200916492 九、發明說明 【發明所屬之技術領域】 本發明係關於製造於聚氧化烯鏈介著尿烷鍵與反應性 矽基結合之氧化烯聚合物之方法。 【先前技術】 將於聚氧化烯鏈的末端具有反應性矽基之聚合物（亦 稱爲變成矽氧烷聚合物）作爲硬化成分之硬化性組成物經 濕分硬化後形成橡膠彈性優良的硬化物。因此，該硬化性 組成物廣泛作爲黏著劑、塗佈劑、封止材使用。其中，亦 以聚氧化烯鏈的末端具有甲基二甲氧基甲矽烷基之變成矽 氧烷聚合物作爲硬化成分之硬化性組成物因具有優良延伸 物性，故可作爲封止材而廣泛被市場接受（參照專利文獻 又，含有將具有聚氧化烯鏈與三烷氧基甲矽烷基之聚 合物作爲硬化成分之硬化性組成物，因硬化速度快速，且 交聯密度較高，故可適用於速硬化性之黏著劑、塗佈劑、 封止材（參照專利文獻2 )。 下述專利文獻3中記載聚氧化烯鏈端介著尿烷鍵結合 三烷氧基甲矽烷基之聚合物。作爲該聚合物的製造方法之 一’記載使聚環氧丙烷多元醇、與分子内具有1個異氰酸 酯基的異氰酸酯取代型三烷氧基矽烷化合物進行尿烷化反 應之方法，該反應中，可使用二丁基錫二月桂酸酯等尿烷 聚合觸媒。 -4- 200916492 作爲一般尿烷聚合觸媒，例如可舉出二丁基錫二月桂 酸酯、二辛基錫二月桂酸酯等有機錫化合物（例如下述專 利文獻4)、三伸乙基二胺、三乙基胺等有機胺或其他鹽 等。且，作爲其他尿烷聚合觸媒，可舉出鉍、鈷、鐵等金 屬鹽化合物。 下述專利文獻5中記載作爲具有水解性矽含有基的有 機聚合物之硬化觸媒的2-乙基己烷酸錫、η-辛酸錫等羧酸 錫（II)、及二丁基錫二月桂酸酯、二丁基錫馬來酸酯等 有機錫（IV )化合物具有優良硬化速度及硬化物性。 [專利文獻1]特開平〇3-〇72527號公報 [專利文獻2]特開平〇3 -047825號公報 [專利文獻3]特開平1 0-245482號公報 [專利文獻4]特開2 003 -8 9742號公報 [專利文獻5]專利第3 7799 5 3號公報 【發明內容】 本發明者等之見解爲，將二丁基錫二月桂酸醋作爲觸 媒使用，製造「於聚氧化烯鏈介著尿烷鍵結合反應性矽基 之聚合物」時，所得之聚合物的貯藏安定性有時並不佳。 作爲使貯藏安定性變差的原因，如上述專利文獻5所記載 ，可考慮爲二丁基錫二月桂酸酯係爲可作爲「於聚氧化烯 鏈介著尿烷鍵結合反應性矽基之聚合物」的硬化觸媒使用 之化合物，即使微量亦存在水分時’藉由於該聚合物中作 爲殘存觸媒所含之二丁基錫二月桂酸酯的作用，可促進該 -5- 200916492 聚合物的反應性矽基與水分之反應而增加黏性 改良該貯藏安定性之方法，一般方法爲減少觸 活性較低的觸媒等方法，該方法中無法充分進 應、或有著反應時間過長等問題。因此，期待 聚氧化烯鏈介著尿烷鍵之反應性矽基的聚合物 性。 本發明係爲有鑑於前述情事所得者，故提 高於聚氧化烯鏈介著尿烷鍵與反應性矽基結合 合物的貯藏安定性之氧化烯聚合物的製造方法 即’本發明爲具有以下要旨者。 (1) 一種氧化烯聚合物（P)之製造方法 氧化Μ鏈介著尿烷鍵與反應性矽基結合之氧化 Ρ)的製造方法，其特徵爲含有 將具有聚氧化烯鏈與羥基的含有羥基之聚 、與下述一般式（1)所示含有異氰酸酯基之 )’於4價單烷基錫觸媒（S )的存在下，使其 反應之步驟者； (Si(-X1)a(-R1)3-a)-Q1-NCO ...(1) (式中’ X1表示碳數1〜6之烷氧基，V表示可 之碳數I〜20之1價有機基（除烷氧基以外）， 1〜20之2價有機基，&表示1〜3之整數；但， 在時’複數的Ri彼此可爲相同或相異’ X1爲 之故。作爲 媒量，使用 行尿烷化反 改良具有於 之貯藏安定 供一種可提 之氧化烯聚 ，其爲於聚 烯聚合物（ 合物（pP ) 化合物（U 進行尿烷化 具有取代基 Q1表示碳數 R1爲複數存 複數存在時 -6- 200916492 ’複數的χ1彼此可爲相同或相異）。 (2) 如上述（丨）所記載之氧化烯聚合物的製造方法 ’其中該4價單烷基錫觸媒（s)爲下述一般式（I) R1 1Sn(OCOR12)3...(I) (式中’ R"表示碳數4〜8之烷基，R12表示碳數2〜17之 烷基；一分子内存在之3個R12彼此可爲相同或相異） 所示第1錫觸媒（S1)、及/或下述一般式（Π) R13Sn(SR14)3... (II) (式中，R13表示碳數1〜8之烷基；R14表示碳數8〜18之 烷基；一分子内存在之3個R14彼此可爲相同或相異）所 示第2錫觸媒（S2 )。 (3) 前述尿烷化反應之反應溫度爲50〜200 °C之上述 (1 )或（2 )所記載之氧化烯聚合物的製造方法。 (4 )將前述尿烷化反應於惰性氣體環境下進行之上 述（1)〜（3)中任一項所記載的氧化烯聚合物之製造方 法。 (5 )對於前述含有羥基之聚合物（PP ) ，4價單烷基 錫觸媒（S)之使用量以質量基準計爲lppm〜l〇〇ppm之 上述（1 )〜（4 )中任一項所記載的氧化烯聚合物之製造 方法。 200916492 (6)前述一般式（1)中之a爲3的上述（1)〜（5 )中任一項所記載的氧化烯聚合物之製造方法。 (7 )對於前述含有羥基之聚合物（pp )的羥基總數 之前述含有異氰酸酯基之化合物（U)的異氰酸酯基總數 之莫耳比（異氰酸酯基/羥基）爲0.80〜1_1〇的上述（1) 〜（6 )中任一項所記載的氧化烯聚合物之製造方法。 (8) 前述含有羥基之聚合物（pP)的每1個羥基之數 平均分子量爲1000〜30000的（1)〜（7)中任一項所記 載的氧化烯聚合物之製造方法。 (9) 前述含有羥基之聚合物（pP)之羥値爲1.6〜 60.0mgKOH/g的上述（1 )〜（8 )中任一項所記載的氧化 烯聚合物之製造方法。 (10) 前述含有羥基之聚合物（pP)爲，於複合金屬 氰化物錯合物之存在下，對於具有活性氫原子之化合物使 環氧化物進行開環聚合所得的含有羥基之聚合物（PP-1 ) 之上述（1 )〜（9 )中任一項所記載的氧化烯聚合物之製 造方法。 (11) 前述一般式（1)中之a爲2，Q1爲伸甲基之上 述（1 )〜（1 〇 )中任一項所記載的氧化烯聚合物之製造 方法。 (1 2 )含有上述（丨）〜（1 1 )中任一項所記載的製 造方法所得之氧化烯聚合物作爲硬化成分之硬化性組成物 〇 藉由本發明之製造方法所得之於聚氧化烯鏈介著尿烷 -8- 200916492 鍵與反應性矽基結合之氧化烯聚合物係爲可提高貯藏安定 性者。 實施發明的最佳型態 <含有羥基之聚合物（pP ) > 本發明所使用的含有羥基之聚合物（pP)係爲具有聚 氧化烯鏈與羥基之聚合物。 含有羥基之聚合物（pP)中的聚氧化烯鏈係以藉由碳 數2〜6之環氧化物的開環聚合所形成之氧化烯的聚合單位 所成者爲佳。具體爲藉由1種以上選自環氧乙烷、環氧丙 烷、環氧丁烷、及環氧己烷所成群之環氧化物的開環聚合 所形成之氧化烯聚合單位所成者爲較佳。藉由環氧丙烷之 開環聚合所形成之氧化烯聚合單位所成者爲特佳。聚氧化 烯鏈爲2種以上之氧化烯聚合單位所成時，2種以上的氧化 烯聚合單位之排列方式可爲嵌段狀或隨機狀。 含有羥基之聚合物（pP )之羥値以1.6〜60.0 mgKOH/g 爲佳，3 ·0 〜15.0mgKOH/g 爲較佳，5.0 〜12 m g Κ Ο H / g爲格外佳。 含有羥基之聚合物（pP)的每1個羥基之數平均分子 暈以1000〜30000爲佳，以3000〜20000爲較佳。 本發明中之數平均分子量（Μη )表示藉由凝膠滲透 層析（GPC )將四氫呋喃作爲移動相所測定之標準聚苯乙 烯換算的數平均分子量（Μη)。 含有羥基之聚合物（pP)之數平均分子量於上述範圍 -9 - 200916492 時，所得之氧化烯聚合物（p)的分子量由黏度及硬化物 之機械物性的觀點來看其爲良好範圍。 作爲含有羥基之聚合物（pP )，於複合金屬氰化物錯 合物之存在下，於具有活性氫原子之化合物使環氧化物進 行開環聚合所得之含有羥基之聚合物（pP-1 )爲佳。 複合金屬氰化物錯合物係以具有有機配位子之複合金 屬氰化物錯合物爲佳。有機配位子係以醚系配位子或醇類 系配位子爲佳。作爲醚系配位子之具體例，可舉出乙二醇 二甲基醚（glyme)、二乙二醇二甲基醚（diglyme)、三 乙二醇二甲基醚。作爲醇類系配位子之具體例，可舉出 tert-丁醇、η-丁醇、sec-丁醇、iso-丁醇、tert-戊醇、iso-戊醇、乙二醇單-tert-丁基醚。 作爲複合金屬氰化物錯合物、以鋅六氰鈷酸鹽爲特佳 〇 具有活性氫原子之化合物係以具有活性氫原子之有機 化合物爲佳，以具有羥基或胺基之化合物爲較佳’具有1 〜4個之羥基的化合物爲特佳。具有活性氫原子之化合物 可使用1種或2種以上。 作爲具有活性氫原子之有機化合物的具體例’可舉出 1種以卜.選自乙二醇、丙二醇、一.丙二醇、丁二醇、六甲 一醇、氫化雙酚A、新戊基甘醇、聚丁二嫌甘醇、二乙二 醇、三乙二醇、聚乙二醇、烯丙醇、甲基儲丙醇、甘油、 三羥甲基甲烷、三羥甲基丙烷、季戊四醇等醇類；聚環氧 丙烷單醇、聚環氧丙烷二醇、聚環氧丙烷三醇、聚環氧乙 -10 - 200916492 烷單醇、聚環氧乙烷二醇、及聚環氧乙烷三醇所成群之聚 合物狀醇類。該聚合物狀醇類之每1個羥基的數平均分子 量係以300〜1500爲佳。 具有活性氫原子之化合物可使用1種或2種以上。使用 具有2種以上之活性氫原子的化合物時，使用具有2個羥基 之聚合物狀醇類、與具有3個羥基之聚合物狀醇類爲佳。 使用本發明中之前述含有羥基之聚合物（pP-1 )時， 將作爲聚合殘渣所含有之複合金屬氰化物錯合物經純化除 去後，可與含有異氰酸酯基之化合物（U)進行尿烷化反 應，或亦可無須純化除去該複合金屬氰化物錯合物下與含 有異氰酸酯基之化合物（U )進行尿烷化反應。 <含有異氰酸酯基之化合物（U) > 本發明所使用的含有異氰酸酯基之化合物（U)係爲 下述一般式（1)所示化合物。式中，a爲1〜3之整數。 (Si(-X1)a(-R1)3-a)-Q，-NCO...(l) 上述式（1)中，R1爲可具有取代基之碳數1〜20的1價有 機基。 但，R1並非烷氧基。 R 1係以碳數8以下的烷基、碳數8以下的氟烷基或苯基 爲佳，以甲基、乙基、丙基、丁基、己基、環己基或苯基 爲較佳。同一分子中存在複數個R1時，這些複數的R1彼 -11 - 200916492 此可爲相同或相異。 上述式（1)中’ χ1表示碳數1〜6之烷氧基。作爲具 體例可舉出甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、 己氧基。以甲氧基爲特佳。且’同一分子中存在複數個 X1時，這些複數之χ1彼此可爲相同或相異。 式（1)中，Q1表示碳數1〜2〇之2價有機基。碳數1〜 1 0之伸烷基爲佳’由取得容易性的觀點來看，以三伸甲基 、伸甲基爲較佳。 含有異氰酸酯基之化合物（U)係以上述一般式（1 )中，a爲3之含有異氰酸酯基之化合物（U-1)爲佳。該 含有異氰酸酯基之化合物（U-1)係以下述一般式（2)所 示。 (Si(-X1)3)-Q1-NCO ... (2) 上述一般式（2)中之X1及Q1’與各上述一般式（1)中 者相同，亦包含該較佳態樣。 又，作爲含有異氰酸酯基之化合物（U-2)，上述一 般式（1 )中之a爲2，且Q1係伸甲基者爲佳。 使用該含有異氰酸酯基之化合物（U-1 )、及（u-2 ) 時，可得到速硬化性優良的氧化烯聚合物（P )。 作爲含有異氰酸酯基之化合物（U-1)之具體例，可 舉出卜異氰酸酯甲基三甲氧基矽烷、2-異氰酸酯乙基三甲 氧基矽烷、3 -異氰酸酯丙基三甲氧基矽烷、3 -異氰酸酯丁 -12- 200916492 基一甲氧基砂院、3 -異氰酸醋戊基三甲氧基砂院、ι_異氰 酸酯甲基三乙氧基矽烷、2_異氰酸酯乙基三乙氧基矽烷、 3 -異氰酸酯丙基三乙氧基矽烷、卜異氰酸酯丙基三甲氧基 砂院、1 -異氰酸酯丙基三乙氧基矽烷。 作爲含有異氰酸酯基之化合物（U_2 )之具體例，可 舉出1-異氰酸酯甲基二甲氧基甲基矽烷。 <尿院化聚合觸媒> 本發明中’製造於聚氧化烯鏈介著尿烷鍵與反應性矽 基結合之氧化烯聚合物（P )時，可使用4價單烷基錫觸媒 (S )(以下亦可僅稱爲錫觸媒（S ))。所謂本說明書中 之「4價單烷基錫觸媒（s )」爲於4價錫上結合有機基所 成的化合物，於錫（Sn )上直接鍵結1個烷基之化合物。 作爲錫觸媒（S)係以下述一般式（I)所示第1錫觸 媒（S1)、或下述一般式（Π)所示第2錫觸媒（S2)爲 佳。亦可倂用第1錫觸媒（S1 )與第2錫觸媒（S2 )。 R11Sn(OCOR12)3-..(I) 上述式（I )中，R 1 1表示碳數4〜8之烷基，R 1 2表示碳數2 〜17之烷基。存在於一分子内的3個Ri2彼此可爲相同或 相異。 R13Sn(SR14)3 ...(H) -13- 200916492 上述式（II)中，R13表示碳數1〜8之院基。R14表不 碳數8〜18之烷基。存在於—分子内的3個R14彼此可爲相 同或相異。 上述式（I)中，R11爲碳數4〜8之烷基’可含有直鏈 狀或分歧結構。較佳爲-n-C4H9、-n-CeH"、-n-C8Hi7。特 佳爲-11-C4H9 ° 上述式（I)中’ R12爲碳數2〜17之烷基’可含有直鏈狀 或分歧結構。較佳爲 _C2H5、-n-C5Hii、-n-C7H丨5、-n-C9H19 、-η-〇ι〖Η23 或-n-ci7H35。特佳爲-n-C7Hi5。 特別爲上述式（I)中之R"爲-n-C4H9，R12爲-n-C7H15之 第1錫觸媒（s 1 ) ’例如以S C A T - 2 4 (製品名’三共有機 合成公司製）爲佳° 第1錫觸媒（S 1 )可單獨使用1種’或組合2種以上使 用。 上述式（II)中’ R13爲碳數1〜8之烷基，可含有直 鏈狀或分歧結構。較佳例子可舉出甲基、丁基、辛基等。 上述式（11)中，Rl4爲碳數8〜18之院基’可含有直 鏈狀或分歧結構。作爲較佳例子可舉出辛基、癸基、十二 烷基、十六烷基、十八烷基等。 作爲Rl3爲甲基時的第2錫觸媒（S2 )之例子，可舉 出單甲基錫三（辛基擴酸基）、單甲基錫二（十一院基磺 醯基）、單甲基錫三（硬脂醯基磺醯基）等。較佳爲單甲 基錫三（十二烷基磺醯基）° -14 - 200916492 作爲R13爲丁基時的第2錫觸媒（S2 )之例子，可舉 出單丁基錫三（辛基磺醯基）、單丁基錫三（十二烷基磺 醯基）、單丁基錫三（硬脂醯基磺醯基）。較佳爲單丁基 錫三（十二烷基磺醯基）。 作爲R13爲辛基時的第2錫觸媒（S2)之例子，可舉 出單辛基錫三（辛基磺醯基）、單辛基錫三（十二烷基磺 醯基）、單辛基錫三（硬脂醯基磺醯基）。較佳爲單辛基 錫三（十二烷基磺醯基）。 特別爲上述式（Π)中之Ri3爲_n_C4H9，爲_n_Ci2ii25 之第2錫觸媒（S2) ’例如以SCAT-9A (製品名，三共有 機合成公司製）爲佳。 第2錫觸媒（S2 )可單獨使用丨種或組合2種以上使用 <氧化烯聚合物（P)之製造方法> 本發明的氧化烯聚合物（P)之製造方法爲具有上述 含有羥基之聚合物（pP)、與含有異氰酸酯基之化合物（ U)於錫觸媒（S)之存在下，使其進行尿烷化反應之步 驟。例如於含有羥基之聚合物（pP )中添加錫觸媒（S ) 並攪拌後，加入含有異氰酸酯基之化合物（U )，保持於 反應溫度下使其進行尿烷化反應。 又，於含有羥基之聚合物（pP)中添加含有異氰酸酯 基之化合物（U)並攪拌後，加入錫觸媒（S )，於保持 所定反應溫度下使其進行尿烷化反應亦可。 -15- 200916492 該尿烷化反應之反應溫度以50〜200 °C爲佳，以7〇〜 1 5 0°C爲特佳。尿烷化反應之反應溫度若爲上述範圍内時 ，使其進行尿烷化反應時可得到錫觸媒（S )的良好觸媒 活性。 尿烷化反應係於惰性氣體環境下，較佳爲氮氣環境下 進行爲佳。 藉由該尿烷化反應得到氧化烯聚合物（p )。具體爲得 到「於含有羥基之聚合物（pp )之聚氧化烯鏈介著尿烷鍵並 導入反應性矽基之氧化烯聚合物（P )」。該反應性矽基係爲 對應含有異氰酸酯基之化合物（U)的「-SiC-XhaC-R^h-a」 之基。具體爲得到於聚氧化烯鏈結合來自含有異氰酸酯基 之化合物（U)的「（SU-X’aC-R’hd-Qi-NHCOO-」之氧 化烯聚合物（P )。 氧化烯聚合物（P )爲該側鏈或末端中之取代基上具 有反應性矽基。末端中之取代基具有反應性矽基者爲較佳 〇 4價單烷基錫觸媒（S )的使用量係對於含有羥基之聚 合物（PP )而言（質量基準，以下相同。）以lppm〜 lOOppm爲佳’以1〇〜50ppm爲較佳。該錫觸媒（s )之使 用量爲1 ppm以上時有利於尿烷化反應之進行，！ 〇〇ppm以 下時可得到氧化烯聚合物（P )之良好貯藏安定性。 又，作爲含有羥基之聚合物（pP )使用前述含有羥基 之聚合物（pP-1 )時，該含有羥基之聚合物（pp])之製 造中所使用的複合金屬氰化物錯合物之使用量僅爲 -16- 200916492 lOOppm以上，錫觸媒（S)的使用量以1〜50ppm爲佳， 以1〜20ppm爲較佳。又，該複合金屬氰化物錯合物之使 用量未達lOOppm時，錫觸媒（S )的使用量以20〜 lOOppm爲佳，以20〜50 ppm爲較佳。 所謂本發明爲4價單烷基錫觸媒（S )之存在下，藉由 使含有羥基之聚合物（pP)與含有異氰酸酯基之化合物（ U )進行尿烷化反應，可得到貯藏安定成優良的「於聚氧 化烯鏈介著尿烷鍵具有反應性矽基之氧化烯聚合物（P ) J ° 又，所得之氧化烯聚合物（P )的硬化性爲良好，特 別使用上述一般式（1)中，a爲3之含有異氰酸酯基之化 合物（U-1)、或上述一般式（1)中，a爲2，Q1爲伸甲 基之含有異氰酸酯基之化合物（U-2 )時，所得之氧化烯 聚合物（P )的速硬化性優良。 藉由如此作爲尿烷化反應之觸媒使用4價單烷基錫觸 媒（S )，可得到良好硬化性與具有貯藏安定性之氧化烯 聚合物（P)。該理由雖未明確，但錫觸媒（S)於尿烷化 反應之反應溫度下顯示良好觸媒活性，此推測爲具有作爲 常溫貯藏時未顯示觸媒活性之金屬系感溫性觸媒的特性。 含有羥基之聚合物（pP )與含有異氰酸酯基之化含物 (U )的尿烷化反應中，對於所使用之含有羥基之聚合物 (pP )的羥基總數’含有異氰酸酯基之化合物（U )的異 氰酸酯基總數之莫耳比（異氰酸酯基/羥基）以0.80〜1.1〇 爲佳，0.85〜1.05爲較佳。 -17- 200916492 該「異氰酸酯基/羥基」之値若爲上述範圍内時，所 得之氧化烯聚合物（p)的貯藏安定性較良好。其理由可 推測爲「異氰酸酯基/羥基」之値爲上述範圍内時，所得 之氧化烯聚合物（p)中即使殘存羥基，該羥基與氧化_ 聚合物（P)中之反應性矽基的交聯反應可受到抑制，並 可抑制貯藏中的增黏。又，推測尿烷化反應中之副反_ ( 脲基甲酸醋化反應（Allophan at ion reaction)、異三 酸酯化反應（Isocyanuration reaction)等。）因受到抑制 ，使得藉由該副反應之反應性砂基的生成難以進行，胃貝宁 藏中之增黏難以產生。 <硬化性組成物> 本發明的製造方法所得之氧化稀聚合物（P )可適用 於硬化性組成物之成分。將氧化烯聚合物（p )作爲硬化 成分的硬化性組成物，於室溫條件下因空氣中的濕氣可加 速水解性矽基的水解及交聯反應，得到交聯密度較高的硬 化物，且具有優良貯藏安定性。 氧化烯聚合物（P)可未除去作爲反應觸媒殘渣所含 之4價單烷基錫觸媒（S)下使用。 硬化性組成物中除氧化烯聚合物（P )以外，亦可適 當地含有硬化觸媒、塡充劑、可塑劑、黏著性賦予劑、脫 水劑、觸變性賦予劑、抗老化劑等。又’氧化烯聚合物（ P )以外可倂用具有反應性矽基之成分。 硬化性組成物可於預先含有硬化觸媒之脫水條件下保 -18- 200916492 存，可爲硬化時與大氣中的濕氣進行反應之一液型，又亦 可爲進行硬化前混和硬化觸媒，藉由混和中及大氣中的水 分使其硬化之二液型。 (硬化觸媒） 硬化觸媒係爲促進氧化烯聚合物（p)之反應性矽基 中之水解反應及/或交聯反應的化合物。