TW390893B - Polyoxyalkylene polyols, polymer polyols, preparation of the same, and preparation of flexible polyurethane foams - Google Patents

Abstract

Propylene oxide is added to an active hydrogen compound in the presence of an alkali metal hydroxide catalyst in an amount of from 0.05 to 0.5 mole per mole of the active hydrogen compound at a reaction temperature of from 60 to 98 DEG C at a reaction pressure less than or equal to 4 kg/cm<2> to prepare a polyoxyalkylene polyol which has a hydroxyl value of from 10 to 35 mg KOH/g, a monol content less than or equal to 15 mol %, a Head-to-Tail bond selectivity greater than or equal to 96 percent, and low viscosity. A polymer polyol is prepared by polymerizing an ethylenically unsaturated monomer in the polyoxyalkylene polyol. A flexible polyurethane foam is prepared by reacting the polyoxyalkylene polyol or the polymer polyol with an organic polyisocyanate compound in the presence of a foaming agent, a catalyst, a surfactant, a crosslinking agent and other additives. The thus-obtained polyurethane foams have less closed cells and are more excellent in properties such as hardness, humid aged compression set and impact resiliency.

Description

A7 B7 五、發明説明（l) 〔產業上之利用領域〕 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 本發明係有關聚氧伸烷基多元醇、聚合物多元醇及軟 質聚胺甲酸酯發泡體之製造方法。詳言之，本發明係有翮 一種在鹼金屬氫氧化物觸媒之存在下，對於活性氳化合物 行環氧烷類（alkylene oxide)加成聚合所得之羥基價為10 〜35 mg KOH/g、一元醇最大含量為15莫耳％、導因於環 氧丙烷加成聚合之頭尾（Head-to-Tail)鍵结最低選擇率為 96%之聚氧伸烷基多元酵及其製造方法；有關一種將該聚 氧伸烷基多元醇與有機聚異氰酸酯化合物，在發泡劑、觸 媒、整泡劑、交聯劑及其他肋劑之存在下，令其反應，而 獲得耐濕熱耐久性獲得改良之軟質聚胺甲酸酯發泡體之製 造方法；有關一種在羥基價為10〜35ing KOH/g、一元醇最 大含畺為15莫耳％、導因於環氧丙烷加成聚合之頭尾 (Head-to-Tail)鍵結最低選擇率為96%之聚氧伸烷基多元 醇中，分散5重量S；重量3；以下的聚合物粒子而成之聚合物 多元醇，以及在該聚氧伸烷基多元醇中，分散30重量 上60重量％ Μ下之玻璃轉移溫度為90〜120C的聚合物粒 子而成之聚合物多元醇，Κ及該等聚合物多元酵之製造方 法；另，本發明又有關一種將含有一種Μ上之此等聚合物 多元醇的多元醇及有機聚異氰酸酯化合物，在發泡劑、觸 媒、整泡劑、交聯劑及其他助劑之存在下，令其反應之炊 質聚胺甲酸酿之製造方法。 〔習用技術之說明〕 按，用於聚胺甲酸酯原料等之聚氧伸烷基多元酵的製造 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -4 - A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 ( 2) 1 1 過 程 中 9 主 要 係 使 用 氫 氧 化 鉀 作 為 細 觸 媒 9 在 利 用 為 環 氧 焼 1 1 類 之 環 氧 丙 焼 之 加 成 而 高 分 子 量 化 時 因 副 反 應 之 故 9 會 1 1 生 成 — 元 醇 9 分 子 量 會 增 大 ， 同 時 其 生 成 量 也 會 增 大 f 此 請 先 1 等 事 實 業 已 為 人 所 熟 知 0 又 1 聚 氧 伸 院 基 多 元 酵 中 之 — 閱 讀 背 1 元 醇 含 量 高 之 場 合 I 在 與 有 機 聚 異 氰 酸 酯 化 合 物 行 胺 甲 酸 Sr 之 注 1 I 酯 化 反 應 時 其 交 聯 及 高 分 子 量 化 會 受 致 妨 礙 9 據 信 此 事 XS 1 1 1 會 導 致 軟 質 聚 胺 甲 酸 酯 發 泡 »18» 體 或 彈 性 體 之 機 械 物 性 低 落 〇 再 | 1 t- 1 於 使 用 氫 氧 化 鉀 觸 媒 之 對 於 活 性 氫 化 合 物 的 環 氧 丙 焼 之 本 頁 加 成 聚 合 中 根 據 習 用 技 術 羥 基 價 為 35 mg KOH/gM 下 的 1 1 高 分 子 量 聚 氧 伸 烷 基 多 元 酵 中 之 一 元 酵 含 量 » 係 超 過 15 其 1 | 耳 % 又 製 造 羥 基 價 在 28 mg KOH/gM 下 之 聚 氧 伸 烷 基 多 訂 元 醇 在 事 實 上 無 法 達 成 〇 1 為 了 解 決 上 逑 問 題 作 為 環 氧 烷 類 (例如環氧丙焼） 加 1 1 成 聚 合 之 觸 媒 1 曾 有 使 用 照 金 屬 Μ 外 之 觸 媒 &gt; 例 如 使 用 络 1 1 合 金 靥 氰 化 物 錯 趙 觸 媒 之 方 法 (USF 382950Ε 0 本 特 開 平 I 2- 115211 號 公 報 9 曰 本 特 開 平 3- -14812號公報） 經 業 者 提 案 1 I 〇 特 別 是 曰 本 特 開 平 3- 14812號中 ，曾將使用鹼金臛作為 1 I 比 較 例 9 強 調 鉻 合 金 屬 氰 化 物 錯 體 之 優 異 性 0 此 等 觸 媒 非 1 1 常 高 價 9 在 工 業 上 使 用 時 ) 經 濟 性 不 佳 9 又 9 作 為 烯 化 氧 1 1 9 將 環 氧 乙 院 加 成 聚 合 時 9 在 觸 媒 使 用 後 9 有 必 要 使 用 鹸 1 1 金 靥 氫 氧 化 物 或 其 烷 氧 化 物 等 再 度 聚 合 9 是 為 其 問 題 0 1 I 又 $ 在 將 聚 氧 伸 烷 基 多 元 醇 中 之 元 酵 含 量 降 低 時 9 聚 1 I 氧 伸 焼 基 多 元 酵 之 粘 度 有 上 昇 的 傾 向 9 而 當 作 為 觸 媒 使 用 1 [ I 絡 合 金 靥 氰 化 物 觸 媒 時 9 聚 氧 伸 惊 基 多 元 酵 之 粘 度 上 昇 尤 1 1 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐〉 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 ( 3) 1 1 I 為 顯 著 9 據 信 t 瑄 是 因 為 9 當 將 作 為 環 氧 烷 類 之 環 氧 丙 烷 1 1 | 加 成 聚 合 時 t 頭 尾 (H e a d- to -T a i 1) 鍵 结 選 擇 率 低 〇 當 多 元 /«—V 1 醇 之 粘 度 高 時 » 在 軟 質 聚 胺 甲 酸 酯 發 泡 體 製 造 之 際 9 在 機 請 先 1 1 1 械 發 泡 成 形 時 » 成 形 安 定 性 或 混 合 性 的 層 面 會 產 生 障 礙 9 讀 背 1 I 面 此 外 r 經 高 分 子 量 化 之 聚 氧 伸 烷 基 多 元 醇 的 用 途 層 面 9 也 之 注 1 1 會 受 到 限 制 〇 事 項 1 I 再 I I 將 —» 元 醇 含 量 高 之 聚 氧 伸 燒 基 多 元 醇 作 為 基 MSS 體 使 用 之 聚 填 寫 合 物 多 元 醇 可 預 見 的 是 9 同 樣 也 有 聚 胺 甲 酸 酯 發 泡 體 等 本 頁 '— 1 | 之 物 性 低 落 的 現 象 〇 1 1 為 了 解 決 Μ 上 之 問 題 f 作 為 環 氧 烷 類 (例如環氧丙烷）加 1 1 成 聚 合 時 之 觸 媒 9 業 界 曾 提 案 使 用 鹸 金 屬 &gt;λ 外 之 觸 媒 * 例 訂 I 如 使 用 絡 合 金 屬 氰 化 物 錯 體 觸 媒 之 方 法 (USP 3829505 9 曰 本 特 開 平 2- 115211 號 公 報 曰 本 特 開 平 3- 14812號公報） » 1 1 I 此 外 將 其 作 為 基 體 之 聚 合 物 多 元 醇 也 曾 有 開 示 〇 在 將 1 1 聚 氧 伸 烧 基 多 元 醇 中 之 一 元 醇 的 含 量 降 低 時 聚 氧 伸 烷 基 1 Ί 多 元 醇 之 粘 度 有 上 昇 的 傾 向 9 而 當 使 用 絡 合 金 屬 氰 化 物 錯 1 | 體 觸 媒 作 為 觸 媒 時 霣 聚 氧 伸 燒 基 多 元 醇 之 粘 度 上 昇 尤 為 顯 1 I 著 9 據 信 t 這 是 因 為 當 將 作 為 環 氧 烷 類 之 環 氧 丙 烷 加 成 聚 1 1 合 時 頭 尾(H e a d -1 C -Ί ' a i 1)鏈 結 選 擇 率 低 所 致 〇 是 Μ 9 據 1 1 信 9 在 此 一 聚 氧 伸 烷 基 多 元 酵 中 ， 將 乙 烯 性 不 飽 和 單 體 白 1 1 由 基 聚 合 所 得 之 聚 合 物 多 元 醇 9 其 粘 度 上 昇 也 是 顯 著 0 當 1 | 聚 合 物 多 元 酵 之 粘 度 高 時 9 在 軟 質 聚 胺 甲 酸 酷 發 泡 體 製 造 1 I 時 之 機 械 發 泡 成 形 之 際 9 成 形 安 定 性 或 混 合 性 的 層 面 會 產 1 1 I 生 障 礙 f 此 外 ， 經 高 分 子 量 化 之 聚 氧 伸 烷 基 多 元 醇 的 用 途 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標隼局員工消費合作社印製 A7 B7 五、發明説明（4) 層面，也會受到限制。 聚合物多元醇* 一般而言，其分敗安定性不佳，粘度高 。特別是聚合物湄度30% Μ上之場合，此一傾向會變得顯 著，因此，利用Κ上述絡合金屬氰化物錯體觸媒所獲得的 聚氧伸烷基多元醇•實質上不可能製造聚合物湄度高的聚 合物多元醇。 為了解決高濃度化時之分散性惡化、粘度上昇之問題， 使用鏈移動劑此舉，業已為人所知。使用烷基磺醇作為鏈 移動劑而獲得低粘度聚合物多元醇之方法，已由業者所提 案（美國發明專利第3953393號公報，日本特開平01 -221 403 號公報）。然而，利用此等方法所獲得之聚合物多元醇， 卻有臭氣之問題，此外，增大聚合物濃度時所產生之粘度 急劇上昇現象也難Κ抑制，因此，難Μ獲得實用之聚合物 多元醇。 此外，作為鏈移動劑，使用硫醇、酮、酵、醛、鹵化合 物、苯衍生物*特別是使用異丙醇之方法，曾為業界所提 案（日本特開昭58-210917號公報）。然而，根據此一方 法，在將高濃度之聚合物多元醇低粘度化之層面，並不夠 充份。 又，作為反應調節劑，使用嗎啉等之胺類的方法，也曾 由業界所提案（日本特開昭63-1 469 1 2號公報），由於係 使用特定之多元酵，因此與本發明不同。 軟質聚胺甲酸酯發泡體，由於具有適度之彈性，且衝擊 吸收性能優異，因此已廣泛地使用於寢具、家具、汽車之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)A7 B7 V. Description of the invention (l) [Application fields in the industry] Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) This invention is related to polyoxyalkylene polyols A method for producing a polymer polyol and a soft polyurethane foam. In detail, the present invention has a hydroxyl value of 10 to 35 mg KOH / g, which is obtained by addition polymerization of an alkylene oxide to an active ammonium compound in the presence of an alkali metal hydroxide catalyst. Polyoxyalkylene polyenzyme having a maximum content of 15 mol% of monohydric alcohol and a minimum selectivity of 96% due to the head-to-tail coupling of propylene oxide addition polymerization, and a method for producing the same ; Regarding a polyoxyalkylene polyol and an organic polyisocyanate compound, in the presence of a foaming agent, a catalyst, a foam stabilizer, a cross-linking agent, and other rib agents, they are allowed to react to obtain heat and humidity resistance Method for producing soft polyurethane foam with improved properties; related to a kind of hydroxyl valence of 10 ~ 35ing KOH / g, maximum alcohol content of monovalent alcohol of 15 mol%, due to propylene oxide addition polymerization A polymer polyol made of polymer particles having a minimum head-to-tail bond selectivity of 96% in a polyoxyalkylene polyol having 5 weight S; weight 3; and the following polymer particles, and In this polyoxyalkylene polyol, 30% by weight and 60% by weight of glass are dispersed. Polymer polyols obtained by shifting polymer particles at a temperature of 90 to 120C, and K and methods for producing the polymer polyenzymes; in addition, the present invention relates to a polymer polyol that will contain one of these polymer polyols. Polyol and organic polyisocyanate compound, a method for producing a cooking polyurethane resin for making them react in the presence of a foaming agent, a catalyst, a foam stabilizer, a cross-linking agent and other auxiliary agents. [Explanation of Conventional Technology] According to the production of polyoxyalkylene polyenzyme used for polyurethane raw materials, etc. This paper is in accordance with China National Standard (CNS) A4 specification (210X297 mm) -4-A7 B7 Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China. 5. Description of the invention (2) 1 1 During the process 9 is mainly the use of potassium hydroxide as a fine catalyst 9 During molecular quantification due to side reactions, 9 will be generated 1 1-the molecular weight of the alcohol 9 will increase, and its production will increase at the same time, so please first 1 and other facts are already well known 0 and 1 polyoxygenated Among the basic multi-enzyme enzymes—reading the occasions where the content of 1-valent alcohol is high I Note 1 to the urethane Sr with organic polyisocyanate compounds I The cross-linking and high molecular weight will be hindered during the esterification reaction 9 It is believed that this is the case XS 1 1 1 will cause soft polyurethane foaming »18» The mechanical and physical properties of the body are reduced. 〇Re | 1 t- 1 in the addition polymerization of propylene oxide for active hydrogen compounds using potassium hydroxide catalyst on this page. The hydroxyl value is 1 at 35 mg KOH / gM according to conventional technology. 1 The high-molecular-weight polyoxyalkylene polyenzyme contains one or more enzymes with a content of more than 15 and 1 | ear%, and the production of polyoxyalkylene polyvalent alcohols with a hydroxyl value of 28 mg KOH / gM cannot actually be achieved 〇1 In order to solve the above problem, as an alkylene oxide (such as propylene oxide) plus 1 1 polymerization catalyst 1 has been used as a catalyst other than metal M &gt; For example, the use of complex 1 1 alloy cyanide wrong Zhao's method of the catalyst (USF 382950E 0 JP-A-H11-115211 9 JP-A-HH-14812) Proposal 1 I 〇 In particular, JP-A-H 3-14812, Use alkaloids as 1 I comparison Example 9 Emphasizes the superiority of chromium metal cyanide complexes 0 These catalysts are not 1 1 Often high price 9 When used in industry) Poor economy 9 and 9 As alkylene oxide 1 1 9 In the polymerization, 9 it is necessary to use 9 after the catalyst is used. 1 1 gold, hydroxide or its alkoxide, etc. 9 is used for re-polymerization. 9 is its problem. When the content of elemental enzyme decreases, the viscosity of 9 poly 1 I polyoxenyl polyenzyme tends to increase. 9 When the 1 [I complex alloy cyanide catalyst is used as the catalyst, the viscosity of polyoxenyl polyenzyme increases. Special 1 1 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) 1 1 I is significant 9 It is believed that t 瑄It is because 9 when propylene oxide which is alkylene oxide is 1 1 | addition polymerization t Head-to-tail (H ea d-to -T ai 1) Low bonding selectivity. 〇 When multi-component / «— V 1 alcohol has high viscosity» During the manufacture of soft polyurethane foam 9 On-line please First 1 1 1 Mechanical foaming molding »There will be obstacles in forming stable or mixed layers 9 Read back 1 I side In addition r Use of polymerized polyoxyalkylene polyols Level 9 Also note 1 1 There will be restrictions. Matters 1 I and II will be-»polyoxyl-based polyhydric alcohols with high alcohol content as the poly-filler polyols used as the base MSS. It is foreseeable that 9 also has polyurethane foam. The physical properties of this page'— 1 | The phenomenon of low physical properties 〇 1 1 To solve the problem on M f As an alkylene oxide (such as propylene oxide) plus 1 1 Catalyst for polymerization 9 The industry has proposed the use of rhenium metal &gt; λ outside Catalysts * Example I If a complex metal cyanide complex catalyst is used (USP 3829505 9 Japanese Patent Application Publication No. 2-115211 Japanese Patent Application Publication No. 3--14812) »1 1 I In addition, it is used as The polymer polyol of the matrix has also been disclosed. When the content of a monohydric alcohol in the 1 1 polyoxyl-based polyol is reduced, the polyoxyalkylene 1 tends to increase the viscosity of the 9 polyol. Metal cyanide error 1 | When the catalyst is used as a catalyst, the viscosity increase of polyoxyalkylene-based polyols is particularly significant 1 I 9 It is believed that this is because when propylene oxide is added as an alkylene oxide Poly 1 1 He head-tail (H ead -1 C -Ί 'ai 1) caused by the low selectivity of the chain. 0 is M 9 According to 1 1 letter 9 In this polyoxyalkylene polyenzyme, ethylenic Unsaturated monomer white 1 1 Polymer polyol 9 It is significant 0 When 1 | Polymer polyenzyme has a high viscosity 9 When mechanical foaming is used in the production of soft polyurethane foam 1 I 9 Molding stability or mixing level will produce 1 1 I Health Obstacle f In addition, the use of high molecular weight polyoxyalkylene polyols 1 1 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumers' Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs A7 B7 5. Description of Invention (4) The level will also be restricted. Polymer polyols * In general, they have poor stability and high viscosity. Especially when the polymer is 30% Μ, this tendency becomes significant. Therefore, polyoxyalkylene polyols obtained by using the above-mentioned complex metal cyanide complex catalyst are virtually impossible. Manufacture of polymer polyols with a high polymer content. In order to solve the problems of deterioration in dispersibility and increase in viscosity when the concentration is increased, it is known to use a chain moving agent. A method for obtaining a low-viscosity polymer polyol using an alkyl sulfo alcohol as a chain shifting agent has been proposed by the industry (U.S. Patent No. 3953393, Japanese Patent Application Laid-Open No. 01-221 403). However, the polymer polyols obtained by these methods have the problem of odor. In addition, it is difficult to suppress the sudden increase in viscosity caused by increasing the polymer concentration. Therefore, it is difficult to obtain a practical polymer. Polyol. In addition, a method using a thiol, a ketone, a leaven, an aldehyde, a halogen compound, a benzene derivative *, and especially an isopropyl alcohol as a chain shifting agent has been proposed in the industry (Japanese Patent Application Laid-Open No. 58-210917). However, according to this method, it is not sufficient to reduce the viscosity of high-concentration polymer polyols. In addition, a method using an amine such as morpholine as a reaction regulator has also been proposed by the industry (Japanese Patent Application Laid-Open No. 63-1 469 1 2). Since it uses a specific polyenzyme, it is compatible with the present invention. different. Soft polyurethane foam, due to its moderate elasticity and excellent impact absorption, has been widely used in bedding, furniture, and automobiles. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297). Li) (Please read the notes on the back before filling in this page)

