polyol (liquid phase) is also reduced, so that by-products such as peroxides and aldehyde compounds can be suppressed.
[0064]
Usually, the purification operation of the crude polyoxyalkylene polyol is carried out in a reactor equipped with a stirrer. An operation of pressurizing and replacing the inside of the reactor several times with an inert gas, or an operation of setting the inside of the reactor to a reduced pressure state, for example, 6650 Pa or less, and leaving it for a while, and then substituting it with an inert gas for several times is repeated. As a result, the oxygen concentration in the gas phase is set to 2% or less. At that time, the oxygen concentration in the gas phase is measured with a trace oxygen analyzer. In particular, the oxygen concentration in the liquid phase is remarkably reduced by making the inside of the reactor in a depressurized state and then performing a pressure replacement operation with an inert gas. The oxygen concentration in the liquid phase after such an operation is preferably 1.3 ppm or less.
[0065]
Method a) is water alone, and method b) is a method of using an inert organic solvent in combination with water and a polyoxyalkylene polyol. In the neutralization, 1 to 20 parts by weight of water (method a) or a mixture of an organic solvent inert to the polyoxyalkylene polyol and water (method b) is used. Preferably it is 1-15 weight part, More preferably, it is 1.2-10 weight part. Water is an essential component, and at least 20% by weight of water in the mixed solvent is required even when an inert organic solvent and water are used for the polyoxyalkylene polyol. When the amount is less than 1 part by weight, the concentration of the phosphazenium compound in the product increases.
[0066]
Examples of the organic solvent inert to the polyoxyalkylene polyol include toluene, hexanes, pentanes, heptanes, butanes, lower alcohols, cyclohexane, cyclopentane, and xylenes among hydrocarbon solvents. The method of distilling off these organic solvents from the polyoxyalkylene polyol is preferably a heating and decompression operation. The temperature at that time is preferably 100 to 140 ° C., and the degree of vacuum is preferably 1330 Pa or less.
[0067]
As the acid for neutralizing the phosphazenium compound or the mixture of the phosphazenium compound and the alkali metal compound, at least one neutralizing agent selected from inorganic acids, inorganic acid acidic salts and organic acids is used. Examples of inorganic acids include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, hydrochloric acid, sulfuric acid, sulfurous acid, and aqueous solutions thereof. Examples of inorganic acid acidic salts include dilithium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, lithium monohydrogen phosphate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, lithium hydrogen sulfate, hydrogen sulfate. Examples thereof include sodium, potassium hydrogen sulfate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and acidic sodium pyrophosphate (for example, sodium hydrogen pyrophosphate). Examples of the organic acid include formic acid, oxalic acid, succinic acid, acetic acid, maleic acid, benzoic acid, p-toluenesulfonic acid, and aqueous solutions thereof. In particular, phosphoric acid, sulfuric acid, hydrochloric acid, maleic acid, and oxalic acid are preferable, and they are preferably used in the form of an aqueous solution.
[0068]
These acids are used in an amount of 0.5 to 8 mol with respect to 1 mol of a phosphazenium compound or a mixture of a phosphazenium compound and an alkali metal compound contained in the crude polyoxyalkylene polyol. Preferably, it is 0.7-6 mol, More preferably, it is 1.2-5 mol. Neutralization is carried out in the range of 50 to 130 ° C. Most preferably, it is 70-95 degreeC. The neutralization time is 0.5 to 3 hours depending on the reaction scale. When the amount of the acid is close to 8 moles relative to 1 mole of the phosphazenium compound, it is preferable to use an acid adsorbent in combination. When the amount is less than 0.5 mol, the phosphazenium compound and / or alkali metal concentration in the polyoxyalkylene polyol tends to increase.
[0069]
After the completion of the neutralization reaction, 100 to 4000 ppm of antioxidant is used with respect to the crude polyoxyalkylene polyol. Preferably, it is 150-3000 ppm, Most preferably, it is 200-1800 ppm. When the antioxidant is less than 100 ppm, a peroxide or an aldehyde compound is easily produced as a by-product. When it exceeds 4000 ppm, the cost of the antioxidant occupying the cost of the polyol increases. Examples of antioxidants include phenolic compounds, amine compounds, phosphite compounds, and cinnamic acid esters that are usually used in the polyurethane field.
[0070]
It is preferred to use an adsorbent with the antioxidant. The adsorbent may be charged after the neutralization reaction or in the vacuum dehydration process. 0.005 to 2.5 parts by weight of an adsorbent that adsorbs acid and alkali components is added to 100 parts by weight of the crude polyoxyalkylene polyol. Preferably, it is 0.02-1.5 weight part, More preferably, it is 0.03-1.1 weight part. As the adsorbent, for example, synthetic magnesium silicate, synthetic aluminum silicate, activated clay, zeolite, acidic clay, synthetic aluminum silicate / magnesium and the like are used. Since treatment with sodium hydroxide is performed in the step of producing the adsorbent, an adsorbent with a small amount of sodium elution is preferable. Specific adsorbents include Tomix series such as Tomix AD-100, Tomix AD-200, Tomix AD-300, Tomix AD-400, Tomix AD-500, Tomix AD-600, Tomix AD-700, Tomix AD. -800, Tomix AD-900 (manufactured by Tomita Pharmaceutical Co., Ltd.), KYOWARD series, such as KYOWARD 200, KYODWARD 300, KYOWARD 400, KYOWARD 500, KYODWARD 600, KYODWARD 700, KYODWARD 1000, It is commercially available under various trade names such as KYOWARD 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.), MAGNESOL (manufactured by DALLAS). These adsorbents may be used alone or in combination of two or more.
[0071]
After charging the adsorbent, water or water and the organic solvent are distilled off under reduced pressure. Although it depends on the reaction scale, it is preferably performed at 100 to 140 ° C. and 1330 Pa for 3 to 12 hours. In particular, in order to remove a low molecular weight aldehyde compound, after adding an antioxidant, 70 to 160 ° C., 39.9 kPa, preferably 26.6 kPa, more preferably 13.3 kPa or less under conditions of nitrogen, It is preferable to introduce an inert gas such as helium or argon. Examples of the decompression processing operation include a method using a vacuum pump or a thin film evaporation method. At that time, a forced circulation stirring membrane type evaporator, a falling film type molecular distillation apparatus, or the like can be used.