作爲具體例可舉 出二丁基錫二乙酸鹽、二丁基錫二月桂酸酯、等有機錫（IV )羧酸鹽；（n-C4H9) 2Sn ( SCH2COO) 2、 (n-C8H17 ) 2Sn ( SCH2COO ) 2、( n-C8H17) 2Sn ( SCH2CH2C00) 2 、（n-CsH”）2 S n ( S C H 2 C Ο O C H 2 C H 2 〇 C O C H 2 S ) 2、 (n-C4H9) 2Sn ( SCH2COO ( iso-C8H17 ) ) 2、 (n-C8H17 ) 2Sn ( SCH2COO ( iso-C8H17 ) ) 2、 (n-C8H17) 2Sn ( SCH2COO ( n-C8H17) ) 2、 (n-C4H9) 2SnS等含硫黄有機錫化合物； (n-C4H9) 2SnO、（n-C8H17) 2SnO 等有機錫氧化物；前 述有機錫氧化物、與例如1種以上選自乙基矽酸酯、馬來 酸二甲酯、馬來酸二乙酯、馬來酸二辛酯、苯二酸二甲酯 、苯二酸二乙酯、及苯二酸二辛酯等所成群的酯化合物之 反應生成物；（n-C4Hq ) 2Sn ( acac ) 2、（ n-C8H!7 ) 2Sn ( acac ) 2 ' (11-C4H9) 2Sn(〇CgHi7) (acac) ' (n-C4H9 ) 2Sn ( OC ( CH3) CHC02C2H5 ) 2、 (n-C8Hi7 ) 2Sn ( OC ( CH3 ) CHC02C2H5) 2、 (11-C4H9 ) 2Sn ( OC8HI7 ) ( OC ( CH3 ) CHC02C2H5 )等 -19- 200916492 螯合錫化合物（但，前述acac表示乙醯基丙酮配位子， OC(CH3) CHC02C2H5表示乙基乙醯乙酸鹽配位子）；前 述螯合錫化合物、與例如1種以上選自四甲氧基矽烷、四 乙氧基矽烷、及四丙氧基矽烷等所成群之1種以上的烷氧 基矽烷之反應生成物；以及 (n-C4H9) 2 ( CH3COO ) SnOSn ( OCOCH3 ) ( n-C4H9): 、(11-C4H9 ) 2 ( CH30 ) SnOSn ( OCH3 ) ( 11-C4H9 ) 2 等含 有-SnOSn-鍵結的有機錫化合物等4價錫化合物。 又，作爲硬化觸媒，可舉出雙（2 -乙基己烷酸）錫、 二（η-辛酸）錫、二環烷酸錫、二硬脂酸錫等2價錫羧酸 鹽類；辛酸、磷酸、ρ-甲苯磺酸、苯二酸等酸性化合物類 ;丁基胺、己基胺、辛基胺、癸基胺、月桂胺等脂肪族單 胺類；伸乙基二胺、己烷二胺等脂肪族二胺類；二伸乙基 三胺、三伸乙基四胺、四伸乙基五胺等脂肪族聚胺類；哌 啶、哌嗪等雜環式胺類；甲基伸烷基二胺等芳香族胺類； 單乙醇胺、二乙醇胺、三乙醇胺等烷醇胺類；三乙基胺等 三烷基胺類；以及作爲環氧樹脂之硬化劑所使用的各種變 性胺等胺化合物類；Ν- β (胺乙基）γ —胺丙基三甲氧基矽 烷、γ —胺丙基三甲氧基矽烷等含有胺基之胺化合物等。 可使用1種彼等化合物，或倂用2種以上。倂用2種類 時’例如活性相異有機錫（IV )化合物之併用、或倂用有 機錫（IV )化合物與胺化合物爲佳。 硬化觸媒係對於氧化烯聚合物（p ) 1 〇 〇質量份而言以 使用0.001〜10質量份爲佳，使用〇1〜5.〇質量份爲較佳。 -20- 200916492 藉由使硬化觸媒的使用量爲0.001質量份以上時，可有效 促進硬化性組成物的硬化速度，藉由使其1 0質量份以下時 可防止機械物性或耐候性之降低。 且，於硬化性組成物，含有氧化烯聚合物（P )以外 含有具有反應性矽基之其他硬化成分時，硬化觸媒之使用 量對於氧化烯聚合物（P)與其他硬化成分之合計100質量 份而言以上述範圍爲佳。 (塡充劑） 作爲塡充劑，例如可舉出以脂肪酸或樹脂酸系有機物 進行表面處理之碳酸鈣、將前述碳酸鈣進一步進行微粉末 化的平均粒徑Ιμηι以下之膠質碳酸鈣、藉由沈降法所製造 之平均粒徑1〜3μηι的輕質碳酸鈣、平均粒徑1〜20μιη之 重質碳酸鈣、其他碳酸鈣類、Fumed二氧化矽、沈降性二 氧化矽、無水矽酸、含水矽酸、碳黑、碳酸鎂、矽藻土、 燒成黏土、黏土、滑石、氧化鈦、膨潤土、有機膨潤土、 氧化鐵、氧化鋅、活性氧化锌、s h i r a s u b a 11 ο ο n s、玻璃球 、有機樹脂球、木粉、紙漿、木綿片、雲母、核桃穀粉、 稻米穀粉、石墨、鋁微粉末、燧石粉末等粉體狀塡充劑； 玻璃纖維、玻璃絲、碳纖維、Kevlar纖維、聚乙烯纖維等 纖維狀塡充劑等。 特別使用上述玻璃球或有機樹脂球時，硬化性組成物 的比重可大幅度降低。 使用塡充劑時，其使用量對於氧化烯聚合物（P )( -21 - 200916492 含有其他硬化成分時則合倂此之合計）1 00質量份而言以 1 000質量份以下爲佳，特別以50〜250質量份。可使用1種 或亦可合倂2種以上的塡充劑。 (可塑劑） 作爲可塑劑可使用公知可塑劑，例如可舉出苯二酸二 辛酯、苯二酸二丁酯、苯二酸丁基苯甲酯等苯二酸酯類； 己二酸二辛酯、琥珀酸雙（2-甲基壬酯）、癸二酸二丁酯 、油酸丁酯等脂肪族羧酸酯類；季戊四醇酯等醇酯類；磷 酸三辛酯、磷酸三羥甲苯酯等磷酸酯類；環氧化大豆油、 4,5-環氧六氫苯二酸二辛酯、環氧硬脂酸苯甲酯等環氧可 塑劑類；氯化石蠟；使2元酸與2元醇進行反應所得之聚酯 類等聚酯系可塑劑類；聚氧丙二醇或其衍生物等聚醚類； 聚-α-甲基苯乙烯、聚苯乙烯等苯乙烯系之寡聚物類；聚 丁二烯、丁二烯-丙烯腈共聚合物、聚氯丁烯、聚異戊二 烯、聚丁烯、氫化聚丁烯、環氧化聚丁二烯等寡聚物類等 高分子可塑劑類。可使用1種或亦可合倂2種以上的可塑劑 〇 使用可塑劑時，其使用量對於氧化烯聚合物（Ρ)( 含有其他硬化成分時則合倂此之合計）1 0 0質量份而言以 1 000質量份以下爲佳，以1〜200質量份爲較佳。 特別將硬化性組成物使用於黏著劑等用途時，不使用 可塑劑時可減少由硬化物之溢出量（滲出液狀成分），塗 膜污染較少故較佳。 -22- 200916492 (黏著性賦予劑） 藉由使用黏著性賦予劑，可改良硬化性組成物與基材 之黏著性。作爲黏著性賦予劑’可舉出含有（甲基）丙烯 醯氧基之矽烷類、含有胺基之矽烷類、含有氫硫基之矽烷 類、含有環氧基之矽烷類、及含有羧基之矽烷類等所謂矽 烷偶合劑之已知化合物。可使用1種或亦可合倂2種以上的 彼等黏著性賦予劑。 使用這些黏著性賦予劑時，該使用量對於氧化烯聚合 物（p )(含有其他硬化成分時則合倂此之合計）1 00質量 份以3 0質量份以下爲佳，以0 . 1〜1 〇質量份爲較佳。黏著 性賦予劑的使用量超過3 0質量份時，硬化性組成物會變硬 且柔軟性會有過於小之情況。 又，作爲黏著性賦予劑使用環氧樹脂、或併用環氧樹 脂與環氧樹脂硬化劑爲佳。將環氧樹脂添加於硬化性組成 物時，其使用量對於氧化烯聚合物（P )(含有其他硬化 成分時則合倂此之合計）100質量份而言以100質量份以下 爲佳，以1〜100質量份爲較佳。環氧樹脂之使用量超過 1 〇〇質量份時，所得之硬化物的硬度較高且柔軟性會有過 小之情況。 (脫水劑） 藉由使用脫水劑，可提高硬化性組成物之貯藏安定性 。特別將硬化性組成物作爲所謂的1液型配合，即自密封 -23- 200916492 谷器放出於大氣中，藉由大氣中的濕氣使硬化成分硬化而 調配時，使用脫水劑爲佳。 作爲脫水劑’可舉出原甲酸院酯類；原乙酸院酯類； 甲基二甲氧基矽烷、乙烯基三甲氧基矽院、四甲氧基砂垸 、四乙氧基砂院等水解性有機砂化合物；水解性有機鈦化 合物等。 將脫水劑添加於硬化性組成物時，該使用量對於氧化 烯聚合物（p)(含有其他硬化成分時則合倂此之合計） 100質星份而3以30質量份以下爲佳，以〇.1〜1〇晳量份爲 較佳。脫水劑之使用量超過3 0質量份時，硬化性組成物之 硬化有時會過慢。 (觸變性賦予劑） 藉由添加觸變性賦予劑可防止下垂。觸變性賦予劑雖 無特別限定’例如可舉出氫化葵花油、脂肪酸醯胺等。硬 化性組成物中添加觸變性賦予劑時之使用量依據可得到所 望的防止垂下性而做適宜選擇。 (抗老化劑） 藉由添加抗老化劑，可提高耐候性及耐光性。抗老化 劑雖無特別限疋’ 一般爲添加於聚尿院樹脂等，可使用1 種以上選自抗氧化劑、抗紫外線劑、及光安定劑等所成群 之抗老化劑。作爲亭體之抗老化劑，已知有受阻胺系、苯 並三唑系、二苯甲酮系、苯酸酯系、氰丙烯酸酯系、丙嫌 -24- 200916492 酸酯系、受阻酚系、磷系、硫系等各種抗老化劑，可由彼 等中選出較適宜的化合物而添加於本發明之硬化性組成物 。添加抗老化劑時的使用量依據可得到所望抗老化性而做 適宜選擇。 (其他添加劑） 硬化性組成物中除上述添加劑以外，亦可適宜地添加 所望添加劑。例如可添加氧化鐵、氧化鉻、氧化鈦等無機 顔料；酞菁藍、酞菁綠等有機顔料；防霉劑；以及發泡劑 等 有關本發明之含有氧化烯聚合物（p )的硬化性組成 物可作爲使用於被覆•密封的硬化組成物、或作爲建築用 密封膠、防水材、黏著劑、塗佈劑使用。 特別爲作爲含有異氰酸酯基之化合物（U)，含有使 用上述一般式（1)中之a爲3的含有異氰酸酯基之化合物 (U-1 )所得之氧化烯聚合物（p )的硬化性組成物，因其 速硬化性優良，可作爲黏著劑使用。 【實施方式】 『實施例] 以下使用實施例對本發明做更詳細説明，但本發明並 非受到這些實施例之限定而解釋者。 (合成例1 ) -25- 200916492 配位子爲tert-丁醇之鋅六氰鈷酸鹽觸媒（ 264mg)的 存在下，於聚環氧丙烷二醇（每1個羥基之數平均分子量 爲5 00 ) ( 3 00g)將環氧丙烷（30g)於140°C下進行開環 聚合後，再將環氧丙烷（297 0g )進行開環聚合得到聚氧 化烯二醇（每1個羥基之數平均分子量爲5 000，羥値 1 1.2mgKOH/g )(以下稱爲含有羥基之聚合物（pPl )) 。鋅六氰鈷酸鹽觸媒中之鈷原子、鋅原子之合計殘存量約 1 Oppm ° (合成例2 ) 配位子於tert -丁醇之鋅六氰鈷酸鹽觸媒（ 456mg)的 存在下，於聚環氧丙烷二醇（每1個羥基之數平均分子量 舄5 00 ) ( 3 00g )將環氧丙烷（30g )於140°C下進行開環 聚合後，再將環氧丙烷（5 3 5 0 g)於140°C下進行開環聚合 而得到聚氧化烯二醇（每1個羥基之數平均分子量爲9000 ’羥値6.3mgKOH/g )(以下稱爲含有羥基之聚合物（pP2 ))。鋅六氰鈷酸鹽觸媒中之鈷原子、鋅原子的合計殘存 量約1 0 p p m。 (實施例1 ) 使用合成例〗所得之含有羥基的聚合物（P P 1 )，以如 表1所示配合製造出氧化烯聚合物。表1中之配合量的單位 爲「g」。 即，於耐壓反應器（内容積5L)中放入含有羥基之聚 -26- 200916492 合物（p P 1 ) 3 0 ο 〇 g，使内溫保持於1 1 〇 °c下進行減壓脫水 。繼續將反應器内環境由氮氣取代，内溫保持於50。(：下， 添加作爲4價單烷基錫觸媒（S)之三共有機合成公司製的 SCAT-24(製品名，上述一般式（I)中之R11爲-n_C4H9, R12 爲-n-C7H15之化合物。）0.15g (對於 ppi 約 50ppm)， 並攪拌後，欲使NCO/OH成爲0.97，投入下述式（3 )所 示之含有異氰酸酯基之化合物（U1)(純度95%) 125.2gBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an oxyalkylene polymer in which a polyoxyalkylene chain is bonded to a reactive sulfhydryl group via a urethane bond. [Prior Art] A curable composition having a reactive sulfhydryl group at the end of a polyoxyalkylene chain (also referred to as a siloxane polymer) as a hardening component is hardened by wet separation to form a rubber elastic excellent hardening Things. Therefore, the curable composition is widely used as an adhesive, a coating agent, and a sealing material. Among them, a curable composition having a methyl methoxycarbonyl group as a hardening component at the terminal of the polyoxyalkylene chain has excellent elongation properties, and thus can be widely used as a sealing material. Accepted by the market (refer to the patent document, the curable composition containing a polymer having a polyoxyalkylene chain and a trialkoxycarbenyl group as a hardening component, which is applicable because the curing rate is fast and the crosslinking density is high. A quick-curing adhesive, a coating agent, and a sealing material (see Patent Document 2). Patent Document 3 below discloses a polymer in which a polyoxyalkylene chain ends with a urethane bond-bonded trialkoxycarbenyl group. As one of the methods for producing the polymer, a method of performing a urethane reaction by using a polypropylene oxide polyol and an isocyanate-substituted trialkoxy decane compound having one isocyanate group in the molecule is described. A urethane polymerization catalyst such as dibutyltin dilaurate can be used. -4- 200916492 As a general urethane polymerization catalyst, for example, dibutyltin dilaurate or dioctyltin dilauric acid can be mentioned. An organic tin compound such as an acid ester (for example, Patent Document 4 below), an organic amine such as triethylamine or triethylamine, or the like, and other urethane polymerization catalysts include ruthenium and cobalt. A metal salt compound such as iron or the like. Patent Document 5 discloses a tin (II) carboxylate such as tin 2-ethylcarboxylate or tin octanoate as a curing catalyst of an organic polymer having a hydrolyzable fluorene-containing group. And an organotin (IV) compound such as dibutyltin dilaurate or dibutyltin maleate, which has an excellent hardening rate and a hardened physical property. [Patent Document 1] JP-A-72725 (Patent Document 2) [Patent Document 3] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. The present inventors have found that the use of dibutyltin dilaurate as a catalyst to produce a polymer in which a polyoxyalkylene chain is bonded to a urethane bond-bonded reactive thiol group is obtained. Stability is sometimes poor. As a source of poor storage stability As described in the above Patent Document 5, it is considered that dibutyltin dilaurate is a compound which can be used as a curing catalyst for a polymer in which a polyoxyalkylene chain is bonded to a reactive sulfhydryl group. Even when a trace amount of water is present, the reaction of the reactive sulfhydryl group with the water can be promoted by the action of dibutyltin dilaurate contained in the polymer as a residual catalyst to increase the viscosity. The method for improving the stability of storage is generally a method of reducing a catalyst having a low tactile activity, a method in which the method is insufficiently sufficient, or a reaction time is too long. Therefore, a polyoxyalkylene chain is expected to be in the urine. The polymerizable property of the reactive sulfhydryl group of the alkane bond. The present invention is an alkylene oxide polymerization which is improved in the storage stability of the urethane bond and the reactive sulfhydryl bond by the polyoxyalkylene chain in view of the above-mentioned