7 A7 ______B7_ 五、發明説明（5) 座墊、家具之緩衝材等等。軟質聚胺甲酸酷發泡物，通常 係由厚塊發泡或熱模發泡而製造。然而，此等發泡體缺乏 柔軟性，且彈性也低，因此，在供人坐於膠乳發泡體上時 ，並無舒適感，是為其缺點。為了改良此一缺點，高彈性 聚胺甲酸酯發泡體已由業界所開發。此一發泡體係藉由： 在聚氧伸烷基多元醇中，將丙烯腈、苯乙烯等之乙烯性不 飽和簞體聚合所得之聚合物多元醇，作為聚氧伸烷基多元 酵之一部份使用，使其與聚異氰酸酯反應.，在發泡終了後 *予Μ短時間放置於室溫〜ιοου等過程而製成。此一高 彈性聚胺甲酸酯發泡體，在供人坐於其上時，感觸非常良 好，因此已廣泛地使用於乘用車之媛衡材。 聚胺甲酸酯由於常用所乘用車之媛街材，因此其強靱性 ’亦即硬度及機械強度乃有必要，但是，習用物卻有酎濕 熱耐久性（通常Κ濕熱殘留應變值（Wet Set)表示）不佳 的問題。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 作為聚胺基甲酸酯發泡體之耐濕熱耐久性的改良手法， 可舉實例為日本特開昭63-7 5021號、特開平02-115211號 、特開平03-068620號、特開平03-0 1 48 12虢等等。然而， 如特開昭63-75021般之藉由併用特殊交聯劑，雖可將附濕 熱附久性作某種程度之改善，但是，當使用份數過多時’ 伸度、抗撕裂強度等之櫬械強度會降低，其耐濕熱耐久性 之改良，有其限度。又，上述特開平02-115211、特開平 03-068620、特開平03-0 1 48 1 2號等中，曾記載藉由使用總 不飽和度低之聚氧伸烷基多元醇，使得耐濕熱耐久性提高 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）. _ g - A7 B7 五、發明#明（6) 。此等聚氧伸烷基多元酵，如上述特許公報中所明確記載 ，係使用二乙基鉛、金屬撲啭、络合金屬氟化物錯體觸媒 等而製成。然而，根據發明人等之再次試驗*發現使用上 述絡合氰化物錯體觸媒等之聚氧伸烷基多元醇所製造的軟 質聚胺甲酸酯發泡性，無法獲得發明人等所期待之提高耐 濕熱耐久性的结果。 〔發明之解決課題〕 本發明之目的，係在提供一種對於活性氫化合物將環氧 烷類加成聚合予κ高分子量化時，其一元醇之含量亦低， 且頭尾（Head-to-Tail)鐽結選擇率高之聚氧伸烷基.多元醇 ，Μ及一種低粘度且分散安定性佳之聚合物多元醇，以及 其製造方法，此外，又提供一種利用此等多元醇所構成之 發泡時的獨立氣泡性低、硬度、濕熱時永久應變、反彈彈 性等之物性優異的軟質聚胺甲酸_發泡體之製造方法。 〔課題之解決手段〕 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 發明人等，為了達成上述目的，進行銳意之研討，終而 發現藉由將鹼金屬氫氧化物觸媒濃度、反應溫度、反應壓 力特定化，而製造特定之聚氧伸烷基多元醇，Κ及藉由使 用該聚氧伸烷基多元醇，在維持特定之聚合物濃度之下， 且聚合物澹度高之場合，將聚合物之玻璃轉移溫度維持於 特定之範圍，而達成上述目的。 具體言之，本發明之第一目的，係在提供一種聚氧伸烷 基多元醇之製造方法，其特激係在： 相對活性氫化合物1莫耳，在0.05〜0.5莫耳之鹼金羼氫 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） _ η _ A7 B7 五、發明説明（7) 氧化物觸媒的存在下，於反應溫度60〜98 °C、反應最大壓 力‘kg/cra2之條件下，將環氧丙烷加成聚合者。 本發明之第二目的，係在提供一種聚氧伸烷基多元醇， 其特激係在： 其羥基價係10〜35mg KOH/g，一元醇最大含量為15莫耳 %，且導因於環氧丙烷加成聚合之頭尾（Head-to Tail)鍵 結最低選擇率，為96%者。 本發明之第三目的，係在提供一種軟質聚胺甲酸酯發泡 體之製造方法*其特徵係在： 將羥基價為10〜35rag KOH/g，一元醇最大含量為15莫耳 %，且導因於環氧丙烷加成聚合之頭尾（Head-to-Tail)鐽 结最低選擇率為96%之聚氧伸烷基多元酵，與聚異氟酸酯 化合物，在觸媒、整泡劑、發，泡劑、交聯劑及其他肋劑之 存在下，令其反應者。 本發明之第四目的，係在提供一種聚合物多元醇，其特 徵係在： 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 0. 在羥基價為10〜35iQg KOH/g，一元醇最大含量為15莫耳 %，且導因於環氧丙烷加成聚合之頭尾（Head-to-Tail)鍵 结最低選擇率為96%之聚氧伸烷基多元醇中，分散5重量 %以上30重量％以下之聚合物粒子而成者。 本發明之第五目的，係在提供一種聚合物多元酵，其特 徵係在： 在羥基價為10〜35 mg KOH/s* —元醇最大含量為15其耳 %，且導因於環氧丙烷加成聚合之頭尾（Head-to-Taio)鍵 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ IQ- A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（ S) 1 1 結 最 低 選 擇 率 為 96% 之 聚 氧 伸 烧 基 多 元 醇 中 9 分 散 30 重 量 1 1 I % Μ 上 60 重 量 % &gt;λ 下 之 玻 璃 轉 移 溫 度 為 90 1 20 t：的 丨聚合 1 物 粒 子 而 成 者 0 請 先 1 Γ 閱 r 本 發 明 之 第 \ - 百 的 .&gt; 係 在 提 供 一 種 聚 合 物 多 元 醇 之 製 造 背 1 Ί， Λ | 方 法 9 其 特 徵 係 在 • « 之 1 注 價 醇 意 I 在 羥 基 為 10 35 mg KOH/g 9 一 元 最 大 含 量 為 15 莫 耳 事 1 項 1 % 9 且 導 因 於 環 氧 丙 烷 加 成 聚 合 之 頭 尾 (H e a d- to -Τ a i 1) 鐽 再 填 w 结 最 低 選 擇 率 為 96% 之 聚 氧 伸 烷 基 多 元 醇 中 f 進 行 乙 烯 性 本 頁 %- 1 不 飽 和 單 體 之 聚 合 者 〇 1 1 本 發 明 之 第 七 巨 的 9 係 在 提 供 一 種 聚 合 物 多 元 醇. 之 製 造 1 方 法 5 其 特 徵 係 在 ♦ • Γ 訂 在 羥 基 價 為 10 &lt;-v_« 35 mg KOH/g 9 一 元 醇 最 大 含 量 為 15 莫 耳 1 % t 且 導 因 於 ΤΒ* 環 氧 丙 烷 加 成 聚 合 之 頭 尾 (H e a d- to -Τ a i 1) 鐽 1 1 結 最 低 選 擇 率 為 96% 之 聚 氧 伸 燒 基 多 元 醇 中 f 在 鏈 移 動 劑 1 1 之 存 在 下 進 行 乙 烯 性 不 飽 和 單 體 之 聚 合 者 Ο t 線 本 發 明 之 第 八 巨 的 9 係 在 提 供 一 種 軟 質 聚 胺 甲 酸 酯 發 泡 1 I 體 之 製 造 方 法 9 其 特 徽 係 在 1 1 將 包 含 上 述 聚 合 物 多 元 醇 之 多 元 醇 與 有 機 聚 異 氰 酸 酯 化 1 1 合 物 9 在 發 泡 劑 觸 媒 整 泡 劑 交 聯 劑 及 其 他 助 劑 之 存 1 1 在 下 9 令 其 反 應 者 0 1 1 聚 氧 伸 烷 基 多 元 醇 之 製 造 方 法 1 I ·.·· 作 為 活 性 氫 化 合 物 % 其 可 舉 實 例 為 Μ 羥 基 数 為 2〜ί « 1 1 1 宜 為 3〜ί 丨之 多 價 醇 類 Λ 糖 類 脂 肪 族 胺 化 合 物 ·&gt; 醇 胺 類 1 1 多 元 胺 類 芳 香 族 胺 化 合 物 多 價 酚 化 合 物 Μ 及 渠 等 之 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） Μ Β7 經濟部中央標準局員工消費合作社印製 五、發明説明 ( 3) 1 i 化 合 物 為 起 始 材 料 之 分 子 量 為 250〜1000之聚氧伸烷基多 1 1 I 元 酵 等 等 0 可 舉 之 較 佳 例 為 ， 乙 二 醇 、 二 甘 酵 、 丙 —* 醇 | 雙 丙 二 醇 4- 丁 二 醇 丙 三 醇 ·&gt; 雙 甘 油 &gt; 己 烷 三 醇 Λ — 羥 請 先 1 I 閲 I &quot; 甲 基 丙 烷 季 戊 四 醇 山 梨 糖 醇 、 糊 精 、 蔗 糖 % 甲 基 苷 讀 背 | I (顶 e t h y 1 g 1 y c 0 X id e) &gt; 雙 酚 A、 雙酚F 二 羥 基 二 笨 基 醚 之 1 I 意 1 | 二 羥 基 聯 苯 *v 對 苯 二 酚 Λ 間 苯 二 酚 1 , 3, 5苯三齡、 萘二 事 項 1 | 醇 胺 基 酚 胺 基 萘 酚 酚 甲 醛 縮 合 物 9 甲 基 二 乙 醇 胺 再 填 C 乙 基 二 異 丙 醇 胺 f — 乙 醇 胺 9 二 乙 醇 胺 9 三 乙 醇 胺 9 乙 二 寫 本 頁 襞 1 胺 丙 二 胺 &gt; 己 二 胺 雙 ( 對 一 胺 基 環 己 基 ) 甲 烷 苯 胺 1 1 甲 苯 胺 甲 苯 二 胺 二 苯 基 甲 烧 二 胺 &gt; 萘 二 胺 等 之 胺 化 1 物 等 之 _. 種 或 兩 種 Μ 上 的 混 合 物 等 等 〇 1 訂 作 為 m 金 屬 氫 氧 化 物 9 其 可 擧 實 例 子 氫 氧 化 鉀 氫 氧 化 1 納 Λ 氫 氧 化 鋰 % 氫 氧 化 铷 氫 氧 化 鉋 等 等 其 中 特 別 好 的 1 1 是 具 有 90 重 量 % 上 之 純 度 含 有 由 氫 氧 化 鉋 ·&gt; 氫 氧 化 1 1 m 所 選 出 之 化 合 物 中 的 至 少 一 種 之 觸 媒 0 線 作 為 環 氧 燒 類 9 其 可 舉 實 例 為 9 除 了 環 氧 丙 烧 Μ 外 &gt; 又 1 I 併 用 選 白 環 氧 乙 烷 1， 2 -環氧丁烷 、2 ,5 — 環 氧 丁 烷 笨 ( 1 | 基 環 氧 乙 烧 9 以 及 其 他 之 碳 數 巨 為 3K上的環氧烷類之- 一 1 1 種 Μ 上 的 化 合 物 之 環 氧 烷 類 9 藉 由 環 氧 丙 烷 加 成 聚 合 而 得 1 1 之 氧 伸 丙 基 基 宜 含 7C &gt;重 量 % K 上 &gt; 最 好 含 有 8C )重 量 % Μ 上 1 | 使 用 0 1 I 對 於 Μ 上 之 活 性 氫 化 合 物 1 在 鹼 金 靥 氫 氧 化 物 觸 媒 之 存 1 1 I 在 下 9 將 環 氧 烷 類 加 成 聚 合 所 得 之 聚 氧 伸 烷 基 多 元 醇 9 其 1 1 羥 基 價 係 10〜 3 5 m ί (OH/i 5， 一 元 醇 最 大 含 虽 為 1! 5莫 耳 % 9 i 1 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明铳明（1〇) - 1 1 I 而 導 因 於 Tf°? 環 氧 丙 烷 加 成 聚 合 之 頭 尾 (H e a d- to -T a i 1) 鍵 结 最 1 1 1 低 選 擇 率 為 96% 9 是 為 其 特 徴 〇 當 羥 基 價 未 達 10 mg KOH/g 1' 請 1 I 時 9 聚 氧 伸 烷 基 多 元 醇 或 將 其 作 為 基 體 而 分 散 乙 烯 % 聚 合 先 物 粒 之 聚 合 物 多 元 醇 的 粘 度 會 變 得 過 高 9 致 在 實 閱 ik 背 面 1. 用 性 上 無 法 配 合 軟 質 聚 胺 甲 酸 酯 發 泡 體 之 用 途 9 又 9 藉 由 之 注 意 1 1 與 有 機 聚 異 氰 酸 酯 之 反 ate 懕 而 預 聚 合 物 時 也 是 9 由 於 高 粘 度 事 項 I 之 故 * 無 法 使 用 0 再 填 寫 ό 本 1 另 —· 方 面 9 根 據 此 種 低 羥 基 價 之 聚 氧 伸 烷 基 多 元 醇 9 頁 1 | 伴 隨 著 高 分 子 量化 f 一 元 醇 含 量 會 增 加 9 以 致 軟 質 聚 胺 甲 1 | 酸 酯 發 泡 體 之 濕 熱 時 的 壓 縮 永 久 trpp 懕 變 或 反 彈 彈 性 或 聚 胺 甲 1 1 I 酸 酯 彈 性 體 之 掷 機 械 物 性 降 低 t 因 此 9 一 元 醇 含 量 有 必 要 保 訂 持 於 15 莫 耳 % K 下 〇 又 當 羥 基 價 超 過 35 m g KOH/g時 $ 在 1 1 既 有 之 多 元 醇 中 t 也 存 有 一 元 醇 含 量 為 15 莫 耳 % 程 度 者 9 1 | 但 是 在 分 子 量 如 此 低 之 狀 況 下 » 並 未 有 軟 質 聚 胺 甲 酸 酯 1 | 發 泡 體 等 中 所 見 之 上 逑 特 性 的 優 良 化 現 象 〇 1 、，』 再 者 此 種 低 一 元 醇 含 量 之 聚 氧 伸 烷 基 多 元 醇 中 之 導 因 1 1 於 ττ» 環 氧 丙 烷 加 成 聚 合 之 頭 尾 (K e s d - • t C -T a ί 1) 鍵 結 選 擇 率 未 1 1 達 96¾ 時 伴 隨 該 頭 尾 (H e a d- t c &gt; -Ta i 1)鏈 結 選 擇 率 降 低 之 1 I 聚 氧 伸 烧 基 多 元 醇 的 粘 度 上 昇 現 象 會 變 得 顯 著 9 而 在 軟 質 1 1 | 聚 胺 甲 酸 酯 發 泡 體 成 形 時 或 藉 由 與 有 機 聚 異 氰 酸 酯 化 合 物 1 1 之 反 應 而 聚· 合 物 化 使 用 的 用 途 方 面 9 會 產 生 問 題 〇 經 上 述 1 1 方 式 構 造 控 制 之 高 分 子 量 聚 氧 伸 烷 基 多 元 醇 製 造 時 $ 有 必 1 1 要 選 擇 Μ 下 之 條 件 實 施 〇 亦 即 對 於 活 性 氫 化 合 物 作 環 氧 1 | 丙 院 加 成 聚 合 時 之 鹼 金 屬 氫 氧 化 物 觸 媒 濃 度 9 相 對 活 性 氫 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -13 - 經濟部中央標準局貝工消費合作社印製 A7 B7 __ 五、發明説明（ Π) 化合物1莫耳，宜為0.05〜0.5萁耳，特別好的是0.1〜0.3 莫耳之範圃。又，反應溫度宜為60〜98t!，特別好的是70 〜90 υ之範困。當相對活性氢化合物1莫耳之鹼金屬氫氧 化物觴媒濃度超邊0.5莫耳時，即使在反應溫度60〜98 t： 下進行環氧丙烷加成聚合時，一元酵含霣也有超過15莫耳 %之傾向，此外，頭尾（Head-to-Tail)鍵结選擇率也有未 達96%之場合，因此，此一範臑不佳。又，相對活性氫化 合物1莫耳之金觴氫氧化物觸媒湄度未達0.05莫耳時， 環氧丙烷加成聚合反懕速度會變慢，至羥基價10〜35 ng KOH/g為止，高分子董化困難。又，在_金靥氫氧化物觸 媒之存在下，對於活性氫化合物行環氣丙烷加成反應所得 之中間體聚合物中，追加驗金雇氫氧化物觸媒實施瓖氧丙 烷加成聚合之場合也是，在金靥Μ氧化物觸媒灌度之合 計S落於上述範圃内之條件下«腌。 在鐮金雇氳氧化物觸媒存在下，對於活性氫化合物實施 環氧丙烷加成聚合時之反應最大壓力宜為Akg/cnMAgOkPa )當反應壓力超過4Ιϊ8/(ϊιπΜ4 901ιΡ3)時，聚氧伸烷基多元酵 中之一元酵含量會增加，Μ致成為低羥基價時，會有超過 15莫耳％之傾向，因此不符所求。 對於活性簏化合物，在ϋ金廳氫氧化物觸媒的存在下， 將環氧丙烷Κ外之環氧烷類•例如將環氧乙烷、1,2—環 氧丁烷等單獨或是與環氧丙烷併用進行加成聚合時之反應 條件，可在上述反懕條件之範匾外，也可在上述範圍内。 在鐮金臞氫氧化物觸媒之存在下，對於活性氫化合物加 本紙張尺度適用中國國家標準（CNS &gt; Α4規格（210X297公釐） -14 _ (請先閲讀背面之注意事項再填寫本頁) 裝-- 1 .訂 I-----( 線— — 1 經濟部中央標準局員工消費合作社印製 A7 B7_______ 五、發明説明（12) 成聚合環氧烷類所得之粗製聚氧伸烷基多元酵中之觸媒， 係可藉利用鹽酸等之無機酸、磷酸、醋酸等之無機酸、二 氧化碳等之中和法，利用吸附劑之吸附除去法，利用水或 水/有機溶媒之水洗法*或是利用雔子交換樹脂之維子交 換法等等的方法除去，而獲得製為。 ※聚合物多元醇之製造方法 以下*玆就聚氧伸烷基多元酵進行說明。 使用之聚氧伸烷基多元醇，係羥基價10〜35Bg KOH/g， 一元酵最大含量為15莫耳％，導因於環氧丙烷加成聚合之 頭尾（Head-to-Tail)鍵结最低選擇率為96%之聚氧.伸烷基 多元醇，可藉上述方法獲得。可使用此一聚氧伸烷基多元 酵之一種或兩種以上的混合物。 當羥基價未達10mg KOH/ng時，聚氧伸烷基多元醇，或 是將其作為基體在其中分散乙烯基聚合物粒子而成的聚合 物多元酵之粘度會變得過高，無法在實際上Μ於軟質聚胺 甲酸酯發泡體之用途。另一方面，根據此種低羥基價之聚 氧伸烷基多元醇，伴随著高分子量化，一元醇含童會增加 ，且軟質聚胺甲酸酯發泡體之溻熱時的壓縮永久應變或反 彈彈性也會降低，因此，作為一元醇含量，有必要保持在 15莫耳％以下。又，當羥基價超過35ng KOH/g時，在既有 之多元醇中，亦存有一元醇含量為15莫耳％程度者，但是 ，如此般之分子量低的場合，軟質聚胺甲酸酯發泡體等之 上述特性的優良化_1„象，並未出現。 再者，此種元酵、含聚氣伸烷基多元酵之導因於 _ ..............- . 本紙張尺度適用中國國家標準（ CNS ) Α4規格（210X297公釐） —1 5 - (請先閲讀背面之注意事項再填寫本頁) 訂，------'银‘ 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明（13 環氧丙烷加成聚合之頭尾（Head-to-Tail)鍵结最低選擇率 未達9 6%時，伴隨著頭尾（1^3€1^〇-73〖1)鍵結率降低之聚 氧伸烷基多元酵的粘度上昇現象會變得顯著，Μ致在軟質 聚胺甲酸酯發泡體成形時，產生問題。 Μ下，茲就聚合物多元醇進行說明。 乙烯性不飽和單體，宜為至少具有可聚合之乙烯性不飽 和基1個Κ上之乙烯性不飽和單體，其可舉實例為：丙烯 腈、甲基丙烯腈、丙烯酸、丙烯酸苯酯、甲基丙烯酸甲酯 、無水甲基丙烯酸、丙烯酿胺、苯乙烯、甲基苯乙烯、苯 基苯乙烯、氯笨乙烯、丁二烯、1,4 -戊二烯、醋酸乙烯 酯等之一種或兩種Μ上的混合物。較好的是單獨之丙烯腈 ，或是丙烯腈與苯乙烯之混合物。 —_.—* ......— — I ； ./ ---------、、 兩烯腈/苯乙比率，Μ重量比計，宜為100/0〜10/ • 一二:^—---- 9 0。當聚合物濃度為30% Μ上時，宜為粘度上昇少之90/ 10〜30/70 ° 乙烯性不飽和窜體之使用量，相對聚氧伸烷基多元醇及 /〆〆. 該單體之全量，通常為(、5〜6 0重晕％，藉此，聚合物濃度 可維持於5〜60重量％。聚合物通常係Κ直徑0.1〜10« m 之微粒分散。 當聚合物濃度為5重量％以上30重量％以下時，可Μ習 用之製造法製造聚合物多元醇。此一場合之條件*可與使 用鏈移動劑之場合相同。當乙烯性不飽和單體只為丙烯腈 時，利用一般之熱分析所测定之玻璃轉移溫度不明確，因 此無法測定，但若為丙烯腈及苯乙烯時，聚合物之玻璃轉 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X29*7公釐） 16 (請先閲讀背面之注意事項再填寫本頁) 訂 A7 B7 五、發明説明（1 4 ) 移溫度成為105〜13〇υ。當聚合物濃度為30重量％以上60 重量％以下時，係使用鏈移動劑。 鏈移動劑通常為胺化合物。胺化合物，係由下列通式 (1)所示： R 17 A7 ______B7_ V. Description of the invention (5) Seat cushion, cushioning material for furniture, etc. Soft polyurethane foam is usually made from thick foam or hot foam. However, these foams lack flexibility and low elasticity. Therefore, they are not comfortable when sitting on a latex foam, which is a disadvantage. In order to improve this disadvantage, highly elastic polyurethane foams have been developed by the industry. This foaming system is used as a polymer polyol obtained by polymerizing acrylonitrile, styrene and other ethylenically unsaturated carcass in polyoxyalkylene polyol. Partially used to make it react with polyisocyanate. It is made after leaving the foam for a short time at room temperature ~ ιοου. This highly elastic polyurethane foam has a very good feeling when it is seated on a person, and therefore it has been widely used as a weight for passenger cars. Polyurethane is commonly used as the street material of passenger cars, so its toughness, that is, hardness and mechanical strength, is necessary. However, conventional materials have wet heat durability (usually KK wet heat residual strain value (Wet Set) means) poor problem. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). As an improved method of moisture and heat resistance of polyurethane foams, for example, Japanese Patent Application Laid-Open 63-7 5021, JP 02-115211, JP 03-068620, JP 03-0 1 48 12 虢 and so on. However, the use of special cross-linking agents, such as JP-A-63-75021, can improve the heat and humidity retention to a certain extent, but when the amount of use is too large, elongation and tear resistance The mechanical strength will be reduced, and the improvement of its humidity and heat resistance has its limits. Also, in the above-mentioned Japanese Patent Application Laid-Open Nos. 02-115211, 03-068620, 03-0 1 48 1 2 and the like, it has been described that the use of polyoxyalkylene polyols having a low total unsaturation makes them resistant to heat and humidity. Increased durability This paper is sized for China National Standard (CNS) A4 (210X 297 mm). _ G-A7 B7 V. Invention # 明 (6). These polyoxyalkylene polyenzymes are made using diethyl lead, metal thorium, complex metal fluoride complex catalyst, etc., as explicitly described in the aforementioned patent publication. However, according to a re-test by the inventors, it was found that the soft polyurethane foam produced by using the polyoxyalkylene polyol of the above complexed cyanide complex catalyst, etc., cannot be expected by the inventors. As a result of improving the resistance to humidity and heat. [Solutions to be Solved by the Invention] The object of the present invention is to provide an alkylene oxide for addition of an active hydrogen compound to a κ polymer, and the content of the monohydric alcohol is also low, and the head-to- Tail) Polyoxyalkylene. Polyols with a high selectivity to knots. Polyols, M and a low viscosity polymer polyol with good dispersion stability, and a method for producing the same. In addition, a polycondensate using these polyols A method for producing a soft polyurethane foam with low closed cells at the time of foaming, excellent hardness, permanent strain in damp heat, and rebound elasticity. [Solutions to solve the problem] Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The inventors, etc., conducted intensive research in order to achieve the above purpose, and eventually found that The metal hydroxide catalyst concentration, reaction temperature, and