[0072]
After performing the operations a) to b), the polyoxyalkylene polyol is recovered by a filtration operation. At that time, a filter aid such as diatomaceous earth or celite may be used.
[0073]
By the above operation, the remaining amount of the phosphazenium compound catalyst in the polyoxyalkylene polyol can be controlled to 150 ppm or less. The concentration of the compound catalyst in the polyol is preferably 100 ppm or less, and most preferably 70 ppm or less. When the residual amount of the compound catalyst in the polyoxyalkylene polyol exceeds 150 ppm, the storage stability of the resin liquid tends to be lowered. Moreover, when the mixture of a phosphazenim compound and an alkali metal compound is used, the residual amount of a phosphazenium compound catalyst is 150 ppm or less, and the residual amount of an alkali metal is 5 ppm or less. Preferably, the residual amount of alkali metal is 3 ppm or less, most preferably 2 ppm or less. When the residual amount of alkali metal exceeds 5 ppm, the storage stability of the resin liquid is lowered.
[0074]
The CPR (value indicating the amount of basic substance in the polyol) of the polyoxyalkylene polyol obtained by the above operation is 5 or less. Preferably, the CPR is 3 or less, most preferably the CPR is 0. When the CPR of the polyoxyalkylene polyol is larger than 5, the storage stability of the resin liquid is lowered.
[0075]
In other words, the polyoxyalkylene polyol of the present invention has a residual amount of phosphazenium compound catalyst of 150 ppm or less, a residual amount of alkali metal of 5 ppm or less, and a CPR of 5 or less. When a resin solution which is a composition for use is prepared, its storage stability is good.
[0076]
Further, the peroxide concentration in the polyoxyalkylene polyol obtained by the above operation is 0.28 mmol / kg or less, preferably 0.20 mmol / kg or less, and most preferably 0.15 mmol / kg or less. When the peroxide concentration exceeds 0.28 mmol / kg, when a tin-based catalyst is used in the reaction with the polyisocyanate compound, the activity of the tin-based catalyst is reduced by the peroxide. Mechanical properties are reduced. Moreover, when the polyoxyalkylene polyol having a peroxide concentration exceeding 0.28 mmol / kg is left in the air, the peroxide becomes an acidic compound, and the acid value in the polyoxyalkylene polyol increases. When the acid value is increased, the reactivity with the polyisocyanate compound is decreased, and the properties of the resulting polyurethane foam are deteriorated or the odor is increased. In order to improve the storage stability of the resin liquid, the peroxide concentration is preferably 0.28 mmol / kg or less, and the antioxidant concentration in the polyol is preferably 100 to 4000 ppm. The acid value of the polyoxyalkylene polyol obtained by such an operation is preferably 0.05 mgKOH / g or less.
[0077]
Next, the polymer-dispersed polyol according to the present invention will be described. The polyoxyalkylene polyol of the present invention described above is used as the polyoxyalkylene polyol which is a dispersion medium for the polymer-dispersed polyol.
[0078]
The polymer-dispersed polyol of the present invention is produced by using the polyoxyalkylene polyol as a dispersion medium and dispersing vinyl polymer fine particles therein. The vinyl polymer may be obtained by polymerizing a vinyl monomer using the polyoxyalkylene polyol as a dispersion medium to disperse the fine particles of the vinyl polymer, or by polymerizing the vinyl monomer in another dispersion system. May be added and dispersed in the polyoxyalkylene polyol.
[0079]
The vinyl monomer used for the production of the vinyl polymer suitably has at least one polymerizable ethylenically unsaturated group. For example, cyano group-containing monomers such as acrylonitrile and methacrylonitrile, methacrylic acid ester monomers such as methyl acrylate, butyl acrylate, stearyl acrylate, hydroxyethyl acrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate, acrylic acid, methacrylic acid, Carboxyl group-containing monomers such as itaconic acid, maleic acid and fumaric acid, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, hydrocarbon monomers such as butadiene, isoprene and 1,4-pentadiene, styrene, α -Aromatic hydrocarbon monomers such as methylstyrene, phenylstyrene, chlorostyrene, halogen-containing monomers such as vinyl chloride and vinylidene chloride, vinyl ethyl ether, vinyl butyl ether Vinyl ethers such as tellurium, vinyl ketones such as vinyl ethyl ketone, vinyl esters such as vinyl acetate, acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, methylenebisacrylamide, etc. Examples include acrylamides and methacrylamides such as N, N-dimethylmethacryloylamide.
[0080]
These may be one kind or a mixture of two or more kinds. Preferred are acrylonitrile alone, a mixture of acrylonitrile and styrene, a mixture of acrylonitrile, styrene and acrylamide, and a mixture of acrylonitrile, styrene and methyl methacrylate. More preferred are acrylonitrile alone, a mixture of acrylonitrile and styrene, and a mixture of acrylonitrile, styrene and acrylamide.
[0081]
As the polymerization initiator for the vinyl monomer, a radical initiator that generates a radical and starts polymerization is usually used. Specific examples include azo compounds such as 2,2′-azobisisobutyronitrile, peroxides such as benzoyl peroxide, t-butyl peroxide and di-t-butyl peroxide, and peroxydisulfides. It is done. The usage-amount of a polymerization initiator is 0.1-10.0 weight% normally with respect to a vinyl monomer, Preferably it is 0.5-5.0 weight%.
[0082]
The amount of the vinyl monomer used is 5 to 50% by weight, preferably 10 to 46% by weight, based on the total weight of the polyoxyalkylene polyol and the vinyl monomer. When the amount of the vinyl monomer used is less than 5% by weight, a sufficient modification effect due to the use of the polymer-dispersed polyol such as polyurethane hardness cannot be obtained. When the usage-amount of a vinyl monomer exceeds 50 weight%, the raise of the viscosity of the polymer dispersion polyol obtained will raise remarkably.