circumstances. The method of producing the article is 'the present invention' has the following gist. (1) A method for producing an oxyalkylene polymer (P), wherein the ruthenium oxide chain is bonded to a reactive sulfhydryl group, and the ruthenium oxide has a polyoxyalkylene chain and a hydroxyl group. a step of reacting a hydroxyl group with an isocyanate group as shown in the following general formula (1) in the presence of a tetravalent monoalkyltin catalyst (S); (Si(-X1)a (-R1)3-a)-Q1-NCO (1) (wherein X1 represents an alkoxy group having 1 to 6 carbon atoms, and V represents a monovalent organic group having a carbon number of 1 to 20 (except In addition to the alkoxy group, a valence organic group of 1 to 20, & represents an integer of 1 to 3; however, at the time 'the plural Ri may be the same or different from each other' X1 is used. As a medium, use The urethane reversal has a storage stability for a oxidizable olefin polymerization, which is a polyene polymer (pP) compound (U has a substituent Q1 for urethane formation, and the carbon number R1 is plural When the complex number exists -6-200916492 'The plural χ1 may be the same or different from each other.) (2) The method for producing an oxyalkylene polymer as described in the above (丨) The monoalkyl tin catalyst (s) is the following general formula (I) R1 1Sn(OCOR12) 3 (I) (wherein ' R" represents an alkyl group having a carbon number of 4 to 8, and R 12 represents a carbon number of 2 The alkyl group of ~17; the three R12s present in one molecule may be the same or different from each other) The first tin catalyst (S1), and/or the following general formula (Π) R13Sn(SR14)3.. (II) (wherein R13 represents an alkyl group having 1 to 8 carbon atoms; R14 represents an alkyl group having 8 to 18 carbon atoms; and 3 R14s in one molecule may be the same or different from each other) (3) The method for producing the oxyalkylene polymer according to the above (1) or (2), wherein the reaction temperature of the urethane reaction is 50 to 200 ° C. The method for producing an oxyalkylene polymer according to any one of the above (1) to (3), which is carried out in an inert gas atmosphere. (5) For the above-mentioned hydroxyl group-containing polymer (PP), a tetravalent single The method for producing an alkylene oxide polymer according to any one of the above (1) to (4), wherein the amount of the alkyl tin catalyst (S) is from 1 ppm to 1 ppm by mass. 200916492 (6) The above (1) in which the a in the general formula (1) is 3 (5) A method for producing an oxyalkylene polymer according to any one of the preceding claims, wherein (7) the total number of isocyanate groups of the isocyanate group-containing compound (U) in the total number of hydroxyl groups of the hydroxyl group-containing polymer (pp) The method for producing an oxyalkylene polymer according to any one of the above (1) to (6), wherein the ratio of the isocyanate group (hydroxyl group) is from 0.80 to 1 〇. (8) A method for producing an oxyalkylene polymer as described in any one of (1) to (7) wherein the number of hydroxyl groups per hydroxyl group-containing polymer (pP) is from 1,000 to 30,000. (9) A method for producing an oxyalkylene polymer according to any one of the above (1) to (8), wherein the hydroxy group of the hydroxyl group-containing polymer (pP) is from 1.6 to 60.0 mgKOH/g. (10) The hydroxyl group-containing polymer (pP) is a hydroxyl group-containing polymer obtained by ring-opening polymerization of an epoxide for a compound having an active hydrogen atom in the presence of a double metal cyanide complex (PP) The method for producing an oxyalkylene polymer according to any one of the above (1) to (9). (11) In the above general formula (1), a is 2, and Q1 is a method for producing an oxyalkylene polymer according to any one of (1) to (1). (1) The curable composition containing the oxyalkylene polymer obtained by the production method according to any one of (1) to (1 1) as a curing component, obtained by the production method of the present invention, and polyoxyalkylene. The oxyalkylene polymer chain-bonded with a urethane-8-200916492 bond to a reactive sulfhydryl group is one that enhances storage stability. The best form of implementing the invention <Hydric group-containing polymer (pP) > The hydroxyl group-containing polymer (pP) used in the present invention is a polymer having a polyoxyalkylene chain and a hydroxyl group. The polyoxyalkylene chain in the hydroxyl group-containing polymer (pP) is preferably a polymerization unit of an alkylene oxide formed by ring-opening polymerization of an epoxide having 2 to 6 carbon atoms. Specifically, the oxyalkylene polymerization unit formed by ring-opening polymerization of one or more epoxides selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and hexylene oxide is Preferably. It is particularly preferred that the alkylene oxide polymerization unit formed by ring-opening polymerization of propylene oxide is formed. When the polyoxyalkylene chain is composed of two or more kinds of alkylene oxide polymerization units, the arrangement of two or more kinds of oxyalkylene polymerization units may be block-like or random. The hydroxy group of the hydroxyl group-containing polymer (pP) is preferably 1.6 to 60.0 mgKOH/g, more preferably 3·0 to 15.0 mgKOH/g, and 5.0 to 12 m g Κ Ο H / g is particularly preferable. The average molecular halo per one hydroxyl group of the hydroxyl group-containing polymer (pP) is preferably from 1,000 to 30,000, more preferably from 3,000 to 20,000. The number average molecular weight (??) in the present invention means a number average polystyrene-converted number average molecular weight (??) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase. When the number average molecular weight of the hydroxyl group-containing polymer (pP) is in the above range of -9 - 200916492, the molecular weight of the obtained oxyalkylene polymer (p) is in a good range from the viewpoint of viscosity and mechanical properties of the cured product. As a hydroxyl group-containing polymer (pP), a hydroxyl group-containing polymer (pP-1) obtained by ring-opening polymerization of an epoxide in a compound having an active hydrogen atom in the presence of a double metal cyanide complex is good. The composite metal cyanide complex is preferably a composite metal cyanide complex having an organic ligand. The organic ligand is preferably an ether-based ligand or an alcohol-based ligand. Specific examples of the ether-based ligand include ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), and triethylene glycol dimethyl ether. Specific examples of the alcohol-based ligand include tert-butanol, η-butanol, sec-butanol, iso-butanol, tert-pentanol, iso-pentanol, and ethylene glycol mono-tert. -butyl ether. As the composite metal cyanide complex, zinc hexacyanocobaltate is preferred, and the compound having an active hydrogen atom is preferably an organic compound having an active hydrogen atom, and a compound having a hydroxyl group or an amine group is preferred. Compounds having 1 to 4 hydroxyl groups are particularly preferred. The compound having an active hydrogen atom may be used alone or in combination of two or more. Specific examples of the organic compound having an active hydrogen atom include one type selected from the group consisting of ethylene glycol, propylene glycol, monopropylene glycol, butanediol, hexamethylene alcohol, hydrogenated bisphenol A, and neopentyl glycol. , polybutane diethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, allyl alcohol, methyl storage of propanol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol and other alcohols Polypropylene oxide monol, polypropylene oxide diol, polypropylene oxide triol, polyepoxyethylene-10 - 200916492 alkyl monool, polyethylene oxide diol, and polyethylene oxide Polymeric alcohols in groups of alcohols. The number average molecular weight per one hydroxyl group of the polymer alcohol is preferably from 300 to 1,500. The compound having an active hydrogen atom may be used alone or in combination of two or more. When a compound having two or more kinds of active hydrogen atoms is used, a polymer alcohol having two hydroxyl groups and a polymer alcohol having three hydroxyl groups are preferred. When the above-mentioned hydroxyl group-containing polymer (pP-1) in the present invention is used, the compound metal cyanide complex compound contained in the polymerization