reaction pressure are specified to produce a specific polyoxyalkylene polyol, and by using the polyoxyalkylene polyol, the specific polymer concentration is maintained. In the case where the polymer has a high degree of viscosity, the glass transition temperature of the polymer is maintained in a specific range to achieve the above-mentioned purpose. Specifically, the first object of the present invention is to provide a method for producing a polyoxyalkylene polyol. The special excitation is: relative molybdenum compound 1 mole, 0.05 ~ 0.5 mole molybdenum The size of hydrogen paper is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) _ η _ A7 B7 V. Description of the invention (7) In the presence of an oxide catalyst, the reaction temperature is 60 ~ 98 ° C, the maximum reaction pressure Addition polymerization of propylene oxide under the conditions of 'kg / cra2. The second object of the present invention is to provide a polyoxyalkylene polyol, whose special excitation is: its hydroxyl valence is 10 ~ 35mg KOH / g, and the maximum content of the monohydric alcohol is 15 mol%, and it is caused by The lowest selectivity for head-to-tail bonding of propylene oxide addition polymerization is 96%. The third object of the present invention is to provide a method for manufacturing a soft polyurethane foam. It is characterized in that the hydroxyl value is 10 ~ 35rag KOH / g, and the maximum content of the monohydric alcohol is 15 mole%. And because of the propylene oxide addition polymerization of the head-to-tail (Head-to-Tail), the minimum selectivity of 96% of polyoxyalkylene polyenzyme, and polyisofluoroate compounds, Foaming agent, hair, foaming agent, cross-linking agent and other rib agents, make them react. The fourth object of the present invention is to provide a polymer polyol, which is characterized by: printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 0. The hydroxyl value is 10 ~ 35iQg KOH / g, polyoxyalkylene with a maximum monohydric alcohol content of 15 mol% and a minimum selectivity of 96% due to the head-to-tail coupling of propylene oxide addition polymerization Based on the polymer polyol, polymer particles of 5 to 30% by weight are dispersed. A fifth object of the present invention is to provide a polymer polyenzyme, which is characterized in that the hydroxyl value is 10 to 35 mg KOH / s *-the maximum content of the hydric alcohol is 15% of its ears, and it is caused by epoxy Head-to-Taio bond for propane addition polymerization This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) _ IQ- A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Explanation (S) The minimum selectivity of the 1 1 junction is 96% in the polyoxyl sintered polyol. 9 is dispersed 30% by weight 1 1 I% Μ is 60% by weight &gt; The glass transition temperature under λ is 90 1 20 t:丨 Polymerize 1 object particle and make 0 Please first 1 Γ rr The first \-hundredth of the present invention. &Gt; It is to provide a polymer polyol production back 1 Ί, Λ | Method 9 is characterized by • « No. 1 Indicated alcohol means I at a hydroxyl group of 10 35 mg KOH / g 9 The maximum element content is 15 moles 1 item 1% 9 and it is caused by the head and tail (H ea d-to -T ai 1) of propylene oxide addition polymerization. In the oxyalkylene polyol, f is a polymer of ethylenic page%-1 unsaturated monomer. 〇1 1 The seventh largest 9 of the present invention is to provide a polymer polyol. Manufacture 1 Method 5 Features ♦ • Γ is set at a hydroxyl value of 10 &lt; -v_ «35 mg KOH / g 9 The maximum monohydric alcohol content is 15 moles 1% t and is due to the head and tail of TB * propylene oxide addition polymerization (H ea d-to-Τ ai 1) 鐽 1 1 The minimum selectivity of the fluorinated polyoxyl-based polyol of 96% is f. Polymerization of ethylenically unsaturated monomers in the presence of the chain shifting agent 1 1 0 t The 9th line of the eighth giant of the present invention provides a soft polymer Method for producing formate foam 1 I body 9 The special emblem is at 1 1 Polyol containing the above polymer polyol and organic polyisocyanate 1 1 Compound 9 Cross-linking in foaming agent catalyst foam stabilizer Presence of agents and other auxiliaries 1 1 Under 9 Make its responders 0 1 1 Production method of polyoxyalkylene polyol 1 I ... As active hydrogen compound% As an example, the number of hydroxyl groups is 2 ~ ί «1 1 1 Polyvalent alcohols Λ sugar aliphatic amine compounds · &gt; alcohol amines 1 1 polyamines aromatic amine compounds polyvalent phenol compounds M and channels 1 1 paper Standards apply to Chinese National Standard (CNS) A4 specifications (210X297 mm) Μ B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) 1 i Compound is a starting material with a molecular weight of 250 ~ 1000 Polyalkylene 1 1 I Wait 0. For example, a preferred example is ethylene glycol, diglycol, propane- * alcohol | dipropylene glycol 4-butanediol glycerol · &gt; diglycerol &gt; hexanetriol Λ — hydroxyl first 1 I read I &quot; methylpropane pentaerythritol sorbitol, dextrin, sucrose% methylglycoside read back | I (topethy 1 g 1 yc 0 X id e) &gt; bisphenol A, bisphenol F dihydroxydi Benzyl ether 1 I means 1 | dihydroxybiphenyl * v hydroquinone Λ resorcinol 1, 3, 5 benzene tertiary, naphthalene matters 1 | alcohol aminophenol amino naphthol phenol formaldehyde condensate 9 Methyldiethanolamine refilled C Ethyl diisopropanolamine f — ethanolamine 9 diethanolamine 9 triethanolamine 9 ethylene disulfide This page 襞 1 amine propanediamine &gt; hexamethylenediamine bis (p-monoaminocyclohexyl) Methane aniline 1 1 Toluidine Toluenediamine diphenyl methylenediamine &gt; Amination of naphthalene diamine 1 _. Species or a mixture of two kinds of M, etc. 〇1 Ordered as m metal hydroxide 9 It can be exemplified by potassium hydroxide 1 Na Λ lithium hydroxide% rubidium hydroxide, etc. Among them, 1 1 is a catalyst having a purity of 90% by weight and containing at least one selected from the group consisting of hydroxide hydroxide 1 &gt; 1 m as an epoxy sintering agent 9 as an example. For 9 in addition to propylene oxide M &gt; another 1 I combined with the selection of white ethylene oxide 1,2-butylene oxide, 2, 5 — butylene oxide (1 | based on ethylene oxide 9 and other The carbon number is 3K of alkylene oxides-1 1 of the compounds of M on the alkylene oxides 9 is obtained by addition polymerization of propylene oxide 1 1 oxypropylene group preferably contains 7C &gt;% By weight K &gt; preferably contains 8C)% by weight Μ on 1 | use 0 1 I For active hydrogen compounds on M 1 in the presence of alkali metal hydroxide hydroxide catalyst 1 1 I below 9 Polyoxyalkylene polyol obtained by addition polymerization of alkylene oxides 9 its 1 1 hydroxyl valence 10 ~ 3 5 m ί (OH / i 5, although the maximum content of monohydric alcohol is 1! 5 mole% 9 i 1 This paper size applies to Chinese National Standard (CNS) Α4 size (210 × 297 mm) A7 B7 Central Standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives. 5. The invention of the invention (1〇)-1 1 I is due to Tf °? Head and tail (H ea d-to-T ai 1) of propylene oxide addition polymerization 1 1 Low selectivity of 96% 9 is its speciality. When the hydroxyl value is less than 10 mg KOH / g 1 'Please 1 I 9 Polyoxyalkylene polyol or use it as a matrix to disperse ethylene% Polymerization precursor particles The viscosity of the polymer polyol will become too high 9 to the back of the actual reading ik 1. Can not be used with soft polyurethane hair The use of foam 9 and 9 By the attention of 1 1 and organic polyisocyanate inverse ate 预 prepolymer is also 9 due to high viscosity matters I * can not be used 0 then fill in this 1 other-· aspect 9 basis Such a low hydroxyl valence polyoxyalkylene polyol 9 page 1 | With the increase in molecular weight f, the monohydric alcohol content will increase by 9 so that the soft polyurethane 1 | permanent trpp compression during the damp heat of the ester foam Or rebound elasticity or the mechanical properties of polyurethane 1 1 I ester elastomers are reduced. Therefore, it is necessary to keep the monohydric alcohol content at 15 mol% K. When the hydroxyl value exceeds 35 mg KOH / g In 1 1 existing polyhydric alcohols, t also has a monohydric alcohol content of 15 mol%. 9 1 | But under such low molecular weight conditions »there is no soft polyurethane 1 | foams, etc. Seen in Phenomenon of the improvement of the characteristics of the upper surface 〇1, 『Furthermore, the reason for this low monohydric polyoxyalkylene polyol is 1 1 at ττ» head and tail of propylene oxide addition polymerization (K esd- • t C -T a ί 1) When the bond selectivity is less than 1 1 up to 96¾, the head selectivity (H ea d- tc &gt; -Ta i 1) decreases with 1 I polyoxyalkylene based multiple The increase in the viscosity of alcohols will become significant. 9 It will occur in the use of polymerized compounds when forming soft 1 1 | polyurethane foams or by reacting with organic polyisocyanate compounds 1 1. 9 Question 〇 When the high molecular weight polyoxyalkylene polyol controlled by the above-mentioned 1 1 structure is manufactured, it is necessary to select 1 1 to implement the conditions under Μ. That is, epoxy 1 is used for active hydrogen compounds. Alkali metal hydroxide catalyst concentration at 9 relative activity 1 This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) -13-Printed by A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs __ 5. Description of the invention (Π) Compound 1 Moore, preferably 0.05 to 0.5 ears, particularly preferably 0.1 to 0.3 moles of Fanpu. In addition, the reaction temperature should be 60 ~ 98t !, particularly preferably 70 ~ 90 υ. When the relative concentration of the active metal compound is 1 mole of the alkali metal hydroxide, the concentration of the alkali metal hydroxide is 0.5 mole, and even at a reaction temperature of 60 to 98 t: when the propylene oxide addition polymerization is carried out, the monoenzyme contains more than 15 Mole% tends to occur, and in addition, there are occasions when the head-to-tail bond selection rate is less than 96%, so this range is not good. In addition, when the relative activity of 1 mol of gold osmium hydroxide catalyst is less than 0.05 mol, the reaction rate of propylene oxide addition polymerization will be slowed to a hydroxyl value of 10 to 35 ng KOH / g. , Polymer Donghua difficult. In addition, in the presence of gold catalyst, the intermediate polymer obtained by cyclopropane addition reaction of active hydrogen compounds was added with gold hydroxide catalyst to carry out oxopropane addition polymerization. The occasion is also that under the condition that the total S of the gold oxide catalyst catalyst fills S falls in the above-mentioned range, «pickled. In the presence of falconium oxide catalyst, the maximum reaction pressure for propylene oxide addition polymerization of active hydrogen compounds should be Akg / cnMAgOkPa.) When the reaction pressure exceeds 4 1ϊ8 / (ϊιπM4 901ιΡ3), polyoxyalkylene The content of the one-element enzyme in the base multi-element enzyme will increase. When M becomes a low hydroxyl value, it tends to exceed 15 mole%, so it is not desirable. For active rhenium compounds, in the presence of rhenium hydroxide catalyst, alkylene oxides other than propylene oxide K are used, for example, ethylene oxide, 1,2-butene oxide, etc. alone or with The reaction conditions when propylene oxide is used in combination for addition polymerization may be outside the range of the above-mentioned reaction conditions or within the above range. In the presence of Siammonium hydroxide catalyst, the Chinese national standard (CNS &gt; A4 specification (210X297 mm)) applies to the paper size of active hydrogen compounds plus this paper -14 _ (Please read the precautions on the back before filling in this Page) Packing-1. Order I ----- (Line--1 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7_______ V. Description of the invention (12) Crude polyoxyethylene stretched from polymerized alkylene oxides The catalyst in alkyl polyenzyme can be neutralized by the use of inorganic acids such as hydrochloric acid, inorganic acids such as phosphoric acid and acetic acid, carbon dioxide, etc., using the adsorption removal method of adsorbents, and using water or water / organic solvents. It is obtained by washing with water washing method * or dimensional exchange method using gardenia exchange resin, etc. ※ Polyol polyol production method is described below * Polyoxyalkylene polyenzyme is described below. Oxyalkylene polyols are hydroxyl groups with a valence of 10 ~ 35Bg KOH / g, and the maximum monovalent enzyme content is 15 mol%, which is due to the lowest choice of head-to-tail linkage for propylene oxide addition polymerization. Polyoxygen with a rate of 96%. Obtained by the above method. One or two or more mixtures of the polyoxyalkylene polyenzyme can be used. When the hydroxyl value is less than 10 mg KOH / ng, the polyoxyalkylene polyol can be used as a matrix. Among them, the viscosity of the polymer polyenzyme obtained by dispersing the vinyl polymer particles will become too high to be practically used for soft polyurethane foam. On the other hand, according to this low hydroxyl value As the polyoxyalkylene polyols increase in molecular weight, the content of monohydric alcohols will increase, and the compression set or rebound elasticity of soft polyurethane foams will decrease when heated, so as It is necessary to keep the monohydric alcohol content below 15 mol%. When the hydroxyl value exceeds 35 ng KOH / g, there is also a monohydric alcohol content of about 15 mol% in the existing polyols. However, In the case of such a low molecular weight, the improvement of the above characteristics of soft polyurethane foams, etc., has not appeared. Moreover, this kind of elementary fermentation, polyalkylene-containing polyenzyme, etc. Caused by _ ..............