[0083]
In the present invention, a chain transfer agent can be used as necessary. Chain transfer agents include alcohols such as isopropanol, mercaptans, halogenated hydrocarbons, triethylamine, tripropylamine, tributylamine, aliphatic tertiary amines such as N, N-diethylethanolamine, N-methylmorpholine, N- Examples include morpholines such as ethyl morpholine, sodium methallyl sulfonate, and sodium allyl sulfonate. Preferred are triethylamine alone or a mixture of triethylamine and isopropanol. The amount of the chain transfer agent used is preferably 0.1 to 10.0% by weight based on the total weight of the polyoxyalkylene polyol and the vinyl monomer.
[0084]
Furthermore, for the purpose of stably dispersing the polymer particles, the polymerization can be performed in the presence of a dispersion stabilizer. As such a dispersion stabilizer, a polyester polyol containing a carbon-carbon unsaturated bond as described in JP-B-49-46556, an acrylic group, a methacryl group, an allyl group, or the like is present at the molecular end. Examples include modified polyols. Further, high molecular weight polyoxyalkylene polyols and polyester polyols that substantially contain no carbon-carbon unsaturated bonds can also be used.
[0085]
In the production of the polymer-dispersed polyol, the polymerization reaction is carried out using the polyoxyalkylene polyol, vinyl monomer, polymerization initiator, and further, if necessary, a chain transfer agent and a dispersion stabilizer. The polymerization reaction can be carried out either batchwise or continuously. The polymerization temperature is determined according to the kind of the polymerization initiator, but is not less than the decomposition temperature of the polymerization initiator, preferably 60 to 200 ° C, more preferably 90 to 150 ° C. The polymerization reaction can be carried out under pressure or at atmospheric pressure.
[0086]
A resin solution for producing a flexible polyurethane foam is prepared using the polyoxyalkylene polyol and the polymer-dispersed polyol detailed above. Usually, the resin liquid is produced by uniformly mixing a polyoxyalkylene polyol, a polymer-dispersed polyol, a foam production catalyst, a foam stabilizer, a crosslinking agent, a flame retardant, and the like and a foaming agent in the range of 10 to 60 ° C. The As the blowing agent, water, an inert gas such as liquefied carbon dioxide, and a mixture thereof are usually used. In particular, the polyoxyalkylene polyol and polymer-dispersed polyol according to the present invention can improve the storage stability of the resin liquid when at least water is used as the foaming agent.
[0087]
The polyoxyalkylene polyol and the polymer-dispersed polyol of the present invention include a wide range of materials such as paints, adhesives, flooring materials, waterproofing materials, sealing agents, shoe soles, elastic reinforcing agents and rollers, and timing belts in addition to flexible polyurethane foams. Excellent mechanical properties can be provided in the polyurethane field. .
[0088]
【Example】
Examples of the present invention will be shown below to clarify the bear of the present invention, but the present invention is not limited to these examples.
In addition, the hydroxyl value (OHV), total unsaturation degree (C = C), molecular terminal primary hydroxylation rate of the polyoxyalkylene polyol or polymer-dispersed polyol shown in the Examples, head-to-tail (Head-to-tail) Tail) Bond selectivity, oxyethylene group content, phosphazenium compound catalyst residue, alkali metal residue, and polymer concentration, as well as settling of flexible polyurethane foam, impact resilience core, hardness 25% ILD, and permanent compression during wet heat The strain was measured by the following method.
(1) Hydroxyl value (hereinafter abbreviated as OHV: unit mgKOH / g) and total unsaturation (hereinafter abbreviated as C = C: unit meq./g)
It calculated | required by the method of JISK-1557 description.
(2) Molecular terminal primary hydroxylation rate (unit: mol%)
Deuterated acetone as a solvent, nuclear magnetic resonance (NMR) apparatus [manufactured by JEOL Ltd., 400 MHz¹³C].
(3) Head-to-Tail bond selectivity (hereinafter abbreviated as HT. Unit: mol%)
Nuclear magnetic resonance (NMR) apparatus [manufactured by JEOL Ltd., 400 MHz¹³C], using deuterated chloroform as a solvent and polyoxyalkylene polyol¹³The C-NMR spectrum was taken, the methyl group signal (16.9 to 17.4 ppm) of the oxypropylene unit of the head-to-tail bond and the head-to-head (Head-to-Head). ) It was calculated | required from ratio of the signal (17.7-18.5 ppm) of the methyl group of the bond | bonded oxypropylene unit. The assignment of each signal was based on the value described in the report of Macromolecules (Vol. 19, pages 1337 to 1343, published in 1986, FC Schilling, AE Tonelli).
[0089]
(4) Content of polyether compound having an oxyethylene group content of at least 85% by weight (unit: ppm)
The polyol heated to 50 ° C. is weighed into a stainless steel centrifuge tube and adjusted to 16 ° C. A centrifuge tube weighing polyol was set in a centrifuge previously adjusted to 16 ° C., and 10,000 r. p. m. Centrifuge for 1 hour under the conditions described above. Remove the centrifuge tube, tilt the tube upside down, and decant at room temperature for 1 hour. Next, diethyl ether is added to the component adhering to the bottom of the centrifuge tube, and centrifugation is performed under the above conditions in a nitrogen atmosphere. After adding diethyl ether to the centrifuge tube again, the diethyl ether solution is filtered under reduced pressure with a membrane filter (pore size 0.45 μm), and the diethyl ether on the filter is removed while ventilating nitrogen. Thereafter, the weight of the filter is measured, and the value is subtracted from the weight of the pre-weighed filter, and then divided by the weight of the polyol used, whereby the oxyethylene group content is at least 85% by weight. The content of the polyether compound (hereinafter abbreviated as the content of the polyether by-product. Unit: ppm) was determined. The oxyethylene group content of the polyether by-product was measured with the aforementioned JEOL nuclear magnetic resonance (NMR) apparatus.
[0090]
(5) Residual amount of phosphazenium compound catalyst (unit: ppm)
This was performed by capillary electrophoresis using a fully automatic CIA system (manufactured by Waters). An aqueous hydrochloric acid solution is added to the polyol, and the phosphazenium compound is extracted into the aqueous hydrochloric acid solution with a shaker. Then, stationary liquid separation was performed, the aqueous phase was separated, and the amount of catalyst remaining was quantified using a capillary electrophoresis analyzer.
(6) Residual amount of alkali metal (unit: ppm)
Quantification was performed with an atomic absorption analyzer (manufactured by Perkin Elma, model: 5100PC type).