residue is purified and removed, and then the urethane can be subjected to the isocyanate group-containing compound (U). The reaction may be carried out or may be subjected to a urethane reaction with the isocyanate group-containing compound (U) without removing the complex metal cyanide complex. <Isocyanate group-containing compound (U) > The isocyanate group-containing compound (U) used in the present invention is a compound represented by the following general formula (1). In the formula, a is an integer of 1 to 3. (Si(-X1)a(-R1)3-a)-Q, -NCO (1) In the above formula (1), R1 is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent . However, R1 is not an alkoxy group. R 1 is preferably an alkyl group having 8 or less carbon atoms, a fluoroalkyl group having 8 or less carbon atoms or a phenyl group, and preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group or a phenyl group. When a plurality of R1 are present in the same molecule, these plural R1 -11 - 200916492 may be the same or different. In the above formula (1), χ1 represents an alkoxy group having 1 to 6 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. The methoxy group is particularly preferred. And when a plurality of X1 are present in the same molecule, the χ1 of these plural numbers may be the same or different from each other. In the formula (1), Q1 represents a divalent organic group having 1 to 2 carbon atoms. The alkylene group having 1 to 10 carbon atoms is preferred. From the viewpoint of availability, it is preferred to use a methyl group and a methyl group. The compound (U) containing an isocyanate group is preferably a compound (U-1) having an isocyanate group in which a is 3 in the above general formula (1). The isocyanate group-containing compound (U-1) is represented by the following general formula (2). (Si(-X1)3)-Q1-NCO (2) X1 and Q1' in the above general formula (2) are the same as those in the above general formula (1), and the preferred embodiment is also included. Further, as the isocyanate group-containing compound (U-2), a in the above general formula (1) is 2, and it is preferred that Q1 is a methyl group. When the isocyanate group-containing compound (U-1) and (u-2) are used, an oxyalkylene polymer (P) excellent in quick-curing property can be obtained. Specific examples of the isocyanate group-containing compound (U-1) include isocyanate methyltrimethoxydecane, 2-isocyanate ethyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and 3-isocyanate.丁-12- 200916492 methoxy-silica, 3-isocyanate pentyl trimethoxy sand, ι_isocyanate methyltriethoxy decane, 2-isocyanate ethyltriethoxy decane, 3 - Isocyanate propyl triethoxy decane, isocyanate propyl trimethoxy sand, 1-isocyanate propyl triethoxy decane. Specific examples of the isocyanate group-containing compound (U_2) include 1-isocyanate methyldimethoxymethylnonane. <Dentalized Polymerization Catalyst> In the present invention, when a polyoxyalkylene chain is bonded to an oxyalkylene polymer (P) in which a urethane bond is bonded to a reactive sulfhydryl group, a tetravalent monoalkyl tin contact can be used. Medium (S) (hereinafter may also be referred to simply as tin catalyst (S)). The "tetravalent monoalkyltin catalyst (s)" in the present specification is a compound obtained by bonding an organic group to tetravalent tin, and a compound of one alkyl group is directly bonded to tin (Sn). The tin catalyst (S) is preferably a first tin catalyst (S1) represented by the following general formula (I) or a second tin catalyst (S2) represented by the following general formula (?). The first tin catalyst (S1) and the second tin catalyst (S2) may also be used. R11Sn(OCOR12)3-..(I) In the above formula (I), R 1 1 represents an alkyl group having 4 to 8 carbon atoms, and R 1 2 represents an alkyl group having 2 to 17 carbon atoms. The three Ri2s present in one molecule may be the same or different from each other. R13Sn(SR14)3 (H) -13- 200916492 In the above formula (II), R13 represents a hospital having a carbon number of 1 to 8. R14 represents an alkyl group having 8 to 18 carbon atoms. The three R14s present in the molecule may be the same or different from each other. In the above formula (I), R11 is an alkyl group having 4 to 8 carbon atoms and may have a linear or branched structure. Preferred are -n-C4H9, -n-CeH", and -n-C8Hi7. Particularly preferred is -11-C4H9 ° wherein 'R12 is an alkyl group having 2 to 17 carbon atoms' in the above formula (I) may have a linear or branched structure. Preferred are _C2H5, -n-C5Hii, -n-C7H丨5, -n-C9H19, -η-〇ι〖Η23 or -n-ci7H35. Particularly good is -n-C7Hi5. In particular, in the above formula (I), R" is -n-C4H9, and R12 is -n-C7H15, the first tin catalyst (s 1 )' is, for example, SCAT - 2 4 (product name 'Sankyo Organic Synthesis Co., Ltd. It is preferable that the first tin catalyst (S 1 ) may be used singly or in combination of two or more. In the above formula (II), R13 is an alkyl group having 1 to 8 carbon atoms and may have a linear or branched structure. Preferable examples thereof include a methyl group, a butyl group, an octyl group and the like. In the above formula (11), Rl4 is a hospital base having a carbon number of 8 to 18 and may have a linear or branched structure. Preferable examples thereof include an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group. Examples of the second tin catalyst (S2) in the case where Rl3 is a methyl group include monomethyltin tris(octyl acid extension group), monomethyltin di(anthracenylsulfonyl group), and single Methyl tin tris(stearylsulfonylsulfonyl) and the like. Preferred is monomethyltin tris(dodecylsulfonyl) ° -14 - 200916492. As an example of the second tin catalyst (S2) when R13 is a butyl group, monobutyltin tris(octylsulfonate) may be mentioned. Mercapto), monobutyltin tris(dodecylsulfonyl), monobutyltin tris(stearylsulfonylsulfonyl). Preferred is monobutyltin tris(dodecylsulfonyl). Examples of the second tin catalyst (S2) when R13 is an octyl group include monooctyltin tris(octylsulfonyl), monooctyltin tris(dodecylsulfonyl), and a single Octyltin tris(stearylsulfonylsulfonyl). Preferred is monooctyltin tris(dodecylsulfonyl). In particular, in the above formula (Π), Ri3 is _n_C4H9, and the second tin catalyst (S2) of _n_Ci2ii25 is preferably SCAT-9A (product name, manufactured by Sankyo Synthetic Co., Ltd.). The second tin catalyst (S2) can be used alone or in combination of two or more. <Production Method of Oxide-Based Polymer (P)> The method for producing an oxyalkylene polymer (P) of the present invention comprises the above-described hydroxyl group-containing polymer (pP) and an isocyanate group-containing compound (U) in tin In the presence of a catalyst (S), it is subjected to a urethane reaction step. For example, after adding a tin catalyst (S) to a hydroxyl group-containing polymer (pP) and stirring, a compound (U) containing an isocyanate group is added, and the urethane reaction is carried out while maintaining the reaction temperature. Further, the compound (U) containing an isocyanate group is added to the hydroxyl group-containing polymer (pP) and stirred, and then a tin catalyst (S) is added thereto, and the urethane reaction may be carried out while maintaining the predetermined reaction temperature. -15- 200916492 The reaction temperature of the urethane reaction is preferably 50 to 200 ° C, and particularly preferably 7 to 150 ° C. When the reaction temperature of the urethane reaction is within the above range, good catalytic activity of the tin catalyst (S) can be obtained when the urethane reaction is carried out. The urethane reaction is preferably carried out under an inert gas atmosphere, preferably under a nitrogen atmosphere. The oxyalkylene polymer (p) is obtained by the urethane reaction. Specifically, it is obtained that "the oxyalkylene polymer (P) in which a polyoxyalkylene chain of a hydroxyl group-containing polymer (pp) has a urethane bond and a reactive sulfhydryl group is introduced". The reactive thiol group is a group corresponding to "-SiC-XhaC-R^h-a" of the compound (U) containing an isocyanate group. Specifically, the oxyalkylene polymer (P) of (SU-X'aC-R'hd-Qi-NHCOO-" derived from the polyoxyalkylene chain-bonded compound (U) containing an isocyanate group is obtained. P) is a reactive sulfhydryl group on the substituent in the side chain or terminal. The substituent in the terminal group having a reactive fluorenyl group is preferably a ruthenium tetravalent tin-based catalyst (S). The hydroxyl group-containing polymer (PP) (quality basis, the same applies hereinafter) is preferably from 1 ppm to 100 ppm, preferably from 1 〇 to 50 ppm. When the amount of the tin catalyst (s) used is 1 ppm or more, it is advantageous. The urethane reaction is carried out, and the storage stability of the oxyalkylene polymer (P) can be obtained at 〇〇ppm or less. Further, the hydroxyl group-containing polymer (pP-) is used as the hydroxyl group-containing polymer (pP). 