-. This paper is of suitable size China National Standard (CNS) Α4 specification (210X297 mm) —1 5-(Please read the precautions on the back before filling out this page) Order, --- 'Silver' Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation Α7 Β7 V. Description of the invention (13 The lowest selectivity of head-to-tail coupling for propylene oxide addition polymerization does not reach 9 6%, accompanied by head-to-tail (1 ^ 3 € 1 ^ 〇- 73 〖1） The viscosity increase of polyoxyalkylene polyenzyme with a reduced bonding rate will become significant, and it will cause problems when the soft polyurethane foam is formed. Under Μ, the polymer The polyol will be described. The ethylenically unsaturated monomer is preferably an ethylenically unsaturated monomer having at least 1 K of polymerizable ethylenically unsaturated group, and examples thereof are: acrylonitrile, methacrylonitrile, acrylic acid, phenyl acrylate , Methyl methacrylate, anhydrous methacrylic acid, acrylamine, styrene, methylstyrene, phenylstyrene, vinyl chloride, butadiene, 1,4-pentadiene, vinyl acetate, etc. One or two mixtures on M. Acrylonitrile alone or a mixture of acrylonitrile and styrene is preferred. —_.— * ......— — I; ./ --------- ,, dienenitrile / styrene ratio, M weight ratio, preferably 100/0 ~ 10 / • One or two: ^ —---- 9 0. When the polymer concentration is above 30% Μ, it should be 90/10 ~ 30/70 ° with less increase in viscosity. The amount of ethylenically unsaturated channel is relative to polyoxyalkylene polyol and / 〆〆. This single The total amount of the body is usually (, 5 to 60% halo%, whereby the polymer concentration can be maintained at 5 to 60% by weight. The polymer is usually dispersed as K particles having a diameter of 0.1 to 10 «m. When the polymer concentration When it is 5 wt% or more and 30 wt% or less, polymer polyols can be manufactured by conventional manufacturing methods. The conditions in this case * can be the same as those in the case of using a chain shifting agent. When the ethylenically unsaturated monomer is only acrylonitrile At this time, the glass transition temperature measured by general thermal analysis is not clear, so it cannot be measured, but if it is acrylonitrile and styrene, the glass paper size of the polymer applies the Chinese National Standard (CNS) Α4 specification (210X29 * 7mm) 16 (Please read the notes on the back before filling in this page) Order A7 B7 V. Description of the invention (1 4) The shift temperature becomes 105 ~ 13〇υ. When the polymer concentration is more than 30% by weight and 60% by weight In the following cases, a chain moving agent is used. To the amine compound, based by the following formula (1): R 1

I N- Rz (1)I N- Rz (1)

I R3 (式中，Ri、尺2及1?3代表氫，碳數目為1〜10之烷基 、碳數目為2〜10之羥烷基，彼此可為相同或不同，不同 時均為氫） 之胺化合物，或是由下列通式（2)所示·· R 1 - N X (2) |_1 經濟部中央標準局員工消費合作社印f (請先閎讀背面之注意事項再填寫本頁) (式中，Χ係代表氧、NR2，R1係代表碳數目為1〜10 之烷基、碳數目為2〜20之羥烷基，R 2係代表氫、碳數目 為1〜10之烷基、碳数目為2〜10之羥烷基） 之胺化合物 。其可舉具體實例為：三乙胺、三丙胺、三丁胺、Ν，Ν -二乙基乙酵胺、Ν-甲基碼啉、乙基碼啉等之胺類。 鏈移動劑之使用量，係因應由鏈移動劑所調節之聚合物 的玻璃轉移溫度而決定，使用的是可使玻璃轉移溫度調節 成90〜120t：，宜調節或95〜1151；之量的鏈移動劑。當玻 璃轉移溫度未達9010時，形成聚胺甲酸酯發泡體時之硬度 本紙張尺度適用中國國家標準（CNS ) Α4規格（210'乂297公釐） _ -I 7 _ 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明#明（15) 等的物性會低落；當玻璃轉移溫度超過120它時，無法獲 得目的之具有低粘度且分散安定性佳之聚合物多元醇。此 種賦與玻璃轉移溫度之鏈移動劑的量，係將聚合物之分子 量調節成30000〜140000之量，相對乙烯性不飽和單體100 重量份，係0. 5〜30重量份，宜為1〜20重量份。 作為觸媒，係使用習知之乙烯基聚合反應用觸媒。其可 舉實例為：過氧化氫、過氧化苯藤、過氧化乙醯、過氧化 特丁基、過氧化二特丁基等之過氧化物，偶氮二異丁腈般 之偶氮化合物，或是過硫酸鹽、過琥珀酸、二異丙基過氧 、二碳醆酯般之過氧化化合物。 相對聚氧伸烷基多元醇及乙烯性不飽和單體之合計重量 ，觸媒係添加0.01〜5重量％，宜添加0.1〜2.0重量％。 基於將聚合物粒子安定地分散之目的，可在分散安定化 劑之存在下進行聚合。作為此種分散安定化劑*其可擧實 例為：日本特公昭49-46 556號公報中所記載之含有碳—碳 不飽和鍵结之聚魅酯多元醇，末端具有丙烯基、甲基丙烯 基、烯丙基等之變性多元醇等。 有關聚合物多元醇之製造，係使用上述聚氧伸烷基多元 醇、乙烯性不飽和單體、鏈移動劑、觸媒，進行聚合反應。 聚合反應可為分批式或連續式。聚合溫度係因應觸媒之 種類決定，其係在觸媒之分解溫度Κ上，宜在6 0〜2 0 0 TC ，最好在90〜160¾下實施。又，聚合反應可在加壓系統 中實施，也可在常壓糸統中實施。 聚合反應終了後，可將所獲得之聚合物多元酵，原狀作 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- —..—一 I ------裝------r — 訂--------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7I R3 (where Ri, ruler 2 and 1 to 3 represent hydrogen, alkyl group having 1 to 10 carbon atoms, and hydroxyalkyl group having 2 to 10 carbon atoms, which may be the same or different from each other, and are all hydrogen at the same time ), Or an amine compound, as shown by the following general formula (2): · R 1-NX (2) | _1 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (Please read the notes on the back before filling out this page ) (In the formula, X represents oxygen, NR2, R1 represents an alkyl group having 1 to 10 carbon atoms, hydroxyalkyl group having 2 to 20 carbon atoms, and R 2 represents an alkyl group having hydrogen and 1 to 10 carbon atoms. Group, hydroxyalkyl group having 2 to 10 carbon atoms). Specific examples thereof include amines such as triethylamine, tripropylamine, tributylamine, N, N-diethylacetamidine, N-methyl codeline, ethyl codeline, and the like. The amount of chain shifting agent used is determined by the glass transition temperature of the polymer adjusted by the chain shifting agent. The amount of chain shifting agent used can be adjusted to 90 ~ 120t :, it should be adjusted or 95 ~ 1151; Chain moving agent. When the glass transition temperature does not reach 9010, the hardness of the polyurethane foam when forming this paper applies the Chinese National Standard (CNS) A4 specification (210 '乂 297 mm) _ -I 7 _ Central Standard of the Ministry of Economy A7, B7 printed by the Bureau ’s Consumer Cooperative, and the physical properties of invention # 明 (15) will be low; when the glass transition temperature exceeds 120, the intended polymer polyol with low viscosity and good dispersion stability cannot be obtained. The amount of such a chain shifting agent that imparts a glass transition temperature is an amount in which the molecular weight of the polymer is adjusted to 30,000 to 140,000, relative to 100 parts by weight of the ethylenically unsaturated monomer, 0.5 to 30 parts by weight, preferably as 1 to 20 parts by weight. As the catalyst, a conventional catalyst for vinyl polymerization reaction is used. Examples include: peroxides such as hydrogen peroxide, benzoyl peroxide, acetamidine peroxide, tert-butyl peroxide, di-tert-butyl peroxide, and azobisisobutyronitrile-like azo compounds, Or persulfate, persuccinic acid, diisopropylperoxy, dicarbamate-like peroxide compounds. Relative to the total weight of the polyoxyalkylene polyol and the ethylenically unsaturated monomer, the catalyst is added in an amount of 0.01 to 5% by weight, preferably 0.1 to 2.0% by weight. For the purpose of stably dispersing polymer particles, polymerization can be performed in the presence of a dispersing stabilizer. As such a dispersing stabilizer, for example, the polymetaester polyol containing a carbon-carbon unsaturated bond described in Japanese Patent Publication No. 49-46 556, has a propylene group and methacrylic acid at the end. Group, allyl and other modified polyols. The polymer polyol is produced by using the above-mentioned polyoxyalkylene polyol, an ethylenically unsaturated monomer, a chain shifting agent, and a catalyst to perform a polymerization reaction. The polymerization reaction can be batch or continuous. The polymerization temperature is determined according to the type of catalyst, and it is based on the decomposition temperature K of the catalyst, which is preferably implemented at 60 ~ 2 0 0 TC, and preferably at 90 ~ 160¾. The polymerization reaction may be carried out in a pressurized system or in a normal pressure system. After the polymerization reaction is over, the obtained polymer polyenzyme can be used as the original paper size as the standard of the Chinese National Standards (CNS) A4 (210X297 mm) -18- —..— 一 I ------ installation ------ r — Order -------- line (please read the notes on the back before filling this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7

五、發明説明（ IQ 為聚胺甲酸酯之原料使用，宜將未反應單體、觸媒之分解 生成物或鍵移動劑等，Μ減壓處理除去後使用。 ※聚胺甲酸酯發泡體之製造方法 作為聚氧伸烷基多元醇*可使用上述之聚氧伸烷基多元 酵。 作為聚合物多元醇，前述之聚合物多元酵，均可原狀適 當地使用。所諝之含有聚合物多元醇之多元醇，係指上述 聚合物多元酵，或是上述聚合物多元醇與其他聚氧伸烷基 多元醇之混合物，宜為粘度300 0c psM下者。有關其他之 聚氧伸烷基多元醇，並無特殊限制，可使用此一領域中迄 今為止所使用者。又，聚合物多元醇之製造中所使用的聚 氧伸烷基多元醇，也可因應必要使用。 本發明中所使用之有機聚異氰酸酿，其實例為：二異氰 酸2,4 -甲次苯酸、二異氟酸2 ,6 -甲次苯酯、該二異氟酸 酯之 80/20 重量比（80/20 — TPI)或 65/35 重量比（65/35 - TD I)之混合物、粗製二異氟酸甲次苯酯（粗製 TDI)、二異 氰酸4，4’ —二苯基甲烷酷（4,4’- MDI)、二異氟酸2,4”-二苯基甲烷酯（2,4’一 MDI)、二異氰酸2,2·—二苯基甲烷 酯（2,2’- MDI)、二異氰酸二苯基甲烷酯之異構物混合物 (MDI)、異氰酸多次甲基多苯酯（粗製 MDI)、二異氰酸 甲苯胺酯、二異氰酸二甲苯酯、二異氰酸戊酯、二異氰酸 異佛爾酮酯、二異氰酸二環己酯、Μ及此等異氰酸酯之碳 化二亞胺變性體、縮二脲變性體、二元體、三元體、或渠 等之混合物。有機多異氰酸酿化合物，係使用1種或混合 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） _ ·) 〇 _ (請先閲讀背面之注意事項再填寫本頁) .-----111·^------4------------ A7 B7 五、發明説明（Γ7) 兩種Μ上使用。 發泡劑係水、三氯一氟甲烷、二氯二氟甲烷、2,2—二 氯-1,1,1 -三氟乙烷、1,1-二氯-卜氟乙烷、二氯甲烷、三 氯三氟乙烷、二溴四氟乙烷、三氯乙烷、戊烷、正己烷等 之一種，或兩種Μ上之混合物；基於環境保護之觀點，宜 單獨使用水。相對聚氧伸烷基多元酵100重量份，發泡劑 之使用量為0.01〜10重量份。 作為本發明中所使用之胺甲酸酯化反應觸媒*係採用習 知者，並無特殊限制。例如，作為胺系觸媒，其可舉實例 為三乙胺、三丙胺、多異丙醇胺、三丁胺、三辛胺、六甲 基二甲胺、Ν-甲基碼啉，Ν-Ζ基碼啉、十八烷基碼啉、 —乙醇胺、二乙醇胺、三乙醇胺、Ν -甲基二乙醇胺、Ν,Η- 二甲基乙酵胺、二乙撐三胺、Ν,Ν，Ν’，Ν’-四甲基乙二胺、 11,^’，^’-四甲基丙二胺、队1«’，《'-四甲基丁二胺、付， Ν,Ν、Ν’-四甲基-1,3-丁二胺、Ν,Ν,Ν',Ν'-四甲基戊撐二 胺、二[2-(Ν,Ν-二甲胺）乙基]醚、Ν,Ν-二甲基芏胺、Η,Ν- 二甲基環己胺、Ν,Ν,Ν’，Ν’-五甲基二乙撐三胺、三乙撐二 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 胺、三乙撐二胺之甲酸及其他之鹽、伯及仲胺之胺基的伸 烷氧化物加成物、Ν,Ν -二烷基哌嗪類之氮雜環化合物、各 種之Ν,Ν’，Ν”-三烷基胺基烷基六氫三吖嗪類、日本特公昭 52-435 1 7號公報之/9 -胺基羰基觸媒，日本特公昭53-1 4278 公報之/9-胺基腈觸媒等等。又，作為有機金靨系觸媒，其 可擧賁例為醋酸錫、辛酸錫、油酸錫、月桂酸錫、二醋酸 二丁基錫鹽、二月桂酸二丁基錫鹽、二丁基錫二氯化物、 本紙張尺度適用中國國家標準（CNS〉Α4規格（210Χ297公釐） _ 0Λ _ 經濟部中央標準局員工消費合作社印製 A7 B7 一 —_ _丨_丨丨丨 ' 11 — &quot; _一 五、發明説明（18) 辛酸鉛、萘酸鉛、萘酸鎳、萘酸鈷等等。此等觸媒，可使 用一種，也可混合使用二種κ上，其使用量，相對具有活 性氫之化合物100重量份，係0.0001〜10.0重量份。 整泡劑係習用之有機矽界面活性劑，其可舉實例為：日 本伏尼卡公司製之 L-520、L-532、L-540、L-544、L-550 、L-3550、 L-5305' L-3600、 L-3601、 L-5305、 L-5307、 L-5309、 L-5710、 L-5720、 L-5740M、 L-6202等，東嫘矽 嗣公司製之 SH-190、SH-194、SH-200、SPX-253、PX-274C 、SF-2961、 SF-2962、 SPX-280A、 SPX-294A等，信越矽酮 公司製之F-114、F-121 &gt; F-122 ' F-220、F-230、F-258、 F-260B - F-317 &gt; F-341、F-601、F-606 - X-20-200 &gt; X-20 -201等，東芝矽酮公司製之TFA-4200、TFA-4202等，格魯 德舒密特公司製之B-4113、東嫘-道康寧公司製之SRX-253 、SRX-274C、SF-296 1、SF-2962等。此等整泡劑之使用量 ，相對具有活性氫化合物之化合物及聚異氰酸酯之總量 100重量份，係Ο.ί〜10重量份，宜為0.1〜5重量份。 交聯劑係乙二醇、丙二醇、二甘醇、三甘醇及1,3-丁二 醇等之單體多元酵，三乙醇胺、二乙醇胺等之烷醇胺類， 乙二胺、二伸乙基三胺、三伸乙基四胺等之脂肪族多胺， 亞甲正氛胺（methylene ortho chloro amine)4,4’-二苯 基甲烷二胺、苯胺、2,4·-甲次苯二胺、2,6'-甲次苯二胺 等之芳香族多胺，Μ及對於此等活性氫化合物加成聚合環 氧乙烷、環氧丙烷等所得之羥基價為200ing K0H/gM上的 化合物。此外，也可使用在氫醌、間苯二酚、苯胺等上加 本紙張尺度適用中國國家標準（CNS ) Μ規格（210 X 297公釐） _ 9 ] _ ---^------— (請先閲讀背面之注意事項再填寫本頁) 訂 &quot; A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 (19) 1 1 成 聚 合 環 氧 乙 烷 &gt; 環 氧 丙 烷 等 所 得 之 羥 基 價 20 0 m S KOH/g 1 1 | 以 上 的 化 合 物 〇 其 使 用 量 9 相 對 聚 氧 伸 燒 基 多 元 醇 1 00重 I 量 份 9 係 0. 1〜10重量份。 請 •1 聞 本 發 明 中 f 除 了 上述 Μ 外 9 邀 可 因 Bfyg 懕 必 要 使 用 安 定 劑 讀 背 i 面 I 填 充 劑 &gt; 著 色 劑 &gt; 難 燃 劑 等 0 之 注 1 1 意 1 I 聚 胺 甲 酸 酯 發 泡 體 之 製 造 方 法 » 係 如 下 所 述 Λ 首 先 * 將 拳 項 1 I 再 1 聚 氧 伸 烷 基 多 元 醇 發 泡 劑 觸 媒 、 整 泡 劑 &gt; 交 聯 劑 及 其 填 寫 § 他 之 肋 劑 一 定 量 混 合 i 製 作 樹 脂 液 0 而 後 決 定 有 機 聚 異 本 頁 1 | 氟 酸 酯 化 合 物 Λ 聚 氧 伸 烷 基 多 元 醇 及 交 聯 劑 之 使 用 量 9 使 1 1 得 有 m 聚 異 氟 酸 酯 化 合 物 中 之 NC0基與樹脂液中之活性氫 1 1 的 當 量 比 (NC0/H) 成為0 .7 1 . 4 0 而後 將樹脂液及有 訂 1M 聚 異 氰 酸 酯 化 合 物 t 調 整 於 一 定 溫 度 例 如 調 整 於 20 I 2 5°C 後 予 Μ 急 速 混 合 j 將 其 流 入 調 溫 於 定 溫 度 例 如 1 1 I 30 70 之 模 具 中 〇 在 反 應 混 合 液 於 模 具 内 發 泡 填 充 後 9 1 在 一 定 溫 度 $ 例 如 室 溫 1 0 0 °c之氛圍下 ，予Μ 1 &amp;置5 30 I 级 分 鐘 促 其 硬 化 後 將 發 泡 體 αΆ 脫 膜 獲 得 軟 質 聚 胺 甲 酸 酯 發 1 | 泡 體 〇 1 1 C 實 施 例 ] I 1 I Μ 下 9 茲 業 若 干 實 施 例 及 比 較 例 將 本 發 明 說 明 之 〇 1 1 羥 基 價 • • Μ 無 水 酞 酸 之 咁 啶 溶 液 酯 化 * 將 過 量 之 無 水 酞 1 1 酸 以 氫 氧 化 納 溶 液 滴 定 ( 根 據 J [S K 1 5 57 之 方 法 ) 〇 1 | 一 元 醇 含 量 • Κ 曰 本 分 光 公 司 製 高 速 液 體 層 析 (HPLC) 裝 1 I 置 9 利 用 胺 基 丙 基 化 學 鍵 結 型 二 氧 化 矽 系 分 雔 柱 9 tiAf 將 己 烷 1 1 | / 2- -丙 醇 之 混 合 液 作 為 溶 離 液 ( 流 速 1 m 1 / ’ in in)- 取 得 聚 氧 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（20) 伸烷基多元酵之溶液色層譜，K示差析射計，由檢知之峰 值面積強度，求取三元醇與一元醇之面積比。 又，由得自同一條件所獲得之分子量不同的三元酵與一 元醇的液體色層譜之溶出峰值時間所作成之較正曲線，求 取聚氧伸烷基多元醇中之三元醇與一元醇之分子量的值。 由與上述三元醇及一元醇有關之面積比及分子量之值，算 出一元醇含量（莫耳％)。 聚氧伸烷基多元醇中之二元酵成份幾乎未檢測出，因此 一元醇含量算出時，無視之。 頭尾鍵結選擇率：使用日本電子公司製之400 MHzC 13磁 核共振（NMR)裝置，Μ重三氯甲烷為溶媒，取得該聚氧伸 烷基之C 13 ΝΜϋ光譜，由頭尾鐽結之環氧丙烷基部份的甲 基之信號（16.9〜17.4 ppm.)及頭頭（head to head)鍵結之 環氧丙烷基部份的甲基之信號（17.7〜18.5ppm)的比求得。 A =頭頭鍵结之甲基的積分值 B =頭尾鍵結之申基的積分值 F= (0 . 5A/ (0 . 5A + B) ) X 100 又，各信號之歸屬，係MMacromolecules 19，1 337 - 1 343，（ 1 986)，F.C.Schi 1 1ing， A.E.Tonelli之報告文獻中所記載者作為參考。 粘度：使用旋轉式粘度計之25t：下的測定值（根據JIS K1557) 〇 聚合物濃度：在聚合物多元醇中添加甲醇，在予充份分 散之後，離心分離之，再測定不溶部份之重量而求得。但 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐) _ 0 , _ —.