(7) Polymer concentration in polymer-dispersed polyol (unit: wt%)
Methanol is added to the polymer-dispersed polyol and dispersed well, and then centrifuged to determine the weight of methanol-insoluble matter. However, the polymer-dispersed polyol using acrylonitrile (AN) alone as a vinyl monomer is determined from the nitrogen content by elemental analysis.
[0091]
(8) Rebound resilience core of flexible polyurethane foam (%), hardness 25% ILD (kgf / 314 cm²), And permanent compression strain during wet heat (%)
It is measured by the method defined in JIS K-6301 and JIS K-6401.
(9) Settling of flexible polyurethane foam (%)
The same resin solution and polyisocyanate compound as in Example 4 or Comparative Example 4 described later are mixed and stirred under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and a foam foaming mold (inner dimensions: 300 mm × 300 mm × 400 mm). The foam is foamed by hand, and the foam foam height (b) 7 minutes after the foaming maximum foaming height (a) and mixing and stirring of the resin liquid and the polyisocyanate compound are started. Measured and calculated by the formula [(ab) × 100 / a].
[0092]
Preparation Example 1
<Synthesis of phosphazenium compound (hereinafter abbreviated as P5NMe2OH)>
In the synthesis of the polyoxyalkylene polyol of the example, a phosphazenium compound synthesized by the following method was used as a catalyst for the epoxide compound.
Weigh 60.20 g of phosphorus pentachloride [manufactured by Junsei Chemical Co., Ltd.] in a 3000 ml three-necked flask equipped with a thermometer and a dropping funnel, and abbreviate 525 ml of orthodichlorobenzene [hereinafter abbreviated as ODCB]. Mitsui Chemicals, Inc.] was added to form a suspension. This was heated to 30 ° C., and 900 ml of ODCB was added to Angew. Chem. Int. Ed. Engl. (1993, 32, 1361- 1363, Reinhard Schwesinger, et al.). A tris (dimethylamino) phosphazene {(Me₂N)_ThreeA solution in which 439.27 g of P = NH} was dissolved was added dropwise over 1 hour. After stirring for 30 minutes at the same temperature, the temperature was raised to 160 ° C. over about 30 minutes, followed by further stirring for 20 hours.
The produced insoluble matter was filtered, ion-exchanged water was added to the filtrate, and a water washing treatment was performed three times. To 1091.2 g of water-insoluble layer (hereinafter abbreviated as organic layer) after washing with water, 619.26 g of ion-exchanged water and 289.5 ml of 1N hydrochloric acid are added, and the aqueous layer is separated, and tetrakis [Tris (Dimethylamino) phosphoranylideneamino] phosphonium chloride {[(Me₂N)_ThreeP = N]_FourP⁺Cl^-}. Further, ion exchange water was added to prepare a 2.5 wt% aqueous solution.
[0093]
Next, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium was applied to a polycarbonate cylindrical column packed with ion-exchange resin Levatit MP-500 (manufactured by Bayer) whose hydroxyl group was exchanged with a 1N aqueous sodium hydroxide solution. A 2.5% by weight aqueous solution of chloride was passed in an upward flow from the bottom of the column at 23 ° C. and SV (Space Velocity) 0.5 (1 / hr), and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxy. Ion exchange was performed on the door. Furthermore, ion exchange water was passed through a column filled with the ion exchange resin, and the phosphazenium compound remaining in the column was recovered. Thereafter, an aqueous solution of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide is subjected to vacuum dehydration treatment at 80 ° C. under a reduced pressure of 7980 Pa for 2 hours, and further at 80 ° C. and 133 Pa under reduced pressure for 7 hours. The powder tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me₂N)_ThreeP = N]_FourP⁺OH^-} (P5NMe2OH) was obtained.
The yield determined from the weight measurement of the compound after drying was 98%. Tetramethylsilane with deuterated dimethylformamide solution as internal standard¹The chemical shift of H-NMR (manufactured by JEOL Ltd., format: 400 MHz NMR) was 2.6 ppm (d, J = 9.9 Hz, 72H). Elemental analysis values were C: 38.28, H: 9.82, N: 29.43, P: 19.94 (theoretical values C: 38.09, H: 9.72, N: 29.61, P: 20.46). In the chemical formula (2), the phosphazenium compound is (1, 1, 1, 1) in the order of a, b, c, and d, R is a methyl group, Q^-Is OH^-Of the hydroxy anion.
[0094]
Preparation Example 2
As the alkali metal compound catalyst used in the examples, a cesium hydroxide solution (manufactured by Kemetal Co., pure grade, 50% by weight) was used.
[0095]
Preparation Example 3
As a catalyst for producing a polyoxyalkylene polyol in a comparative example, double metal cyanide complex {Zn described in US Pat. No. 5,144,093 (column 4, line 52 to column 5, line 4)_Three[Co (CN)₆]₂-2.48 DME-4.65H₂0 ・ 0.94ZnCl₂Hereinafter abbreviated as DMC} (DME is an abbreviation for dimethoxyethane).
[0096]
Preparation Example 4
Potassium hydroxide [manufactured by Nippon Soda Co., Ltd., purity: 96% by weight] was used as an alkali metal catalyst for the addition polymerization of ethylene oxide to the polyoxypropylene polyol obtained using DMC as a catalyst.
<Polyoxyalkylene polyol synthesis apparatus>
Below, the synthesis | combination of a polyoxyalkylene polyol is demonstrated. Polyoxyalkylene polyol synthesizing and purifying apparatus includes a stirrer, a thermometer, a pressure gauge, a nitrogen inlet, an oxygen measurement line in the gas phase, and an internal volume of 2.5 L, 6 L equipped with an epoxide compound inlet as a monomer, and A 9 L pressure-resistant autoclave (manufactured by Nitto High Pressure) was used. Hereinafter, the synthesizer is abbreviated as autoclave. During the synthesis and purification of the polyoxyalkylene polyol, the rotational speed is 100 to 350 r. p. m. Stirring was performed under the conditions of
[0097]
Example 1
<Polyoxyalkylene polyol A>
To a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 0.012 mol of P5NMe2OH and 0.06 mol of toluene (special grade manufactured by Wako Pure Chemical Industries) are added to 1 mol of glycerin, and nitrogen is added. Was introduced through a capillary tube, and dehydration under reduced pressure and toluene removal were performed for 5 hours under the conditions of 105 ° C. and 1330 Pa or less (water content 95 ppm). Thereafter, the contents of the flask were charged into an autoclave under a nitrogen atmosphere, and after several substitutions with nitrogen, the reaction temperature was changed from atmospheric pressure to 70 ° C., and the OHV was 38 under the conditions that the maximum pressure during the reaction was 392 kPa. Multistage addition polymerization of propylene oxide was carried out until it became .8 mgKOH / g.