1), the amount of the composite metal cyanide complex used in the production of the hydroxyl group-containing polymer (pp)) is only -16 - 200916492 lOOppm or more, and the amount of the tin catalyst (S) is 1 Preferably, it is preferably 50 ppm, preferably 1 to 20 ppm. Further, the use of the composite metal cyanide complex When the amount is less than 100 ppm, the amount of the tin catalyst (S) used is preferably from 20 to 100 ppm, preferably from 20 to 50 ppm. The present invention is in the presence of a tetravalent monoalkyl tin catalyst (S). By subjecting a hydroxyl group-containing polymer (pP) to a compound (U) containing an isocyanate group to a urethane reaction, it is possible to obtain an excellent oxidation stability in which a polyoxyalkylene chain has a reactive thiol group via a urethane bond. The olefin polymer (P) J °, the curable property of the obtained oxyalkylene polymer (P) is good, and in particular, the compound (U-1) containing an isocyanate group in which a is 3 in the above general formula (1), Or in the above general formula (1), when a is 2 and Q1 is a compound (U-2) containing an isocyanate group which is a methyl group, the obtained oxyalkylene polymer (P) is excellent in rapid hardenability. The catalyst for urethane reaction uses a tetravalent monoalkyltin catalyst (S) to obtain an oxyalkylene polymer (P) having good hardenability and storage stability. Although this reason is not clear, tin catalyst ( S) shows good catalyst activity at the reaction temperature of the urethane reaction, which is presumed to have a normal temperature The characteristic of the metal-based thermosensitive catalyst which does not show the catalytic activity during storage. In the urethane reaction of the hydroxyl group-containing polymer (pP) and the isocyanate group-containing compound (U), the hydroxyl group used is used. The total number of hydroxyl groups of the polymer (pP) 'the total number of isocyanate groups of the isocyanate group-containing compound (U) is preferably from 0.80 to 1.1%, preferably from 0.85 to 1.05. 200916492 When the "isocyanate group/hydroxy group" is in the above range, the obtained oxyalkylene polymer (p) has a good storage stability. The reason for this is presumed to be that the "isocyanate group / hydroxyl group" is in the above range, and even if a hydroxyl group remains in the obtained oxyalkylene polymer (p), the hydroxyl group and the reactive sulfhydryl group in the oxidized polymer (P) The cross-linking reaction can be inhibited and the viscosity-increasing in storage can be suppressed. Further, it is presumed that the ruthenium reaction (Allophan at ion reaction, Isocyanuration reaction, etc.) is suppressed by the side reaction. The formation of reactive sand groups is difficult to carry out, and the viscosity increase in the stomach benign is difficult to produce. <Sclerosing Composition> The oxidized and dilute polymer (P) obtained by the production method of the present invention can be applied to a component of a curable composition. The oxyalkylene polymer (p) is used as a hardening component of the hardening component, and at room temperature, the hydrolysis and hydrolysis reaction of the hydrolyzable sulfhydryl group can be accelerated by moisture in the air to obtain a cured product having a high crosslinking density. And has excellent storage stability. The oxyalkylene polymer (P) may be used without being removed as a tetravalent monoalkyltin catalyst (S) contained in the reaction catalyst residue. The curable composition may contain, in addition to the alkylene oxide polymer (P), a curing catalyst, a chelating agent, a plasticizer, an adhesion imparting agent, a dehydrating agent, a thixotropic imparting agent, an anti-aging agent, and the like. Further, a component having a reactive sulfhydryl group may be used in addition to the oxyalkylene polymer (P). The hardenable composition may be stored in a dehydration condition containing a hardening catalyst in advance, and may be a liquid type which reacts with moisture in the atmosphere during hardening, or may be a mixed hardening catalyst before hardening. A two-liquid type that is hardened by mixing water in the atmosphere. (Curing the catalyst) The curing catalyst is a compound which promotes the hydrolysis reaction and/or the crosslinking reaction in the reactive sulfhydryl group of the oxyalkylene polymer (p). Specific examples thereof include dibutyltin diacetate, dibutyltin dilaurate, and the like organotin (IV) carboxylate; (n-C4H9) 2Sn (SCH2COO) 2, (n-C8H17) 2Sn (SCH2COO) 2 , (n-C8H17) 2Sn ( SCH2CH2C00) 2 , (n-CsH") 2 S n ( SCH 2 C Ο OCH 2 CH 2 〇COCH 2 S ) 2, (n-C4H9) 2Sn ( SCH2COO ( iso-C8H17 ) 2, (n-C8H17) 2Sn ( SCH2COO ( iso-C8H17 ) ) 2, (n-C8H17) 2Sn ( SCH2COO ( n-C8H17) ) 2, (n-C4H9) 2SnS and other sulfur-containing organotin compounds; (n -C4H9) an organotin oxide such as 2SnO or (n-C8H17) 2SnO; and the organotin oxide, for example, one or more selected from the group consisting of ethyl phthalate, dimethyl maleate, diethyl maleate, a reaction product of a group of ester compounds such as dioctyl maleate, dimethyl phthalate, diethyl phthalate, and dioctyl phthalate; (n-C4Hq) 2Sn ( acac ) 2 , (n-C8H!7) 2Sn ( acac ) 2 ' (11-C4H9) 2Sn(〇CgHi7) (acac) ' (n-C4H9 ) 2Sn ( OC ( CH3) CHC02C2H5 ) 2, (n-C8Hi7 ) 2Sn ( OC ( CH3 ) CHC02C2H5) 2, (11-C4H9 ) 2Sn ( OC8HI7 ) ( OC ( CH3 ) CHC02C2H5 ) etc. - 19-200916492 Chelating tin compound (however, the above acac represents an acetylacetone ligand, OC(CH3)CHC02C2H5 represents an ethylacetamidine acetate ligand); and the chelate tin compound, for example, one or more selected a reaction product of one or more kinds of alkoxydecane groups, such as tetramethoxy decane, tetraethoxy decane, and tetrapropoxy decane; and (n-C4H9) 2 (CH3COO) SnOSn (OCOCH3) (n-C4H9): a tetravalent tin compound such as an organotin compound containing a -SnOSn-bond, such as (11-C4H9) 2 (CH30) SnOSn ( OCH3 ) ( 11-C4H9 ) 2 , and as a hardening catalyst. Examples thereof include divalent tin carboxylates such as bis(2-ethylhexanoic acid) tin, bis(η-octanoic acid) tin, tin naphthenate, and tin distearate; octanoic acid, phosphoric acid, and ρ- Acidic compounds such as toluenesulfonic acid and phthalic acid; aliphatic monoamines such as butylamine, hexylamine, octylamine, mercaptoamine, and laurylamine; aliphatic diamines such as ethyldiamine and hexanediamine Amines; aliphatic polyamines such as di-ethyltriamine, tri-ethylidene tetraamine, tetra-ethylpentamine; heterocyclic amines such as piperidine and piperazine; methylalkyl Aromatic amines such as amines; alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; trialkylamines such as triethylamine; and various amine compounds such as denatured amines used as hardeners for epoxy resins An amine group-containing amine compound such as Ν-β (aminoethyl)γ-aminopropyltrimethoxydecane or γ-aminopropyltrimethoxydecane. One type of these compounds may be used, or two or more types may be used. When two types are used, for example, a combination of an active phase organotin (IV) compound or an organic tin (IV) compound and an amine compound is preferred. The hardening catalyst is preferably used in an amount of 0.001 to 10 parts by mass based on the oxyalkylene polymer (p) 1 〇 by mass, and preferably 〇1 to 5. 