200904852 九、發明說明 【發明所屬之技術領域】 本發明係關於多元醇的製造方法及藉由該製造方法所 製造的多元醇。 【先前技術】 作爲針對所謂的地球溫暖化的最大的環境問題之手段 ’強烈要求大氣中的二氧化碳排出量的減少，利用石油或 煤等的資源之先前技術的化學工業，會因爲資源的燃燒而 增加了二氧化碳的排出量，惟，若利用天然油的動植物油 等之生質（biomass)，可壓低二氧化碳的排出量。生質 ’並不限定在動植物油或其改性物，亦可使用藉由植物的 發酵所得到的乳酸、環狀酯的丙交酯、聚乳酸等。 但是’泡沬、樹脂、彈性體、塗料、接著劑等之聚胺 基甲酸乙酯製品，係以多元醇與聚異氰酸酯作爲主原料而 製造’此外，多元醇亦被廣泛使用於作爲各種油劑的原料 。先前技術所使用的多元醇爲石油衍生，目前爲止，提議 身爲原料的多元醇的至少一部份爲疏水性植物油衍生的多 元醇’使製品的耐水熱性提高的技術，惟，尙未有考量二 氧化碳的排出量的減少，而提高原料中生質比例的例子。 汽車座椅用緩衝墊所使用的聚胺基甲酸乙酯泡沫，使 其原料的至少一部份爲植物油衍生的多元醇之技術被提出 ’藉由此技術，可得到在壓低燃燒處分時的二氧化碳排出 量’同時在機械的物性亦與使用先前技術石油衍生的原料 200904852 者相冋之聚胺基甲酸乙醋泡沫（參考專利文獻1〜3)。 作爲原料使用之植物油衍生的多元醇，若與其他的聚 醚多元醇混合後使用’所得到的聚胺基甲酸乙酯的物性種 類變豐富’惟’植物油衍生的多元醇，一般的而言因爲親 水性不高’故與其他的聚醚多元醇的相溶性低，此外，因 爲植物油其結構受到限制，若可得到經高分子量化的植物 油衍生的多元醇’可製造具有各種物性的聚胺基甲酸乙酯 製品’再者’羥基與異氰酸酯基的反應，以一級羥基的活 性最高’因此’多元醇具有愈多一級羥基，與聚異氰酸酯 的反應性愈高。 因此，提議使爲植物油衍生的多元醇之箆麻油，與環 氧丙院或環氧乙院進行開環加成的技術（參考專利文獻 2~4 )。篦麻油係以篦麻醇酸甘油酯爲主成分，此篦麻醇 酸具有1個二級羥基，由動植物油衍生且具有羥基者只有 篦麻油。箆麻油適合作爲天然油衍生的多元醇的起始劑。 專利文獻2〜4的技術，係使此二級羥基與環氧丙烷或環 氧乙院進行開環加成，藉此，可於篦麻油導入聚醚鏈，所 得到的多元醇，可改善與其他的聚醚多元醇的相溶性，此 外，藉由環氧丙烷或環氧乙烷的開環加成可使篦麻油高分 子量化，此外，因爲可使二級羥基變成一級羥基，故可得 到與聚異氰酸酯的反應性高的多元醇。以下，被製造的多 元醇所具有的羥基中的一級羥基的比例稱爲一級化率。 此外，使氫化篦麻油1莫耳（mol )與環氧乙烷 40〜3 00莫耳（mol)進行開環加成之聚氧乙烯硬化篦麻油 200904852 ，被廣泛地使用於作爲界面活性劑（參考專利文獻5 )。 如上述，作爲對篦麻油或氫化篦麻油等開環加成環氧 烷之觸媒，通常，使用爲鹼觸媒的氫氧化鉀或氫氧化鈉等 的鹼金屬化合物。惟，鹼金屬化合物係環氧烷的反應速度 慢，另一方面，爲了提高反應速度而增加觸媒使用量，故 反應後的觸媒去除等的處理變煩雜，此外，使用鹼金屬化 合物時，因爲篦麻油所具有的酯鍵發生開裂或酯交換反應 ，故所製造的多元醇含有多量的脂肪酸的低分子縮合物等 副產物（參考專利文獻6 )。 此外，對聚酯多元醇開環加成環氧烷的反應，使用如 BF3醚錯合物的酸觸媒作爲觸媒，惟，此時因爲聚酯多元 醇内的酯鍵發生開裂，故高分子量的聚酯多元醇的製造很 難。因此，在此觸媒的存在下，以篦麻油作爲起始劑製造 多元醇，則會因爲分解而產生低分子量的副產物。 另一方面，有使用不是鹼觸媒或酸觸媒之複合金屬氰 化物錯合物觸媒，使篦麻油或改性篦麻油與環氧烷進行開 環加成之分子量分布窄的多元醇的製造方法（參考專利文 獻7 )。其中，改性篦麻油之意，係指將篦麻油施以酯交 換反應、氫化反應、鈉還原反應等處理後所得到者’惟’ 此專利文獻7的技術，係環氧烷爲使用環氧乙烷時’篦麻 油或改性篦麻油所具有的複數的羥基’與環氧乙烷產生不 均一地開環加成，因此，要以少量的環氧乙烷製造一級化 率高的多元醇很難，若可用少量的環氧乙烷使篦麻油的二 級羥基變成一級羥基，可使所製造的多元醇中起始劑的部 200904852 份所佔有的比例（生質度）變高。 專利文獻8，係提議使用爲陽離子聚合觸媒之具有3 個含氟苯基的硼化合物，使篦麻油與環氧烷進行開環加成 之技術，惟，專利文獻8所揭示的技術，爲使碳數爲3〜1 2 的環氧烷進行開環加成之技術。 此外，提議使用複合金屬氰化物錯合物觸媒製造聚酯 醇，然後使用陽離子聚合觸媒之含有3個含氟苯基的硼化 合物，使所製造的聚酯多元醇與環氧乙烷進行開環加成之 技術（參考專利文獻9 )，惟，並有關於對路易斯酸的陽 離子聚合觸媒之酯鍵的安定性的記載。 此外，提議對與聚異氰酸酯的反應性低的天然油衍生 的多元醇，導入一級羥基的技術（參考專利文獻1 0 )，此 技術係在特殊的金屬觸媒存在下，使大豆油與一氧化碳與 氫進行反應，於大豆油的雙鍵部份導入羰基，然後，使被 導入的羰基再於氫進行反應而成爲一級羥基。因爲箆麻油 的主要構成成分之篦麻醇酸具有1個雙鍵，藉由此技術可 導入一級羥基，惟，此技術係所使用的觸媒非常貴，又需 要煩雜的製造製程。 〔專利文獻1〕特開2005 -3 2043 1號公報 〔專利文獻2〕特開2 0 0 5 - 3 2 04 3 7號公報 〔專利文獻3〕特開2 0 0 6 - 2 1 4 5號公報 〔專利文獻4〕特開2006- 1 04404號公報 〔專利文獻5〕特開2 0 0 2 - 3 0 92 8 8號公報 〔專利文獻6〕特表2 0 0 3 - 5 1 1 5 3 2號公報 200904852 〔專利文獻7〕特開平5 - 1 63 3 42號公報 〔專利文獻8〕特開2 0 0 0 - 3 4 4 8 8 1號公報 〔專利文獻9〕美國特許第6392076號說明書 〔專利文獻10〕美國特許申請公開第2005/0070620 號說明書 【發明內容】 〔發明所欲解決之課題〕 如上述’先前技術的多元醇的製造方法，無法以篦麻 油作爲起始劑’在不使起始劑產生分解下，以高的生質度 製造一級化率高的多元醇。 本發明的課題係提供以篦麻油作爲起始劑，不會因爲 起始劑的分解而產生低分子量的副產物，環氧乙烷與起始 劑中的羥基均勻地開環加成，即使高生質度，一級化率亦 高的多元醇的製造方法。 〔用以解決課題之手段〕 爲了達成上述的課題’本發明係提供一種多元醇的製 造方法’其係在陽離子聚合觸媒的存在下，使由篦麻油及 箆麻油縮合物所選出的至少一種的起始劑與雜環狀化合物 進行開環加成之多元醇的製造方法，其特徵係該雜環狀化 合物爲由環狀醚及環狀酯所成的群所選出的化合物，其至 少一部份爲環氧乙烷；陽離子聚合觸媒係具有含氟芳基或 含氟芳基氧基之由鋁化合物及硼化合物所成的群所選出的 -9- 200904852 至少1種的觸媒。 本發明的多元醇的製造方法’其中該雜環狀化合物由 環氧乙院單獨構成，或爲環氧乙院與ε -己內醋的組合、或 環氧乙烷與環氧丙烷的組合較佳。 此外’上述雜環狀化合物中的環氧乙烷的比例爲3 〇 莫耳％以上較佳。 此外，起始劑的羥基每lmol，與1〜2〇m〇l的環氧乙 院進行開環加成。上述起始劑較佳。 此外’本發明的多元醇中的該起始劑殘基的比例爲 30〜95質量％較佳。 此外，上述陽離子聚合觸媒爲三（五氟苯基）硼烷或 三（五氟苯基）鋁較佳。 此外，相對於上述起始劑的總量，添加以質量比而言 爲10〜200Ppm的上述陽離子聚合觸媒較佳 此外，本發明係提供藉由上述的製造方法所製造的 多元醇。 而且，使用本發明的多元醇所製造的聚胺基甲酸乙酯 製品。 〔發明的效果〕 依據本發明的多元醇的製造方法，可製造不含有因爲 起始劑的分解而產生低分子量的副產物，含有環氧乙烷的 雜環狀化合物與起始劑中的羥基均勻地開環加成之高生質 度且一級化率高的多元醇。 -10- 200904852 此外’本發明若使用生質度高的多元醇，可製造環境 負擔小的聚胺基甲酸乙酯製品。 〔實施發明之最佳形態〕 本發明的多元醇的製造方法，係在特定的陽離子聚合 觸媒的存在下’使由篦麻油及篦麻油縮合物所選出的至少 一種的起始劑與含有環氧乙烷的雜環狀化合物進行開環加 成之方法。 再者，本發明中’篦麻油縮合物之意，係指使篦麻油 或水添篦麻油（氫化篦麻油）水解所得到的羥基羧酸進行 脫水縮合後所得到的酯化合物，惟脫水縮合，可爲僅羥基 羧酸的縮合’亦可爲羥基羧酸與篦麻油或水添箆麻油的縮 合。 〔起始劑〕 本發明係使用以具有1個二級羥基的篦麻醇酸爲主要 構成脂肪酸之篦麻油、或篦麻油縮合物作爲起始劑，篦麻 油縮合物的製造方法並沒有特別的限制，例如可列舉以下 2例。 (1 )箆麻油經水解所得到的篦麻醇酸、與篦麻油之間進 行酯化反應之方法。 (2 )篦麻醇酸彼此進行縮合反應，進行該縮合物、與依 官能基數選擇的低分子量多元醇的酯化反應之方法。此時 ’脂肪酸可使用1 2-羥基硬酯酸（篦麻醇酸的氫化物）取 -11 - 200904852 代篦麻醇酸、或與篦麻醇酸一起使用。 上述（2 )中，作爲與脂肪酸的縮合物進行反應的低 分子量多元醇，可列舉下述的化合物。 2元醇：乙二醇、二乙二醇、丙二醇、二丙二醇、 1,3-丙二醇、1，4-環己二醇、1,3-丁 二醇、1,4-丁 二醇、 1,6-環二醇、1,4·環己烷二甲醇等。 3元以上的多元醇：甘油、二甘油、三羥田基丙烷、 季戊四醇、二季戊四醇、三季戊四醇、蔗糖等。 此外’可列舉使多元醇類與環氧烷進行開環加成後所 得到的數平均分子量150-1000的低分子量聚醚多元醇。 此外，脂肪酸的縮合反應並非特別地需要觸媒，但酯 化反應使用觸媒較佳，作爲觸媒，可列舉鹼性金屬化合物 或酸性化合物。作爲鹼性金屬化合物，可列舉氫氧化鈣、 甲氧化鈉等。作爲酸性化合物，可列舉二氯化錫、p-甲苯 磺酸、烷氧基鈦等之路易斯酸或布朗斯台德酸。 本發明中，作爲起始劑使用的篦麻油或篦麻油縮合物 的羥基價（mgKOH/g)，通常爲 25〜350，40〜200較佳， 5 0〜]70更佳。羥基價若爲25以上，藉由陽離子聚合觸媒 之環氧乙烷的開環加成反應變均勻，一級化率亦容易提高 ’此外，羥基價若爲3 5 0以下，則所製造的多元醇的生質 度變大。 〔陽離子聚合觸媒〕 本發明的特徵，係使用具有1個以上的含氟芳基或含 -12 - 200904852 氟芳基氧基之由鋁化合物及硼化合物所成的群所選出的至 少1種’作爲陽離子聚合觸媒，亦即本發明中之陽離子聚 合觸媒，爲鋁化合物或硼化合物，然而，此陽離子聚合觸 媒具有1個以上之含氟芳基或含氟芳基氧基。 作爲含氟芳基，可列舉五氟苯基、四氟苯基、三氟苯 基、3,5-雙（三氟甲基）三氟苯基、3，5_雙（三氟甲基） 苯基、2-全氟萘基、2-全氟聯苯基等。 此外’作爲含氟芳基氧基，可列舉上述含氟芳基鍵結 於氧原子的含氟芳基氧基。 作爲具有至少1個含氟芳基或含氟芳基氧基之鋁化合 物或硼化合物，例如以特開2 0 0 0 - 3 4 4 8 8 1號公報、特開 2005 - 8 2 73 2號公報、或國際公開03/00750號文獻所記載 的路易斯酸的鋁化合物或硼化合物較佳，此外，特表 2003 -5 〇 1 524號公報或特表2003 - 5 1 03 74號公報所記載的 鎗鹽之鋁化合物或硼化合物較佳。 作爲路易斯酸的鋁化合物，可列舉例如三（五氟苯基 )鋁、三（五氟苯基氧基）鋁。 此外’作爲路易斯酸的硼化合物，可列舉例如三（五 氟苯基）硼烷、三（五氟苯基氧基）硼烷，其中又以三（ 五氟苯基）硼烷對於環氧乙烷的開環加成反應的觸媒活性 尚，故特別佳。 作爲鑰鹽的對陽離子，以三苯甲基陽離子（Ph3c+) 或苯胺陽離子（PhNR3+ ; Ph=苯基基，R = H、烷基等）較 佳’作爲鑰鹽，以三苯甲基四（五氟苯基）硼酸酯或 -13- 200904852 N，N’-二甲基苯銨四（五氟苯基）硼酸酯爲特別佳。 〔雜環狀化合物〕 本發明所使用的雜環狀化合物，爲選自環狀醚 酯所成的群之化合物，含有環氧乙烷作爲其至少一 亦即，本發明中之雜環狀化合物，可僅爲環氧乙烷 爲環氧乙烷與其他的雜環狀化合物的組合。 使用環氧乙烷與其他的雜環狀化合物的組合進 加成反應時，可順序使環氧乙烷與其他的雜環狀化 行反應，亦可使環氧乙烷與其他的雜環狀化合物的 進行反應。使其順序反應時，使其他的雜環狀化合 反應後，再使環氧乙烷進行反應，由可提高一級羥 例之觀點而言較佳。 作爲環狀醚，以具有含有1個或2個醚性氧 3 ~6員環之化合物較適當，亦可具有側鏈。具體而 列舉單環氧化合物、氧雜環丁烷化合物、四氫呋喃 爲環狀醚，以碳數2以上的單環氧化合物較佳，以 、縮水甘油醚、縮水甘油酯更佳，以碳數3-6的環 特別佳。 作爲具體的環狀醚，可列舉環氧乙烷、環氧丙 化苯乙烯、1,2 -環氧丁烷' 2,3 -環氧丁烷、環己烯 化物'丁基縮水甘油醚、縮水甘油丙烯酸酯、氧雜 化合物、四氫呋喃等。 作爲環狀酯，以環上具有含有1或2個羰基氧 及環狀 部份， ，亦可 行開環 合物進 混合物 物進行 基的比 原子的 言，可 等’作 環氧烷 氧烷爲 院、氧 -】，2-氧 環丁烷 基單元 -14 - 200904852 的5〜1 0員環之化合物較適當，亦可具有側鏈。具體而言 ’可列舉內酯或丙交酯等，作爲環狀酯，以ε -己內酯、γ-戊內酯、γ-丁內酯等之內酯較佳，特別佳爲ε-己內酯。 本發明中作爲可與環氧乙烷一起使用的雜環狀化合物 ，以環氧丙烷、ε -己內酯較佳，以環氧丙烷爲特別佳。亦 即’本發明中作爲雜環狀化合物，較佳爲環氧乙烷單獨構 成、環氧乙烷與ε-己內酯的組合、或環氧乙烷與環氧丙烷 的組合，更佳爲環氧乙烷單獨構成、環氧乙烷與環氧丙烷 的組合，特別佳爲環氧乙烷單獨構成。 此外，與起始劑反應的全雜環狀化合物中所含有的環 氧乙烷的比例，以30莫耳％以上較佳，50莫耳％以上更佳 ，80莫耳％以上爲特別佳。 〔藉由陽離子聚合觸媒之雜環狀化合物的開環加成〕 本發明中，使起始劑與雜環狀化合物進行開環加成時 ，使該起始劑的羥基每lmol，與 1〜20mol環氧乙烷進行 開環加成較佳，若起始劑所具有的二級羥基1個與1分子 的環氧乙烷進行開環加成，此二級羥基變換成一級羥基， 亦即，二級羥基置換成2-羥基環氧基。本發明係藉由使用 特定的陽離子觸媒，相對於起始劑中的複數的二級羥基， 環氧乙烷約均等地反應，即使羥基每1個的平均的環氧乙 烷反應分子數少，二級羥基變換成一級羥基的比例亦高， 所以，若相對於起始劑的羥基1 mol之環氧乙烷的開環加 成量爲1 mol以上’可得到一級羥基的比例充分高的多元 -15- 200904852 醇’ 一級羥基的比例高的多元醇，與聚異氰酸酯的反應性 變高。此外，若相對於起始劑的羥基1 mol之環氧乙烷的 開環加成量爲2 0 m ο 1以下’則可製造生質度高的多元醇。 作爲與聚異氰酸酯的反應性高且壓低二氧化碳的排出 重之聚胺基甲酸乙醋製品的原料，爲了得到更佳的多元醇 ’使起始劑的羥基1 m ο 1開環加成〗〜；ι 〇 ^ 〇 1的環氧乙烷較 佳’開環加成1 . 5〜6 m ο 1的環氧乙烷更佳。 於本發明’使其開環加成雜環狀化合物，使所得到的 多兀醇中的起始劑殘基的比例符合3 〇〜9 5質量％較佳，此 外，上述比例若爲40〜95質量％更佳，若爲50〜85質量％ 又更佳。若使其開環加成雜環狀化合物而使所得到的多元 醇中的起始劑殘基的比例成爲9 5質量％以下，所製造的多 元醇的羥基的一級化率變高’與聚異氰酸酯的反應性提高 ’又’若使其開環加成雜環狀化合物而使所得到的相對於 多元醇的起始劑的比例成爲3 0質量％以上，則生質度變高 ，相對於多元醇的酯鍵成分變多，以該多元醇作爲原料所 製造的聚胺基甲酸乙酯製品的強度提高。 此外’雜環狀化合物’在添加時混入水分，則會產生 陽離子聚合觸媒的使用量增加等不佳的狀況。 上述的水分量係相對於雜環狀化合物的總量爲 lOOppm以下較佳，6〇ppm以下更佳，4〇ppm以下爲特別 佳’水分的下限並沒有特別的限制’但一般而言含有 1 ppm以上的水分’此外’若爲3ppm程度爲止的水分，實 質上沒有問題’若使水分量爲lOOppm以下，高分子多聚 -16- 200904852 物等的副產物減少，此外，不易引起陽離子聚合觸媒的失 活。因爲可減少陽離子聚合觸媒的使用量，故較爲經濟， 且製造多元醇後的處理步驟亦變得較簡便。 本發明之將雜環狀化合物開環加成至篦麻油或篦麻油 縮合物的具體的順序如下所示。 在具備攪拌機及冷卻夾套的耐壓反應器中’投入作爲 起始劑之篦麻油或篦麻油縮合物，再添加選自上述鋁化合 物及硼化合物所成的群的至少1種作爲陽離子聚合觸媒， 其中，起始劑係在添加陽離子聚合觸媒前，預先加熱、減 壓後脫水較佳。藉由降低起始劑所含有的水分量，可壓低 高分子多聚物等的副產物’此外’陽離子聚合觸媒不易失 活，可減少所使用的觸媒量。起始劑所含有的水分量，係 相對於起始劑的總量爲2 0 0 p p m以下較佳，1 〇 〇 p p m以下更 佳，5 Oppm以下爲特別佳，下限並沒特別的限制，但一般 而言含有5ppm以上的水分。 添加於起始劑的陽離子聚合觸媒的添加量，相對於起 始劑的總量，以質量比而言爲1 0〜2 0 0 P P m的範圍較佳， 20〜150ppm更佳，30〜lOOppm又更佳。若所使用的陽離子 聚合觸媒的量爲200ppm以下’不易發生陽離子聚合觸媒 所含有的水分所造成的觸媒的失活等問題’此外’若所使 用的陽離子聚合觸媒的量爲〗0PPm以上’可得到充分的反 應速度，陽離子聚合觸媒中所含有的水分量低時’在上述 的範圍内儘可能減少觸媒量較佳。 本發明的多元醇的製造方法’係冷卻反應容器的同時 -17- 200904852 ，調節雜環狀化合物供給至反應容器内的供給速度，使反 應容器内溫度保持在所望的溫度較佳，反應容器内溫度通 常爲-15〜140°C，0〜120°C較佳，20〜9(TC更佳。聚合時間通 常爲0 · 5 ~ 2 4小時，1〜1 2小時較佳。 藉由本發明的製造方法所製造的多元醇，必要時進行 純化。所製造的多元醇具有酯鍵，因此，與藉由鹼性化合 物分解觸媒比較下，藉由無機吸附劑吸附、過濾分別較佳 。作爲無機吸附劑，可列舉例如合成矽酸鹽（矽酸鎂、矽 酸鋁等）、離子交換樹脂、活性白土等，藉由鹼性化合物 進行中和純化時，減少所使用的鹼性化合物量較佳。 