When the change in the internal pressure of the autoclave ceased, a pressure reduction treatment was performed at 665 Pa for 30 minutes at the same temperature, and then the internal temperature was raised to 130 ° C. and a pressure reduction treatment was performed for 1 hour at 1330 Pa or less at the same temperature. . The addition polymerization reaction of ethylene oxide was performed until the OHV was 33 mgKOH / g under the conditions of an internal temperature of 130 ° C. and a maximum reaction pressure of 617 kPa. When there was no change in the internal pressure, a reduced pressure treatment was carried out at 665 Pa for 30 minutes at the same temperature to obtain a crude polyoxyalkylene polyol containing a phosphazenium compound (molecular end ethylene oxide content: 15% by weight). Hereinafter, the crude polyoxyalkylene polyol is referred to as crude polyol A.
[0098]
Crude polyol A was charged into an autoclave under a nitrogen atmosphere, heated to 80 ° C., and then the autoclave was reduced in pressure to 2660 Pa at the same temperature and held for 8 minutes under the same conditions. Then, after pressurizing with nitrogen to 392 kPa, the pressure was released to obtain an atmospheric pressure state. Next, 7 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol A, and then 3 moles of phosphoric acid (75.1% by weight of an aqueous solution) is added to 1 mole of the phosphazenium compound in the crude polyol A. Form) was quickly charged and neutralized at 80 ° C. for 2 hours.
After the completion of the neutralization reaction, 1200 ppm of an antioxidant (trade name: IRGANOX1010, manufactured by Ciba Geigy Co., Ltd.) was charged with respect to 100 parts by weight of the crude polyol A, followed by dehydration under reduced pressure, and a pressure of 13.3 kPa. At that time, 2.0 parts by weight of the adsorbent AD-600 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was quickly charged with respect to 100 parts by weight of the crude polyol A. Finally, vacuum nitrogen bubbling was performed for 4 hours under the conditions of 105 ° C. and 2660 Pa while aeration of nitrogen in the liquid phase. After changing from reduced pressure to atmospheric pressure with nitrogen, vacuum filtration was performed with 5C filter paper (retained particle size 1 μm) manufactured by Advantech Toyo Co., Ltd. packed with Celite to purify the polyoxyalkylene polyol.
The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification operation is 33.1 mgKOH / g, and the total unsaturation degree (C = C) is 0.010 meq. / G, the primary hydroxylation rate was 85.2 mol%, and HT was 96.8 mol%. Further, the content of the polyether by-product in the polyoxyalkylene polyol was 2 ppm, and the oxyethylene group content of the compound was 94% by weight. The residual amount of the phosphazenium compound catalyst in the polyol was 17 ppm.
[0099]
Example 2
<Polyoxyalkylene polyol B>
In a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 0.009 mol of P5NMe2OH and 0.003 mol of cesium hydroxide (in the form of a 50% by weight aqueous solution) and 1 mol of glycerin; 0.09 mol of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added, nitrogen was introduced through a capillary tube, and dehydration under reduced pressure and detoluene were performed at 105 ° C. and 1330 Pa or less for 7 hours (water content 87 ppm). ). Thereafter, the contents of the flask were charged into an autoclave under a nitrogen atmosphere, and after several substitutions with nitrogen, the reaction temperature was changed to 80 ° C. from the atmospheric pressure state, and the OHV was 28 mgKOH under the condition that the maximum pressure during the reaction was 392 kPa. Multistage addition polymerization of propylene oxide was carried out until it reached / g.
When the change in the internal pressure of the autoclave ceased, a pressure reduction treatment was performed at 665 Pa for 30 minutes, and then the internal temperature was raised to 130 ° C., and the pressure reduction treatment was performed at the same temperature for 1330 Pa or less for 1 hour. The addition polymerization reaction of ethylene oxide was performed until the OHV was 24 mgKOH / g under the conditions of an internal temperature of 130 ° C. and a maximum reaction pressure of 617 kPa. When there was no change in the internal pressure, a reduced pressure treatment was carried out at 665 Pa for 30 minutes at the same temperature to obtain a crude polyoxyalkylene polyol containing a phosphazenium compound and a cesium compound (molecular end ethylene oxide content: 15% by weight) . Hereinafter, the crude polyoxyalkylene polyol is referred to as crude polyol B.
[0100]
Crude polyol B was charged into an autoclave under a nitrogen atmosphere, heated to 80 ° C., and then the autoclave was reduced in pressure to 2660 Pa at the same temperature and held for 8 minutes under the same conditions. Then, after pressurizing with nitrogen to 392 kPa, the pressure was released to obtain an atmospheric pressure state. Next, 10 parts by weight of ion exchange water is added to 100 parts by weight of the crude polyol B, and then 4 moles of phosphoric acid (75.1 weights per mole of the mixture of the phosphazenium compound and the cesium compound in the crude polyol B. % Aqueous solution) was quickly charged and neutralized at 80 ° C. for 2 hours.
After completion of the neutralization reaction, 100 ppm by weight of the crude polyol B was charged with 1000 ppm of antioxidant [manufactured by Ciba Geigy Co., Ltd., trade name: IRGANOX1010], dehydrated under reduced pressure, and the pressure was 13.3 kPa. At that time, 1.8 parts by weight of the adsorbent AD-600 [manufactured by Yoshitomi Pharmaceutical Co., Ltd.] was quickly charged with respect to 100 parts by weight of the crude polyol B. Finally, vacuum nitrogen bubbling was performed for 4 hours under the conditions of 105 ° C. and 2660 Pa while aeration of nitrogen in the liquid phase. After changing from reduced pressure to atmospheric pressure with nitrogen, vacuum filtration was performed with 5C filter paper (retained particle size 1 μm) manufactured by Advantech Toyo Co., Ltd. packed with Celite to purify the polyoxyalkylene polyol.