〇 by mass. -20-200916492 When the amount of the curing catalyst is 0.001 parts by mass or more, the curing rate of the curable composition can be effectively promoted, and when it is 10 parts by mass or less, the mechanical properties or the weather resistance can be prevented from being lowered. . Further, when the curable composition contains another hardening component having a reactive sulfhydryl group other than the oxyalkylene polymer (P), the amount of the curing catalyst used is 100 in total for the oxyalkylene polymer (P) and other hardening components. The above range is preferred in terms of parts by mass. (Mixed Agent) Examples of the chelating agent include calcium carbonate surface-treated with a fatty acid or a resin acid-based organic material, and colloidal calcium carbonate having an average particle diameter of Ιμηι or less, which is further finely powdered with the calcium carbonate. Light calcium carbonate having an average particle diameter of 1 to 3 μηι manufactured by a sedimentation method, heavy calcium carbonate having an average particle diameter of 1 to 20 μm, other calcium carbonates, Fumed cerium oxide, sedimentary cerium oxide, anhydrous citric acid, water containing Tannin, carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, iron oxide, zinc oxide, active zinc oxide, shirasuba 11 ο ο ns, glass sphere, organic resin Ball, wood powder, pulp, wood wool, mica, walnut grain, rice grain, graphite, aluminum powder, vermiculite powder, etc.; glass fiber, glass fiber, carbon fiber, Kevlar fiber, polyethylene fiber, etc.塡 剂 and so on. When the above glass ball or organic resin ball is used in particular, the specific gravity of the curable composition can be greatly reduced. When the chelating agent is used, the amount of the oxyalkylene polymer (P) (the total of the other hardening components is -21 - 200916492) is preferably 1 000 parts by mass or less, particularly preferably 100 parts by mass or less. Take 50 to 250 parts by mass. One type or two or more types of chelating agents may be used. (Plasticizer) A known plasticizer can be used as the plasticizer, and examples thereof include benzoic acid esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzoate; adipic acid An aliphatic carboxylic acid ester such as octyl ester, bis(2-methyldecyl succinate), dibutyl sebacate or butyl oleate; an alcohol ester such as pentaerythritol ester; trioctyl phosphate and trishydroxytoluic acid Phosphates such as esters; epoxidized soybean oil, 4,5-epoxy hexahydrophthalic acid dioctyl ester, epoxy benzoic acid benzoate and other epoxy plasticizers; chlorinated paraffin; a polyester-based plasticizer such as polyester obtained by reacting a dihydric alcohol; a polyether such as polyoxypropylene glycol or a derivative thereof; a styrene-based oligomer such as poly-α-methylstyrene or polystyrene Polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, epoxidized polybutadiene, etc. Molecular plasticizers. One type or two or more types of plasticizers may be used. When a plasticizer is used, the amount of the plasticizer used is 1.0 part by mass for the oxyalkylene polymer (the total of other hardening components). It is preferably 1 000 parts by mass or less, preferably 1 to 200 parts by mass. In particular, when the curable composition is used for an adhesive or the like, it is preferable to reduce the amount of the hardened material (exuding liquid component) when the plasticizer is not used, and the coating film is less contaminated. -22- 200916492 (Adhesiveness-imparting agent) The adhesion of the curable composition to the substrate can be improved by using an adhesion-imparting agent. Examples of the tackifiers include decanes containing (meth) acryloxy group, decanes containing an amine group, decanes containing a thiol group, decanes containing an epoxy group, and decane having a carboxyl group. A known compound of a so-called decane coupling agent. One type or two or more types of adhesion imparting agents may be used. When the adhesiveness-imparting agent is used, the amount of the oxyalkylene polymer (p) (in combination with other hardening components) is preferably 100 parts by mass or less, and more preferably 30 parts by mass or less. 1 〇 by mass is preferred. When the amount of the tackifier is more than 30 parts by mass, the curable composition becomes hard and the flexibility is too small. Further, as the tackifier, an epoxy resin or an epoxy resin and an epoxy resin hardener are preferably used in combination. When the epoxy resin is added to the curable composition, the amount thereof to be used is preferably 100 parts by mass or less based on 100 parts by mass of the oxyalkylene polymer (P) (inclusive of the other hardening component). 1 to 100 parts by mass is preferred. When the amount of the epoxy resin used exceeds 1 part by mass, the hardness of the obtained cured product is high and the flexibility is too small. (Dehydrating agent) By using a dehydrating agent, the storage stability of the curable composition can be improved. In particular, when the curable composition is blended as a so-called one-liquid type, that is, the self-sealing -23-200916492 is placed in the atmosphere, and the hardening component is hardened by moisture in the atmosphere, a dehydrating agent is preferably used. Examples of the dehydrating agent include hydrolyzate orthoacetate esters; orthoacetic acid esters; hydrolysis of methyl dimethoxy decane, vinyl trimethoxy fluorene, tetramethoxy cerium, tetraethoxy sand or the like. Organic sand compound; hydrolyzable organic titanium compound. When the dehydrating agent is added to the curable composition, the amount of the deuterated polymer (p) (the total of the other hardening components is combined) is 100 mass stars and 3 is preferably 30 parts by mass or less. 〇.1~1 〇 量 份 is preferred. When the amount of the dehydrating agent used exceeds 30 parts by mass, the hardening of the curable composition may be too slow. (Thixotropic agent) The sagging property can be prevented by adding a thixotropic agent. The thixotropy-imparting agent is not particularly limited, and examples thereof include hydrogenated sunflower oil and fatty acid decylamine. The amount of use of the thixotropy-imparting agent in the hardening composition is appropriately selected depending on the desired droop-preventing property. (Anti-aging agent) By adding an anti-aging agent, weather resistance and light resistance can be improved. The anti-aging agent is not particularly limited. In general, it is added to a polyurethane resin or the like, and one or more anti-aging agents selected from the group consisting of an antioxidant, an ultraviolet ray inhibitor, and a light stabilizer can be used. As an anti-aging agent for a pavilion, a hindered amine type, a benzotriazole type, a benzophenone type, a benzoate type, a cyanoacrylate type, a C--24-200916492 acid ester type, and a hindered phenol type are known. Various anti-aging agents such as phosphorus and sulfur may be added to the curable composition of the present invention by selecting a suitable compound from them. The amount of the anti-aging agent to be added is appropriately selected depending on the desired anti-aging property. (Other Additives) In addition to the above additives, the curable composition may be suitably added with a desired additive. For example, an inorganic pigment such as iron oxide, chromium oxide or titanium oxide; an organic pigment such as phthalocyanine blue or phthalocyanine green; an antifungal agent; and a foaming agent and the like can be added to the oxyalkylene polymer (p) containing the present invention. The composition can be used as a hardened composition for coating and sealing, or as a sealant for construction, a waterproof material, an adhesive, and a coating agent. In particular, the compound (U) containing an isocyanate group contains a hardenable composition of an oxyalkylene polymer (p) obtained by using the isocyanate group-containing compound (U-1) having a a of 3 in the above general formula (1). It is used as an adhesive because of its excellent speed hardening property. [Embodiment] The present invention will be described in more detail below by way of examples, but the invention should not be construed as limited. (Synthesis Example 1) -25- 200916492 The ligand is a tert-butanol zinc hexacyanocobaltate catalyst (264 mg) in the presence of a polypropylene oxide diol (the average molecular weight per one hydroxyl group is 5 00 ) (300 g) propylene oxide (30 g) was subjected to ring-opening polymerization at 140 ° C, and then propylene oxide (297 0 g) was subjected to ring-opening polymerization to obtain a polyoxyalkylene diol (per hydroxy group). The number average molecular weight is 5,000, and oxindole 1 1.2 mgKOH/g) (hereinafter referred to as a hydroxyl group-containing polymer (pPl)). The total residual amount of cobalt atom and zinc atom in the zinc hexacyanocobaltate catalyst is about 1 Oppm ° (Synthesis Example 2) The presence of a ligand in tert-butanol zinc hexacyanocobaltate catalyst (456 mg) Next, propylene oxide (30 g) was