此外，在多元醇的純化前後必要時可添加習知的多元 醇的各種安定劑，長期間貯藏多元醇時，可藉由抗氧化劑 、防蝕劑等，防止多元醇的劣化。作爲安定劑，可使用例 如阻酚系化合物、含氮化合物、鹼金屬或鹼土類金屬的氫 氧化物、無機鹽、及羧酸鹽所成的群所選出的至少1種。 藉由本發明的製造方法使所製造的多元醇與聚異氰酸 酯進行反應，可製造聚胺基甲酸乙酯製品，此時，本發明 的多元醇，可單獨作爲原料，亦可與其他的多元醇混合後 作爲原料。 先前技術的聚胺基甲酸乙酯製品，大部份是使用實質 上由聚氧乙烯及/或聚氧丙烯所成的聚醚多元醇作爲原料 。另一方面，以本發明的多元醇作爲原料的聚胺基甲酸乙 酯製品’比起先前技術的聚胺基甲酸乙酯製品，不僅是環 境負擔小，耐水熱性、耐候性、柔軟性及機械物性亦優異 -18- 200904852 本發明的多元醇’因爲環境負擔小，故適用於作爲被 大量消耗的胺基甲酸乙酯樹脂的原料較佳，作爲大量被消 耗的胺基甲酸乙酯樹脂’例如軟質胺基甲酸乙酯泡沫，其 中在車輛用緩衝墊，特別是汽車用椅墊緩衝墊，使用以本 發明的多元醇爲原料的胺基甲酸乙酯樹脂較佳。 作爲製造聚胺基甲酸乙酯製品時所使用的聚異氰酸酯 ’可列舉芳香族聚異氰酸酯、脂肪族聚異氰酸酯、脂環族 聚異氰酸酯、此等聚異氰酸酯的改性體等。 作爲芳香族聚異氰酸酯，可列舉甲苯撐二異氰酸酯、 二苯基甲烷二異氰酸酯、聚伸甲基聚苯基聚異氰酸酯等。 此外，作爲脂肪族聚異氰酸酯，可列舉六伸甲基二異 氰酸酯、二甲苯撐二異氰酸酯、二環己基甲烷二異氰酸醋 、離胺酸二異氰酸酯、四甲基二甲苯撐二異氰酸酯等。 此外，作爲脂環族聚異氰酸酯，可列舉異氟爾酮二異 氰酸酯等。 【實施方式】 〔實施例〕 以下，列舉實施例及比較例，具體地說明本發明，惟 ’本發明並不限定於以下的記載所限定及所解釋的內容。 〔起始劑的羥基數〕 作爲起始劑使用的篦麻油或篦麻油縮合物的羥基數， -19- 200904852 藉由測量羥基價（mgKOH/g)而得到，羥基價係依據JIS-K- 1 5 5 7所測量的値，以酸價（mgKOH/g)進行修正。 此外，藉由本發明的製造方法所製造的多元醇，藉由 凝膠滲透層析法（GPC )進行分析，算出重量平均分子量 (Mw) /數平均分子量（Μη)，惟，Mw及Μη爲聚苯乙 烯換算分子量。 〔所製造的多元醇的羥基的一級化率〕 藉由本發明的製造方法所得到的多元醇之全羥基中一 級羥基所佔的比例，藉由】H-NMR法測量。首先，調製多 元醇的CDC13溶液，添加三氟乙酸酐，藉此，於室溫可輕 易地以三氟乙酸酯化多元醇的羥基。以三氟乙酸被酯化的 碳上的甲川氫原子（相當於鍵結於二級羥基的碳原子之氫 原子）與亞甲基氫原子（相當於鍵姑於一級羥基的碳原子 之氫原子）的波峰位移至低磁場側，經由此化學位移而歸 屬於被以三氟乙酸酯化的甲川氫原子及亞甲基氫原子的波 峰，計算此等的波峰面積強度。全羥基中一級羥基所佔的 比例（一級化率），相對於上述甲川氫原子的波峰面積強 度的2倍與上述亞甲基氫原子的波峰面積強度的總和，算 出上述亞甲基氫原子的波峰面積的比例。 例如，起始劑的篦麻油或篦麻油縮合物與環氧乙烷進 行開環加成時，藉由以三氟乙酸酯化全羥基而位移至低磁 場側之甲川氫原子的多重波峰，出現在5.00〜5.1 Oppm (四 甲基矽烷基準），此外，亞甲基氫原子的三重線波峰係出 -20- 200904852 現在4·48〜4.50ppm (四甲基矽烷基準），藉由 的面積強度，計算出羥基的一級化率（％ )。 〔所製造的多元醇的生質度〕 本發明中之生質度，係相對於作爲起始劑 油或篦麻油縮合物、與被開環加成的雜環狀化 量，以篦麻油或篦麻油縮合物的質量％表示。 〔起始劑〕 作爲篦麻油縮合物，係使小倉合成工業公 001 (羥基數2_8，藉由鹽酸中和滴定之鹼度以 爲27 7ppm，羥基價66. lmgKOH/g )中和處理 爲用於中和殘留鹼之中和處理，係以KOH 1 0%過剩量添加5%硫酸水溶液，以60°c加熱 以8 0°C減壓脫水2小時。使用中和處理後所得 縮合物（水分含量（質量比例）爲60ppm )。 此外，作爲篦麻油，係使用伊藤製油公司 Η·30(羥基數 2.7，羥基價 162KOHmg/g)， 分含量爲80ppm。 〔雜環狀化合物〕 以下的例子，使用環氧乙烷單獨構成作爲 物（以下’僅簡稱爲EO ) ，EO的水分含量爲 此等的波峰 使用的篦麻 合物的總重 司製的KG-KOH換算 後使用；作 中和當量的 2小時後， 到的篦麻油 製的URIC-篦麻油的水 雜環狀化合 5 p p m以下 -21 - 200904852 〔實施例1〕 在具備葉輪（攪拌葉徑爲反應器内徑的5 〇 % )攪拌裝 置的5L反應容器内，投入起始劑之上述的篦麻油縮合物 (KG-001的縮合物）495g、與陽離子聚合觸媒之三（五 氟苯基）硼院（TPFPB) 60mg，反應容器内進行氮氣置換 後，將反應容器内溫度昇溫至6 5。(：，3 0分鐘後，開始Ε Ο 的添加’因爲EO添加的同時開始發熱，故藉由冷卻水使 反應容器内溫度保持在70°C，一邊進行攪拌（220rpm (每 分鐘220轉）），一邊添加35g的EO，EO的添加後，再 以7 0 °C進行6 0分鐘的反應，儘可能減少未反應的ε 〇後 ’進行1小時的減壓脫氣，得到多元醇A。 所製造的多元醇A與原料的篦麻油縮合物之經由GPC 所得到的分子量分布曲線，列示於圖1。 〔實施例2〕 除了起始劑的量爲452 g、EO的添加量爲99g以外， 其餘與實施例1同樣的方法製造多元醇B，所製造的多元 醇B與原料的篦麻油縮合物之分子量分布曲線，列示於圖 2。 〔實施例3〕 除了使起始劑的量爲3 9 1 g、E〇的添加量爲8〗g，使 用二苯甲基（肆五氟苯基）硼酸酯（TrTPFPB )作爲陽離 -22- 200904852 子聚合觸媒以外，其餘與實施例1同樣的方法製造多元醇 C，所製造的多元醇C與原料的篦麻油縮合物的分子量分 布曲線，列示於圖3 ° 〔實施例4〕 除了使用篦麻油（URIC-H-30 ) 3 07g作爲起始劑，添 加49g的EO、50mg的 TPFPB以外，其餘與實施例ι同 樣作法，製造多元醇D ’所製造的多元醇D與原料的篦麻 油的分子量分布曲線，列示於圖4。 〔實施例5〕 除了使用篦麻油（URIC-H-30 ) 250g作爲起始劑，添 加106g的 EO、50mg的TPFPB以外，其餘與實施例ι 同樣地製造多元醇E，所製造的多元醇E與原料的篤麻油 的分子量分布曲線，列示於圖5。 以下，列示以複合金屬氰化物錯合物（D M C )觸媒或; ΚΟΗ觸媒取代陽離子聚合觸媒之比較例。 〔比較例1〕 於具備葉輪（攪拌葉徑爲反應器内徑的50%)攪拌裝 置之5L反應容器内，投入上述的篦麻油縮合物（KG-001 的縮合物）3 00g、與複合金屬氰化物錯合物觸媒（基於特 開200 5 - 1 5 7 8 6號公報的記載’由ZnCl2水溶液、κ3〔 c〇 (CN ) 6〕水溶液、及tert-丁基醇所製造者，配位基爲 -23- 200904852 tert-丁基醇系的複合金屬氰化物錯合物觸媒；以下，稱爲 DMC觸媒。）20mg，反應容器内進氮氣置換後，使反應 容器内溫度昇溫至120°C，添加30g的EO，然後，以 220rpm進行攪拌，於30分鐘左右在發熱的同時内壓開始 降低（DMC觸媒的活性化），再攪拌3 0分鐘後，逐次少 量添加55g的EO，最後添加85g的EO，在這期間，將反 應容器内溫度保持在120°C，一邊以220rpm進行擾持一邊 添加EO ’ EO的添加結束後，再以120°C進行60分鐘加熱 及攪拌，然後進行3 0分鐘的減壓脫氣，如上述所製造的 多元醇F與原料的篦麻油縮合物的分子量分布曲線，列示 於圖6。 〔比較例2〕 於具備葉輪（攪拌葉徑爲反應器内徑的50%)攪拌裝 置的5L反應容器内，投入篦麻油（URIC-H-30) 300g及 DMC觸媒20mg’反應容器内進行氮氣置換後，將反應容 器内溫度昇溫至120°C，添加70g的EO，然後，以 220rPm進行攪拌，則於30分鐘左右在發熱的同時内壓開 始降低（D M C觸媒的活性化），再攪拌3 0分鐘後，逐次 少量添加8 0 g的Ε Ο，最後添加1 5 〇 g的Ε 0，在這期間， 將反應容器内溫度保持在1 2 0 t，一邊以2 2 0 rp m進行攪拌 一邊添加Ε Ο ’ E 0的添加結束後，再以1 2 〇 t進行6 0分鐘 加熱及攪拌’然後進行3 0分鐘的減壓脫氣，如上述所製 造的多元醇G與原料的篦麻油縮合物的分子量分布曲線， -24- 200904852 列示於圖7。 〔比較例3〕 除了使DMC觸媒活性化後的EO的添加量爲147S以 外，其餘與比較例2同樣方法製造多元醇Η，所製造的多 元醇Η與原料的篦麻油的分子量分布曲線，列示於圖8。 〔比較例4〕 於具備葉輪（攪拌葉徑爲反應器内徑的50% )攪拌裝 置的5L反應容器内，投入篦麻油（URIC-H-30) 650g及 作爲觸媒之純度95%的片狀的1<：〇}1的5.45§，反應容器内 進行氮氣置換後，將反應容器内溫度昇溫至l〗〇°C，進行 2小時減壓脫水，然後，用氮氣使内壓爲〇.4MPa，於其中 導入EO使其反應，此時，一邊使反應容器内溫度保持在 約115°C，一邊以22〇rpm進行攪拌，最後使43 5 g的EO 進行反應，反應結束後，一邊使反應容器内溫度保持在 115 °C —邊進行60分鐘的減壓脫氣，如上述所製造的多元 醇I與原料的篦麻油的分子量分布曲線，列示於圖9。 實施例及比較例中之起始劑、陽離子聚合觸媒、環氧 乙烷的使用量列示於表1，此外，將所製造的多元醇的分 析結果列示於表2。 -25- 200904852 〔表1〕 起始劑 起始劑 量(g) 陽離子聚合 觸媒 觸媒量 (mg) EO添加量 (g) EO添加量 (mol)/起始 齊!j OH(mol) 實施例I KG-001 (縮合物） 495 TPFPB 60 35 1.6 2 KG-001 (縮合物） 452 TPFPB 60 99 4.2 3 KG-001 備合物） 391 TrTPFPB 60 81 4.0 4 URIC- H-30 307 TPFPB 50 49 1.2 5 URIC- H-30 250 TPFPB 50 106 3.3 比較例1 KG-001 (縮合物） 300 DMC 20 85 5.7 2 URIC- H-30 300 DMC 20 150 3.9 3 URIC- H-30 300 DMC 20 217 6.1 4 URIC- H-30 650 KOH 5450 435 5.3 -26- 200904852 〔表2〕 所製造的多 元醇 GPC (Μη) GPC Mw/Mn 一級化率 (%、 生質度 (%) 實施例1 多元醇A 2940 1.67 86 93.4 2 多元醇B 3650 1.60 97 82.0 3 多元醇C 3300 1.71 75 82.8 4 多元醇D 1480 1.04 53 86.2 5 多元醇E 1880 1.16 79 69.3 比較例1 多元醇F 3420 1.42 70 77.3 2 多元醇G 1770 1.40 28 66.7 3 多元醇Η 2160 1.47 37 58.0 4 多元醇I 1780 1.64 72 59.9 使用DMC觸媒作爲觸媒，使篦麻油縮合物與EO進行 反應後所製造的多元醇F (比較例1 )，如圖6所示，不 會因爲起始劑的分解而產生低分子量的副產物，惟，所製 造的多元醇F，低分子量的起始劑的波峰變小，分子量分 布變大’亦即，多元醇F係 EO與起始劑不均勻地反應， 因此’多元醇F加成多量的EO，儘管生質度低，羥基的 一級化率亦低（表2 )。 此外，使用D M C觸媒，使篦麻油與E 0進行反應後所 製造的多元醇G (比較例2 )，如圖7所示，幾乎看不到 篦麻油的波峰往高分子量側移動，一部份的篦麻油與Ε Ο 進行反應的寬峰見於高分子量側，此外，加成多量的ΕΟ ，儘管生質度低，羥基的一級化率亦低（表2 )。 此外’比多元醇G (比較例2)使更多的Ε 0進行反 應的多元醇Η (比較例3 )，亦如圖8所示，幾乎看不到 箆麻油的波峰往高分子量側移動，一部份的篦麻油與Ε0 -27- 200904852 進行反應的寬峰見於高分子量側，此寬峰大於多元醇G的 波峰，如上述，加成更多的E 0，儘管生質度更低’羥基 的一級化率幾乎未被改善（表2 )。 使用KOH觸媒，使篦麻油與EO進行反應後所製造的 多元醇I (比較例4 )，如圖9所示，因爲起始劑的分解 而產生低分子量的副產物，此外，比起篦麻油，高分子量 側的分子量分布亦變化，亦即，多元醇I係EO與起始劑 不均勻地反應，此外，加成多量的EO，儘管生質度低， 羥基的一級化率亦低（表2 )。 另一方面，使用陽離子聚合觸媒之三（五氟苯基）硼 烷，使篦麻油縮合物與EO進行反應後所製造的多元醇A (實施例1 )及多元醇B (實施例2 )，如圖1及圖2所 示，不會因爲起始劑的分解而產生低分子量的副產物，此 外，EO與篦麻油縮合物均勻地反應，故多元醇A及多元 醇B，與多元醇F (比較例1 )比較下，僅加成少量的EO ，故生質度高，且羥基的一級化率高。 此結果，使用三苯甲基（肆五氟苯基）硼酸酯作爲陽 離子聚合觸媒之多元醇C (實施例3 )亦相同，如圖3所 示，多元醇C沒有因爲起始劑的分解所造成的低分子量的 副產物，僅加成少量的EO，生質度高、且羥基的一級化 率高。 此外，如圖4所示，使用三（五氟苯基）硼院作爲陽 離子聚合觸媒，使篦麻油與EO進行反應後所製造的多元： 醇D (實施例4)，與多元醇G (比較例2 )及多元醇η ( -28- 200904852 比較例3 )比較下，EO均勻地反應，無因爲起始 而產生低分子量的副產物，此外，分子量分布非 此外，僅加成少量的 EO，故生質度高、且羥基 率高。 此結果，實施例5亦約相同，如圖5所示， (實施例5 )多少可看到E 0不均勻地與起始劑 的高分子量側的波峰，惟，可看到起始劑的大部 高分子量側的波峰，Ε Ο均勻地反應。 如上述，本發明的多元醇的製造方法，不會 劑的分解而產生低分子量的副產物，可使E 0與 勻地進行反應，可製造高生質度且羥基的一級化 元醇。 〔產業上的可利用性〕 以本發明的篦麻油、或篦麻油縮合物作爲起 造的多元醇，使其與聚異氰酸酯反應而製造各種 乙酯製品。 此外’本發明的多元醇可在與異氰酸酯的反 任意地使其與鏈延長劑進行反應。 本發明的多元醇’適合用於潤滑脂用、金屬 壓縮機油等之機能油劑、界面活性劑、油墨分散 且’亦適合作爲含有聚合物微粒子之聚合物分散 原料。 再者’本發明引用2007年3月28日申請的 劑的分解 常狹窄， 的一級化 多元醇E 進行反應 份移動至 因爲起始 起始劑均 率高的多 始劑所製 胺基甲酸 應時，可 加工油、 劑等，而 多元醇的 曰本特許 -29· 200904852 出願2 0 0 7 - 0 8 5 6 1 0號的說明書、申請專利範圍、圖面及摘 要的所有内容，揭示於本發明的說明書。 【圖式簡單說明】 〔圖1〕多元醇Α(實施例1)的凝膠滲透色層分析 中的分子量分布曲線。 〔圖2〕多元醇B(實施例2)的凝膠滲透色層分析 中的分子量分布曲線。 〔圖3〕多元醇C(實施例3)的凝膠滲透色層分析 中的分子量分布曲線。 〔圖4〕多元醇D(實施例4)的凝膠滲透色層分析 中的分子量分布曲線。 〔圖5〕多元醇E (實施例5 )的凝膠滲透色層分析 中的分子量分布曲線。 〔圖6〕多元醇F(比較例1)的凝膠滲透色層分析 中的分子量分布曲線。 〔圖7〕多元醇G(比較例2)的凝膠滲透色層分析 中的分子量分布曲線。 〔圖8〕多元醇H(比較例3)的凝膠滲透色層分析 中的分子量分布曲線。 