The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification operation is 24.2 mgKOH / g, and the total unsaturation degree (C = C) is 0.015 meq. / G, the primary hydroxylation rate was 86.5 mol%, and HT was 96.3 mol%. Further, the content of the polyether by-product in the polyoxyalkylene polyol was 50 ppm, and the content of the oxyethylene group in the compound was 95% by weight. The residual amount of phosphazenium compound catalyst in the polyol was 35 ppm, and the residual amount of alkali metal (cesium) was 0.5 ppm.
[0101]
Comparative Example 1
<Polyoxyalkylene polyol C>
Addition of 0.03 parts by weight of DMC to 100 parts by weight of polypropylene polyol MN1000 [Mitsui Chemicals, Inc .; OHV168 mgKOH / g] with propylene oxide added to glycerin, and vacuum dehydration at 105 ° C. and 1330 Pa or less for 3 hours Went. Next, the compound was charged into an autoclave, and propylene oxide addition polymerization was carried out until the OHV was 38.8 mgKOH / g under conditions of a reaction temperature of 70 ° C. and a maximum pressure of 392 kPa during the reaction, and a crude polyoxypropylene containing DMC A polyol was obtained.
2.22 parts by weight of 50% by weight potassium hydroxide (KOH) aqueous solution was added to 100 parts by weight of the polyoxypropylene polyol, and dehydration was performed at 105 ° C. and 2660 Pa for 1 hour. Thereafter, 3 parts by weight of water and 5 parts by weight of AD-600 (manufactured by Tomita Pharmaceutical Co., Ltd.) were added, and the mixture was stirred for 2 hours at 90 ° C. in a nitrogen atmosphere. Advantech Toyo Co., Ltd. 5C filter paper (retained particle size 1 μm) The solution was filtered under reduced pressure. After filtration, dehydration under reduced pressure was performed at 120 ° C. and 1330 Pa or less for 1 hour to remove DMC. In order to carry out addition polymerization of ethylene oxide, 2.5 parts by weight of 50% by weight KOH aqueous solution was added to 100 parts by weight of polyoxypropylene polyol after removal of DMC, and dehydration treatment was performed at 105 ° C. and 1330 Pa or less for 1 hour. . The compound was charged into an autoclave, and after substitution with nitrogen, ethylene oxide was charged and reacted until the OHV reached 33.0 mgKOH / g under the conditions of a reaction temperature of 130 ° C. and a maximum pressure during the reaction of 490 kPa. After the reaction, a reduced pressure treatment was performed to obtain a crude polyoxyalkylene polyol (molecular end ethylene oxide content: 15% by weight).
[0102]
Next, 1.05 mol of phosphoric acid (75.1 wt% phosphoric acid aqueous solution) with respect to 1 mol of potassium in the crude polyoxyalkylene polyol, and 4 parts by weight of ion exchange with respect to 100 parts by weight of the crude polyether polyol. Water was charged and a neutralization reaction was performed at 80 ° C. for 2 hours. Thereafter, 1200 ppm of an antioxidant (manufactured by Ciba Geigy Co., Ltd., trade name: IRGANOX1010) and 8000 ppm of an adsorbent KW-700SN (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and finally the water was distilled off under reduced pressure. And dehydration under reduced pressure at 105 ° C. and 1330 Pa for 3 hours.
After changing from reduced pressure to atmospheric pressure with nitrogen, reduced pressure filtration was performed with 5C filter paper (retained particle size 1 μm) manufactured by Advantech Toyo Co., Ltd. to recover the polyoxyalkylene polyol. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the potassium removal operation is 33.3 mgKOH / g, and the total unsaturation (C = C) is 0.011 meq. / G, the primary hydroxylation rate was 80.1 mol%, and HT was 87.5 mol%. In addition, the content of the polyether by-product in the polyoxyalkylene polyol was 1310 ppm, and the oxyethylene group content of the compound was 92% by weight. The residual amount of alkali metal (potassium) in the polyol was 6.5 ppm.
[0103]
Comparative Example 2
<Polyoxyalkylene polyol D>
Addition of 0.03 parts by weight of DMC to 100 parts by weight of polypropylene polyol MN1000 [Mitsui Chemicals, Inc .; OHV168 mgKOH / g] with propylene oxide added to glycerin, and vacuum dehydration at 105 ° C. and 1330 Pa or less for 3 hours Went. Next, the compound was charged into an autoclave, and propylene oxide addition polymerization was performed until the OHV was 28.2 mgKOH / g under the conditions of a reaction temperature of 80 ° C. and a maximum pressure of 392 kPa during the reaction, and a crude polyoxypropylene containing DMC. A polyol was obtained.
To 100 parts by weight of the polyoxypropylene polyol, 2.0 parts by weight of 50% by weight potassium hydroxide (KOH) aqueous solution was added, and dehydration was performed at 105 ° C. and 2660 Pa for 1 hour. Thereafter, 8 parts by weight of water and 5 parts by weight of AD-600 (manufactured by Tomita Pharmaceutical Co., Ltd.) were added, and the mixture was stirred for 2 hours at 90 ° C. in a nitrogen atmosphere. Advantech Toyo Co., Ltd. 5C filter paper (retained particle size 1 μm) The solution was filtered under reduced pressure. After filtration, dehydration under reduced pressure was performed at 120 ° C. and 1330 Pa or less for 1 hour to remove DMC. In order to perform addition polymerization of ethylene oxide, 3.5 parts by weight of 50% by weight KOH aqueous solution was added to 100 parts by weight of the polyoxypropylene polyol after removal of DMC, and dehydration was performed at 105 ° C. and 1330 Pa or less for 1 hour. . The compound was charged into an autoclave and purged with nitrogen. Then, ethylene oxide was charged and reacted until the OHV reached 24.0 mgKOH / g under the conditions of a reaction temperature of 130 ° C. and a maximum pressure during the reaction of 490 kPa. After the reaction, a reduced pressure treatment was performed to obtain a crude polyoxyalkylene polyol (molecular end ethylene oxide content: 15% by weight).
