JP3713719B2 - Method for producing polysiloxane - Google Patents

Description

（ここで、Ｒ² ，Ｒ³ は、それぞれ炭素数１〜８のアルキル基、フェニル基、炭素数２〜８のアルケニル基、３−グリシドキシプロピル基または３−クロロプロピル基であり、Ｒは炭素数１〜８のアルキル基であり、ｍ，ｎはそれぞれ３以下の正の整数、ｘは０を含まない１．０以下の数である）
（２）一般式Ｒ¹ Ｓｉ（ＯＲ）₃ で示されるトリアルコキシシラン化合物（Ｂ）と一般式Ｒ² Ｒ³ Ｓｉ（ＯＲ）₂ で示されるシラン化合物（Ｃ）とを酸触媒の存在下で共加水分解縮合反応させるに際して、最初に（Ｂ）を酸触媒、シラン総モルの３〜４倍の水、親水性溶媒の存在下に加水分解縮合反応させ、つづいて反応混合物中に（Ｃ）と、三次元性ポリマーにリニアー性シラン化合物をブロック状に共重合させるために必要な縮合触媒を添加して共加水分解縮合反応させることを特徴とする式〔化５〕で示されるオルガノポリシロキサンの製造法。
【化５】

（ここで、Ｒ¹ ，Ｒ² ，Ｒ³ は、それぞれ炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基、３−グリシドキシプロピル基、３−メタクリロキシプロピル基、３−メルカプトプロピル基、３−クロロプロピル基、エポキシシクロヘキシルエチル基またはフェニル基であり、Ｒは炭素数１〜８のアルキル基であり、ｍ，ｌはそれぞれ３以下の正の整数、ｙは０を含まない１．０以下の数である）
（３）テトラアルコキシシラン（Ａ）が、テトラメトキシシランもしくはテトラエトキシシランまたはこれらの加水分解物であるメチルシリケート５９（ＳｉＯ₂ 含有率約５９％のオリゴマー）もしくはエチルシリケート４０（ＳｉＯ₂含有率約４０％のオリゴマー）のいずれかである前記（１）に記載の製造法。
（４）トリアルコキシシラン化合物（Ｂ）が、ビニルトリアルコキシシラン、３−グリシドキシプロピルトリアルコキシシラン、３−メタクリロキシプロピルトリアルコキシシラン、３−メルカプトプロピルトリアルコキシシシラン、エポキシシクロヘキシルエチルトリアルコキシシラン、３−クロロプロピルトリアルコキシシラン、フェニルトリアルコキシシラン（ここでアルコキシはメトキシまたはエトキシである）のいずれかである前記（２）に記載の製造法。
（５）シラン化合物（Ｃ）が、３−グリシドキシプロピルアルキルジアルコキシシラン、３−クロロプロピルアルキルジアルコキシシラン、ジアルキルジアルコキシシラン、フェニルアルキルジアルコキシシラン（ここでアルキルはメチルまたはエチルであり、アルコキシはメトキシまたはエトキシである）のいずれかである前記（１）乃至（４）のいずれか１項に記載の製造法。
【０００５】
本発明の構成と効果につき以下に詳述する。本発明は、一般式Ｓｉ（ＯＲ）₄ で示されるテトラアルコキシシラン（Ａ）と一般式Ｒ¹ Ｓｉ（ＯＲ）₃ で示されるトリアルコキシシラン化合物（Ｂ）及び一般式Ｒ² Ｒ³ Ｓｉ（ＯＲ）₂ で示されるシラン化合物（Ｃ）の内から（Ａ）と（Ｃ）、（Ｂ）と（Ｃ）の異なる２種の組み合わせで触媒量の酸触媒下で共加水分解縮合反応させるに際して、（Ａ）や（Ｂ）の三次元構造性のアルコキシシランを単独に加水分解してオリゴマーのブロックを形成せしめる。しかる後に（Ｃ）成分のリニアー形成ジアルコキシシランを加水分解共縮合させる二段加水分解縮合によるブロック状共重合体を製造する方法に関する。Ｒ ¹ とＲ ² が有機官能基を有するシリルプロピル基の場合、例えば３−メタクリロキシプロピル基を有するトリアルコキシシランや低級アルキルジアルコキシシランでは一般に加水分解速度はテトラアルコキシシランに比較して遅いので触媒を添加する必要がある。触媒種としては有機錫化合物等が好適に使用される。反応溶剤としては、親水性溶剤叉は親水性溶剤を含む混合溶剤が好適に使用される。加水分解に必要な水の量はシラン総モルの３〜４倍モルが好適である。ここでＲ ¹ とＲ ² は３−グリシドキシプロピル基やビニル基等の有機官能基を含むシランカップリング剤やＣ₁ 〜Ｃ₈ の飽和炭化水素基、フェニル基あるいはアルケニル基が適応される。アルコキシ基ＯＲはＣ₁ 〜Ｃ₈ の飽和アルコールより製造したものであり、反応速度を考慮するとＣ₁ 〜Ｃ₃ が好適に使用される。本発明により製造される共加水分解縮合化合物は〔化４〕、〔化５〕で示される常温でオイル状ないし樹脂状であり、かつ生成したシラノール基はそれぞれｘ＝１．０以下、ｙ＝１．０以下もしくはｘ＋ｙ＝２．０以下である常温で安定なオルガノポリシロキサンである。ｘ及びｘ＋ｙがこれ以上だと生成したポリマーはゲル化物を含んだりゲル体である。
【０００６】
次に加水分解触媒としての酸であるが、触媒量の酸があればよく酸濃度は特に規定しない。例えば希釈した酸を規定量の水の分だけ添加する方法もある。酸の種類としては酢酸等の有機酸や塩酸、硫酸等の無機酸あるいは強酸性イオン交換樹脂のいずれも使用出来るが好ましくは加水分解速度の早い無機酸が推奨される。
【０００７】
シラノール縮合触媒として作用する広範な種類の物質のいずれもが本発明に用いる事が出来る。かかる物質には、例えば、ジブチル錫ジラウレート、酢酸第一錫、オクタン酸第一錫の様な有機錫化合物、あるいはナフテン酸亜鉛、オクタン酸亜鉛、２−エチルヘキサン酸及びナフテン酸コバルトの如き金属カルボキシレート、チタニウムエステル及びキレートが挙げられる。好ましい化合物は有機錫化合物で特に錫カルボキシレート、例えばジブチル錫ジラウレート、ジブチル錫ジアセテートがある。
縮合触媒量は触媒量であれば特に規定しないが一般的にはシラン総量の０．０５％以下で行われる。
【０００８】
加水分解を充分行わせる為の水の量はシラン総モルに対して３〜４倍モル、好ましくは３．５倍モル以上の添加が必要である。反応溶媒としては親水性溶媒単独でもよいが、親水性溶媒の混合溶媒や親油性と親水溶媒の混合溶媒も適応出来る。例えば、メタノール、エタノール、アセトン、ターシャリブタノール、ジアセトンアルコール等の親水性溶媒、あるいはキシレン／アルコール、トルエン／アルコール等の混合溶媒も使用できる。