〔圖9〕多元醇Ϊ (比較例4 )的凝膠滲透色層分析中 的分子量分布曲線° -30-BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyol and a polyol produced by the method. [Prior Art] As a means for the so-called maximum environmental problem of global warming, 'there is a strong demand for the reduction of carbon dioxide emissions in the atmosphere, and the chemical industry of the prior art that utilizes resources such as petroleum or coal, because of the burning of resources. The amount of carbon dioxide is increased. However, if biomass (biomass) such as animal oil or the like is used, the amount of carbon dioxide can be reduced. The raw material 'is not limited to animal and vegetable oils or modified products thereof, and lactic acid obtained by fermentation of plants, lactide of a cyclic ester, polylactic acid or the like can also be used. However, 'polyurethane products such as foams, resins, elastomers, paints, and adhesives are produced by using polyols and polyisocyanates as main raw materials.' In addition, polyols are also widely used as various oils. Raw materials. The polyol used in the prior art is petroleum-derived. So far, at least a part of the polyol which is a raw material is proposed to be a hydrophobic vegetable oil-derived polyol, which has improved the heat resistance of the product, but it has not been considered. An example in which the amount of carbon dioxide is reduced and the ratio of biomass in the raw material is increased. The technique of using a polyurethane foam for a cushion for a car seat to make at least a part of the raw material thereof a vegetable oil-derived polyol is proposed by the technique that carbon dioxide can be obtained when the combustion is depressed. The amount of discharge 'at the same time, the physical properties of the machine are also the same as those of the prior art petroleum-derived raw material 200,904,852 (refer to Patent Documents 1 to 3). When a vegetable oil-derived polyol used as a raw material is mixed with other polyether polyols, the obtained physical property of the polyurethane is rich in 'physical oil-derived polyols, generally because The hydrophilicity is not high, so it has low compatibility with other polyether polyols. In addition, because the structure of the vegetable oil is limited, if a polymer oil-derived polyol can be obtained, a polyamine group having various physical properties can be produced. The ethyl formate product 'further' reacts with a hydroxyl group and an isocyanate group, and has the highest activity of the primary hydroxyl group. Therefore, the polyhydric alcohol has more than one primary hydroxyl group, and the reactivity with the polyisocyanate is higher. Therefore, a technique of ring-opening addition of castor oil which is a vegetable oil-derived polyol to cyclooxygen or epoxy epoxide is proposed (refer to Patent Documents 2 to 4). Castor oil is mainly composed of ricinoleic acid, which has one secondary hydroxyl group, and is derived from animal and vegetable oils and has hydroxyl groups only castor oil. Castor oil is suitable as a starter for natural oil derived polyols. In the techniques of Patent Documents 2 to 4, the secondary hydroxyl group is subjected to ring-opening addition to propylene oxide or epoxy enamel, whereby the polyether chain can be introduced into castor oil, and the obtained polyol can be improved. The compatibility of other polyether polyols, in addition, the ring-opening addition of propylene oxide or ethylene oxide can be used to quantify castor oil, and furthermore, since the secondary hydroxyl group can be converted into a primary hydroxyl group, A polyol having high reactivity with a polyisocyanate. Hereinafter, the ratio of the primary hydroxyl group in the hydroxyl group which the produced polyol has is referred to as the primary conversion ratio. In addition, polyoxyethylene hardened castor oil 200904852 which is subjected to ring-opening addition of hydrogenated castor oil 1 mole (mol) and ethylene oxide 40 to 300 moles (mol) is widely used as a surfactant ( Refer to Patent Document 5). As described above, as a catalyst for ring-opening addition of alkylene oxide such as castor oil or hydrogenated castor oil, an alkali metal compound such as potassium hydroxide or sodium hydroxide which is an alkali catalyst is usually used. However, the reaction rate of the alkali metal compound-based alkylene oxide is slow, and on the other hand, in order to increase the reaction rate and increase the amount of catalyst used, the treatment such as catalyst removal after the reaction becomes complicated, and when an alkali metal compound is used, Since the ester bond of castor oil undergoes cracking or transesterification, the produced polyol contains a by-product such as a low molecular weight condensate of a large amount of fatty acid (refer to Patent Document 6). Further, in the reaction of ring-opening addition of an alkylene oxide to a polyester polyol, an acid catalyst such as a BF3 ether complex is used as a catalyst, but at this time, since the ester bond in the polyester polyol is cracked, it is high. The manufacture of molecular weight polyester polyols is difficult. Therefore, in the presence of this catalyst, the production of a polyol using castor oil as a starting agent produces a low molecular weight by-product due to decomposition. On the other hand, there is a mixed metal cyanide complex catalyst which is not a base catalyst or an acid catalyst, and a castor oil or a modified castor oil and an alkylene oxide are subjected to ring-opening addition of a polyol having a narrow molecular weight distribution. Manufacturing method (refer to Patent Document 7). The term "modified castor oil" refers to a technique in which castor oil is subjected to a transesterification reaction, a hydrogenation reaction, a sodium reduction reaction, etc., and the technique of Patent Document 7 is used. In the case of ethane, the complex hydroxyl group of castor oil or modified castor oil is heterogeneously ring-opened with ethylene oxide. Therefore, it is necessary to produce a polyol having a high primary rate with a small amount of ethylene oxide. It is difficult, if a small amount of ethylene oxide can be used to change the secondary hydroxyl group of the castor oil into a primary hydroxyl group, the ratio (biomass) occupied by the 200,904,852 parts of the initiator of the produced polyol can be increased. Patent Document 8 proposes a technique of using a boron compound having three fluorine-containing phenyl groups as a cationic polymerization catalyst to form a ring-opening addition of castor oil and alkylene oxide. However, the technique disclosed in Patent Document 8 is A technique of subjecting an alkylene oxide having a carbon number of 3 to 1 2 to ring-opening addition. Further, it is proposed to use a double metal cyanide complex catalyst to produce a polyester alcohol, and then to use a cationic polymerization catalyst containing three fluorophenyl group-containing boron compounds to carry out the produced polyester polyol and ethylene oxide. The technique of ring-opening addition (refer to Patent Document 9), but there is a description about the stability of the ester bond of a cationic polymerization catalyst for a Lewis acid. Further, a technique of introducing a primary hydroxyl group to a natural oil-derived polyol having low reactivity with a polyisocyanate is proposed (refer to Patent Document 10), which is a method of making soybean oil and carbon monoxide in the presence of a special metal catalyst. Hydrogen is reacted to introduce a carbonyl group into the double bond portion of the soybean oil, and then the introduced carbonyl group is further reacted with hydrogen to form a primary hydroxyl group. Since ricinoleic acid, which is a main component of castor oil, has one double bond, a primary hydroxyl group can be introduced by this technique. However, the catalyst used in this technique is expensive and requires a complicated manufacturing process. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-3 2043 No. 1 (Patent Document 2) Japanese Patent Publication No. 2 0 0 5 - 3 2 04 3 7 (Patent Document 3) Special Opening 2 0 0 6 - 2 1 4 5 [Patent Document 4] JP-A-2006-104040 (Patent Document 5) JP-A-2002-00-88-88 (Patent Document 6) Special Table 2 0 0 3 - 5 1 1 5 3 Japanese Laid-Open Patent Publication No. Hei. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. 