[0104]
Subsequently, 1.05 mol of phosphoric acid (75.1 wt% phosphoric acid aqueous solution) with respect to 1 mol of potassium in the crude polyoxyalkylene polyol and 8 parts by weight of ion exchange with respect to 100 parts by weight of the crude polyether polyol. Water was charged and a neutralization reaction was performed at 80 ° C. for 2 hours. Thereafter, 1000 ppm of an antioxidant (manufactured by Ciba Geigy Co., Ltd., trade name: IRGANOX1010) and 8000 ppm of an adsorbent KW-700SN (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and finally the water was distilled off under reduced pressure. And dehydration under reduced pressure at 105 ° C. and 1330 Pa for 3 hours.
After changing from reduced pressure to atmospheric pressure with nitrogen, reduced pressure filtration was performed with 5C filter paper (retained particle size 1 μm) manufactured by Advantech Toyo Co., Ltd. to recover the polyoxyalkylene polyol. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the potassium removal operation is 24.1 mgKOH / g, and the total unsaturation (C = C) is 0.015 meq. / G, the primary hydroxylation rate was 83.2 mol%, and HT was 88.2 mol%. Further, the content of the polyether by-product in the polyoxyalkylene polyol was 1500 ppm, and the oxyethylene group content of the compound was 96% by weight. The residual amount of alkali metal (potassium) in the polyol was 8.2 ppm.
[0105]
The analysis results of the polyoxyalkylene polyols obtained in Examples 1-2 and Comparative Examples 1-2 are shown in [Table 1].
<Explanation of symbols in [Table 1]>
The polyol in Table 1 is an abbreviation for polyoxyalkylene polyol, a polyol production catalyst, a phosphazenium compound used in Examples, PZN, cesium hydroxide CsOH, and a double metal cyanide complex used in Comparative Examples. DMC and potassium hydroxide were abbreviated as KOH. OHV and C = C are abbreviations for hydroxyl value and total degree of unsaturation, respectively. Head-to-tail binding selectivity was abbreviated as HT. Moreover, the residual amount of the phosphazenium compound catalyst in the polyoxyalkylene polyol was described as a residual amount of the phosphazenium compound catalyst. The remaining amount of alkali metal was determined as the remaining amount of alkali metal.
[0106]
[Table 1]

Subsequently, the polymer-dispersed polyol was produced using the polyols obtained in Examples 1 and 2 and Comparative Examples 1 and 2.
[0107]
Example 3
<Polymer-dispersed polyol E>
A 1 liter autoclave equipped with a thermometer, a stirrer, and a liquid feeding device was charged with polyol A in a full liquid state, and the temperature was raised to 120 ° C. while stirring. Subsequently, 77.6 parts by weight of polyol A, 22.4 parts by weight of acrylonitrile (manufactured by Mitsui Chemicals Co., Ltd.), and azobisisobutyronitrile (hereinafter abbreviated as AIBN) which is a radical initiator 0. The liquid mixture uniformly mixed at a ratio of 35 parts by weight was continuously charged into the autoclave, and a polymer-dispersed polyol was continuously obtained from the discharge port. At this time, the reaction pressure was 444 kPa and the residence time was 50 minutes. After reaching a steady state, the obtained reaction solution was subjected to vacuum suction treatment at 120 ° C. and 2660 Pa for 4 hours to remove unreacted vinyl monomers and the like, and polymer dispersed polyol E was obtained. The hydroxyl value (OHV) of the polymer-dispersed polyol was 26.1 mgKOH / g, and the polymer concentration was 20.7% by weight.
[0108]
Comparative Example 3
<Polymer-dispersed polyol F>
Polyol C was charged to a 1 liter autoclave equipped with a thermometer, a stirrer, and a liquid feeder, and the temperature was raised to 120 ° C. while stirring. Subsequently, 77.6 parts by weight of polyol C, 22.4 parts by weight of acrylonitrile (manufactured by Mitsui Chemicals, Inc.) and azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a radical initiator 0. The mixed liquid uniformly mixed at a ratio of 35 parts by weight was continuously charged into the autoclave, and a polymer-dispersed polyol was continuously obtained from the discharge port. At this time, the reaction pressure was 444 kPa and the residence time was 50 minutes. After reaching a steady state, the obtained reaction solution was subjected to vacuum suction treatment at 120 ° C. and 2660 Pa for 4 hours to remove unreacted vinyl monomers and the like, and polymer dispersed polyol F was obtained. The hydroxyl value (OHV) of the polymer-dispersed polyol was 26.3 mgKOH / g, and the polymer concentration was 20.5% by weight.
[0109]
Example 4 and Comparative Example 4
In order to clarify the effects of the polyoxyalkylene polyol and polymer-dispersed polyol obtained by the present invention, examples of producing a resin solution for flexible polyurethane foam and foam using these polyols are shown below. The raw materials used in Example 4 and Comparative Example 4 are shown below. The present invention is not limited to these examples.
<Preparation of resin solution>
Resin solution: Example 4 (resin solution G), Comparative example 4 (resin solution H)
Polyoxyalkylene polyol: Example 4 (B), Comparative Example 4 (D)
Polymer-dispersed polyol: Example 4 (E), Comparative Example 4 (F)
Crosslinking agent: DEOA (Mitsui Chemicals, diethanolamine)
Foaming agent: ion exchange water
Catalyst-1: L-1020 [manufactured by Active Materials Chemical Co., Ltd., tertiary amine catalyst (33% by weight diethylene glycol solution of triethylenediamine)]
Catalyst-2: TMDA (manufactured by Active Materials Chemical Co., Ltd., tertiary amine catalyst (bisdimethylaminoethyl ether in 70% by weight diethylene glycol solution))
Foam stabilizer: L-5309; Silicone foam stabilizer manufactured by Nihon Unicar Company
[0110]
60 parts by weight of polyol and 40 parts by weight of polymer-dispersed polyol were weighed into a polycup, and then 3.4 parts by weight of water, 1.1 parts by weight of DEOA, 0.7 parts by weight of L-1020, 0.1 parts by weight of TMDA, And 1.0 part by weight of L-5309 was added. The internal temperature was adjusted to 25 ° C., and uniform mixing was performed at the same temperature to prepare a resin liquid (Example 4: Resin liquid G, Comparative Example 4: Resin liquid H). The obtained resin solution was cooled to 20 ° C., sealed in a metal container in a nitrogen atmosphere, and stored in a constant temperature oven at 20 ° C. for 15 days.