【０００９】
本発明で得られたオルガノポリシロキサンオイルの溶解性の測定はガラスサンプル管に本発明の油状オルガノポリシロキサンのサンプル１００ｍｇを採り、これに１ｍｌの各溶媒を加えて肉眼観察により溶け易さを判定する方法で行った。その結果は易溶、溶解、微溶（微白濁）、難溶（白濁）、不溶の５段階表示で行った。本発明のオルガノポリシロキサンは一般に次の（ａ）〜（ｄ）の様な手段で上記一般式で示されるものである事を確認出来る。
（ａ）赤外吸収スペクトル（ＩＲ）の解析
３４５０ｃｍ^-1付近のＳｉ−ＯＨの特徴的吸収、３０００ｃｍ ^-1 〜２９００ｃｍ ^-1 付近のＣＨ結合に基づく数本の吸収、１１００ｃｍ ^-1 〜１０００ｃｍ ^-1 付近のＳｉ−Ｏ−Ｓｉのブロードな吸収が現れる。３４５０ｃｍ^-1付近の吸収ピークと２９４０ｃｍ^-1付近の吸収ピークとの吸光度（ｌｏｇＩ₀ ／Ｉ）比はシラノール基含有率の相対値の指標となる。すなわち、この値が１．０以下であれば常温で安定なシラノール基を有したオイルである。この値が１．０以上では数十℃の加熱で樹脂状態の固体を呈するオルガノポリシロキサンポリマーである。一方メタクリロキシ基を有するポリマーでは２９００ｃｍ^-1付近のＣＨ結合に基づく数本の吸収、１７２０ｃｍ^-1の−Ｃ＝ＣＣＯＯ−吸収，１６４０ｃｍ^-1付近のＣ＝Ｃ吸収、１１００ｃｍ^-1〜１０００ｃｍ^-1付近のＳｉ−Ｏ−Ｓｉのブロードな吸収が現れる。３４５０ｃｍ^-1付近の吸収ピークと１７２０ｃｍ^-1付近の吸収ピークとの吸光度（ｌｏｇＩ₀ ／Ｉ）比はシラノール基含有率の相対値の指標となる。すなわち、この値が１．０以下であれば常温で安定なシラノール基を有したオイルである。この値が１．０以上では数十℃の加熱で樹脂状態の固体を呈するオルガノポリシロキサンポリマーである。
（ｂ）¹ Ｈ−核磁気共鳴スペクトル（¹ Ｈ−ＮＭＲ）
本発明のオルガノポリシロキサン中の水素原子の個数や結合様式、更に重水素置換により（Ｓｉ）−ＯＨである確認、水素原子の比から（Ｓｉ）−ＯＨの個数を知る事が出来る。
（ｃ）エポキシ酸素量の定量
オキシラン酸素の定量はＨＢｒ−酢酸の滴定法により求める。
（ｄ）炭素、水素（ＣＨ）元素分析
ミクロ元素分析法により炭素、水素含有率を知る事が出来る。粘度データーの測定は東京計器（株）製回転粘度計‘ＶＩＳＣＯＮＩＣ’を用いて２５℃恒温で行った。
【００１０】
【発明の効果】
本発明の二段加水分解縮合による製造方法ではブロック状のコポリマーを製造出来るので生成したオルガノポリシロキサンは、後述した実施例において証明されている如く、ポリマー中に常温にて安定なシラノール基を有し、使用アルコキシ原料由来の有機官能基を１ないし２個有する事からマルチファンクショナルな反応性オルガノポリシロキサンと言える。また、本ポリマーの末端基はシラノールである。本発明の製造法によるオルガノポリシロキサンは大抵のメチル系ポリシロキサンが有機溶媒や有機樹脂に溶解ないし親和性を持つていないのに対して本発明によるオルガノポリシロキサンは多種類の有機溶媒に溶解する。また多種類の有機樹脂に親和性を示す。これら特徴より変性シリコーンオイルとしての用途は勿論、その他離型剤、剥離紙用シリコーン、パーソナルケア用シリコーン、塗料添加剤、シリコーン粘着剤、接着シール材、変性シリコーンシラント他広範囲の用途に展開出来る有用なものである。また、２種類以上のポリマーで構成されるポリマーアロイやブレンドに於いて、異種樹脂同志の界面に作用して混練を容易ならしめたり、ポリマー間のカップリングも期待される。本発明を更に具体的に説明する為に以下実施例をあげて説明するが、本発明はこれらの実施例に限定されるものではない。
【００１１】
実施例１
シラノール基含有ポリシロキサン−３−グリシドキシプロピルメチルポリシロキサン共重合オイルの合成Ｓ５２０／正珪酸エチル＝２／１（モル）
１Ｌの三口フラスコに多摩化学社製の正珪酸エチル（テトラエトキシシラン）７０ｇを採り、反応溶剤としてトルエン／メタノール＝６０／４０の混合溶媒５００ｍｌを加える。加水分解触媒として塩酸を触媒量と３．５倍モルの水６４ｍｌを加えて常温下に３０分間攪拌反応せしめる。ガスクロマトグラフィー（ＧＣ）にて正珪酸エチルのピークの消失を確認する。チッソ社製Ｓ５２０（３−グリシドキシプロピルメチルジメトキシシラン）の１４８ｇと縮合触媒としてジブチル錫ジラウレートの０．０５ｇを添加し、常温にて攪拌下に３〜５時間加水分解縮合反応させる。ＧＣにてＳ５２０及びこれのオリゴマーピーク消失を確認して反応終了とする。ウォーターバスにて加温し強攪拌下でメタノール及び共沸溶剤を留去する。残留液を３００ｍｌフラスコに移し、オイルバスにて加温し強攪拌下で残留トルエン及び塩酸を含む水を留去せしめる。こうして得られた油状オルガノポリシロキサンは１１９ｇで理論収率の９８％、無色微かに甘い香りのする透明粘性液体、オキシラン酸素含有８．０％、Ｃ４３．７％、Ｈ７．９％であった。実験式Ｃ _１４ Ｈ _２９．４ Ｏ _６．７ Ｓｉ _３ に対する計算値であるオキシラン酸素８．３％、Ｃ４３．８％，Ｈ８．０％、Ｏ２６．５％、Ｓｉ２１．９％によく一致した。粘度は７，８００センチポイズ（２５℃）であった。ＩＲチャート及びＮＭＲチャートを図１、図２に示した。なおＮＭＲで１．９６ｐｐｍのシグナルがＯＨに基づく事の証明は図３に示した重水素置換により確認した。肉眼観察による溶け易さの判定結果は、トルエン、ヘキサン、アセトンに易溶、メタノール、酢酸エチル、メチルエチルケトン、クロロホルムに溶解、エタノールに微溶（微白濁）、イソプロパノールに難溶（白濁）、水に不溶であった。前記、３４５０ｃｍ^-1付近の吸収ピークと２９４０ｃｍ^-1付近の吸収ピークとの吸光度（ｌｏｇＩ₀ ／Ｉ）比は繰り返し実験でそれぞれ０．７０、０．８２であった。構造式下記〔化７〕とシグナルの関係は表１の如くである。
【００１２】
【化７】