6392076 [Patent Document 10] US Patent Application Publication No. 2005/0070620 [Draft of the Invention] [Problems to be Solved by the Invention] As described above, the method for producing a polyol of the prior art cannot use castor oil as a starting agent. The decomposition agent is decomposed to produce a polyol having a high degree of primaryization at a high degree of biomass. The object of the present invention is to provide castor oil as a starting agent, which does not produce low molecular weight by-products due to decomposition of the initiator, and evenly open-loop addition of the hydroxyl groups in the ethylene oxide and the initiator, even if high-quality A method for producing a polyol having a high degree of quality and a high degree of first-order. [Means for Solving the Problem] In order to achieve the above-mentioned problem, the present invention provides a method for producing a polyhydric alcohol, which is characterized in that at least one selected from the group consisting of castor oil and castor oil condensate is present in the presence of a cationic polymerization catalyst. A method for producing a polyvalent alcohol which is subjected to ring-opening addition of a starting compound and a heterocyclic compound, characterized in that the heterocyclic compound is a compound selected from the group consisting of a cyclic ether and a cyclic ester, at least one of which The part is ethylene oxide; the cationic polymerization catalyst is at least one type of catalyst selected from the group consisting of an aluminum compound and a fluorine-containing aryl group, which is composed of an aluminum compound and a boron compound. The method for producing a polyol according to the present invention, wherein the heterocyclic compound is composed of a single epoxy compound, or a combination of epoxy epoxide and ε-caprolactone, or a combination of ethylene oxide and propylene oxide. good. Further, the ratio of ethylene oxide in the above heterocyclic compound is preferably 3 〇 mol% or more. Further, the hydroxyl group of the initiator is subjected to ring-opening addition per 1 mol of the epoxy compound of 1 to 2 〇m〇l. The above starting agent is preferred. Further, the ratio of the initiator residue in the polyol of the present invention is preferably from 30 to 95% by mass. Further, the above cationic polymerization catalyst is preferably tris(pentafluorophenyl)borane or tris(pentafluorophenyl)aluminum. Further, it is preferable to add the above cationic polymerization catalyst in a mass ratio of 10 to 200 Ppm with respect to the total amount of the above-mentioned initiator. Further, the present invention provides a polyol produced by the above production method. Further, a polyurethane product produced using the polyol of the present invention is used. [Effects of the Invention] According to the method for producing a polyhydric alcohol of the present invention, a by-product which does not contain a low molecular weight due to decomposition of the initiator, a heterocyclic compound containing ethylene oxide, and a hydroxyl group in the initiator can be produced. A polyol having a high degree of homogeneity and a high degree of primaryization, which is uniformly opened and added. -10-200904852 Further, in the present invention, when a polyol having a high degree of biomass is used, a polyurethane product having a small environmental burden can be produced. [Best Mode for Carrying Out the Invention] The method for producing a polyhydric alcohol according to the present invention is a method of forming at least one initiator and ring containing a castor oil and a castor oil condensate in the presence of a specific cationic polymerization catalyst. A method of ring-opening addition of a heterocyclic compound of oxyethane. In the present invention, the term "castor oil condensate" means an ester compound obtained by dehydrating condensation of hydroxycarboxylic acid obtained by hydrolyzing castor oil or water-added castor oil (hydrogenated castor oil), but dehydration condensation. The condensation of only the hydroxycarboxylic acid can also be the condensation of a hydroxycarboxylic acid with castor oil or water-added castor oil. [Starting agent] In the present invention, castor oil having a primary hydroxyl group as a main constituent fatty acid or castor oil condensate is used as a starting agent, and a method for producing a castor oil condensate is not particularly preferable. The limitation is, for example, the following two examples. (1) A method of esterifying reaction between ricinoleic acid obtained by hydrolysis of castor oil and castor oil. (2) A method in which ricinoleic acid is subjected to a condensation reaction with each other to carry out an esterification reaction with the condensate and a low molecular weight polyol selected based on the number of functional groups. At this time, the fatty acid can be obtained by using 1,4-hydroxystearic acid (hydride of ricinoleic acid) -11 - 200904852 ricinoleic acid or with ricinoleic acid. In the above (2), examples of the low molecular weight polyol which is reacted with a condensate of a fatty acid include the following compounds. 2-alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1 , 6-ring diol, 1,4-cyclohexane dimethanol, and the like. Polyols of 3 or more yuan: glycerin, diglycerin, trihydroxyl base propane, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, and the like. Further, a low molecular weight polyether polyol having a number average molecular weight of 150 to 1,000 obtained by subjecting a polyol to an alkylene oxide to undergo ring-opening addition can be mentioned. Further, the condensation reaction of the fatty acid does not particularly require a catalyst, but the esterification reaction is preferably carried out by using a catalyst, and examples of the catalyst include an alkali metal compound or an acidic compound. Examples of the basic metal compound include calcium hydroxide and sodium methoxide. The acidic compound may, for example, be a Lewis acid such as tin dichloride, p-toluenesulfonic acid or titanium alkoxide or a Bronsted acid. In the present invention, the valence (mgKOH/g) of the castor oil or castor oil condensate used as the initiator is usually 25 to 350, preferably 40 to 200, more preferably 50 to 70. When the valence of the hydroxy group is 25 or more, the ring-opening addition reaction of ethylene oxide by the cationic polymerization catalyst becomes uniform, and the degree of first-ordering is also easily improved. Further, if the valence of the hydroxy group is 305 or less, the manufactured plural is produced. The degree of bioavailability of the alcohol becomes large. [Cation polymerization catalyst] The present invention is characterized in that at least one selected from the group consisting of an aluminum compound and a boron compound having one or more fluorine-containing aryl groups or -12 - 200904852 fluoroaryloxy groups is used. 