--------- (請先閲讀背面之注意事項再填寫本頁)V. Description of the invention (IQ is used as the raw material of polyurethane. It is advisable to use unreacted monomers, catalyst decomposition products, or bond shifting agents, etc., after removing it under reduced pressure. ※ Polyurethane hair As a method for producing a foam, the above-mentioned polyoxyalkylene polyalcohol can be used as the polyoxyalkylene polyalcohol. As the polymer polyol, the aforementioned polymer polyalcohol can be appropriately used as it is. Polyols of polymer polyols refer to the polymer polyols described above, or mixtures of the polymer polyols and other polyoxyalkylene polyols, preferably those having a viscosity of 300 0c psM or less. Related to other polyoxylates The alkyl polyol is not particularly limited, and it can be used so far in this field. In addition, the polyoxyalkylene polyol used in the production of polymer polyol can also be used as necessary. The present invention Examples of organic polyisocyanates used in the process are: 2,4-dibenzoic acid diisocyanate, 2,6-methylphenyl diisofluoride, and 80 / 20 weight ratio (80/20 — TPI) or 65/35 weight ratio (65/35-T DI) mixture, crude methylphenyl diisofluorate (crude TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), diisofluoric acid 2,4 " -Isomerization of diphenylmethane (2,4'-MDI), 2,2- · diphenylmethane diisocyanate (2,2'-MDI), isomerization of diphenylmethane diisocyanate Mixture (MDI), Methyl Polyphenyl Isocyanate (crude MDI), Toluidine diisocyanate, Xylyl diisocyanate, Amyl diisocyanate, Isophor diisocyanate Ketone esters, dicyclohexyl diisocyanate, M and carbodiimide denaturants, biuret denaturants, dimers, ternaries, or channels of these isocyanates. Organic polyisocyanates Sour brewing compounds, use 1 type or mixed. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) _ ·) 〇_ (Please read the precautions on the back before filling this page) .---- -111 · ^ ------ 4 ------------ A7 B7 V. Description of the invention (Γ7) It is used on two kinds of M. Foaming agent water, trichloromonofluoromethane, Dichlorodifluoromethane, 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-bufluoro Ethane, dichloromethane, trichlorotrifluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, n-hexane, etc., or a mixture of two kinds of M; from the viewpoint of environmental protection, Water is used alone. The amount of foaming agent is 0.01 to 10 parts by weight relative to 100 parts by weight of polyoxyalkylene polyenzyme. As the urethanation reaction catalyst used in the present invention *, a person skilled in the art There are no special restrictions. For example, as an amine catalyst, examples include triethylamine, tripropylamine, polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, and N-methylamine. Phenylline, N-Z-based phenylline, octadecyl phenylline, -ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, fluorenyl-dimethylacetamide, diethylenetriamine , N, N, N ', N'-tetramethylethylenediamine, 11, ^', ^ '-tetramethylpropanediamine, team 1 «'," '-tetramethylbutanediamine, Ν, Ν, Ν'-tetramethyl-1,3-butanediamine, Ν, Ν, Ν ', Ν'-tetramethylpentanediamine, bis [2- (Ν, Ν-dimethylamine) Ethyl] ether, Ν, Ν-dimethylamidamine, hydrazone, Ν-dimethylcyclohexylamine, Ν, Ν, Ν ', Ν'-Pentamethyldiethylenetriamine, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Formic acid and other salts, amine alkylene oxide adducts of primary and secondary amines, N, N-dialkylpiperazine nitrogen heterocyclic compounds, various N, N ', N "-trioxane Aminoamine alkyl hexahydrotriazine, Japanese Patent Publication No. 52-435 17 / 9-aminocarbonyl catalyst, Japanese Patent Publication No. 53-1 4278 / 9-aminonitrile catalyst, etc. Wait. Examples of organic gold catalysts include tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and the like. Paper size applies to Chinese national standard (CNS> A4 specification (210 × 297 mm) _ 0Λ _ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 I — — _ 丨 _ 丨 丨 丨 '11 — &quot; _ 一 五 、 发明Explanation (18) Lead octoate, lead naphthalate, nickel naphthalate, cobalt naphthalate, etc. These catalysts can be used alone or in combination of two kinds of kappa. Parts by weight are from 0.0001 to 10.0 parts by weight. Foam stabilizers are customary silicone surfactants, and examples are: L-520, L-532, L-540, and L-544 made by Vonika, Japan. , L-550, L-3550, L-5305 'L-3600, L-3601, L-5305, L-5307, L-5309, L-5710, L-5720, L-5740M, L-6202, etc., SH-190, SH-194, SH-200, SPX-253, PX-274C, SF-2961, SF-2962, SPX-280A, SPX-294A, etc. manufactured by Toyo Silicon Corporation, Shin-Etsu Silicon F-114, F-121 &gt; F-122 'F-220, F-230, F-258, F-260B-F-317 &gt; F-341, F-601, F-606- X-20-200 &gt; X-20-201, etc., TFA-4200, TFA-4202, etc. manufactured by Toshiba Silicone Corporation, B-4113 manufactured by Grudder Schmitt, SRX manufactured by Toyo-Dow Corning Corporation -253, SRX-274C, SF-296 1, SF-2962, etc. The amount of these foam stabilizers is 100 parts by weight relative to the total amount of compounds having active hydrogen compounds and polyisocyanates, and is 0. ί ~ 10 weight It is preferably 0.1 to 5 parts by weight. Crosslinking agents are monomeric polyenzymes such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 1,3-butanediol, and alkane such as triethanolamine and diethanolamine. Alcohol amines, aliphatic polyamines such as ethylenediamine, diethylene triamine, triethylene tetramine, etc., methylene ortho chloro amine 4,4'-diphenylmethanediamine Aromatic polyamines such as aniline, 2,4 · -m-phenylenediamine, 2,6'-m-phenylenediamine, etc., and M and ethylene oxide, propylene oxide for addition polymerization of these active hydrogen compounds The resulting compound has a hydroxyl value of 200 ing KOH / gM. In addition, Used for adding hydroquinone, resorcinol, aniline, etc. The paper size is applicable to Chinese National Standard (CNS) M specifications (210 X 297 mm) _ 9] _ --- ^ ------— (Please (Please read the notes on the back before filling this page) Order &quot; A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (19) 1 1 Polymerized ethylene oxide &gt; 1 ~ 10 重量 份。 Valence 20 0 m S KOH / g 1 1 | compound above 〇 The amount of use 9 relative to the polyoxyl-based sintered polyol 100 weight I amount of 9 parts 0.1 to 10 parts by weight. Please note: 1. In addition to the above M in the present invention, please use Bfyg. Stabilizers are necessary to read the back surface. I fillers &gt; colorants &gt; flame retardants etc. 0 note 1 1 meaning 1 I polyurethane Production method of ester foam »is as follows Λ first * the boxer 1 I then 1 polyoxyalkylene polyol blowing agent catalyst, foam stabilizer &gt; crosslinking agent and its filling § other A certain amount of the rib agent is mixed i to make a resin solution 0 and then the organic polyisocyanate is determined. Page 1 | The amount of fluoroester compound Λ polyoxyalkylene polyol and crosslinker 9 is used to make 1 1 have m polyisofluoroester. The equivalent ratio (NC0 / H) of the NC0 group in the compound to the active hydrogen 1 1 in the resin liquid becomes 0.7 1. 4 0, and then the resin liquid and the ordered 1M polyisocyanate compound t are adjusted to a certain temperature, for example, to 20 I 2 After 5 ° C, make rapid mixing j and pour it into a mold that is adjusted to a constant temperature, such as 1 1 I 30 70. After the reaction mixture is foamed and filled in the mold, 9 1 at a certain temperature, such as room temperature 1 0 At 0 ° C, give M 1 &amp; set it for 5 30 I minutes to promote its hardening and release the foam αΆ to obtain a soft polyurethane hair 1 | foam 〇1 1 C Example] I 1 Below Μ 9 Several examples and comparative examples of the present invention will esterify the OH value of the description of the present invention. • Μ anhydrous pyrimidine solution of pyridine is esterified. * Anhydrous phthalic acid 1 1 acid is titrated with a sodium hydroxide solution ( According to J (SK 1 5 57 method) 〇1 | Monohydric alcohol content • κ High-speed liquid chromatography (HPLC) device 1 manufactured by Benben Spectroscopy Co., Ltd. 9 Ion aminopropyl chemically bonded silica column 9 tiAf Hexane 1 1 | / 2- -propanol mixture For dissolving liquid (flow rate 1 m 1 / 'in in)-get polyoxygen 1 1 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by A7 B7, Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Explanation of the invention (20) The chromatogram of the solution of the alkylene polyenzyme, K is a differential spectrometer. From the detected peak area intensity, the area ratio of triol to monool is obtained. In addition, based on a comparison curve obtained from the dissolution peak time of the liquid chromatogram of a trivalent enzyme and a monohydric alcohol having different molecular weights obtained from the same condition, the triol and monohydric alcohol in the polyoxyalkylene polyol were obtained Value of molecular weight of alcohol. The monohydric alcohol content (mol%) was calculated from the values of the area ratio and molecular weight related to the above trihydric alcohols and monohydric alcohols. The binary enzyme component in polyoxyalkylene polyols is almost undetectable, so it is ignored when calculating the monoalcohol content. Head-to-tail bonding selectivity: A 400 MHz C 13 magnetic nuclear resonance (NMR) device manufactured by Japan Electronics Co., Ltd. was used, and M heavy chloroform was used as a solvent to obtain the C 13 NM 氧 spectrum of the polyoxyalkylene group. The ratio of the signal (16.9 to 17.4 ppm.) Of the methyl group of the propylene oxide portion and the signal (17.7 to 18.5 ppm) of the methyl group of the propylene oxide portion to be bonded to the head to head . A = integrated value of the methyl group of the head-to-head bond B = integrated value of the base of the head-to-tail bond F = (0.5 A / (0.5 A + B)) X 100 In addition, the assignment of each signal is MMacromolecules 19 , 1 337-1 343, (1 986), FCSchi 1 1ing, AETonelli's report documents for reference. Viscosity: Measured at 25t using a rotary viscometer (according to JIS K1557). ○ Polymer concentration: Add methanol to the polymer polyol, disperse it after centrifugation, and measure the insoluble portion. Determined by weight. But this paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) _ 0, _ —.--------- (Please read the precautions on the back before filling this page)

，1T i·^ A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 (21) 1 1 1 9 單 獨 使 用 丙烯 腈之聚 合 物 多 元 醇 9 係 利 用 元 素 分 析由 氮 1 1 I 部 份 求 得 〇 | Tg (玻璃轉移溫度）： 使 用 帕 金 路 瑪 公 司 製 之 DSC-7 ， 請 先 ] Μ 在 氮 氛 圍 下 於昇 溫速度 20K/ n i η之條件下利用熱分析求得。 讀 背 1 I 聚 氧 伸 烷 基多 元醇之 評 估 之 1 I 意 1 1 1 . 聚 氧 伸 烷 基多 元酵之 製 造 事 瑁 1 I 再 1 實 施 例 1 填 寫 多 元 醇 A : 對於丙三醇1 莫 耳 &gt; 添 加 0 . 13 莫 耳 之 氫 氧化 m 本 頁 V_✓ 1 1 9 在 100C下脫水6小時 後 * 將 環 氧 丙 烷 在 反 ttfg 懕 溫 度 9 5 t： 1 1 反 rrttx 懕 最 大 壓力 3,5kg/ cm2 (440kPa )之條件下加成.聚合， 1 獲 得 羥 基 價 3 3 m g _/g之 聚 氧 伸 丙 基 多 元 醇 〇 其 次 ，將 為 1 訂 該 聚 氧 伸 丙 基多 元醇之 15 重 量 % 的 Ttm 環 氧 乙 烷 在 100 t：下加 I 成 之 9 獲 得 羥基 價 2 8 m g KOH/g之 聚 氧 伸 烷 基 多 元 醇 。其 粘 1 1 1 度 為 1140 C P s/2 5t：。， _ 1 從 與 上 述 三元 醇及一 元 醇 有 關 之 面 積 比 及 分 子 量 之值 f 1 線 算 出 一 元 醇 含量 (奠耳％ ) 為 13 .0 莫 耳 % 〇 又 9 由 於 聚氧 伸 1 | 燒 基 多 元 醇 中之 二醇成 份 幾 乎 未 檢 測 出 9 因 此 —· 元 醇含 量 1 I 算 出 時 無 視 之0 Η-T(頭 尾 )鍵结選擇率為96. 7莫耳％。结 1 1 果 係 示 於 表 1中 〇 1 1 實 施 例 2 1 1 多 元 醇 B :對j 玲丙三酵] 莫 耳 9 添 加 0 42 莫 耳 之 氫 氧化 絶 1 1 ， 在 1 0 0 1C下脫水6小時 後 9 將 環 氧 丙 烧 在 反 應 溫 度 65 t： 1 1 I 反 應 最 大 壓 力2 0 k g / c I if (30 Ok Pa)之條件下加成聚合之 9 1 1 1 獲 得 羥 基 價 5 0 mi ;ΚΟΗ/g之 聚 氧 伸 丙 基 多 元 酵 〇 而 後 ，又 將 1 1 -24 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標隼局員工消費合作社印製 A7 B7__ 五、發明説明（22) 環氧丙烷在反應溫度75TC、反應最大壓力3kg/cnf (4 0 0kPa&gt; 之條件下加成聚合之，獲得羥基價28mg K〇H/g之聚氧伸丙 基多元酵。依與實施例1相同之方法所獲得之一元酵含量 為11.9莫耳％，粘度'為1250〇93/25&lt;^，卜1'鍵结選擇率為 96.2莫耳％。结果係示於表1中。 實施例3 多元醇C:對於丙三醇1莫耳，添加0.2 3莫耳之氫氧化铯 ，在10 0 Ό下脫水6小時後，將環氧丙烷在反應溫度80¾、 反應最大壓力3.5kg/cnf(4 40kPa)之條件下加成聚合i， 獲得羥基價28mg K〇H/g之聚氧伸丙基多元醇。其次，將為 該聚氧伸丙基多元醇之15重量％的環氧乙烷’在100Ό下 加成之，獲得羥基價24mg ΚΟΗ/g之聚氧伸烷基多元酵。依 與實施例1相同之方法所獲得之一元酵含量為8.0萁耳％， 粘度為1 650〇93/25&lt;〇,*11-1'鐽結選擇率為96.3莫耳％。结 果係示於表1中。 實施例4 多元醇D:對於丙三酵1莫耳，添加0.23莫耳之氫氧化鉀 ，在100°C下脫水6小時後，將環氧丙烷在反應溫度70t：、 反應最大壓力S.Skg/cm2 (440kPa)之條件下加成聚合之， 獲得羥基價33Bg KOH/g之聚氧伸丙基多元酵。其次，將為 該聚氧伸丙基多元酵之15重量％之環氧乙烷，在100¾之 條件下加成之，獲得羥基價2 9mg Κ0Η“之聚氧伸烷基多元 酵。依與實胞例1相同之方法所獲得之一元醇含量為11.9 莫耳％，粘度為1100〇?3/25&lt;〇，11-1'鍵结選擇率為96.5莫 本紙張尺度適用中國國家標準（CNS ) M規格（210x297公釐） _ 25 - (請先閱讀背面之注意事項再填寫本頁) ^------- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（23) 耳％。结果係示於表1中。 實施例5 多元醇E:對於羥基價450fflg KOH/g之季戊四酵的環氧丙 垸加成物1莫耳，添加0.23莫耳之氫氧化鉋，在100°C下脫 水6小時後，將環氧丙烷在反應溫度、反應最大壓力 3.5kg/cnf(440kPa)之條件下加成聚合之，獲得羥基價 50mg KOH/g之聚氧伸丙基多元醇。而後，又將環氧丙烷在 反應溫度9(TC、反應最大壓力hSkg/ctfUAOkPa)之條件 下加成聚合之，獲得羥基價29ing KOH/g之聚氧伸丙基多元 醇。其次，又將為該聚氧伸丙基多元醇之15重量％之環氧 乙烷，在loot：下加成之，獲得羥基價25ms KOH/g之聚氣 伸垸基多元醇。 實施例6 多元醇F:對於丙三醇1莫耳，添加〇·13莫耳之氫氧化絶 ，在100¾下脫水6小時後，將環氧丙烷在反應溫度60 °c、 反應最大壓力2.0ύ/(^ (3〇〇kPa)之條件下加成聚合之’ 獲得羥基價50mg KOH/g之聚氧伸丙基多元醇。而後’又將 環氧丙烷在反應溫度60C、反應最大壓力2.0kg/ctf( 300kPa)之條件下加成聚合之，獲得羥基價KOH/g之 聚氧伸丙基多元醇。依與實施例1相同之方法所獲得之— 元醇含量為14.6莫耳％，粘度為23〇〇〇03/25&lt;〇，11-1&lt;鍵結 選擇率為97.0其耳％。結果係示於表1中。 實施例7 多元酵G:對於丙三酵1莫耳，添加0.23奠耳之氫氧化铯 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -26- (請先閲讀背面之注意事項再填寫本頁) - ..線· 經.濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（24) 及0.10莫耳之氫氧化魏I，在loot：下脫水6小時後，將環氧 丙烷在反應溫度8〇υ、反應最大壓力2.5kg/cnf (350kPa) 之條件下加成聚合之，獲得羥基價50mg KOH/g之聚氧伸丙 基多元醇。