【００１３】
【表１】

【００１４】
実施例１と同様な製造方法でＳ５２０／正珪酸エチルのモル比を変えて得た上記化７の構造式を有するポリマーの仕込モル比と粘度の関係を図４に示した。図４より明かな様に三次元構造性モノマー成分が多いポリマー程粘度が急速に高まる結果である。極めて理論に従った結果である。
【００１５】
実施例２
実施例１と同じＳ５２０／正珪酸エチルのモル比で一括仕込（一段法）と本発明（二段法）比較の為の加水分解縮合反応をさせた。各シラン成分の測定はガスクロマトグラフィー（カラム：シリコンＳＥ３０）で反応追試の形で実施した。比較法（一段法）Ｓ５２０／正珪酸エチルのモル比＝２／１で一括仕込でシラン総モルの３．５倍量の０．１規定塩酸水（加水触媒）及び触媒量の有機錫化合物を添加して常温にて加水分解縮合反応させた。反応スタート後の経過時間と各成分のパーセント測定結果を表２にまとめた。なおＳ５２０−１ＭはＳ５２０のモノメトキシモノシラノール体であり、Ｓ５２０−０ＭはＳ５２０のジシラノール体である。
【００１６】
【表２】

【００１７】
本法（二段法）Ｓ５２０／正珪酸エチルのモル比＝２／１でまづ正珪酸エチルのみをシラン総モルの３．５倍量の０．１規定塩酸水（加水触媒）で常温にて１５分間加水分解反応させる。その後所定量のＳ５２０と触媒量の有機錫縮合触媒を添加して加水分解縮合反応させた。表３にＳ５２０添加後の経過時間と各成分のパーセント測定結果をまとめた。
【００１８】
【表３】