'As the cationic polymerization catalyst, that is, the cationic polymerization catalyst in the present invention is an aluminum compound or a boron compound, however, the cationic polymerization catalyst has one or more fluorine-containing aryl groups or fluorine-containing aryloxy groups. Examples of the fluorine-containing aryl group include pentafluorophenyl, tetrafluorophenyl, trifluorophenyl, 3,5-bis(trifluoromethyl)trifluorophenyl, and 3,5-bis(trifluoromethyl). Phenyl, 2-perfluoronaphthyl, 2-perfluorobiphenyl, and the like. Further, the fluorine-containing aryloxy group may be a fluorine-containing aryloxy group in which the above-mentioned fluorine-containing aryl group is bonded to an oxygen atom. As an aluminum compound or a boron compound having at least one fluorine-containing aryl group or a fluorine-containing aryloxy group, for example, JP-A-2000- 3 4 4 8 8 1 and JP-A-2005- 8 2 73 2 The aluminum compound or the boron compound of the Lewis acid described in the publication of Japanese Patent Publication No. WO 03/00750 is also preferably described in Japanese Patent Laid-Open Publication No. JP-A No. 2003-5-1, No. The aluminum compound of the gun salt or the boron compound is preferred. Examples of the aluminum compound of the Lewis acid include tris(pentafluorophenyl)aluminum and tris(pentafluorophenyloxy)aluminum. Further, 'as a boron compound as a Lewis acid, for example, tris(pentafluorophenyl)borane, tris(pentafluorophenyloxy)borane, wherein tris(pentafluorophenyl)borane is used for the epoxy B. The catalytic activity of the ring-opening addition reaction of an alkane is particularly good. As the counter cation of the key salt, a trityl cation (Ph3c+) or an aniline cation (PhNR3+; Ph=phenyl group, R=H, an alkyl group, etc.) is preferably used as a key salt, and a trityl group is used. Pentafluorophenyl)borate or -13- 200904852 N,N'-dimethylanilinium tetrakis(pentafluorophenyl)borate is particularly preferred. [Heterocyclic Compound] The heterocyclic compound used in the present invention is a compound selected from the group consisting of a cyclic ether ester, and contains ethylene oxide as at least one of them, and a heterocyclic compound in the present invention. It is only possible that ethylene oxide is a combination of ethylene oxide and other heterocyclic compounds. When an addition reaction of ethylene oxide and another heterocyclic compound is carried out, ethylene oxide may be sequentially reacted with other heterocyclic groups, and ethylene oxide and other heterocyclic rings may be used. The reaction of the compound proceeds. When the reaction is carried out in the same order, it is preferred to carry out the reaction of the other heterocyclic compound and then react the ethylene oxide to improve the primary hydroxyl group. The cyclic ether is preferably a compound having one or two etheric oxygen atoms of 3 to 6 members, and may have a side chain. Specifically, a monoepoxy compound, an oxetane compound, and tetrahydrofuran are cyclic ethers, and a monoepoxy compound having a carbon number of 2 or more is preferable, and a glycidyl ether or a glycidyl ester is more preferable, and a carbon number is 3 The ring of -6 is especially good. Specific examples of the cyclic ether include ethylene oxide, epoxidized styrene, 1,2-butylene oxide ' 2,3-butylene oxide, and cyclohexenyl 'butyl glycidyl ether. Glycidyl acrylate, oxa compound, tetrahydrofuran, and the like. As a cyclic ester, having a ring containing 1 or 2 carbonyl oxygen and a cyclic moiety, or a specific atom of a ring-opening compound into a mixture, may be used as an alkyl alkoxylated alkane. The compound of the 5~10 member ring of the hospital, oxygen-], 2-oxocyclobutane unit-14 - 200904852 is suitable, and may have a side chain. Specifically, a lactone or a lactide may be mentioned, and as the cyclic ester, a lactone such as ε-caprolactone, γ-valerolactone or γ-butyrolactone is preferred, and ε-hexyl is particularly preferred. Lactone. In the present invention, as the heterocyclic compound which can be used together with ethylene oxide, propylene oxide and ε-caprolactone are preferred, and propylene oxide is particularly preferred. That is, in the present invention, as the heterocyclic compound, a combination of ethylene oxide alone, a combination of ethylene oxide and ε-caprolactone, or a combination of ethylene oxide and propylene oxide is preferred. Ethylene oxide alone, a combination of ethylene oxide and propylene oxide, particularly preferably ethylene oxide alone. Further, the proportion of the ethylene oxide contained in the wholly heterocyclic compound which reacts with the initiator is preferably 30 mol% or more, more preferably 50 mol% or more, and particularly preferably 80 mol% or more. [Cyc ring-opening addition of a heterocyclic compound by a cationic polymerization catalyst] In the present invention, when the initiator and the heterocyclic compound are subjected to ring-opening addition, the hydroxyl group of the initiator is made per 1 mol, and It is preferred to carry out ring-opening addition of ~20 mol of ethylene oxide. If the first hydroxyl group of the initiator has a ring-opening addition with one molecule of ethylene oxide, the secondary hydroxyl group is converted into a primary hydroxyl group. That is, the secondary hydroxyl group is substituted with a 2-hydroxy epoxy group. In the present invention, by using a specific cationic catalyst, ethylene oxide is relatively uniformly reacted with respect to a plurality of secondary hydroxyl groups in the initiator, even if the average number of ethylene oxide reaction molecules per one hydroxyl group is small. The ratio of the secondary hydroxyl group to the primary hydroxyl group is also high. Therefore, if the amount of the ring-opening addition of ethylene oxide of 1 mol to the hydroxyl group of the initiator is 1 mol or more, the ratio of the primary hydroxyl group can be sufficiently high. Poly--15-200904852 Polyol The polyol having a high proportion of primary hydroxyl groups has high reactivity with polyisocyanate. Further, when the ring-opening addition amount of ethylene oxide of 1 mol with respect to the hydroxyl group of the initiator is 20 m ο 1 or less, a polyol having a high degree of homogeneity can be produced. As a raw material of a polyaminoethylene formate product having high reactivity with a polyisocyanate and a low pressure of carbon dioxide, in order to obtain a better polyol, the hydroxyl group of the initiator is 1 m ο 1 ring-opening addition 〜; The ethylene oxide of ι 〇^ 〇1 is preferably 'open-loop addition 1. 5~6 m ο 1 of ethylene oxide is more preferable. In the present invention, the ring-opening addition of a heterocyclic compound is carried out so that the ratio of the initiator residue in the obtained polyterpene alcohol is preferably from 3 〇 to 9.5 mass%, and further, the above ratio is 40 〜 More preferably, 95% by mass is more preferably 50 to 85% by mass. When the ratio of the initiator residue in the obtained polyol is 95% by mass or less by ring-opening addition of a heterocyclic compound, the degree of primary hydroxylation of the produced polyol becomes high. When the reactivity of the isocyanate is increased, and the ratio of the obtained initiator to the polyol is 30% by mass or more, the degree of biomass is increased, The ester bond component of the polyol is increased, and the strength of the polyurethane product produced by using the polyol as a raw material is improved. Further, when the "heterocyclic compound" is mixed with water at the time of addition, the amount of use of the cationic polymerization catalyst is increased, which is not preferable. The above-mentioned water content is preferably 100 ppm or less based on the total amount of the heterocyclic compound, more preferably 6 〇 ppm or less, and 4 〇 ppm or less is particularly preferably 'the lower limit of moisture is not particularly limited' but generally contains 1 When the water content of the ppm is more than 3 ppm, there is substantially no problem. If the water content is 100 ppm or less, the by-products such as the polymer poly-16-200904852 are reduced, and the cationic polymerization is less likely to be caused. The inactivation of the media. Since the amount of the cationic polymerization catalyst can be reduced, it is economical, and the processing steps after the production of the polyol are also relatively simple. The specific sequence of the ring-opening addition of the heterocyclic compound to the castor oil or castor oil condensate of the present invention is shown below. In a pressure-resistant reactor equipped with a stirrer and a cooling jacket, a castor oil or a castor oil condensate as a starter is added, and at least one selected from the group consisting of the above-mentioned aluminum compound and a