而後，又將環氧丙烷在反應溫度80 t：、反應最 大壓力2.5kg/ci#(350kPa)之條件下加成聚合之，獲得羥 基價33mg KOH/g之聚氧伸丙基多元醇。依與實施例1相同 之方法所獲得之一元醇含量為10.5莫耳％，粘度為 95〇(^3/251〇，}1-1'鍵结選擇率為96.3莫耳％。结果係示於 表2中。 實施例8 多元醇H:對於丙三醇1莫耳，添加0.23莫耳之氫氧化筢 ，在100 °C下脫水6小時後，將環氧丙烷在反應溫度80 °C、 反應最大壓力S.Skg/cra2 (440kPa)之條件下加成聚合之， 獲得羥基價33 mg KOH/s之聚氧伸丙基多元醇。其次，將為 該聚氧伸丙基多元醇之15重量％之環氧乙烷，在100¾下 加成之，獲得羥基價28 mg ΚΟΗ/g之聚氧伸烷基多元醇。依 與實施例1相同之方法所獲得之一元醇含量為7.2奠耳％ * 粘度為1 290〇?3/25°(0，[1-1'鐽结選擇率為96.4莫耳％。结 果係示於表2中。 實施例9 多元酵I:對於丙三醇1莫耳，添加0.2 3莫耳之氫氧化筢 ，在100 °C下脫水6小時後，將環氧丙烷在反應溫度80t：、 反應最大壓力(440kPa)之條件下加成聚合之， 獲得羥基價25mg ΚΟΗ/g之聚氧伸丙基多元醇。其次，將為 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） .〇7 _ (請先閲讀背面之注意事項再填寫本頁) 訂 .丨線 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（25) 該聚氧伸丙基多元醇之15重量％之環氧乙烷，在100 °C下 加成之，獲得羥基價21mg KOH/g之聚氧伸烷基多元醇。依 與實施例1相同之方法所獲得之一元醇含量為10.5莫耳％ ，粘度為1950cps/25 1C，Η-T,鍵结選擇率為97:0莫耳％。 结果係示於表2中。 實施例1 0 多元酵J:對於丙三醇1莫耳，添加0.23莫耳之氫氧化筢 ，在1 0 0 °C下脫水6小時後，將環氧丙烷在反應溫度8 0 °C、 反應最大壓力S.Skg/cin2 (440kPa)之條件下加成聚合之， 獲得羥基價20mg KOH/g之聚氧伸丙基多元醇。其次，將為 該聚氧伸丙基多元醇之15重畺％之環氧乙烷，在1〇〇υ下 加成之，獲得羥基價17ng KOH/g之聚氧伸烷基多元酵。依 與實施例1相同之方法所獲得之一元醇含量為14. 0莫耳％ ，粘度為2380〇?5/25°(：，{1-1]'鍵結選擇率為97.2莫耳％。 結果係示於表2中。 實施例11 多元醇K:對於季戊四醇1莫耳，添加0.23莫耳之氫氧化 筢，在100 °C下脫水6小時後，將環氧丙烷在反應溫度80t： 、反應最大壓力S.Skg/cra2 (440kPa)之條件下加成聚合之 ，獲得羥基價33rag ΚΟΗ/g之聚氧伸丙基多元酵。其次*將 為該聚氧伸丙基多元醇之15重量％之環氧乙烷，在l〇〇t： 下加成之，獲得羥基價2 8mg K0H/g之聚氧伸烷基多元醇。 依與實胞例1相同之方法所獲得之一元醇含量為9.5其耳％ *粘度為142(^口3/25&lt;0，11-1'鐽結選擇率為9 6.5莫耳％。 (請先閱讀背面之注意事項再_舄本頁)， 1T i · ^ A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) 1 1 1 9 Polymer polyols using acrylonitrile alone 9 The elemental analysis is performed by nitrogen 1 1 I 〇 | Tg (glass transition temperature): DSC-7 manufactured by Parkin Luma is used, please first] Μ Calculated by thermal analysis under a nitrogen atmosphere at a temperature rising rate of 20K / ni η. Read back 1 I Evaluation of Polyoxyalkylene Polyols 1 I Meaning 1 1 1. Production of Polyoxyalkylene Polyols 1 I Re 1 Example 1 Fill in Polyol A: For Glycerol 1 Mo Ear &gt; Add 0. 13 Moore's Hydroxide m V_✓ 1 1 9 After dehydration at 100C for 6 hours * Propylene oxide at reverse ttfg 懕 temperature 9 5 t: 1 1 reverse rrttx 懕 maximum pressure 3, Addition under the conditions of 5kg / cm2 (440kPa). Polymerization, 1 to obtain a polyoxypropylene polyol with a hydroxyl value of 3 3 mg / g. Second, it will be 1 order of 15 weight of the polyoxypropylene polyol. % Of Ttm ethylene oxide was added at 100 t: 9% to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOH / g. Its stickiness is 1140 C P s / 2 5t :. , _ 1 Calculate the monohydric alcohol content (mole%) from the line ratio and molecular weight value f 1 related to the above triols and monohydric alcohols to 13.0 mole% 〇 and 9 because of polyoxyl 1 | 7mol%. The diol component in the polyol was hardly detected. Therefore, the alcohol content of 1-I was disregarded when calculating the 0Η-T (head-to-tail) bond selectivity rate of 96.7 mole%. Results 1 1 The results are shown in Table 1. 0 1 1 Example 2 1 1 Polyol B: To j-Mingeranase] Moore 9 Add 0 42 Moore's Hydroxide 1 1 at 1 0 0 1C After 6 hours of dehydration, 9 propylene oxide was burned at a reaction temperature of 65 t: 1 1 I maximum reaction pressure 20 kg / c I if (30 Ok Pa) addition polymerization of 9 1 1 1 to obtain a hydroxyl value of 5 0 mi; ΚΟΗ / g of polyoxypropylene propionase, and then 1 1 -24-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Employees' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Preparation of A7 B7__ V. Description of the invention (22) Propylene oxide was subjected to addition polymerization under the conditions of a reaction temperature of 75 TC and a maximum reaction pressure of 3 kg / cnf (400 kPa &gt;) to obtain a polyoxygen stretching with a hydroxyl value of 28 mg K0H / g. Polypropylenzyme. The content of the monoenzyme obtained in the same manner as in Example 1 was 11.9 mole%, the viscosity was '12500093/25 &lt; ^, and the bond selectivity of Bu1' was 96.2 mole%. Results The system is shown in Table 1. Example 3 Polyol C: Glycerol was 1 mole, 0.23 moles of cesium hydroxide was added, and after dehydration at 100 ° F for 6 hours, propylene oxide was reacted at a reaction temperature of 80¾ and a maximum reaction pressure of 3.5kg / cnf (4 40kPa). Addition polymerization i to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mg KOH / g. Secondly, 15% by weight of ethylene oxide 'of the polyoxypropylene polyol was added at 100 ° C. In other words, a polyoxyalkylene polyenzyme having a hydroxyl value of 24 mg KOΗ / g was obtained. The content of the monoenzyme obtained by the same method as in Example 1 was 8.0 mole%, and the viscosity was 1 650〇93 / 25 &lt; 〇, * The selectivity of 11-1 'knots was 96.3 mole%. The results are shown in Table 1. Example 4 Polyol D: For glycerol 1 mole, 0.23 mole of potassium hydroxide was added at 100 ° C After 6 hours of dehydration, propylene oxide was subjected to addition polymerization under the conditions of a reaction temperature of 70t: and a maximum reaction pressure of S.Skg / cm2 (440kPa) to obtain a polyoxypropylene polyenzyme having a hydroxyl value of 33Bg KOH / g. Secondly, 15% by weight of ethylene oxide of the polyoxypropylene polyenzyme was added under the condition of 100¾ to obtain a polymer having a hydroxyl value of 29 mg κ0Η. Polyalkylene polyenzyme. The monohydric alcohol content obtained by the same method as in Example 1 was 11.9 mol%, and the viscosity was 110.003 / 25 &lt; 〇, 11-1 'bond selectivity was 96.5 moben Paper size applies Chinese National Standard (CNS) M specification (210x297 mm) _ 25-(Please read the notes on the back before filling this page) ^ ------- Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (23) Ear%. The results are shown in Table 1. Example 5 Polyol E: For 1 mol of propylene oxide adduct of pentaerythritol with a hydroxyl value of 450 fflg KOH / g, 0.23 mol of hydroxide hydroxide was added, and after dehydration at 100 ° C for 6 hours, The propylene oxide was subjected to addition polymerization under the conditions of a reaction temperature and a reaction maximum pressure of 3.5 kg / cnf (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 50 mg KOH / g. Then, propylene oxide was subjected to addition polymerization at a reaction temperature of 9 (TC, maximum reaction pressure hSkg / ctfUAOkPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 29 ing KOH / g. Secondly, 15 weight% of ethylene oxide of the polyoxypropylene polyol is added under a lot of water to obtain a polyoxyalkylene polyol having a hydroxyl value of 25 ms KOH / g. Example 6 Polyol F: For 1 mol of glycerol, 0.13 mol of hydroxide was added, and after dehydration at 100¾ for 6 hours, propylene oxide was reacted at a reaction temperature of 60 ° C and a maximum reaction pressure of 2.0 ̊ / (^ (30000Pa)) under the condition of addition polymerization to obtain a polyoxypropylene polyol having a hydroxyl value of 50mg KOH / g. Then, propylene oxide was further reacted at a temperature of 60C and a maximum pressure of 2.0kg. Addition polymerization under the conditions of / ctf (300kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of KOH / g. Obtained in the same manner as in Example 1-the content of the diol is 14.6 mole%, the viscosity It was 230,000 / 25 &lt; 0, 11-1 &lt; and the selectivity of the bond was 97.0% of its ears. The results are shown in Table 1. Example 7 Polyenzyme G: For malonase 1 mole, 0.23 was added Moore's cesium hydroxide This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) -26- (Please read the precautions on the back before filling this page)-.. A7 B7 printed by the Consumers' Cooperative of the Central Bureau of Standards 5. Description of the Invention (24) and 0.10 Mole of Hydroxide I, after dehydration for 6 hours, Polypropylene oxide was subjected to addition polymerization under the conditions of a reaction temperature of 80 ° and a maximum reaction pressure of 2.5 kg / cnf (350 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 50 mg KOH / g. Then, the epoxy Propane was polymerized by addition at a reaction temperature of 80 t: and a maximum reaction pressure of 2.5 kg / ci # (350 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. The same as in Example 1 The content of the monohydric alcohol obtained by the method was 10.5 mol%, and the viscosity was 95 ° (^ 3 / 251〇,) 1-1 ′ bond selectivity was 96.3 mol%. The results are shown in Table 2. Example 8 Polyol H: For 1 mol of glycerol, add 0.23 mol of europium hydroxide, and after dehydrating at 100 ° C for 6 hours, propylene oxide is reacted at a reaction temperature of 80 ° C and a maximum pressure of S.Skg / cra2 (440 kPa) under conditions of addition polymerization to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / s. Secondly, it will be 15% by weight of ethylene oxide of the polyoxypropylene polyol, Addition at 100¾ yields a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOΗ / g. The monohydric alcohol obtained by the same method as in Example 1 contains The amount was 7.2 mole%. * The viscosity was 1 290 ° 3/25 ° (0, [1-1 'knot selectivity was 96.4 mole%. The results are shown in Table 2. Example 9 Multiple Enzyme I: For 1 mole of glycerol, 0.2 3 mole of rhenium hydroxide was added, and after dehydration at 100 ° C for 6 hours, propylene oxide was subjected to addition polymerization at a reaction temperature of 80t: and a maximum reaction pressure (440kPa). In this way, a polyoxypropylene polyol having a hydroxyl value of 25 mg of KOH / g was obtained. Secondly, the Chinese national standard (CNS) A4 specification (210X297 mm) will be applied to this paper size. 〇7 _ (Please read the notes on the back before filling this page) Order. Line A7 B7 Staff of the Central Standards Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (25) 15% by weight of ethylene oxide of the polyoxypropylene polyol was added at 100 ° C to obtain a polyoxyalkylene having a hydroxyl value of 21 mg KOH / g Based polyol. The monohydric alcohol content obtained by the same method as in Example 1 was 10.5 mol%, the viscosity was 1950 cps / 25 1C, Η-T, and the bond selectivity was 97: 0 mol%. The results are shown in Table 2. Example 1 0 Polyenzyme J: For 1 mol of glycerol, 0.23 mol of rubidium hydroxide was added, and after dehydration at 100 ° C for 6 hours, propylene oxide was reacted at a reaction temperature of 80 ° C. Addition polymerization under the condition of maximum pressure S.Skg / cin2 (440kPa), to obtain a polyoxypropylene polyol having a hydroxyl value of 20 mg KOH / g. Next, 15 weight% of ethylene oxide of the polyoxyalkylene polyhydric alcohol was added at 100 υ to obtain a polyoxyalkylene polyenzyme having a hydroxyl value of 17 ng KOH / g. The monohydric alcohol content obtained by the same method as in Example 1 was 14.0 mol%, and the viscosity was 2380-5 / 25 ° (:, {1-1] 'bond selectivity was 97.2 mol%. The results are shown in Table 2. Example 11 Polyol K: 1 mole of pentaerythritol, 0.23 mole of rhenium hydroxide was added, and after dehydration at 100 ° C for 6 hours, propylene oxide was reacted at a temperature of 80 t: Addition polymerization under the conditions of the maximum reaction pressure S.Skg / cra2 (440kPa) to obtain a polyoxypropylene polyenzyme having a hydroxyl value of 33rag KOΗ / g. Secondly * will be 15 weight of the polyoxypropylene polyol % Of ethylene oxide was added at 100 t: to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOH / g. The monohydric alcohol content obtained in the same manner as in Cell Example 1 It is 9.5% of its ear * Viscosity is 142 (^ 3/25 &lt; 0,11-1 'knot selection rate is 9 6.5 mole%. (Please read the precautions on the back before _ 舄 this page)