【００１９】
表２と表３の結果から明かの如く、従来法である一段法では正珪酸エチルがほとんど加水分解しなくなる現象が生じる。この原因はＳ５２０の加水縮合を促進する為の有機錫触媒添加と関連しているが、無縮合触媒下での一段反応では正珪酸エチルの加水に５日、Ｓ５２０は２０日でも完全に加水縮合しない大きな遅延を生じて実用上問題がある。
【００２０】
実施例３
３−グリシドキシプロピルメチルポリシロキサン、シラノール基含有３−メタクリロキシプロピルポリシロキサン共重合オイルの合成Ｓ５２０／Ｓ７１０＝２／１（モル）
１Ｌの三口フラスコにチッソ（株）社製のＳ７１０（３−メタクリロキシプロピルトリメトキシシラン）の６２ｇを採り、反応溶剤としてトルエン／メタノール＝６０／４０の混合溶媒５００ｍｌを加える。加水分解触媒として塩酸を触媒量と３．５倍モルの水４８ｍｌを加えて常温下に３０分間攪拌反応せしめる。ガスクロマトグラフィー（ＧＣ）にてＳ７１０のピークの消失を確認する。チッソ社製Ｓ５２０の１１０ｇと縮合触媒としてジブチル錫ジラウレートの０．０５ｇを添加し、常温にて攪拌下に３〜５時間加水分解縮合反応させる。ＧＣにてＳ５２０及びこれのオリゴマーピーク消失を確認して反応終了とする。ウォオーターバスにて加温し強攪拌下でメタノール及び共沸溶剤を留去する。残留液を３００ｍｌフラスコに移し、オイルバスにて加温し強攪拌下で残留トルエン及び塩酸を含む水を留去せしめる。こうして得られた油状オルガノポリシロキサンは１２３ｇで理論収率の９８％、無色無色透明粘性液体である。粘度は２５０センチポイズ（２５℃）であった。ＩＲチャート及びＮＭＲチャートを図５、図６に示した。なおＮＭＲで１．９３ｐｐｍのシグナルがＯＨに基づく成分を含む事の証明は図７に示した重水素置換により確認した。ＩＲ及びＮＭＲの結果解析より得られた油状オルガノポリシロキサンの示性式は（Ｃ _７ Ｈ _１４ Ｏ _３ Ｓｉ） _２ ・（Ｃ _７ Ｈ _１１．８ Ｏ _３．９ Ｓｉ） _１ である。肉眼観察による溶け易さの判定結果は、トルエンに易溶、アセトン、メタノール、酢酸エチル、メチルエチルケトン、クロロホルム、エタノール、イソプロパノールに溶解、但しアルコールには溶解が若干遅い、ｎ−ヘキサンに難溶、水に不溶であった。前記、３４５０ｃｍ^-1付近の吸収ピークと１７２０ｃｍ^-1付近の吸収ピークとの吸光度（ｌｏｇＩ₀ ／Ｉ）比は０．２５であった。構造式は下記〔化８〕の如くでシグナルの関係は表４に示した。
【００２１】
【化８】

【００２２】
【表４】

【００２３】
実施例３と同様な製造方法でＳ５２０／Ｓ７１０のモル比を変えて得た上図の構造式を有するポリマーの仕込モル比と粘度の関係を図８に示した。図８より明かな様に三次元構造性モノマー成分が多いポリマー程粘度が急速に高まる結果である。極めて理論に従った結果である。
【００２４】
比較例１
一段法による３−グリシドキシプロピルメチルポリシロキサン、シラノール基含有３−メタクリロキシプロピルポリシロキサン共重合オイルの合成実施例３ではＳ５２０／Ｓ７１０モル比＝８／１〜１／８の範囲で２段法での製造であるが、本比較例ではＳ５２０とＳ７１０を一括仕込して触媒量の塩酸とジブチル錫ジラウレートを添加してメタノール／トルエン混合溶剤中にて、シラン総モルの３．５倍量の水を加えて加水分解縮合反応せしめた。単離したオルガノポリシロキサンオイルの粘度と仕込シランモル比率の関係を図９に示した。図９で明かの如くＳ５２０／Ｓ７１０＝８／１〜１／８の範囲で粘度変化は２００〜１７００センチポイズ（２５℃）と僅かであり、本発明による２段法（図８）と製造法の違いがポリマー構造に大きく影響している事を表している。すなわち３次元構造成分であるＳ７１０とリニアー成分であるＳ５２０の共加水縮合ではＳ７１０成分比が高まるにつれて増粘（架橋成分の増大）している事が理解される。一段法では加水分解速度の違い等からブロック状ポリマー同志の結合生成が少ない結果を意味しているものと考えられる。
【図面の簡単な説明】
図１〜９は、本発明の実施例の説明図である。
【図１】ＩＲチャートを示す。
【図２】ＮＭＲチャートを示す。
【図３】ＮＭＲチャートを示す。
【図４】ポリマーの仕込モル比と粘度の関係を示す。
【図５】ＩＲチャートを示す。
【図６】ＮＭＲチャートを示す。
【図７】ＮＭＲチャートを示す。
【図８】ポリマーの仕込モル比と粘度の関係を示す。
【図９】製品粘度と仕込シランモル比の関係を示す。[0001]
[Industrial application fields]
The present invention relates to a novel organopolysiloxane and a method for producing the same.
[0002]
[Prior art and its problems]
Conventionally, co-hydrolysis of silane has been performed by simultaneously charging two or more silanes. The conventional method of using hydrolyzate of silane is to stop the hydrolysis to a low degree in a solvent and use it as a primer to the extent that an alkoxy group remains, or to separate and use it as an oligomer stable at room temperature. It was customary. However, a three-dimensional structural polymer having a silanol group and an organic functional group that are stable at room temperature has not been known, and there is no report of isolating this.
[0003]
[Problems to be solved by the invention]
The present invention provides a novel organopolysiloxane having a silanol group and an organic functional group which are stable at room temperature, a polymer skeleton structure in a block shape, and three-dimensional and linear properties, and a method for producing the same. The terminal group of this polymer is silanol. The inventor has conducted intensive research to find a polysiloxane having the structure described above and a method for producing the polysiloxane. As a result, it was found that the compound and its production method can be effectively achieved by the two-stage hydrolysis condensation reaction described later, and the present invention was completed based on this finding. In the production method by the two-stage hydrolytic condensation reaction according to the present invention, the organopolysiloxane produced in the solvent by this reaction is isolated from the solvent and used as an oil or resinous material that can be handled stably at room temperature for various uses. It is an object. Therefore, as shown in the examples described later, when silanes having significantly different hydrolysis rates are produced by batch preparation, the three-dimensional structural silane component is difficult to block and the linear component is shorter than the linear component. The condition is that only a polymer having a low viscosity is obtained as a structured polymer. Therefore Oh Le Ganoderma polysiloxane not according to the manufacturing method when the object of the present invention can not be obtained.
[0004]
[Means for Solving the Problems]
The present invention has the following configurations (1) to (5) .
(1) Cohydrolysis of a tetraalkoxysilane (A) represented by the general formula Si (OR) ₄ and a silane compound (C) represented by the general formula R ² R ³ Si (OR) ₂ in the presence of an acid catalyst. In carrying out the condensation reaction, first, (A) is subjected to a hydrolytic condensation reaction in the presence of an acid catalyst, 3 to 4 times the total moles of silane , and a hydrophilic solvent, and then (C) and tertiary A method for producing an organopolysiloxane represented by the formula [Chemical Formula 4], wherein a condensation catalyst necessary for copolymerizing a linear silane compound in a block form is added to an intrinsic polymer and subjected to a cohydrolysis condensation reaction .
[Formula 4]