boron compound is added as a cationic polymerization touch. The medium, wherein the initiator is preheated and dehydrated after depressurization is preferred before the addition of the cationic polymerization catalyst. By lowering the amount of water contained in the initiator, it is possible to reduce by-products such as high molecular weight polymers, and the cationic polymerization catalyst is less likely to be deactivated, and the amount of catalyst used can be reduced. The amount of water contained in the initiator is preferably 200 ppm or less based on the total amount of the initiator, more preferably 1 〇〇ppm or less, and particularly preferably 5% or less, and the lower limit is not particularly limited, but Generally, it contains 5 ppm or more of water. The amount of the cationic polymerization catalyst to be added to the initiator is preferably in the range of 10 to 2 0 0 PP m in terms of mass ratio, more preferably 20 to 150 ppm, and 30 to 30 parts by mass based on the total amount of the initiator. lOOppm is even better. When the amount of the cationic polymerization catalyst to be used is 200 ppm or less, the problem of deactivation of the catalyst due to the water contained in the cationic polymerization catalyst is less likely to occur. 'In addition, the amount of the cationic polymerization catalyst used is 0 ppm. When the above is sufficient, a sufficient reaction rate is obtained, and when the amount of water contained in the cationic polymerization catalyst is low, it is preferable to reduce the amount of the catalyst as much as possible within the above range. The method for producing a polyhydric alcohol of the present invention is a method of cooling a reaction vessel while -17-200904852, adjusting the supply rate of the heterocyclic compound to the reaction vessel, and maintaining the temperature in the reaction vessel at a desired temperature, preferably in the reaction vessel. The temperature is usually -15 to 140 ° C, preferably 0 to 120 ° C, and 20 to 9 (TC is more preferred. The polymerization time is usually 0 · 5 to 24 hours, preferably 1 to 12 hours. By the present invention The polyol produced by the production method is purified if necessary. The produced polyol has an ester bond, and therefore, it is preferably adsorbed and filtered by an inorganic adsorbent as compared with a basic compound decomposition catalyst. Examples of the adsorbent include synthetic citrate (magnesium citrate, aluminum citrate, etc.), ion exchange resin, activated clay, and the like, and it is preferred to reduce the amount of the basic compound used when performing neutralization purification by a basic compound. In addition, various stabilizers of conventional polyols may be added before and after the purification of the polyol, and when the polyol is stored for a long period of time, the deterioration of the polyol may be prevented by an antioxidant, an anticorrosive agent or the like. As the stabilizer, at least one selected from the group consisting of a hindered phenol compound, a nitrogen-containing compound, a hydroxide of an alkali metal or an alkaline earth metal, an inorganic salt, and a carboxylate can be used. The polyhydric alcohol product can be produced by reacting the produced polyol with a polyisocyanate. In this case, the polyol of the present invention can be used as a raw material alone or as a raw material after being mixed with other polyols. Most of the polyurethane products are made of a polyether polyol substantially composed of polyoxyethylene and/or polyoxypropylene as a raw material. On the other hand, the polyol of the present invention is used as a raw material. The urethane product 'is not only environmentally burdened, but also excellent in water heat resistance, weather resistance, flexibility, and mechanical properties compared to the polyurethane urethane product of the prior art. -18-200904852 The polyol of the present invention Since the environmental burden is small, it is preferably used as a raw material of a urethane resin which is consumed in a large amount, and is used as a large amount of urethane resin which is consumed, for example, a soft amine group. The ethyl acrylate foam, in which a urethane resin based on the polyol of the present invention is preferably used in a vehicle cushion, particularly a cushion for a vehicle, as a raw material for producing a polyurethane. Examples of the polyisocyanate to be used include an aromatic polyisocyanate, an aliphatic polyisocyanate, an alicyclic polyisocyanate, and a modified form of such a polyisocyanate. Examples of the aromatic polyisocyanate include tolylene diisocyanate and diphenyl group. Methane diisocyanate, polymethyl polyphenyl polyisocyanate, etc. Further, as the aliphatic polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, and an amine are mentioned. Oxydiisocyanate, tetramethylxylene diisocyanate, etc. Further, examples of the alicyclic polyisocyanate include isophorone diisocyanate. [Embodiment] [Embodiment] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the contents defined and explained below. [Number of hydroxyl groups of the initiator] The number of hydroxyl groups of the castor oil or castor oil condensate used as the initiator, -19-200904852 is obtained by measuring the hydroxyl value (mgKOH/g), and the hydroxyl value is based on JIS-K- The measured enthalpy of 1 5 5 7 is corrected by the acid value (mgKOH/g). Further, the polyol produced by the production method of the present invention is analyzed by gel permeation chromatography (GPC) to calculate a weight average molecular weight (Mw) / number average molecular weight (?η), but Mw and Μ are poly The molecular weight in terms of styrene. [Primary Rate of Hydroxyl Group of Polyol Produced] The ratio of the primary hydroxyl group in the total hydroxyl group of the polyol obtained by the production method of the present invention is measured by the H-NMR method. First, a CDC13 solution of a polyhydric alcohol is prepared, and trifluoroacetic anhydride is added, whereby the hydroxyl group of the polyol can be easily esterified with trifluoroacetate at room temperature. a hydrogen atom of a methine on a carbon to be esterified with trifluoroacetic acid (corresponding to a hydrogen atom bonded to a carbon atom of a secondary hydroxyl group) and a hydrogen atom of a methylene atom (a hydrogen atom corresponding to a carbon atom of a primary hydroxyl group) The peak shift of the peak to the low magnetic field side is attributed to the peak of the hydrogen atom and the methylene hydrogen atom esterified with trifluoroacetate via this chemical shift, and the peak area intensity is calculated. The ratio of the primary hydroxyl group in the total hydroxyl group (first-order rate) is calculated by summing the peak area intensity of the above-mentioned atomic hydrogen atom with the peak area intensity of the above-mentioned methylene hydrogen atom, and calculating the above-mentioned methylene hydrogen atom The proportion of the peak area. For example, when the castor oil or castor oil condensate of the initiator is subjected to ring-opening addition to ethylene oxide, the multiple peaks of the hydrogen atom of the hydrogen atom on the low magnetic field side are displaced by esterification of the total hydroxyl group with trifluoroacetic acid. Appears in 5.00~5.1 Oppm (tetramethyl sulfonium), in addition, the triplet peak of the methylene hydrogen atom is -20-200904852 and now 4·48~4.50ppm (tetramethyl fluorenyl quasi), by the area Intensity, the primary rate (%) of the hydroxyl group was calculated. [Biomass of Polyol Produced] The degree of homogeneity in the present invention is based on the amount