P $ 言 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -2 8 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（26) 結果係示於表2中。 比較例1 多元醇B:對於丙三酵1莫耳，添加0.37莫耳之氫氧化鉀 ，在100&quot;C下脫水6小時後，環氧丙烷在反應溫度115t： 、反應最大壓力Skg/ci^UgOkPa)之條件下加成聚合之， 獲得羥基價33mg KOH/g之聚氧伸丙基多元醇。其次，將為 該聚氧伸丙基多元醇之15重量&gt; 之環氧乙烷，在100t：下 加成之，獲得羥基價28nig KOH/g之聚氧伸烷基多元醇。依 與實施例1相同之方法所獲得之一元醇含量為29.3莫耳％ ，粘度為1150〇?3/2510*}1-1'鍵结選擇率為96.3莫耳％。 结果係示於表3中。 比較例2 多元醇Μ :對於丙三醇1莫耳，添加由鋅一鈷氟化物興氯 化鉾、水、二甲氧基乙醇所構成之所謂之絡合金屬氰化錯 體觸媒（DMI)6.93s*再將環氧丙烷在反應溫度90Ό、反應 最大壓力Ikg/cnf (490kPa)之條件下加成聚合之，獲得羥 基價33iug KOH/g之聚氧伸丙基多元醇。而後，將DMC觸媒 ，以氨水抽出，水洗後，相對含於聚氧伸丙基多元酵中之 丙三酵1莫耳，添加0.23莫耳之氫氧化鉀，在lOOt：下脫水 6小時後，將為該聚氧伸丙基多元酵之15重量％之環氧乙 烷加成聚合之，獲得羥基價28mg KOH/g之聚氧伸烷基多元 酵。依與實施例1相同之方法所獲得之一元醇含量為9.6奠 耳％*粘度為3080〇口3/2510，[1-1'鍵结選擇率為85.4莫耳 %。結果係示於表3中。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再本頁) -裝. 訂 線 -29 - A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 (： Π) 1 1 1 比 較 例 3 1 1 I 多 元 醇 N ： 對於丙三醇1 莫 耳 9 添加〇 . 23莫耳之 氫氧化鉋 | f 在 1 0 0 t：下脫水6小時後 9 將 環 氧丙烷在反應溫 度 80 t：、 請 先 1 反 nta 懕 最 大 壓 力 3‘5kg/cnf (440kPa )之條件下加成聚合之， 讀 背 | I 獲 得 羥 基 價 50mg KOH/g之 聚 氧 伸 丙基多元酵。而 後，又將 之 注 1 I 意 1 I 環 氧 丙 烷 在 反應溫度l ο ο υ、 反應最大壓力3 . 5kg / c nf 事 if 1 1 再 1 (440kP a )之 條件下加成聚 合 之 9 獲得羥基價28mg KOH/g之 填 寫 ¥ 聚 氧 伸 丙 基 多元醇。依與 實 施 例 1相同之方法所獲得之一 本 頁 S_✓ 1 I 元 醇 含 量 為 22 . 9莫耳％， 粘 度 為 1200cps/25〇C， Η-T鐽结 1 1 選 擇 率 為 97 ,5莫耳％。结 果 係 示 於表3中。 1 比 較 例 4 1 訂 多 元 醇 0 對於丙三醇1 莫 耳 添加〇 . 53莫耳之 氫氧化筢 I 9 在 100°C下脫水6小時後 9 將 環 氧丙烷在反應溫 度 9 0。(〇、 1 1 I 反 應 最 大 壓 力 3 . 5 k g / c mM 4 4 0 k P a ).之條件下加成聚合之， 1 獲 得 羥 基 價 117nig KOH/g 之 聚 氧 伸丙基多元醇。 而後，又 1 線 將 τ«π» 環 氧 丙 烷 在反應溫度9 0 V 、 反 應最大壓力3.5k g / C 1Π2 ( 1 | 440kPa )之條件下加成聚合之 &gt;獲得羥基價lling KOH/g之 1 1 聚 氧 伸 丙 基 多元酵。依與 實 施 例 1相同之方法所獲得之一 1 1 1 元 醇 含 量 為 22 . 7莫耳％， 粘 度 為 1160cps/25〇C， Η-T鍵结 1 1 選 擇 率 為 9£ .4莫耳％。結 果 係 示 於表3中。 1 1 比 較 例 5 1 I 多 元 醇 P :對於丙三酵] 莫 耳 9 添加〇 . 2 3莫耳之 氫氧化絶 1 1 I » 在 1 0 0 1C下脫水6小時後 9 將 TWI 環 氧丙烷在反應溫 度 95υ、 1 1 1 反 tttof 懕 最 大 壓 力4 k g / c m2 ( 4 9 0 k P a )之條件下加成聚 合之，獲 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) A7 B7 五、發明説明（28) 得羥基價117mg KOH/g之聚氧伸丙基多元醇。而後，又將 環氧丙烷在反應溫度95°C、反應最大壓力LSkg/cffl2 (540kPa)之條件下加成聚合之，獲得經基價28mg K0H/g2 聚氧伸丙基多元醇。依與實施例1相同之方法所獲得之一 元醇含量為17.7莫耳％，粘度為1110〇?5/25°0，11-1&lt;鍵結 選擇率為96.9莫耳％。結果係示於表3中。 質施例、比較例中之聚氧伸烷基多元醇，在反應終了後 均於其中添加水及磷酸而予中和之後，再予減壓乾燥，將 生成之鹼金屬磷酸鹽的结晶Μ過滤除去之後，Μ前述1之方 法測定羥基價、粘度、一元醇含量、Η-T鍵结選擇率。 實施例及比較例，係綜合表示於表1〜表3中，表中之起 始材料Α係丙三醇，起始材料Β係季戊四醇之環氧丙烷加成 物（羥基價450mg KOH/g)。觸媒A係指氫氧化鉋，觸媒B係 指氫氧化鉀，觸媒C係指氫氧化踟.，觸媒D係指鋅一鈷氰化 物與氯化鋅、水、二甲氧基乙醇所構成之絡合金屬氰化錯 體（DMC觸媒）。 ' 又，P 0係環氧丙烷之簡稱，E 0係環氧乙烷之簡稱。 —II----— -I (請先閲讀背面之注意事項再填寫本頁) --訂. 經濟部中央標準局員工消費合作社印製 31 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（29) (表1) 經濟部中央標準局員工消費合作社印製 多元醇 1 A 2 B 實施例 3 4 C D 5 E 6 F 起始材料Α(莫耳） 1 1 1 1 — 1 起始材料B(莫耳） 一 — — 一 1 — 觸媒A(莫耳） 0.13 0.43 0.23 一 0.23 0.13 觸媒B (莫耳） — 一 — 0.23 — 一 觸媒C(莫耳） — — — — —： — 觸媒D(s) — 一 — — — — P0加成聚合溫度反應前半 95 65 80 70 80 60 (t：) 反應後半 95 75 80 70 90 60 最大壓力 尽應前半 3.5 2.0 3.5 3.5 3.5 2.0 (kgf/cnf)反應後半 3.5 3.0 3.5 3.5 3.5 2.0 P0加成後之羥基價（mgKOH/g) 33 28 28 33 29 16 E0加成聚合溫度（10 ) 100 — 80 100 100 一 最大壓力（kgf/cnf) 3.5 — 3.5 3.5 3.5 — 羥基價（msKOH/g) 28 28 24 29 25 17 粘度（cps/25t：) 1140 1250 1650 1100 1800 2300 一元酵含量（莫耳：U) 13.0 11.9 8.0 13.7 14.3 14.6 Η - T鍵結選擇率（莫耳％ ) 96.7 96.2 96.3 96.5 96.4 97.0 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)P $ The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -2 8-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (26) The results are shown in Table 2 . Comparative Example 1 Polyol B: For 1 mole of glycerol, 0.37 mole of potassium hydroxide was added, and after dehydration at 100 &quot; C for 6 hours, the propylene oxide was at a reaction temperature of 115t: and the maximum reaction pressure Skg / ci ^ UgOkPa) under conditions of addition polymerization to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. Next, 15 weight &gt; of ethylene oxide of the polyoxyalkylene polyol was added at 100 t to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 nig KOH / g. The monohydric alcohol content obtained in the same manner as in Example 1 was 29.3 mol%, and the viscosity was 1150/3/2510 *} 1-1 ′ bond selectivity was 96.3 mol%. The results are shown in Table 3. Comparative Example 2 Polyol M: For 1 mol of glycerol, a so-called complex metal cyanide catalyst (DMI) composed of zinc-cobalt fluoride, thallium chloride, water, and dimethoxyethanol was added. ) 6.93 s * and propylene oxide is additionally polymerized under the conditions of a reaction temperature of 90 ° C and a maximum reaction pressure of 1 kg / cnf (490 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 iug KOH / g. Then, the DMC catalyst was extracted with ammonia water, and after washing with water, 0.23 mol of potassium hydroxide was added to the glycerol in polyoxyl propylene polyenzyme, and after dehydration for 6 hours at 100t: 15% by weight of ethylene oxide was polyaddition polymerized to obtain a polyoxyalkylene polyenzyme having a hydroxyl value of 28 mg KOH / g. The content of the monohydric alcohol obtained in the same manner as in Example 1 was 9.6 mol% * viscosity was 3,080,3 / 2510, and the [1-1 'bond selectivity was 85.4 mol%. The results are shown in Table 3. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before this page)-Packing. -29-A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (: Π) 1 1 1 Comparative Example 3 1 1 I Polyol N: Glycerol 1 Mole 9 Added 0.23 Molar Hydroxide Plane | f Dehydration at 1 0 0 t: 6 hours Then 9 add propylene oxide at a reaction temperature of 80 t :, please first add 1 nta 懕 maximum pressure 3'5kg / cnf (440kPa) addition polymerization, read back | I get a hydroxyl value of 50mg KOH / g polymer Oxypropylenzyme. Then, it was added 1 I to 1 I propylene oxide at the reaction temperature l ο ο υ, the maximum reaction pressure 3.5 kg / c nf if 1 1 and then 1 (440kP a) addition polymerization to obtain 9 Fill in the hydroxyl value of 28mg KOH / g ¥ Polyoxypropylene polyol. One of the pages obtained by the same method as in Example 1 S_✓ 1 The content of monohydric alcohol is 22.9 mol%, the viscosity is 1200cps / 25 ° C, the Η-T 鐽 junction 1 1 selectivity is 97,5 Mole%. The results are shown in Table 3. 1 Comparative Example 4 1 Polyol 1 Mole added to glycerol 0.53 Molar osmium hydroxide I 9 After dehydration at 100 ° C for 6 hours 9 Epoxypropane was reacted at a reaction temperature of 90. (〇, 1 1 I reaction maximum pressure 3.5 k g / c mM 4 40 k P a). Under the conditions of addition polymerization, 1 to obtain a hydroxyl valence of 117nig KOH / g of polyoxyethylene propylene polyol. Then, in another line, τ «π» propylene oxide was subjected to addition polymerization under the conditions of a reaction temperature of 90 V and a maximum reaction pressure of 3.5 kg / C 1Π2 (1 | 440kPa) to obtain a hydroxyl value of lling KOH / g. 1 1 Polyoxypropyl Polyenzyme. According to the same method as in Example 1, one of the 11-valent alcohol content was 22.7 mol%, the viscosity was 1160 cps / 25 ° C, and the Η-T bond 1 1 selectivity was 9. 4 mol. %. The results are shown in Table 3. 1 1 Comparative Example 5 1 I Polyol P: For glycerol] Mole 9 Added 0.2 3 Molar Hydroxide 1 1 I »After 6 hours of dehydration at 1 0 0 1C 9 TWI propylene oxide Addition polymerization under the conditions of reaction temperature of 95 υ, 1 1 1 reverse tttof 懕 maximum pressure 4 kg / c m2 (49 0 k P a), obtained 1 1 This paper size applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm) A7 B7 V. Description of the invention (28) A polyoxyl propylene polyol having a hydroxyl value of 117 mg KOH / g was obtained. Then, propylene oxide was additionally polymerized under the conditions of a reaction temperature of 95 ° C and a maximum reaction pressure of LSkg / cffl2 (540kPa) to obtain a polyoxypropylene polyol having a base value of 28 mg K0H / g2. The monohydric alcohol content obtained in the same manner as in Example 1 was 17.7 mol%, and the viscosity was 1110 5/25 ° 0, 11-1 &lt; the bond selectivity was 96.9 mol%. The results are shown in Table 3. After the reaction, the polyoxyalkylene polyols in the quality examples and comparative examples were added with water and phosphoric acid to neutralize them, and then dried under reduced pressure, and the crystals M of the generated alkali metal phosphate were filtered. After removal, the hydroxyl value, viscosity, monohydric alcohol content, and fluorene-T bond selectivity were measured by the method described in 1 above. Examples and comparative examples are comprehensively shown in Tables 1 to 3. The starting material A in the table is glycerol, and the starting material B is a propylene oxide adduct of pentaerythritol (hydroxyl value 450 mg KOH / g). . Catalyst A refers to hydroxide planer, catalyst B refers to potassium hydroxide, catalyst C refers to thorium hydroxide, and catalyst D refers to zinc-cobalt cyanide and zinc chloride, water, and dimethoxyethanol. The complex metal cyanide complex (DMC catalyst). In addition, P 0 is an abbreviation of propylene oxide, and E 0 is an abbreviation of ethylene oxide. —II ----— -I (Please read the notes on the back before filling out this page) --Order. Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 31 This paper size applies to the Chinese National Standard (CNS) A4 specifications ( 210X297 mm) A7 B7 V. Description of the invention (29) (Table 1) Polyols printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1 A 2 B Example 3 4 CD 5 E 6 F Starting material A (Moore) 1 1 1 1 — 1 Starting material B (Mole) One — One 1 — Catalyst A (Mole) 0.13 0.43 0.23 One 0.23 0.13 Catalyst B (Mole) — One — 0.23 — One Catalyst C ( Moore) — — — — — :: — Catalyst D (s) — One — — — — P0 Addition polymerization temperature First half of reaction 95 65 80 70 80 60 (t :) Second half of reaction 95 75 80 70 90 60 The first half of the reaction is 3.5 2.0 3.5 3.5 3.5 2.0 (kgf / cnf) The second half of the reaction is 3.5 3.0 3.5 3.5 3.5 2.0 P0 hydroxyl value after addition (mgKOH / g) 33 28 28 33 29 16 E0 addition polymerization temperature (10) 100 — 80 100 100 a maximum pressure (kgf / cnf) 3.5 — 3.5 3.5 3.5 — hydroxyl value (msKOH / g) 28 28 24 29 25 17 viscosity (cps / 2 5t :) 1140 1250 1650 1100 1800 2300 Monovalent yeast content (Mole: U) 13.0 11.9 8.0 13.7 14.3 14.6 Η-T bond selection rate (Mole%) 96.7 96.2 96.3 96.5 96.4 97.0 This paper size applies to Chinese national standards ( CNS) Α4 size (210X 297 mm) (Please read the precautions on the back before filling this page)

、1T 丨線 32 A7 B7 五、發明説明（30) (表2) 經濟部中央標準局員工消費合作社印製 多元醇 7 G 8 Η 實施例 9 10 I J 11 Κ 起始材料A(莫耳） 1 1 1 1 — 起始材料B(莫耳） — — — 1 觸媒A(莫耳） 0.23 0.23 0.23 0.23 0.23 觸媒B (莫耳） — — 一 — — 觸媒C(莫耳） 0.10 一 — — —1 觸媒D(s) — — — — — P0加成聚合溫度反應前半 80 80 80 80 80 CC ) 反應後半 80 80 80 80 80 最大壓力 尽應前半 2.5 3.5 3.5 3.5 3.5 (kgf/cnf)反應後半 2,5 3.5 3.5 3.5 3.5 P0加成後之羥基價UsKOH/g) 33 33 25 20 33 E0加成聚合溫度（它） 一 100 100 100 100 最大壓力（kgf/cra2) 3.5 3.5 3.5 3.5 羥基價（msKOH/g) 34 28 21 17 28 粘度（cps/2510 ) 950 1290 1950 2380 1420 一元酵含虽（萁耳！η 10.5 7.2 10.5 14.0 9.5 Η_Τ鍵结選擇率（莫耳％) 96.3 96.4 97.0 97.2 96.5 (請先閱讀背面之注意事項再填寫本頁)1T 丨 line 32 A7 B7 V. Description of the invention (30) (Table 2) Polyol 7 G 8 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 9 10 IJ 11 Κ Starting material A (Mole) 1 1 1 1 — Starting material B (Mole) — — — 1 Catalyst A (Mole) 0.23 0.23 0.23 0.23 0.23 Catalyst B (Mole) — — — — Catalyst C (Mole) 0.10 1 — — —1 Catalyst D (s) — — — — — P0 Addition polymerization temperature First half of reaction 80 80 80 80 80 CC) Second half of reaction 80 80 80 80 80 Maximum pressure should be the first half 2.5 3.5 3.5 3.5 3.5 (kgf / cnf) Second half of the reaction 2,5 3.5 3.5 3.5 3.5 P0 Addition of hydroxyl value UsKOH / g) 33 33 25 20 33 E0 addition polymerization temperature (it)-100 100 100 100 Maximum pressure (kgf / cra2) 3.5 3.5 3.5 3.5 hydroxyl Valence (msKOH / g) 34 28 21 17 28 Viscosity (cps / 2510) 950 1290 1950 2380 1420 Monovalent enzyme (Alcohol! Η 10.5 7.2 10.5 14.0 9.5 Η_Τ bond selectivity (mol%) 96.3 96.4 97.0 97.2 96.5 (Please read the notes on the back before filling this page)

本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 五、發明説明（31) (表3) A7 B7 經濟部中央標準局員工消費合作社印製 多元醇 1 L 2 Η 比較例 3 4 Η 0 5 Ρ 起始材料A(莫耳） 1 1 1 1 1 起始材料B(莫耳） — — — — — 觸媒A(莫耳） — — 0.23 0.53 0.23 觸媒B (莫耳） 0.37 . — — — 一 觸媒C(莫耳） - — 一 — 一 觸媒D(g) 一 6.93 — 一 — P0加成聚合溫度反應前半 115 90 80 90 95 (V ) 反應後半 115 90 100 90 95 最大壓力 反應前半 5.0 4.0 3.5 3.5 4.0 (kgf/cra2)反應後半 5.0 4.0 3.5 3.5 4.5 P0加成後之羥基價（mgKOH/g) 33 33 28 31 28 E0加成聚合溫度（°C) 100 100 — 一 一 最大壓力（ksf/cnf ) 5.0 4.0 — — — 羥基價（mgKOH/g) 28 28 28 31 28 粘度（cps/25C ) 1150 3080 1200 1160 1110 一元醇含量（莫耳：《) 29.3 9.6 22.9 22.7 17.7 Η_ Τ鍵结選擇率（莫耳％) 96.3 85.4 97.5 95.4 96.9 (請先閱讀背面之注意事項再填寫本頁) -----?Ll.r;---------- -------4------------- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（32) 經濟中央標隼局員工消費合作社印製 2. 聚 合 物 多 元 酵 之 製造 製 造 例 1 聚 合 物 多 元 酵 C ： 在附有溫度計、 攪扫 ί裝置、 送液裝置 之 容 量 為 1升的壓熱器中， 將實施例3所 得之 多 元酵 C饋入 成 充 滿 狀 態 一 面 予Μ攪 拌 $ 一面 予Μ 昇溫 至 120 t：為止 0 而 後 9 將 預 先 Μ 表4所示比率混合之多元醇C 、偶 氮二異 丁 腈 丙 烯 腈 之 混 合液連 鑕 地 裝入 該壓 熱器 9 由排 出口連 續 地 獲 得 聚 合 物 多 元醇。 此 時 ，反 應壓 力係 3 . 5kg/ c nf， 滯 留 時 間 係 50分 鐘 。在到 達 恒 常狀 態後 ，將 所 獲得 之反應 液 Μ 120¾ 2 0m mH g作4小 時 之 減壓 吸引 處理 f 而除 去未反 atxt 應 單 體 獲 得 聚 合 物多元 醇 〇 結果 係示 於表 4中。 製 造 例 2 聚 合 物 多 元 醇 L 在附有溫度計 &gt;授拌装置 &gt;送液裝置 之 容 量 為 1升的壓熱器中 將比較例1所 得之 多 元醇 L饋入 成 充 滿 狀 態 一 面 予Μ攪 拌 一面 予Μ 昇溫 至 120 t：為止 0 而 後 f 將 預 先 Μ 表4所示比率混合之多元醇L 、偶 氮二異 丁 腈 丙 烯 腈 之 混 合液連 壤 地 裝入 該壓 熱器 9 由排 出口連 續 地 獲 得 聚 合 物 多 元醇。 此 時 ，反 應壓 力係 3 . 5kg/ C 1#， 滯 留 時 間 係 50分 鐘 。在到 達 恒 常狀 態後 ，將 所 獲得 之反應 液 Μ 120 °C 、2 0 π 1 in H g作4小 時 之 減壓 吸引 處理 9 而除 去未反 〇tif 愿 單 體 » 獲 得 聚 合 物多元 醇 〇 結果 係示 於表 4中。 製 造 例 3 聚合物多元醇Μ:在附有溫度計、攪拌裝置、送液裝置之 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） — A7 B7 五、發明説明（33) 容量為1升的壓熱器中，將比較例2所得之多元醇Μ饋入成 充滿狀態，一面予Μ撹拌，一面予Μ昇溫至12010為止。 而後，將預先Κ表4所示比率混合之多元醇Μ、偶氮二異丁 腈、丙烯腈之混合液連續地裝入該壓熱器，由排出口連續 地獲得聚合物多元醇。此時，反應壓力係S.Skg/cm2，滯 留時間係50分鐘。在到達恒常狀態後，將所獲得之反應液 M12010、20mmHg作4小時之減壓吸引處理，而除去未反應 單體，獲得聚合拗多元酵。結果係示於表4中。 就製造例1〜3所獲得之聚合物多元醇，依前述方法測定 其羥基價、粘度。又，由根據元素分析之氮含量.，求取聚 合物濃度。表中之AIBN，係偶氮二異丁腈之簡稱，AN係丙 烯腈之簡稱。 (請先閲讀背面之注意事項再填寫本頁) -----------眷衣---- 經濟部中央標準局員工消費合作社印製 ml I !1 - - II 1 I . 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（34) (表4) 聚合物多元醇 1 C 製造例 2 L 3 Μ 多元酵C (重量份） 77.6 — — 多元酵L (重量份） —+ 77.6 — 多元醇Μ (重量份） — — 77.6 ΑΙΒΝ (重量份） 0.35 0.35 0.35 AN (重量份） 22.4 22.4 22.4 羥基價（m g K 0 H / g ) 19.5 22.8 22.8 粘度（cps/25t：) 4800 3600 9540 聚合物濃度（重量96) 21.0 20.6 20.9 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 3.聚胺甲酸酯發泡體之製造 除了上述聚氧伸烷基多元酵及聚合物多元醇以外，使用 K下所示之原料。 (觸媒- l)ti〗nic〇 L-1020:活材Chemical公司製之胺系 觸媒（三乙撐二胺之33%二甘醇溶液） (觸媒-2)Miax A-l: ARCO公司製之胺系觸媒 (交聯劑-1)KL-210 :三井東壓化學公司製，羥基價830 m g K 0 H / g之胺系交聯劑 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(36 ) 之過程。 異氰酸酯與樹脂液之活性氫的當量比（NCO/H)，係1.00 所獲得之發泡體的物性，係示於表5中。 比較例6 於此比較例中，除了將實施例12中之多元酵C變更成多 元醇L，將聚合物多元醇C變更成聚合物多元醇LM外，其 他係實施與實施例12相同之過程。 