(Wherein R ² and R ³ are each an alkyl group having 1 to 8 carbon atoms, a phenyl group , an alkenyl group having 2 to 8 carbon atoms , a 3-glycidoxypropyl group, or a 3-chloropropyl group; Is an alkyl group having 1 to 8 carbon atoms, m and n are each a positive integer of 3 or less, and x is a number of 1.0 or less not including 0 )
(2) A trialkoxysilane compound (B) represented by the general formula R ¹ Si (OR) ₃ and a silane compound (C) represented by the general formula R ² R ³ Si (OR) ₂ in the presence of an acid catalyst. In carrying out the cohydrolysis condensation reaction, first, (B) is subjected to a hydrolysis condensation reaction in the presence of an acid catalyst, 3 to 4 times the total moles of silane water, and a hydrophilic solvent, and then (C) in the reaction mixture. And an organopolysiloxane represented by the formula [Chemical Formula 5], wherein a condensation catalyst necessary for copolymerizing a linear silane compound in a block form is added to a three-dimensional polymer and subjected to a cohydrolysis condensation reaction Manufacturing method.
[Chemical formula 5]

^{(Wherein, R 1, R 2, R} 3 are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, 3-glycidoxypropyl group, 3-methacryloxy propyl, 3-mercapto A propyl group, a 3-chloropropyl group, an epoxycyclohexylethyl group, or a phenyl group, R is an alkyl group having 1 to 8 carbon atoms, m and l are each a positive integer of 3 or less, and y does not include 0. 1.0 or less )
(3) Tetraalkoxysilane (A) is tetramethoxysilane or tetraethoxysilane or a hydrolyzate thereof, methyl silicate 59 (an oligomer having a SiO ₂ content of about 59%) or ethyl silicate 40 (a SiO ₂ content of about a process according to (1) is either 40% of the oligomers).
(4) trialkoxysilane compound (B) is vinyltrialkoxysilane , 3-glycidoxypropyltrialkoxysilane , 3-methacryloxypropyltrialkoxysilane , 3-mercaptopropyltrialkoxysilane , epoxycyclohexylethyltrialkoxy The production method according to the above (2), which is any one of silane , 3-chloropropyltrialkoxysilane , and phenyltrialkoxysilane (wherein alkoxy is methoxy or ethoxy ) .
(5) The silane compound (C) is 3-glycidoxypropylalkyldialkoxysilane , 3-chloropropylalkyldialkoxysilane , dialkyldialkoxysilane , phenylalkyldialkoxysilane (wherein alkyl is methyl or ethyl) The method according to any one of (1) to (4), wherein alkoxy is any one of methoxy and ethoxy .
[0005]
The configuration and effects of the present invention will be described in detail below. The present invention have the general formula Si (OR) trialkoxysilane compound represented tetraalkoxysilane represented by ₄ (A) and the general formula _{^{R 1 Si (OR) 3 (}} B) and the general formula R ² R ³ Si (OR ) from among the silane compounds represented by ₂ (C) and (a) (C), when is a cohydrolysis condensation reaction in the presence of an acid catalyst a catalytic amount in two different combinations of (B) (C), and The three-dimensional structural alkoxysilane (A) or (B) is hydrolyzed independently to form an oligomer block. Thereafter, the present invention relates to a method for producing a block copolymer by two-stage hydrolytic condensation in which the linear-forming dialkoxysilane as the component (C) is hydrolyzed and co-condensed . R ¹ And R ² When is a silylpropyl group having an organic functional group, for example, a trialkoxysilane having a 3-methacryloxypropyl group or a lower alkyl dialkoxysilane generally has a slower hydrolysis rate than tetraalkoxysilane, so a catalyst needs to be added. There is. As the catalyst species, an organic tin compound or the like is preferably used. As the reaction solvent , a hydrophilic solvent or a mixed solvent containing a hydrophilic solvent is preferably used. The amount of water required for hydrolysis is preferably 3 to 4 moles of the total moles of silane. Where R ¹ And R ² 3-glycidoxypropyl group or a saturated hydrocarbon group of the silane coupling agent and C ₁ -C ₈ containing organic functional group such as a vinyl group, a phenyl group or an alkenyl group is indicated. Alkoxy groups OR are those prepared from saturated alcohols of _{C 1 ~C 8, C 1 ~C} 3 is preferably used in consideration of the reaction rate. The cohydrolyzed condensation compound produced by the present invention is oily or resinous at room temperature represented by [Chemical Formula 4] and [Chemical Formula 5] , and the produced silanol groups are each x = 1.0 or less, y = It is an organopolysiloxane that is stable at room temperature and is 1.0 or less or x + y = 2.0 or less. When x and x + y are more than this, the produced polymer contains a gelled product or is a gel.
[0006]
Next, although it is an acid as a hydrolysis catalyst, there should just be a catalyst amount of acid and acid concentration is not prescribed | regulated. For example, there is a method in which diluted acid is added by a specified amount of water. As the type of acid, either an organic acid such as acetic acid, an inorganic acid such as hydrochloric acid or sulfuric acid, or a strongly acidic ion exchange resin can be used, but an inorganic acid having a high hydrolysis rate is preferred.
[0007]
Any of a wide variety of substances that act as silanol condensation catalysts can be used in the present invention. Such materials include, for example, organotin compounds such as dibutyltin dilaurate, stannous acetate, stannous octoate, or metal carboxy such as zinc naphthenate, zinc octoate, 2-ethylhexanoic acid and cobalt naphthenate. The rate, titanium ester, and chelate are mentioned. Preferred compounds are organotin compounds, especially tin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate.
The amount of the condensation catalyst is not particularly limited as long as it is a catalyst amount, but is generally 0.05% or less of the total amount of silane.
[0008]
The amount of water for allowing sufficient hydrolysis to be added is 3 to 4 times mol, preferably 3.5 times mol or more based on the total mol of silane . The reaction solvent may be a hydrophilic solvent alone, but a mixed solvent of a hydrophilic solvent or a mixed solvent of a lipophilic and a hydrophilic solvent can also be applied. For example, a hydrophilic solvent such as methanol, ethanol, acetone, tertiary butanol and diacetone alcohol, or a mixed solvent such as xylene / alcohol and toluene / alcohol can be used.
[0009]