of the heterocyclic compound which is a starter oil or a castor oil condensate and a ring-opening addition, and is castor oil or The mass % of the castor oil condensate is expressed. [Initiator] As a castor oil condensate, it is used for the neutralization treatment of Kokura Synthetic Industrial Co., Ltd. (hydroxyl number 2-8, alkalinity by hydrochloric acid neutralization titration of 27 7 ppm, hydroxyl value 66. lmgKOH/g) Neutralization of the residual alkali was carried out by adding a 5% sulfuric acid aqueous solution in an excess amount of KOH 10%, and dehydrating at 80 ° C for 20 hours under reduced pressure at 80 ° C. The condensate obtained after the neutralization treatment (water content (mass ratio) was 60 ppm) was used. Further, as the castor oil, Ito Oil Co., Ltd. Η·30 (hydroxyl group 2.7, hydroxyl group 162 KOH mg/g) was used, and the content was 80 ppm. [Heterocyclic compound] The following examples are made of ethylene oxide alone (hereinafter referred to as EO only), and the moisture content of EO is the total weight of the ramie compound used for the peak of KG. - After KOH conversion, after 2 hours of neutralization equivalent, the water-heterocyclic compound of the URAC-castor oil produced by castor oil is 5 ppm or less - 21 - 200904852 [Example 1] 5% of the castor oil condensate (condensation of KG-001) of the above-mentioned castor, and the third of the cationic polymerization catalyst (pentafluorobenzene) were placed in a 5 L reaction vessel of a stirring apparatus of 5 〇% of the inner diameter of the reactor. 60 mg of boron compound (TPFPB), and the temperature inside the reaction vessel was raised to 65 after nitrogen substitution in the reaction vessel. (: After 30 minutes, the addition of Ε Ε was started. Since EO was added and heat was generated at the same time, stirring was carried out while maintaining the temperature in the reaction vessel at 70 ° C by cooling water (220 rpm (220 rpm)) After adding 35 g of EO and adding EO, the reaction was carried out at 70 ° C for 60 minutes, and the unreacted ε 〇 was reduced as much as possible, and then degassed under reduced pressure for 1 hour to obtain a polyol A. The molecular weight distribution curve obtained by GPC of the produced castor oil condensate of the polyol A and the raw material is shown in Fig. 1. [Example 2] Except that the amount of the initiator was 452 g and the amount of EO added was 99 g. The polyol B was produced in the same manner as in Example 1, and the molecular weight distribution curve of the produced castor oil condensate of the polyol B and the raw material is shown in Fig. 2. [Example 3] In addition to the amount of the initiator It is 3 9 1 g, E 〇 is added in an amount of 8 μg, and diphenylmethyl (nonyl pentafluorophenyl) borate (TrTPFPB ) is used as the cation-catalyst of cation--22-200904852, and the rest is implemented. In the same manner as in Example 1, the polyol C was produced, and the produced polyol C and the raw material were produced. The molecular weight distribution curve of the castor oil condensate is shown in Fig. 3 ° [Example 4] Except that castor oil (URIC-H-30) 3 07g was used as a starter, 49 g of EO and 50 mg of TPFPB were added, Example 1 In the same manner, the molecular weight distribution curve of the castor oil produced by the polyol D' and the castor oil produced by the polyol D' is shown in Fig. 4. [Example 5] In addition to the use of castor oil (URIC-H-30) 250 g The polyol E was produced in the same manner as in Example ι except that 106 g of EO and 50 mg of TPFPB were added as a starter, and the molecular weight distribution curve of the produced polyol E and the castor oil of the raw material is shown in Fig. 5. A comparative example in which a cationic metal cyanide complex (DMC) catalyst or a ruthenium catalyst is substituted for a cationic polymerization catalyst is shown. [Comparative Example 1] An impeller is provided (the stirring blade diameter is 50% of the inner diameter of the reactor) In the 5 L reaction vessel of the stirring device, 300 g of the castor oil condensate (condensation product of KG-001) and the composite metal cyanide complex catalyst (based on the special opening 50 5 - 1 5 7 8 6) were charged. The description of the bulletin 'from ZnCl2 aqueous solution, κ3[c〇 ( CN) 6] Aqueous solution and tert-butyl alcohol, the ligand is -23-200904852 tert-butyl alcohol-based composite metal cyanide complex catalyst; below, referred to as DMC catalyst.) After 20 mg of the reaction vessel was purged with nitrogen, the temperature in the reaction vessel was raised to 120 ° C, 30 g of EO was added, and then stirred at 220 rpm, and the internal pressure began to decrease while heating for about 30 minutes (DMC catalyst) After activation for 30 minutes, 55 g of EO was added in small portions, and finally 85 g of EO was added. During this period, the temperature in the reaction vessel was maintained at 120 ° C, and EO ' EO was added while disturbing at 220 rpm. After the addition was completed, heating and stirring were carried out at 120 ° C for 60 minutes, and then degassing under reduced pressure for 30 minutes, and the molecular weight distribution curve of the castor oil condensate of the above-produced polyol F and the raw material was listed. Figure 6. [Comparative Example 2] In a 5 L reaction vessel equipped with a stirring device (an agitating blade diameter of 50% of the inner diameter of the reactor), 300 g of castor oil (URIC-H-30) and 20 mg of DMC catalyst were placed in a reaction vessel. After the nitrogen gas was replaced, the temperature in the reaction vessel was raised to 120 ° C, and 70 g of EO was added. Then, the mixture was stirred at 220 rPm, and the internal pressure began to decrease (activation of the DMC catalyst) at about 30 minutes. After stirring for 30 minutes, 80 g of ruthenium was added in small portions, and finally 15 〇g of Ε 0 was added. During this period, the temperature in the reaction vessel was maintained at 1 2 0 t while being carried out at 2 2 0 rp m. After stirring, the addition of Ε Ο 'E 0 was completed, and then heating and stirring was carried out for 60 minutes at 1 2 〇t, and then degassing under reduced pressure for 30 minutes, and the hydrazine of the polyol G and the raw material produced as described above. The molecular weight distribution curve of the sesame oil condensate, -24-200904852 is shown in Fig. 7. [Comparative Example 3] A molecular weight distribution curve of the produced hydrazine and the raw material castor oil was produced in the same manner as in Comparative Example 2 except that the amount of EO added after the activation of the DMC catalyst was 147 s. Listed in Figure 8. [Comparative Example 4] In a 5 L reaction vessel equipped with a stirring device (an agitating blade diameter of 50% of the inner diameter of the reactor), 650 g of castor oil (URIC-H-30) and a tablet having a purity of 95% as a catalyst were charged. Shape 1 <: 5.15 of the 〇}1, after the nitrogen substitution in the reaction vessel, the temperature in the reaction vessel was raised to 1 〇 ° C, and the pressure was reduced under reduced pressure for 2 hours, and then the internal pressure was 〇. 4 MPa with nitrogen gas. The EO was introduced and reacted therein. At this time, while maintaining the temperature in the reaction vessel at about 115 ° C, the mixture was stirred at 22 rpm, and finally 43 5 g of EO was reacted. After the reaction was completed, the reaction vessel was allowed to stand. The internal temperature was maintained at 115 ° C for 60 minutes under reduced pressure degassing. The molecular weight distribution curve of the castor oil as described above and the castor oil