[0111]
<Manufacture of flexible polyurethane foam>
Polyisocyanate compound for production of flexible polyurethane foam: (polyisocyanate compound) Cosmonate TM-20 [Mitsui Chemicals, Inc., polyisocyanate, mixture of TDI-80 and polymeric MDI in an 80:20 weight ratio]
The resin solution stored for 15 days in a constant temperature oven at 20 ° C. was adjusted to 25 ° C. Next, Cosmonate TM-20 was adjusted to 25 ° C. in such an amount that the equivalent ratio (NCO / H) of active hydrogen and isocyanate group in the resin liquid was 1.00. Next, the mixture was vigorously stirred and mixed with the previously prepared resin solution for 6 seconds, poured into a 60 ° C. aluminum test mold (inner dimensions 400 × 400 × 100 mm) pre-applied with a commercially available release agent, and then the lid was closed and clamped Sealed and foam cured. Six minutes after the start of stirring, the test mold was unclamped, the hardened flexible polyurethane foam was removed from the mold, and the thickness was reduced by 80% using a roller to completely connect the bubbles (crushing operation). A flexible polyurethane foam was obtained 24 hours after foaming. Various physical properties of the obtained flexible polyurethane foam were measured by the above methods. The evaluation results are shown in [Table 2].
[0112]
[Table 2]

[0113]
<Consideration of Examples>
From [Table 2], a polyoxyalkylene polyol having less polyether by-products of Examples and having a head-to-tail bond selectivity of 95 mol% or more, and The foam properties after 15 days at 20 ° C. of the resin liquid prepared from the polymer-dispersed polyol using it as a dispersion medium are as follows: polyether by-product exceeds 1200 ppm, and Head-to-Tail Low settling, rebound resilience, high hardness, and low permanent compression strain at the time of wet heat compared to foam physical properties of resin liquids using polyoxyalkylene polyols with polymer selectivity less than 95 mol% and polymer-dispersed polyols I understand that. From the polyoxyalkylene polyol according to the present invention and the polymer-dispersed polyol using the same as a dispersion medium, a flexible polyurethane foam excellent in the storage stability of the resin liquid, the molding stability, and the mechanical properties can be obtained.
[0114]
【The invention's effect】
According to the present invention, the minimum selectivity of head-to-tail bond by propylene oxide addition polymerization is 95 mol%, the molecular terminal primary hydroxylation rate is at least 40 mol%, the content of oxyethylene groups The content of the polyether compound in which is at least 85% by weight is 1200 ppm or less, the hydroxyl value is 5 to 70 mgKOH / g, and the hydroxyl value (OHV) and the total unsaturation degree (C = C) are the above formulas (1 ) And a polymer-dispersed polyol using the polyoxyalkylene polyol as a dispersion medium are provided.
The polyoxyalkylene polyol and polymer-dispersed polyol of the present invention having the above properties are excellent in reactivity with the polyisocyanate compound, and in the production of a polyurethane resin, the storage stability of the resin liquid when water is used as a foaming agent. Excellent in properties. Furthermore, by using the polyoxyalkylene polyol and polymer-dispersed polyol of the present invention, a polyurethane resin excellent in mechanical properties and molding stability can be obtained.
Therefore, the polyoxyalkylene polyol and polymer-dispersed polyol of the present invention can be used in a wide range of fields as materials such as polyurethane foams, particularly high-elasticity polyurethane foams, elastomers, sealings, adhesives, flooring materials, and shoe soles.

Claims (8)

Water is removed from the active hydrogen compound or a mixture containing the alkali metal salt or alkaline earth metal salt of the active hydrogen compound before the addition polymerization of the epoxide compound to reduce the water content in the mixture to 1000 ppm or less. Chemical formula (1)

[In the chemical formula (1), a, b, c and d are each a positive integer of 0 to 3, but all of a, b, c and d are not 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations, T ^r− represents an inorganic anion having a valence of r], or a chemical formula (2)

[In the chemical formula (2), a, b, c and d are each a positive integer of 0 to 3, but all of a, b, c and d are not 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion, or a carboxy anion] and is a polyoxyalkylene polyol obtained by addition polymerization of an epoxide compound containing propylene oxide and ethylene oxide to an active hydrogen compound. The minimum selectivity of head-to-tail bond by propylene oxide addition polymerization is 95 mol%, the molecular terminal primary hydroxylation rate is at least 40 mol%, and the content of oxyethylene groups is The content of the polyether compound at least 85% by weight is 1200 ppm or less, the hydroxyl value is 5 to 70 mgKOH / g, and the hydroxyl value (OHV) and the total unsaturation degree (C = C) are expressed by the formula (1).
[Equation 1]
[Expression 1]
C = C ≦ 1.2 / OHV (1)
The polyoxyalkylene polyol characterized by having the relationship represented by these. 2. The polyoxyalkylene polyol according to claim 1, wherein the residual amount of the phosphazenium compound is 150 ppm or less. 3. The polyoxyalkylene polyol according to claim 1 , wherein the catalyst is a mixture obtained by adding an alkali metal compound to a phosphazenium compound, the residual amount of the phosphazenium compound catalyst is 150 ppm or less, and the residual amount of alkali metal is 5 ppm or less. Mixed compound catalyst, a polyoxyalkylene polyol according to claim 3, characterized in that it comprises an alkali metal compound 5-50 mol%. Polyoxyalkylene polyol according to claim 3, wherein A alkali metal compound is characterized in that it is a cesium compound.   A polymer-dispersed polyol in which fine particles of vinyl polymer are dispersed in the polyoxyalkylene polyol according to any one of claims 1 to 5, wherein the concentration of the vinyl polymer is 5 to 50% by weight. A polymer-dispersed polyol.   The polymer-dispersed polyol according to claim 6, wherein the vinyl polymer is a polymer of a monomer having at least one ethylenically unsaturated group. Mode Nomar is acrylonitrile, mixtures of acrylonitrile and styrene, the polymer-dispersed polyol according to claim 7, characterized in that the monomer selected from a mixture of acrylonitrile and styrene and acrylamide.