The solubility of the organopolysiloxane oil obtained in the present invention is measured by taking 100 mg of the oily organopolysiloxane sample of the present invention in a glass sample tube and adding 1 ml of each solvent to this to determine the ease of dissolution by visual observation. It was done by the method. The results were displayed in five levels: readily soluble, soluble, slightly soluble (slightly cloudy), hardly soluble (cloudy), and insoluble. The organopolysiloxane of the present invention is generally in the unit, such as the following (a) ~ (d) can ensure that is represented by the above general formula.
(A) the characteristic absorption of the Si-OH in the vicinity of the analysis 3450 cm ^-1 in the infrared absorption spectrum (IR), several of absorption based on the CH bond in the vicinity of ^{3000cm -1 ~2900cm -1, 1100cm -1 ~1000cm} -1 Broad absorption of nearby Si—O—Si appears. The absorbance (log I ₀ / I) ratio between the absorption peak near 3450 cm ⁻¹ and the absorption peak near 2940 cm ⁻¹ is an indicator of the relative value of the silanol group content. That is, if this value is 1.0 or less, the oil has a silanol group that is stable at room temperature. When this value is 1.0 or more, it is an organopolysiloxane polymer that exhibits a resinous solid when heated to several tens of degrees Celsius. On the one hand, a polymer having a methacryloxy group absorption of several based on CH bond at around 2900cm ^-1, -C = CCOO- absorption of 1720 cm ^-1, C = C absorption in the vicinity of 1640cm ^-1, 1100cm ^-1 ~1000cm around ^-1 Broad absorption of Si-O-Si appears. The absorbance (log I ₀ / I) ratio between the absorption peak near 3450 cm ^{−1 and} the absorption peak near 1720 cm ⁻¹ is an indicator of the relative value of the silanol group content. That is, if this value is 1.0 or less, the oil has a silanol group that is stable at room temperature. When this value is 1.0 or more, it is an organopolysiloxane polymer that exhibits a resinous solid when heated to several tens of degrees Celsius.
(B) ¹ H-nuclear magnetic resonance spectrum ( ¹ H-NMR)
The number of (Si) -OH can be determined from the number of hydrogen atoms in the organopolysiloxane of the present invention, the bonding mode, confirmation of (Si) -OH by deuterium substitution, and the ratio of hydrogen atoms.
(C) Quantification of the amount of epoxy oxygen The oxirane oxygen is quantified by the HBr-acetic acid titration method.
(D) Carbon, hydrogen (CH) elemental analysis The carbon and hydrogen content can be known by microelemental analysis. The viscosity data was measured at a constant temperature of 25 ° C. using a rotational viscometer “VISCONIC” manufactured by Tokyo Keiki Co., Ltd.
[0010]
【The invention's effect】
Since the block copolymer can be produced by the production method by the two-stage hydrolytic condensation of the present invention, the produced organopolysiloxane has a silanol group which is stable at room temperature in the polymer as proved in Examples described later. In addition, since it has 1 to 2 organic functional groups derived from the alkoxy raw material used, it can be said to be a multi-functional reactive organopolysiloxane . Moreover, the terminal group of this polymer is silanol. The organopolysiloxane produced by the production method of the present invention is not soluble or compatible with most organic polysiloxanes in organic solvents or organic resins, whereas the organopolysiloxane of the present invention is soluble in many kinds of organic solvents. . It also has affinity for many types of organic resins. Based on these characteristics, it can be used as a modified silicone oil, as well as other release agents, release paper silicones, personal care silicones, paint additives, silicone adhesives, adhesive sealants, modified silicone silanes, and a wide range of other applications. it is useful. In addition, polymer alloys and blends composed of two or more types of polymers are expected to act on the interfaces between different resins to facilitate kneading and coupling between polymers. In order to describe the present invention more specifically, examples will be described below, but the present invention is not limited to these examples.
[0011]
Example 1
Synthesis of Silanol Group-Containing Polysiloxane-3-Glycidoxypropylmethyl Polysiloxane Copolymer Oil S520 / Ethyl Normal Silicate = 2/1 (Mole)
70 g of normal ethyl silicate (tetraethoxysilane) manufactured by Tama Chemical Co., Ltd. is taken into a 1 L three-necked flask, and 500 ml of a mixed solvent of toluene / methanol = 60/40 is added as a reaction solvent. As a hydrolysis catalyst, hydrochloric acid is added in a catalytic amount and 64 ml of 3.5 times moles of water, and the mixture is stirred at room temperature for 30 minutes. The disappearance of the peak of normal ethyl silicate is confirmed by gas chromatography (GC). 148 g of S520 (3-glycidoxypropylmethyldimethoxysilane) manufactured by Chisso Corporation and 0.05 g of dibutyltin dilaurate as a condensation catalyst are added and subjected to hydrolysis and condensation reaction at room temperature with stirring for 3 to 5 hours. After confirming S520 and disappearance of the oligomer peak thereof by GC, the reaction is completed. Heat in a water bath and distill off methanol and azeotropic solvent with vigorous stirring. The residual liquid is transferred to a 300 ml flask, heated in an oil bath, and water containing residual toluene and hydrochloric acid is distilled off under strong stirring. The oily organopolysiloxane thus obtained was 119 g and had a theoretical yield of 98%, a transparent viscous liquid having a colorless and slightly sweet scent, oxirane oxygen content of 8.0%, C43.7% and H7.9%. The calculated values for the empirical formula C ₁₄ H _29.4 O _6.7 Si ₃ were in good agreement with oxirane oxygen 8.3%, C 43.8%, H 8.0%, O 26.5% and Si 21.9%. The viscosity was 7,800 centipoise (25 ° C.). The IR chart and NMR chart are shown in FIGS. It was confirmed by NMR that the 1.96 ppm signal was based on OH by deuterium substitution shown in FIG. The results of easiness of dissolution by visual observation are as follows. Easily soluble in toluene, hexane and acetone, dissolved in methanol, ethyl acetate, methyl ethyl ketone and chloroform, slightly soluble in ethanol (slightly cloudy), hardly soluble in isopropanol (cloudy), in water It was insoluble. The absorbance of the absorption peak and 2940 cm ^-1 vicinity of the absorption peak near 3450cm ^-1 (logI ₀ / I) ratio was respectively repeated experiments 0.70,0.82. Table 1 shows the relationship between the following structural formula [Chemical Formula 7] and signals.
[0012]
[Chemical 7]