of the raw material is shown in Fig. 9 . The amounts of the initiator, the cationic polymerization catalyst, and the ethylene oxide used in the examples and the comparative examples are shown in Table 1, and the results of the analysis of the produced polyols are shown in Table 2. -25- 200904852 [Table 1] Starting agent starting dose (g) Cationic polymerization catalyst amount (mg) EO addition amount (g) EO addition amount (mol) / starting Qi! j OH (mol) Example I KG-001 (condensate) 495 TPFPB 60 35 1.6 2 KG-001 (condensate) 452 TPFPB 60 99 4.2 3 KG-001 preparation) 391 TrTPFPB 60 81 4.0 4 URIC- H-30 307 TPFPB 50 49 1.2 5 URIC- H-30 250 TPFPB 50 106 3.3 Comparative Example 1 KG-001 (condensate) 300 DMC 20 85 5.7 2 URIC- H-30 300 DMC 20 150 3.9 3 URIC- H-30 300 DMC 20 217 6.1 4 URIC- H-30 650 KOH 5450 435 5.3 -26- 200904852 [Table 2] Polyol GPC (Μη) GPC Mw/Mn produced First-order rate (%, Biomass (%) Example 1 Polyol A 2940 1.67 86 93.4 2 Polyol B 3650 1.60 97 82.0 3 Polyol C 3300 1.71 75 82.8 4 Polyol D 1480 1.04 53 86.2 5 Polyol E 1880 1.16 79 69.3 Comparative Example 1 Polyol F 3420 1.42 70 77.3 2 Polyol G 1770 1.40 28 66.7 3 Polyol Η 2160 1.47 37 58.0 4 Polyol I 1780 1.64 72 59.9 Using DMC catalyst as a catalyst to make castor oil condensate react with EO The produced polyol F (Comparative Example 1), as shown in Fig. 6, does not produce a low molecular weight by-product due to decomposition of the initiator, but the produced polyol F, the peak of the low molecular weight initiator As the size becomes smaller, the molecular weight distribution becomes larger, that is, the polyol F-based EO reacts unevenly with the initiator, so that the polyol F is added with a large amount of EO, and although the degree of biomass is low, the primary rate of the hydroxyl group is also low ( Further, in the polyol G (Comparative Example 2) produced by reacting castor oil with E 0 using a DMC catalyst, as shown in Fig. 7, the peak of the castor oil was hardly observed to the high molecular weight side. Moving, a part of the broad peak of the reaction between castor oil and Ε 见 is found on the high molecular weight side. In addition, a large amount of hydrazine is added, and although the degree of biomass is low, the primary rate of hydroxy group is also low (Table 2). Further, in the polyol Η (Comparative Example 3) in which more Ε 0 was reacted than the polyol G (Comparative Example 2), as shown in Fig. 8, almost no peak of castor oil was observed to move toward the high molecular weight side. A broad fraction of the reaction of a portion of castor oil with Ε0-27-200904852 is found on the high molecular weight side, which is greater than the peak of polyol G, as described above, adding more E0, albeit with lower biomass. The primary rate of hydroxyl groups was hardly improved (Table 2). The polyol I (Comparative Example 4) produced by reacting castor oil with EO using a KOH catalyst, as shown in Fig. 9, produces a low molecular weight by-product due to decomposition of the initiator, and further, compared with hydrazine Sesame oil, the molecular weight distribution on the high molecular weight side also changes, that is, the polyol I EO reacts unevenly with the initiator, and in addition, a large amount of EO is added, and although the degree of biomass is low, the primary rate of the hydroxyl group is also low ( Table 2 ). On the other hand, a polyol A (Example 1) and a polyol B (Example 2) produced by reacting a castor oil condensate with EO using a cationic polymerization catalyst tris(pentafluorophenyl)borane As shown in FIG. 1 and FIG. 2, low molecular weight by-products are not generated by decomposition of the initiator, and EO and castor oil condensate are uniformly reacted, so polyol A and polyol B, and polyol In the comparison of F (Comparative Example 1), only a small amount of EO was added, so that the degree of biomass was high and the degree of primary hydroxylation was high. As a result, the same was observed for the polyol C (Example 3) using trityl (nonyl pentafluorophenyl) borate as the cationic polymerization catalyst. As shown in Fig. 3, the polyol C was not used because of the initiator. The low molecular weight by-product caused by the decomposition is only added with a small amount of EO, and the degree of homogeneity is high and the degree of primary hydroxylation is high. Further, as shown in FIG. 4, a trivalent (pentafluorophenyl) boron compound was used as a cationic polymerization catalyst to produce a mixture of castor oil and EO: alcohol D (Example 4), and polyol G ( Comparative Example 2) and Polyol η (-28-200904852 Comparative Example 3) Comparison, EO was uniformly reacted, and no low molecular weight by-product was produced due to the initiation. Further, the molecular weight distribution was not added, and only a small amount of EO was added. Therefore, the quality of the product is high and the hydroxyl group rate is high. As a result, Example 5 was also about the same, as shown in Fig. 5, (Example 5) how much E 0 was unevenly observed with the peak of the high molecular weight side of the initiator, but the initiator was observed. Most of the peaks on the high molecular weight side, Ε Ο reacted evenly. As described above, in the method for producing a polyhydric alcohol of the present invention, a low molecular weight by-product is produced without decomposition of the agent, and E 0 can be reacted uniformly, whereby a primary acid having a high degree of bioavailability and having a hydroxyl group can be produced. [Industrial Applicability] The castor oil or the castor oil condensate of the present invention is used as a polyol to be produced and reacted with a polyisocyanate to produce various ethyl ester products. Further, the polyol of the present invention can be optionally reacted with a chain extender in opposition to isocyanate. The polyol ' of the present invention is suitably used as a functional oil agent for a grease, a metal compressor oil, a surfactant, an ink dispersion, and is also suitable as a polymer dispersion material containing polymer microparticles. Furthermore, the present invention cites the decomposition of the agent which is applied for on March 28, 2007, and the primary polyol 100 is moved to a portion of the amine which is prepared by a multi-starter having a high initial initiator ratio. At the time, the oil, the agent, etc. can be processed, and the contents of the specification, patent application scope, drawings and abstracts of the patent -29 -29 200904852 of the polyol are disclosed in The description of the invention. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A molecular weight distribution curve in gel permeation chromatography of a polyol hydrazine (Example 1). [Fig. 2] A molecular weight distribution curve in gel permeation chromatography of Polyol B (Example 2). [Fig. 3] A molecular weight distribution curve in gel permeation chromatography of Polyol C (Example 3). [Fig. 4] A molecular weight distribution curve in gel permeation chromatography of Polyol D (Example 4). [Fig. 5] A molecular weight distribution curve in gel permeation chromatography of Polyol E (Example 5). Fig. 6 is a graph showing the molecular weight distribution curve in the gel permeation chromatography of the polyol F (Comparative Example 1). Fig. 7 is a graph showing the molecular weight distribution curve in the gel permeation chromatography of the polyol G (Comparative Example 2). [Fig. 8] A molecular weight distribution curve in gel permeation chromatography of Polyol H (Comparative Example 3). [Fig. 9] Molecular weight distribution curve in gel permeation chromatography of polyol hydrazine (Comparative Example 4) ° -30-