subjected to ring-opening polymerization at 140 ° C in a polypropylene oxide diol (average molecular weight per hydroxy group of 50,000) (300 g), followed by propylene oxide ( 5 3 5 0 g) ring-opening polymerization at 140 ° C to obtain a polyoxyalkylene diol (the average molecular weight per hydroxy group is 9000 'hydroxy 値 6.3 mg KOH / g) (hereinafter referred to as a polymer containing a hydroxyl group) (pP2)). The total residual amount of cobalt atoms and zinc atoms in the zinc hexacyanocobaltate catalyst is about 10 p p m . (Example 1) Using a hydroxyl group-containing polymer (P P 1 ) obtained in Synthesis Example, an oxyalkylene polymer was produced as shown in Table 1. The unit of the compounding amount in Table 1 is "g". That is, a poly-6-200916492 compound (p P 1 ) 3 0 ο 〇g containing a hydroxyl group was placed in a pressure-resistant reactor (internal volume 5 L), and the internal temperature was maintained at 1 1 〇 ° c for decompression. Dehydration. The internal environment of the reactor was continuously replaced by nitrogen and the internal temperature was maintained at 50. (:, SCAT-24 manufactured by Sankyo Organic Synthesis Co., Ltd. as a tetravalent monoalkyltin catalyst (S) (product name, R11 in the above general formula (I) is -n_C4H9, and R12 is -n- Compound of C7H15.) 0.15 g (about 50 ppm for ppi), and after stirring, to make NCO/OH 0.97, the isocyanate group-containing compound (U1) represented by the following formula (3) (purity: 95%) 125.2 g
Si(-OCH3)3-CH2CH2CH2NCO ...(3) 繼續將内溫保持於8 0 °C下8小時，將含有羥基之聚合 物（PP1 )與含有異氰酸酯基之化合物（U1 )進行尿烷化 反應。反應終了後’分析反應器内容物的結果，確認具有 羥丙烯鏈與「（Si(-OCH3)3)-CH2CH2CH2NHCOO-」所示取 代基之氧化烯聚合物（P1)的生成。 (實施例2 ) 實施例1中，將4價單烷基錫觸媒（S )之配合量變更爲 0.09g (對pPl約30ppm)以外，與實施例1同様方法下進行反 應，得到具有羥丙烯鏈與「（Si(-OCH3)3)-CH2CH2CH2NHCOO- 」所示取代基之氧化烯聚合物（P 2 )。 (實施例3 ) -27- 200916492 貫施例2中取代含有羥基之聚合物（pP1)使用合成 例2所得之含有羥基之聚合物（pP2)的同時，將含有異 氰酸酯基之化合物（U1)的配合量變更爲70.4g以外，與 實施例2同樣方法下進行反應’得到具有羥丙烯鏈與「 (Si(-0CH3)3)-CH2CH2CH2NHC00-」所示取代基的氧化烯 聚合物（P3 )。 (比較例1〜5 ) 如表1所示配合下，使用過去尿烷聚合觸媒，製造出 氧化烯聚合物（P4、P5、P6、P7、P8 )。 即，取代實施例1中之4價單烷基錫觸媒（S )，比較 例1、2中使用二丁基錫二月桂酸鹽（試藥），比較例3中 使用二辛基錫馬來酸鹽（製品名：SCAT-51、三共有機合 成公司製），比較例4中使用辛酸鉍（試藥），比較例5中 使用二辛酸脂肪酸鹽（製品名：SCAT-52A，三共有機合 成公司製）。觸媒之配合量如表1所示。其他進行與實施 例1之同樣步驟。 (硬化性之評估） 對於實施例1〜3及比較例1〜5所得之各氧化烯聚合物 P 1〜P8，以下述方法評估其硬化性。 即，聚合物30g中充分混合二辛基酞酸酯2〇g、離子 交換水〇.15g、重質碳酸鈣（製品名：WhitonSB :白石鈣 公司製）l〇g、有機錫觸媒（二丁基錫氧化物與二辛基酞 -28- 200916492 酸酯之加熱反應物，製品名：No91 8、三共有機合成公司 製）〇 · 7 5 g後得到硬化性組成物。將所得之硬化性組成物 投入於不鏽鋼製容器中，流入氮氣並使其去泡後，靜置於 100 °C烤箱，並馴養30分鐘得到厚度9mm之硬化體。其後 ，將硬化體於室溫下冷卻1 5分鐘，測定硬化體之表面硬度 。硬度的測定爲使用數値硬度計DD2-C型（高分子計器 公司製：AskaC2型），測定5處並算出其平均値的方法進 行。測定結果如表1所示。 (貯藏安定性之評估） 對於實施例1〜3及比較例1〜5所得之各氧化烯聚合物 P 1〜P8，以下述方法評估其貯藏安定性。 即，於氧化烯聚合物中添加作爲抗老化劑之季戊四醇 肆[3- ( 3,5-二-tert-丁基-4-羥基苯基）丙酸酯](製品名： IrganoxlOlO、C iba Speciality Chemicals 公司製）至 0.5 質 量％，將加熱下使其均勻地溶解者轉移至1 0 0 m 1的玻璃容 器中作爲樣品’進行貯藏安定性試驗。 試驗爲首先測定樣品之初期黏度（2 5。(：）後，將樣品 加溫至5 0 °C，保持5 0 °C之狀態下於2週後及4週後測定各樣 品的黏度（貯藏後黏度）。黏度之測定使用E型黏度計（ 製品名：VISCONIC EHD型、TOKIMEC公司製的輥爲 N 〇 . 4 )進行測定。黏度的測定溫度爲2 5。(：，自5 0。(：下貯藏 中之樣品’取出其一部份，並於25°C下冷却者使用於黏度 之測定上。 -29- 200916492 由所得之初期黏度値與貯藏後黏度値，藉下式（A ) 求得增黏率（單位：％ )。其結果如表1所示。經時性增 黏率之增加程度越小，貯藏安定性則顯示越佳。 增黏率（％) =(貯藏後黏度-初期黏度）/初期黏度xl〇〇...(A) -30- 200916492 【I嗽】 比較例5 (P8) 1- 3000 125.2 0.15 8% 19% 比較例4 (P7) 3000 125.2 ι- 0.15 17% 30% % 比較例3 (P6) 3000 125.2 0.15 17% 35% 比較例2 (P5) 3000 125.2 0.09 16% 29% \〇 比較例1 (P4) 3000 125.2 0.15 19% 36% 實施例3 (P3) 3000 70.4 0.09 (Ν 卜 實施例2 (P2) 3000 125.2 0.09 Ο CN 實施例1 (P1) 3000 125.2 0.15 (Ν 口 Μ /—V Ο. Q, rV1 I I θ <π <π « 踩齩餵 g S氍 _權ιί 翻翻瞰 蚺擗挪I <(ιπ <(rti <(m 1邶氍 氍 _ π拔 ^ 1 11 lit S5 f骢魑 蠛 :_城]壊棚 g 1欝价 f 11 !1 ΐΗ- 1! 5〇°C 2星期後 50°C 4星期後 硬度測定値 觸媒 增黏率(％) -31 - 200916492 如表1之結果所示’有關本發明之實施例1〜3所製造 之氧化烯聚合物（P1 )〜（P3 )、與比較例1〜5所製造之 氧化烯聚合物（P4 )〜（P8 )相比較，硬化體之硬度爲相 等，但貯藏安定性大大地提高。由此可知，使用本發明之 4價單烷基錫觸媒（S )製造氧化烯聚合物（P )時’可不 損害硬化性下，大幅度地提高貯藏安定性。 以下表示使用實施例1所製造之氧化烯聚合物（P1) 製造硬化性組成物的例子（製造例1〜3 )。 (製造例1 ) 於實施例1所製造之聚合物（pi ) 100g中，添加重質 碳酸鈣（製品名：WhitonSB，白石鈣公司製）75g、表面 處理碳酸鈣（製品名：白艷華CCR、白石工業公司製） 7 5 g、作爲可塑劑之二辛基酞酸酯2 0 g、作爲觸變性賦予劑 之脂肪酸醯胺（製品名：迪司巴隆#6500，楠本化成公司 製）3g、作爲黏著性賦予劑之胺矽烷偶合劑（N- ( 2-胺乙 基）-3-胺丙基三甲氧基矽烷、信越化學工業公司製）2g 及環氧矽烷偶合劑（3-環氧丙氧基丙基三甲氧基矽烷、信 越化學工業公司製）lg、作爲脫水劑之乙烯基三甲氧基矽 烷（信越化學工業公司製）3g、作爲抗老化劑之伸乙基雙 (羥乙烯）雙[3-(5-tert-丁基-4-羥基-m -甲苯基）丙酸酯 ](製品名'Irganox245、Ciba Speciality Chemicals 公司 製）1 g，以3支輥得到均句混合物。 其後於該混合物中加入作爲錫觸媒之二丁基錫氧化物 -32- 200916492 與二辛基酞酸酯之加熱反應物（製品名：No91 8 ’三共有 機合成公司製）2 g，攪拌混合後得到硬化性組成物。 其後，馬上製造於JISA578 7所記載的Η型試驗體， 於室溫馴養7天，繼續於5〇°C下馴養7天。其後，實施拉伸 試驗，拉伸物性的測定結果爲良好之物性。 (製造例2 ) 於實施例1所製造之聚合物（PI) l〇〇g中添加重質碳 酸鈣（製品名：Supers、九尾鈣公司製）75g、表面處理 碳酸鈣（製品名：Calfaine200M，九尾鈣公司製）65g、 做無丙烯酸系可塑劑之分子量3 000的丙烯酸聚合物（製品 名：UP 1 000，東亜合成公司製）40g、與製造例1相同之 觸變性賦予劑3g、氧化鈦（製品名：R820，石原產業公司 製）1 〇g、作爲黏著性賦予劑與製造例1相同之胺矽烷偶合 劑2g及與製造例1相同之環氧矽烷偶合劑1 g、與製造例1 相同之脫水劑3 g、與製造例1相同之抗老化劑1 g、滑石（ 製品名：T滑石，竹原化學工業公司製）1 g、聚丙烯腈系 有機樹脂球（製品名·· M F L -1 0 0 S C A，松本油脂製藥公司 製）3 g，以3支輥成爲均勻混合物。 於該混合物中加入作爲錫觸媒之二丁基雙乙醯基丙酮 錫（製品名：尼耳斯坦U220，日東化成公司製）2g，經 攪拌混合後得到硬化性組成物。 對於所得之硬化性組成物，實施與製造例1相同之拉 伸試驗，測定拉伸物性得到良好物性。 -33- 200916492 (製造例3 ) 於實施例1所製造之聚合物（PI ) I00g中添加與製造 例1相同之重質碳酸鈣2 0 g、與製造例1相同之表面處理碳 酸鈣120g、作爲可塑劑之分子量3000聚環氧丙烷二醇40g 、作爲觸變性賦予劑之氫化葵花油（製品名：迪司巴隆 #3 05，楠本化成公司製）3g、作爲脫水劑之乙基矽酸酯（ 試藥）3g、作爲抗老化劑之季戊四醇肆[3- ( 3,5-二-tert-丁基-4-羥基苯基）丙酸酯](製品名：IrganoxlOlO、Ciba Speciality Chemicals 公司製）lg、及雙（2，2,6,6-四甲基-4-酿 Π定基）癸二酸醋（製品名：Tinuvin770、Ciba Speciality Chemicals 公司製）lg、Mica ( MK-200 ·' Coopchemical 公 司製）〇 . 5 g、與製造例2相同之有機樹脂球3 g，以3支輥成 爲均勻混合物。 於該混合物中加入預先混合雙（2 -乙基己烷酸）錫3 g 與月桂胺1 g之溶液4g之硬化觸媒，經攪拌混合後得到硬 化性組成物。 對於所得之硬化性組成物，與製造例1同樣地實施拉 伸試驗，測定拉伸物性後得到良好物性。 [產業上可利用性] 本發明所得之於聚氧化烯鏈介著尿烷鍵與反應性矽基 結合之氧化烯聚合物爲貯藏安定性優良，含有該氧化烯聚 合物之硬化性組成物經濕氣硬化後形成橡膠彈性優良的硬 -34- 200916492 化物，可作爲防水劑、黏著劑、塗佈劑、封止材等使用。 且，於2007年5月29日申請之曰本專利出願2007-1 4 1 705號的說明書、申請專利範圍、及摘要之全内容皆引 用於此，作爲本發明說明書的揭示內容。 -35-Si(-OCH3)3-CH2CH2CH2NCO (3) The internal temperature was maintained at 80 ° C for 8 hours, and the hydroxyl group-containing polymer (PP1 ) and the isocyanate group-containing compound (U1) were subjected to urethane formation. reaction. After the completion of the reaction, the results of the contents of the reactor were analyzed, and the formation of the oxyalkylene polymer (P1) having a hydroxypropene chain and a substituent represented by "(Si(-OCH3)3)-CH2CH2CH2NHCOO-" was confirmed. (Example 2) In Example 1, except that the amount of the tetravalent monoalkyltin catalyst (S) was changed to 0.09 g (about 30 ppm for pPl), the reaction was carried out in the same manner as in Example 1 to obtain a hydroxyl group. An oxyalkylene polymer (P 2 ) having a propylene chain and a substituent represented by "(Si(-OCH3)3)-CH2CH2CH2NHCOO-". (Example 3) -27-200916492 In the second embodiment, the hydroxyl group-containing polymer (pP1) was used instead of the hydroxyl group-containing polymer (pP2) obtained in Synthesis Example 2, and the isocyanate group-containing compound (U1) was used. The reaction was carried out in the same manner as in Example 2 except that the amount of the compound was changed to 70.4 g. The oxyalkylene polymer (P3) having a hydroxypropene chain and a substituent represented by "(Si(-0CH3)3)-CH2CH2CH2NHC00-" was obtained. (Comparative Examples 1 to 5) As shown in Table 1, an oxyalkylene polymer (P4, P5, P6, P7, P8) was produced by using a conventional urethane polymerization catalyst. Namely, in place of the tetravalent monoalkyltin catalyst (S) in Example 1, dibutyltin dilaurate (reagent) was used in Comparative Examples 1 and 2, and dioctyltin maleic acid was used in Comparative Example 3. Salt (product name: SCAT-51, manufactured by Sankyo Organic Synthesis Co., Ltd.), bismuth octoate (test drug) was used in Comparative Example 4, and dioctanoic acid fatty acid salt was used in Comparative Example 5 (product name: SCAT-52A, tri-organic synthesis) Company system). The amount of the catalyst is shown in Table 1. The same procedure as in Example 1 was carried out. (Evaluation of Curability) The respective oxyalkylene polymers P 1 to P8 obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated for their hardenability by the following method. That is, in the 30 g of the polymer, 2 〇g of dioctyl phthalate, 15 g of ion-exchanged water, and calcium carbonate (product name: Whiton SB: manufactured by Shiraishi Sangyo Co., Ltd.) l〇g, organic tin catalyst (two) were sufficiently mixed. A heating reaction product of a butyl tin oxide and a dioctyl hydrazine-28-200916492 acid ester, product name: No. 91, manufactured by Sankyo Organic Synthesis Co., Ltd., 〇·7 5 g, to obtain a curable composition. The obtained curable composition was placed in a stainless steel container, and nitrogen gas was poured into the container to be defoamed, and then placed in an oven at 100 ° C for 30 minutes to obtain a hardened body having a thickness of 9 mm. Thereafter, the hardened body was cooled at room temperature for 15 minutes, and the surface hardness of the hardened body was measured. The hardness was measured by using a number 値 hardness meter DD2-C type (AkaC2 type manufactured by Polymer Co., Ltd.), and measuring five places and calculating the average enthalpy. The measurement results are shown in Table 1. (Evaluation of Storage Stability) With respect to each of the oxyalkylene polymers P 1 to P8 obtained in Examples 1 to 3 and Comparative Examples 1 to 5, the storage stability was evaluated by the following method. That is, pentaerythritol 肆[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is added as an anti-aging agent to an oxyalkylene polymer (product name: IrganoxlOlO, C iba Speciality) The product was subjected to a storage stability test by transferring it to a glass container of 1000 m 1 by heating to 0.5% by mass. The test is to first determine the initial viscosity of the sample (25. (:), then warm the sample to 50 ° C, maintain the temperature of 50 ° C in 2 weeks and 4 weeks after the determination of the viscosity of each sample (storage After the viscosity was measured, the viscosity was measured using an E-type viscometer (product name: VISCONIC EHD type, TOKIMEC company's roll N 〇. 4 ). The measurement temperature of the viscosity was 25 (.: from 50). : The sample under storage 'takes out part of it and cools it at 25 ° C for use in the determination of viscosity. -29- 200916492 From the initial viscosity 所得 and the viscosity after storage 値, by the following formula (A) The viscosity increase rate (unit: %) was obtained. The results are shown in Table 1. The smaller the increase of the time-dependent viscosity increase rate, the better the storage stability is. The viscosity increase rate (%) = (post-storage viscosity) - Initial viscosity) / Initial viscosity xl 〇〇... (A) -30- 200916492 [I 嗽] Comparative Example 5 (P8) 1-3000 125.2 0.15 8% 19% Comparative Example 4 (P7) 3000 125.2 ι- 0.15 17% 30% % Comparative Example 3 (P6) 3000 125.2 0.15 17% 35% Comparative Example 2 (P5) 3000 125.2 0.09 16% 29% \〇Comparative Example 1 (P4) 3000 125.2 0.15 19% 36% Example 3 (P3) 3000 70.4 0.09 (ΝExample 2 (P2) 3000 125.2 0.09 Ο CN Example 1 (P1) 3000 125.2 0.15 (Ν口Μ / -V Ο. Q, rV1 II θ <π <;π « 齩 齩 feeding g S氍_权ιί 翻翻蚺擗蚺擗 I <(ιπ <(rti <(m 1邶氍氍_ π拔^ 1 11 lit S5 f骢魑蠛:_城] 壊 shed g 1 欝 price f 11 !1 ΐΗ - 1! 5 〇 °C after 2 weeks 50 ° C after 4 weeks hardness measurement 値 catalyst viscosity increase rate (%) -31 - 200916492 As shown in the results of Table 1 'The oxyalkylene polymers (P1) to (P3) produced in Examples 1 to 3 of the present invention were compared with the oxyalkylene polymers (P4) to (P8) produced in Comparative Examples 1 to 5, and the hardened bodies were compared. The hardness is equal, but the storage stability is greatly improved. Thus, it can be seen that when the oxyalkylene polymer (P) is produced by using the tetravalent monoalkyl tin catalyst (S) of the present invention, the hardness can be greatly impaired. The storage stability was improved. The following is an example of producing a curable composition using the oxyalkylene polymer (P1) produced in Example 1 (Production Examples 1 to 3). (Production Example 1) In a 100 g of the polymer (pi) produced in Example 1, 75 g of heavy calcium carbonate (product name: Whiton SB, manufactured by Shiraishi Calcium Co., Ltd.) and surface-treated calcium carbonate (product name: Bai Yanhua CCR, Baishi) were added. 7 g, 7 g of dioctyl phthalate as a plasticizer, and 3 g of a fatty acid guanamine (product name: Desi Balong #6500, manufactured by Kusumoto Kasei Co., Ltd.) as a thixotropic agent Acridine coupling agent (N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.) 2g and epoxy decane coupling agent (3-glycidoxy-oxygen) Propyl propyl trimethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd.) lg, vinyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a dehydrating agent, 3 g of ethyl bis(hydroxyethylene) double as an anti-aging agent 3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (product name: Irganox 245, manufactured by Ciba Speciality Chemicals Co., Ltd.) 1 g, and a mixture of three rolls was obtained. Then, 2 g of a heating reaction product (product name: No. 91 8 'Sankyo Organic Synthesis Co., Ltd.) of dibutyltin oxide-32-200916492 and dioctyl decanoate as a tin catalyst was added to the mixture, and the mixture was stirred and mixed. A hardenable composition is obtained afterwards. Thereafter, the sputum type test body described in JISA578 7 was immediately produced, domesticated at room temperature for 7 days, and further domesticated at 5 ° C for 7 days. Thereafter, a tensile test was carried out, and the measurement results of the tensile physical properties were good physical properties. (Production Example 2) 75 g of heavy calcium carbonate (product name: Supers, manufactured by Nine-tail Calcium Co., Ltd.) and surface-treated calcium carbonate (product name: Calfaine 200M) were added to the polymer (PI) l〇〇g produced in Example 1. 65 g of an acrylic polymer (product name: UP 1 000, manufactured by Tosoh Corporation) having a molecular weight of 3,000, which is made of a non-acrylic plasticizer, and a thixotropy-imparting agent 3 g, which is the same as that of Production Example 1. Titanium oxide (product name: R820, manufactured by Ishihara Sangyo Co., Ltd.) 1 〇g, 2 g of an amine decane coupling agent similar to that of Production Example 1 as an adhesion-imparting agent, and 1 g of the same epoxy decane coupling agent as in Production Example 1, and production Example 1 3 g of the same dehydrating agent, 1 g of the same anti-aging agent as in Production Example 1, talc (product name: T talc, manufactured by Takehara Chemical Industry Co., Ltd.) 1 g, polyacrylonitrile-based organic resin ball (product name·· MFL -1 0 0 SCA, manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd.) 3 g, with 3 rolls into a homogeneous mixture. 2 g of dibutyl acetophenone acetonide (product name: Nierstein U220, manufactured by Nitto Kasei Co., Ltd.) as a tin catalyst was added to the mixture, and the mixture was stirred and mixed to obtain a curable composition. The obtained sclerosing composition was subjected to the same tensile test as in Production Example 1, and the tensile properties were measured to obtain good physical properties. -33-200916492 (Production Example 3) 20 g of the ground calcium carbonate and 120 g of the surface-treated calcium carbonate similar to the production example 1 were added to the polymer (PI) I00g produced in the first embodiment. 40 g of polypropylene oxide diol as a plasticizer, hydrogenated sunflower oil as a thixotropic imparting agent (product name: Desi Balong #3 05, manufactured by Kuipan Chemical Co., Ltd.), and ethyl citric acid as a dehydrating agent Ester (reagent) 3 g, pentaerythritol 肆 [3-( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as an anti-aging agent (product name: IrganoxlOlO, manufactured by Ciba Speciality Chemicals) ) lg, and bis(2,2,6,6-tetramethyl-4-branches) azelaic acid vinegar (product name: Tinuvin770, manufactured by Ciba Speciality Chemicals) lg, Mica ( MK-200 ·' Coopchemical 5 g of the same organic resin ball as in Production Example 2, and a uniform mixture of 3 rolls. To the mixture, 4 g of a solution of 3 g of bis(2-ethylhexanoic acid) tin and 1 g of laurylamine was mixed, and the mixture was stirred and mixed to obtain a hardening composition. The obtained curable composition was subjected to a tensile test in the same manner as in Production Example 1, and the tensile properties were measured to obtain good physical properties. [Industrial Applicability] The oxyalkylene polymer obtained by the present invention in which a polyoxyalkylene chain is bonded to a reactive sulfhydryl group via a urethane bond is excellent in storage stability, and a hardenable composition containing the oxyalkylene polymer is subjected to After moisture hardening, it forms a hard-hardened rubber-34-200916492 compound, which can be used as a water repellent, an adhesive, a coating agent, a sealing material, and the like. The entire contents of the specification, the scope of the patent application, and the abstract of the patent application of the Japanese Patent Application No. 2007-1 4 1 705, filed on May 29, 2007, are incorporated herein by reference. -35-