[0013]
[Table 1]

[0014]
FIG. 4 shows the relationship between the charged molar ratio and the viscosity of the polymer having the structural formula of Chemical Formula 7 obtained by changing the molar ratio of S520 / normal ethyl silicate by the same production method as in Example 1. As is clear from FIG. 4, the viscosity increases more rapidly as the polymer has more three-dimensional structural monomer components. This is a very theoretical result.
[0015]
Example 2
In the same molar ratio of S520 / normal ethyl silicate as in Example 1, the batch preparation (one-stage method) and the hydrolysis-condensation reaction for comparison of the present invention (two-stage method) were performed. Each silane component was measured by gas chromatography (column: silicon SE30) in the form of a reaction follow-up. Comparative method (one-step method) S520 / normal ethyl silicate molar ratio = 2/1 and charged in a batch with 0.1N hydrochloric acid water (hydrocatalyst) 3.5 times the total silane mole and a catalytic amount of organotin compound It was added and subjected to hydrolysis condensation reaction at room temperature. The elapsed time after the start of the reaction and the percentage measurement results of each component are summarized in Table 2. S520-1M is a monomethoxymonosilanol body of S520, and S520-0M is a disilanol body of S520.
[0016]
[Table 2]

[0017]
This method (two-step method) S520 / normal ethyl silicate molar ratio = 2/1. First, only normal ethyl silicate was brought to room temperature with 0.1N hydrochloric acid (hydrocatalyst) 3.5 times the total amount of silane. For 15 minutes. Thereafter, a predetermined amount of S520 and a catalytic amount of an organic tin condensation catalyst were added to cause a hydrolysis condensation reaction. Table 3 summarizes the elapsed time after the addition of S520 and the percentage measurement results of each component.
[0018]
[Table 3]

[0019]
As is clear from the results in Tables 2 and 3, the conventional one-stage method causes a phenomenon in which normal ethyl silicate hardly hydrolyzes. This cause is related to the addition of organotin catalyst to promote the hydrolysis of S520, but in a one-step reaction under a non-condensation catalyst, 5 days for the addition of normal ethyl silicate and S520 for the complete hydrolysis even for 20 days. There is a practical problem with a large delay.
[0020]
Example 3
Synthesis of 3-glycidoxypropylmethylpolysiloxane and silanol group-containing 3-methacryloxypropylpolysiloxane copolymer oil S520 / S710 = 2/1 (mol)
62 g of S710 (3-methacryloxypropyltrimethoxysilane) manufactured by Chisso Corporation is taken into a 1 L three-necked flask, and 500 ml of a mixed solvent of toluene / methanol = 60/40 is added as a reaction solvent. As a hydrolysis catalyst, hydrochloric acid is added in a catalytic amount and 48 ml of 3.5 times moles of water, and the mixture is stirred at room temperature for 30 minutes. The disappearance of the peak of S710 is confirmed by gas chromatography (GC). 110 g of S520 manufactured by Chisso Corporation and 0.05 g of dibutyltin dilaurate as a condensation catalyst are added and subjected to hydrolysis and condensation reaction at room temperature with stirring for 3 to 5 hours. After confirming S520 and disappearance of the oligomer peak thereof by GC, the reaction is completed. Heat in a water bath and distill off methanol and azeotropic solvent with vigorous stirring. The residual liquid is transferred to a 300 ml flask, heated in an oil bath, and water containing residual toluene and hydrochloric acid is distilled off under strong stirring. The oily organopolysiloxane thus obtained was 123 g, 98% of the theoretical yield, and was a colorless, colorless and transparent viscous liquid. The viscosity was 250 centipoise (25 ° C.). IR chart and NMR chart are shown in FIGS. It was confirmed by NMR that the 1.93 ppm signal contained a component based on OH by deuterium substitution shown in FIG. The characteristic formula of the oily organopolysiloxane obtained from IR and NMR analysis is (C ₇ H ₁₄ O ₃ Si) ₂ · (C ₇ H _11.8 O _3.9 Si) ₁ It is. The results of the determination of easiness of dissolution by visual observation are as follows: Easily soluble in toluene, dissolved in acetone, methanol, ethyl acetate, methyl ethyl ketone, chloroform, ethanol, isopropanol, but slightly soluble in alcohol, slightly soluble in n-hexane, water It was insoluble. The absorbance (log I ₀ / I) ratio between the absorption peak near 3450 cm ^{−1 and} the absorption peak near 1720 cm ⁻¹ was 0.25. The structural formula is as shown in [Chemical Formula 8] below, and the signal relationship is shown in Table 4.
[0021]
[Chemical 8]

[0022]
[Table 4]

[0023]
FIG. 8 shows the relationship between the charged molar ratio of the polymer having the above structural formula obtained by changing the molar ratio of S520 / S710 by the same production method as in Example 3 and the viscosity. As is clear from FIG. 8, the viscosity increases more rapidly as the polymer has more three-dimensional structural monomer components. This is a very theoretical result.
[0024]
Comparative Example 1
Synthesis of 3-glycidoxypropylmethylpolysiloxane and silanol group-containing 3-methacryloxypropylpolysiloxane copolymer oil by one-stage method In Example 3, S520 / S710 molar ratio = two-stage in the range of 8/1 to 1/8 In this comparative example, S520 and S710 are charged together, a catalytic amount of hydrochloric acid and dibutyltin dilaurate are added, and the amount is 3.5 times the total mole of silane in a methanol / toluene mixed solvent. The water was added to cause hydrolysis and condensation reaction. The relationship between the viscosity of the isolated organopolysiloxane oil and the charged silane molar ratio is shown in FIG. As apparent from FIG. 9, the viscosity change is as small as 200 to 1700 centipoise (25 ° C.) in the range of S520 / S710 = 8/1 to 1/8. This shows that the difference greatly affects the polymer structure. That is, it is understood that in the cohydrocondensation of S710 as a three-dimensional structural component and S520 as a linear component, the viscosity increases (increases in crosslinking component) as the S710 component ratio increases. In the one-stage method, it is considered that the result is that there is little bond formation between the block polymers due to differences in hydrolysis rate and the like.
[Brief description of the drawings]
1-9 is explanatory drawing of the Example of this invention.
FIG. 1 shows an IR chart.
FIG. 2 shows an NMR chart.
FIG. 3 shows an NMR chart.
FIG. 4 shows the relationship between the charged molar ratio of polymer and viscosity.
FIG. 5 shows an IR chart.
FIG. 6 shows an NMR chart.
FIG. 7 shows an NMR chart.
FIG. 8 shows the relationship between the charged molar ratio of polymer and the viscosity.
FIG. 9 shows the relationship between product viscosity and charged silane molar ratio.

Claims (5)

A tetraalkoxysilane (A) represented by the general formula Si (OR) ₄ and a silane compound (C) represented by the general formula R ² R ³ Si (OR) ₂ are subjected to a cohydrolytic condensation reaction in the presence of an acid catalyst. In this case, first, (A) is subjected to a hydrolytic condensation reaction in the presence of an acid catalyst, 3 to 4 times the total moles of silane , and a hydrophilic solvent, followed by (C) and a three-dimensional polymer in the reaction mixture. A process for producing an organopolysiloxane represented by the formula [Chemical Formula 1], wherein a co-hydrolysis condensation reaction is carried out by adding a condensation catalyst necessary for copolymerizing a linear silane compound in a block form .

(Wherein R ² and R ³ are each an alkyl group having 1 to 8 carbon atoms, a phenyl group , an alkenyl group having 2 to 8 carbon atoms , a 3-glycidoxypropyl group, or a 3-chloropropyl group; Is an alkyl group having 1 to 8 carbon atoms, m and n are each a positive integer of 3 or less, and x is a number of 1.0 or less not including 0 ) Cohydrolysis general formula R ¹ Si (OR) trialkoxysilane compound represented by ₃ (B) and the general formula R ² R ³ Si (OR) a silane compound represented by ₂ and (C) in the presence of an acid catalyst In the condensation reaction, first, (B) is subjected to a hydrolytic condensation reaction in the presence of an acid catalyst, 3 to 4 times the total moles of silane , and a hydrophilic solvent, followed by (C) and tertiary reaction in the reaction mixture. A method for producing an organopolysiloxane represented by the formula [Chemical Formula 2], comprising adding a condensation catalyst necessary for copolymerizing a linear silane compound into a block form to an intrinsic polymer and subjecting it to a cohydrolysis condensation reaction .

^{(Wherein, R 1, R 2, R} 3 are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, 3-glycidoxypropyl group, 3-methacryloxy propyl, 3-mercapto A propyl group, a 3-chloropropyl group, an epoxycyclohexylethyl group, or a phenyl group, R is an alkyl group having 1 to 8 carbon atoms, m and l are each a positive integer of 3 or less, and y does not include 0. 1.0 or less ) Tetraalkoxysilane (A) is tetramethoxysilane or tetraethoxysilane or a hydrolyzate thereof methyl silicate 59 (an oligomer having a SiO ₂ content of about 59%) or ethyl silicate 40 (a SiO ₂ content of about 40%). The production method according to claim 1, which is any one of oligomers) . Trialkoxysilane compound (B) is vinyltrialkoxysilane , 3-glycidoxypropyltrialkoxysilane , 3-methacryloxypropyltrialkoxysilane , 3-mercaptopropyltrialkoxysilane , epoxycyclohexylethyltrialkoxysilane , 3 - process according to claim 2 is either chloropropyl trialkoxysilane, phenyl trialkoxysilane (wherein the alkoxy is methoxy or ethoxy). Silane compound (C) is 3-glycidoxypropylalkyldialkoxysilane , 3-chloropropylalkyldialkoxysilane , dialkyldialkoxysilane , phenylalkyldialkoxysilane (wherein alkyl is methyl or ethyl, alkoxy is The method according to any one of claims 1 to 4, which is any one of methoxy and ethoxy .

Images