異氟酸酯與樹脂液之活性氫的當量比（NC0/H)，係1.00 。所獲得之發泡體的物性，係示於表5中。 比較例7 於本比較例中，除了將實施例12中之多元醇C變更成多 元醇Μ，將聚合物多元醇C變更成聚合物多元醇MM外，其 他係實施與實施例12相同之過程。 異氰酸酯與樹脂液之活性氫的當量比（NC0/H)，係1.00 。所獲得之發泡體的物體，係示於表5中。 比較例7所獲得之發泡體（使用絡合金屬氰化錯體觸媒） ，與實施例所獲得之發泡體相較，獨立氣泡性非常之強， 發泡體之泡體也羼粗大。 (請先閱讀背面之注意事項再填寫本頁) _裝- 訂* '線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） A7 B7 五、發明説明（Έ) (整泡劑-1): SRX-274C:東嫘一道康寧公司矽酮公司製 整 泡劑 (異氛酸酯- 1) ：Co s m ο η at e TH-20 ： 三 井 東 壓 化 學 公司 9 ... ··....· TD 1-80與 Ρο 1 y hi e lie MD I之80 : 20重 量 比 的 混 合 物 物 性測定係 根 據 JIS κ- 630 1 及 J IS K-640 1 實施 &gt;實施例 比 較例中之 密 度， 係指 整 體密度。 施 例12 混 合Μ下之 七 個成 份， 製 作樹脂液 〇 多 元酵C 60 重 量 份 聚 合物多元 醇 c 40 重 量 份 水 3.0 重 量 份 觸 媒-1 0.5 重 量 份 觸 媒-2 0.1 重 量 份 交 聯劑-1 3.0 重 量 份 整 泡劑-1 1.0 重 量 份 在 上述樹脂 液 ί 07 . 6重量份中，混合3S 丨重 量 份 異 氟 酸酯 -------©^1----„ltrJ------故 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張又度適用中國國家標準（CNS ) A4規格（210X297公釐） -1*將其立刻注入預先調整於6〇υ之內部尺寸為400X400 XlOOram之模具内，閉合蓋子將其發抱。在ΙΟΟΌ之熱風電 爐中將其加熱硬化7分鐘之後，將發泡體由模具取出。所 獲得之發泡體之物性係示於表5中。 異氰酸酯與樹脂液之活性氫的當量比（NC0/H)，係1.00。 實施例13〜17 於此等實施例中，除了將實施例12中之多元醇C變更成 多元醇E、H、I、J、KM外，其他係實施與實施例12相同 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（3 Ο (表5) 12 13 實施例 14 15 16 17 fcfc較例 6 7 多元醇 C E H I J K L M 聚合物多元醇 C C C C C C L M (物性） 密度（kg/m3 ) 54.0 54.4 54.1 54.3 54.2 54.3 54.4 54.9 硬度25%ILD 18.0 18.5 19.1 17.5 16.4 19.2 18.6 18.2 (kg/314cnf) 濕熱耐久性 5096 ¥et Set (96) 7.5 7.7 8.0 7.4 7.4 7.9 14.1 18.0 (請先閲讀背面之注意事項再填寫本頁) Θ裝. 、1Τ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） •i u L-1020:活材Chemical公司製之觸媒 A7 B7 五、發明説明（3S) 於實施例12〜14、17中，在發泡體密度=54〜55kg/m3 、25% ILD = 18 〜201^/314(:1112 之狀況下，tfet Set 係 7〜8»； 。相對於此，於比較例6〜7中，在大致同等之密度、硬度之 下，50% Wet Set係14〜18%。由此结果可知.本實施例中 所示之軟質聚胺甲酸酯，其耐濕熱耐久性有效地獲得改良。 ※聚合物多元醇之評估 1.聚氧伸烷基多元醇之製造 實施例、比較例中所用之原料、簡稱及分析法，係說明 如下。 多元醇A〜E:製造例1〜5所得之聚氧伸烷基多元醇 觸媒（1):氫氧化鉋 觸媒（2):氫氧化鉀 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 觸媒（3):鋅一鈷氛化合物與氯化鋅、水、.二甲氧基乙 醇所構成之所謂之絡合金靥氰化錯體觸媒 P0 :環氧丙烷 E0 :環氧乙烷 AN :丙烯腈 St :苯乙烯 TEA :三乙胺 NEM: N -甲基嗎啉 AIBN :偶氮二異丁腈 A I V N :偶氮二異戊腈 聚合物多元酵a〜i:實施例18〜22、比較例8〜11所獲 得之聚合物多元醇 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） j ! 經濟部中央標準局員工消費合作杜印製 本紙張尺度適用中國國家標準（CNS ) Μ規格（210Χ297公釐） A7 B7 五、發明説明（39) 水：離子交換水 L-1020 :活材Chemical公司製之觸媒 X-DM ：活材Chemica 1公司製之觸媒 KL-21 0 :三井東壓化學公司製之交聯劑 L-530 9 ：日本伏尼卡公司製之界面活性劑 TM-20: TD 1-80/20(二異氰酸2,4-甲次苯酯與二異氰酸 2,6-甲次苯酯之重童比80對20之混合物）與三井東壓公司 製之Cosmonate MDI-CR之重量比80對20之混合物 發泡體諸物性·•根據JIS K-6301、J IS K-6401測定。 1.聚氧伸烷基多元醇之製造 製造例1〜4 將觸媒（1)或（2)添加於丙三醇中，在100¾下脫水6小時 後，依表6所示之條件將環氧丙烷加成聚合，然後再將該 聚氧伸垸基多元醇之15重量％之環氧乙烷加成聚合◊反應 終了後，將水及磷酸添加中和後，予Μ減壓乾燥，將生成 之鹼金屬磷酸鹽之结晶Μ過滹除去，獲得多元醇Α〜D。物 性值係示於表6中。 製造例5 將觸媒（3)6.93g添加於丙三醇中，依表6中所示之條件 ，將環氧丙烷加成聚合。而後，以氨水將觸媒（3)抽出* Μ水洗將聚氧伸丙基多元酵精製後，將氫氧化鉀K相對丙 三醇1莫耳為0.23莫耳之量添加之，於100¾下減壓脫水6 小時。而後，將環氧乙烷依表6中所示之條件加成聚合。 反應終了後，添加水及磷酸中和後，予K減壓乾燥，將生 42 (請先閲讀背面之注意事項再填寫本頁) 丨©裝------------線--- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（40) 成之鹼金屬磷酸鹽之结晶Μ過漶除去，獲得多元醇物 性值係示於表6中。 (表6) 製造例1 製造例2 製造例3 製造例4 製造例5 多元酵 A B C D E 丙三醇箕耳 1.00 1.00 1.00 1.00 1.00 觸媒（1)莫耳 0.23 0.23 ― ― 一 觸媒（2)冥耳 ― ― 0.37 0.37 0.23 觸媒（3) g 一. ― ― - 6.93 P0加成 反應溫度 t 80 80 115 115 90 最大壓力kgf/cm2_ 3.5 3.5 4.0 4.0 4.0 羥基價（nigKOH/g) 37 28 37 28 28 E0加成 反應溫度 1C 80 80 115 115 90 最大壓力kgf/cnf 3.5 3.5 4.0 4.0 4.0 羥基價（msKOH/s) 33.8 23.5 33.4 24.0 24.0 一元醇含量（莫耳％) 6.7 8.0 24.0 35.5 11.0 頭尾（選擇率《 96.8 96.4 96.3 96.4 86.4 粘度（cps/2510) 1100 1650 900 1400 3300 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） IL — -^---^-------.------J 線 (請先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（4 !) 2,聚合物多元醇之製造 實施例18〜24，比較例8〜12 在附有溫度計、攪拌裝置、送液裝置之容量為1升的壓 熱器中，將多元醇饋入成充滿狀態，一面予Μ搅拌，一面 予Μ昇溫至120 °C。而後，將預先Μ表7、8所示比率混合 之多元醇、ΑΙΒΝ或AIVN、AN、St、TEA或ΝΕΜ之混合液連續 地裝入該壓熱器，由排出口連續地獲得聚合物多元醇。此 時，反應壓力係S.Skg/cffl2 (440kPa)，滯留時間係50分鐘 。在到達恒常狀態後，將所獲得之反應液M120°C、 20mmHg作4小時之減壓吸引處理，而除去未反應單.體及TEA 或NEM，獲得聚合物多元醇a〜1。結果係示於表7、8中。 -,.1 \—/ ^.»-------衣------^c-txΛ------錄 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 經濟部中央標準局員工消費合作社印製 A7 _____B7 五、發明説明（42) (表7) 18 19 實顏 20 21 22 23 24 聚雜多元醇 a d e f J k 多元酵A (重量份) 一 47.55 53.33 53.33 — 一 一 多元醇B (重量份） 77.60 — — 一 46.86 46.86 46.86 Μ (重量份） 22.40 41.96 37.34 30.34 42.51 30.34 30.34 St (重量份） — 10.49 9.33 16.33 10.63 16.33 16.33 TEA (重童份） 一 4.00 1.00 1.00 4.00 一 — NEM (重量份） 一 一 一 — — 2.00 2.00 AIBH (重量份） 0.35 0.26 0.26 0.26 0.26 0.26 — AIVN (重量份） 3.00 羥基價(msKOH/g) 19.5 19.7 18.6 18.6 15.3 18.9 19.1 粘度(cps/25t：) 4800 6600 6840 6500 13200 6300 6600 聚合物濃度（重量％) 21.0 47.6 44.8 44.0 50.0 43.8 44.2 Tg〇C) — 99 115 118 99 112 111 凝集粒子 無 無 無 無 無 無 無 iL-n- n I I ---- I n (請先閲讀背面之注意事項再填寫本頁) ^^1-----.&gt;彐....一,JKn m In · ί-^_*·--β% d- — ,.------- 本紙張尺度適用中周國家標準（CNS ) A4規格（210X297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（43) (表8) 比較例 8 9 10 11 12 聚合物多元醇 b C h 1 2 多元酵A (重量份） ― ― 一 53.33 53.33 多元酵C (重量份） 一 ― 53.33 ― ― 多元醇D (重量份） 77.60 ― ― 一 — 多元醇E (重量份） ― 75.97 一 AN (重量份） 22.40 18.97 37.34 37.34 37.34 St (重量份） 一 5.07 9.33 9.33 9.33 TEA (重量份） 一 ― ― ― NEM (重量份） ― ― 一 ― ― AIBN (重量份） 0.35 0.35 0.26 0.26 一 AIVN (重量份） ― 一 ― ― 0.26 羥基價（ragKOH/g) 19.8 18.1 18.5 18.9 19.3 粘度(cps/25°C) 4100 12000 14500 15000 15200 聚合物濃度（重量％) 20.8 22.3 44.2 44.0 43.8 Tg(°C) 一 112 123 125 125 凝集粒子 無 有 有 有 有 (請先閲讀背面之注意事項再填寫本頁) L---^---5¾-- ’訂：------ J線 — ^------- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） Λ Η 經濟部中央標準局員工消費合作社印製 A7 _B7___五、發明説明（44) 3.聚胺甲酸酯發泡體之製造 實施例25〜26，比較13〜14 ，將聚合物多元酵、多元醇、水、L-1020、X-DM、KL-210 、L-5309依表9所示之比率攪拌混合*製成榭脂預混合物 ，將其調整成25 °C。而後，將用量為使NCO基與樹脂預混 合物之活性氫的當量比為1.00之調整成25t：的TM-20’ Μ 及早先所調製之樹脂脂預混合物，Μ能獲得具有目的密度 之發泡體之方式調整其使用量，而後再予剌烈攪拌混合6 秒鐘，再予注入預先加熱於601C之預塗佈有市售之離型劑 的鋁製測試模中，而後，蓋上蓋子，Κ夾具將其密閉，再 予發泡硬化。由攪拌開始3分鐘後，將模子之夾具卸除* 將硬化之軟質聚胺甲酸酯發泡體脫模，將發泡體*以手按 壓時之力量的大小程度，評估其獨立氣泡性。而後’使用 輥子將其Κ厚度壓縮80%之方式’予Κ碾壓。24小時後’ 测定諸物性。發泡體物性係示於表9中。 {請先閲讀背面之注意事項再填寫本頁) ---------r---¾ 裝------Ά·;ΤΓ·------線 I ^------- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公後） 1 A7This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) V. Description of the invention (31) (Table 3) A7 B7 Polyol printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1 L 2 Η Comparative Example 3 4 Η 0 5 Ρ Starting material A (Mole) 1 1 1 1 1 Starting material B (Mole) — — — — — Catalyst A (Mole) — — 0.23 0.53 0.23 Catalyst B (Mole) 0.37 . — — — One catalyst C (Mole)-— One — One catalyst D (g) One 6.93 — One — P0 Addition polymerization temperature First half of reaction 115 90 80 90 95 (V) Second half of reaction 115 90 100 90 95 Maximum pressure first half of reaction 5.0 4.0 3.5 3.5 4.0 (kgf / cra2) second half of reaction 5.0 4.0 3.5 3.5 4.5 hydroxyl value after addition of P0 (mgKOH / g) 33 33 28 31 28 E0 addition polymerization temperature (° C) 100 100 — -11 Maximum pressure (ksf / cnf) 5.0 4.0 — — — Hydroxyl valence (mgKOH / g) 28 28 28 31 28 Viscosity (cps / 25C) 1150 3080 1200 1160 1110 Monohydric alcohol content (Moore: ") 29.3 9.6 22.9 22.7 17.7 Η_ Τ bond selection rate (mol%) 96.3 85.4 97.5 95.4 96.9 (Please read the notes on the back first (Fill in this page again) -----? Ll.r; ---------- ------- 4 ------------- This paper size applies China National Standard (CNS) A4 specification (210X297mm) A7 B7 V. Description of the invention (32) Printed by the Consumers' Cooperative of the Central Economic Standards Bureau 2. Manufacturing and manufacturing of polymer polyenzyme 1 Polymer polyenzyme C: in In a autoclave with a capacity of 1 liter attached to a thermometer, a stirring device, and a liquid feeding device, the multivariate enzyme C obtained in Example 3 was fed into a full state while the mixture was stirred and the temperature was raised to 120 t: So far, 0 and 9 are continuously charged into the autoclave 9 with a mixture of polyol C and azobisisobutyronitrile-acrylonitrile mixed in the ratio shown in Table 4 in advance, and polymer polyol is continuously obtained from the discharge port. At this time, the reaction pressure is 3.5 kg / c nf, and the residence time is 50 minutes. After reaching a steady state, the obtained reaction solution M 120¾ 2 m mH g was subjected to a reduced pressure suction treatment f for 4 hours while removing the non-reverse atxt reaction monomer to obtain a polymer polyol. The results are shown in Table 4. Production Example 2 Polymer Polyol L In a 1-liter autoclave with a thermometer &gt; mixing device &gt; liquid-feeding device, the polyol L obtained in Comparative Example 1 was fed to a full state while being stirred. On the one hand, the temperature was raised to 120 t: 0, and then f. The mixed liquid of polyol L and azobisisobutyronitrile-acrylonitrile mixed in the ratio shown in Table 4 in advance M was charged into the autoclave in a row and discharged from the outlet. Polymer polyols are continuously obtained. At this time, the reaction pressure is 3.5 kg / C 1 #, and the residence time is 50 minutes. After reaching a steady state, the obtained reaction solution M 120 ° C, 20 π 1 in H g was subjected to a reduced-pressure suction treatment 9 for 4 hours to remove the unreacted monomers. 获得 t. The system is shown in Table 4. Manufacturing Example 3 Polymer Polyol M: In the case of a thermometer, stirring device, and liquid feeding device (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ) — A7 B7 V. Explanation of the invention (33) In the autoclave with a capacity of 1 liter, the polyol M obtained in Comparative Example 2 was fed into a full state, and the mixture was heated to M1 while being heated to 12010. Then, the mixed solution of the polyol M, azobisisobutyronitrile, and acrylonitrile mixed in the ratio shown in Table 4 in advance was continuously charged into the autoclave, and the polymer polyol was continuously obtained from the discharge port. At this time, the reaction pressure was S.Skg / cm2, and the residence time was 50 minutes. After reaching a steady state, the obtained reaction solution M12010 and 20 mmHg were subjected to a reduced-pressure suction treatment for 4 hours to remove unreacted monomers, thereby obtaining a polymerized polyenzyme. The results are shown in Table 4. Regarding the polymer polyols obtained in Production Examples 1 to 3, the hydroxyl value and viscosity were measured according to the methods described above. The polymer concentration was determined from the nitrogen content. Based on elemental analysis. AIBN in the table is the abbreviation of azobisisobutyronitrile, and AN is the abbreviation of acrylonitrile. (Please read the precautions on the back before filling out this page) ----------- Dependence Clothing ---- Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ml I! 1--II 1 I. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (34) (Table 4) Polymer polyol 1 C Manufacturing example 2 L 3 MU polyenzyme C (parts by weight) 77.6 — — Polylase L (parts by weight) — + 77.6 — Polyol M (parts by weight) — — 77.6 ΑΙΒΝ (parts by weight) 0.35 0.35 0.35 AN (parts by weight) 22.4 22.4 22.4 Hydroxyl valence (mg K 0 H / g) 19.5 22.8 22.8 Viscosity (cps / 25t :) 4800 3600 9540 Polymer concentration (weight 96) 21.0 20.6 20.9 (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 3. Polyurethane For the production of the ester foam, in addition to the polyoxyalkylene polyenzyme and polymer polyol described above, the raw materials shown below K are used. (Catalyst-l) ti〗 nicOL-1020: Amine catalyst made by Biomass Chemical (33% diethylene glycol solution of triethylene diamine) (Catalyst-2) Miax Al: Made by ARCO Amine catalyst (crosslinking agent-1) KL-210: manufactured by Mitsui Toya Chemical Co., Ltd., amine crosslinking agent with hydroxyl value of 830 mg K 0 H / g This paper is in accordance with Chinese national standard (CNS> A4) (210X297 mm) The process of printing A7 B7 by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The invention description (36). The equivalent ratio of active hydrogen of isocyanate and resin liquid (NCO / H) is the foam obtained by 1.00 The physical properties are shown in Table 5. Comparative Example 6 In this comparative example, except that the polyenzyme C in Example 12 was changed to the polyol L, and the polymer polyol C was changed to the polymer polyol LM. The other processes were performed in the same manner as in Example 12. The equivalent ratio (NC0 / H) of the active hydrogen of the isofluoric acid ester to the resin solution was 1.00. The physical properties of the obtained foam are shown in Table 5. Comparative Example 7 In this comparative example, except that the polyol C in Example 12 was changed to a polyol M, and the polymer polyol C was changed to a polymerization Except for the polyol MM, the same procedure was carried out as in Example 12. The equivalent ratio of the active hydrogen of the isocyanate to the resin liquid (NC0 / H) was 1.00. The objects of the obtained foam are shown in Table 5. Compared with the foam obtained in Example 7, the foam obtained in Comparative Example 7 (using the complex metal cyanide catalyst) has very strong closed cells, and the foam of the foam is also (Please read the precautions on the back before filling in this page) _Package-Order * 'The size of the thread paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 V. Description of the invention (Έ) (Foaming agent-1): SRX-274C: Tokai Aichi Corning Corporation Silicone Foaming Agent (Isocyanate-1): Co sm ο η at e TH-20: Mitsui Toya Chemical Co., Ltd. 9. .. ·· .... · TD 1-80 and ο 1 y hi elie MD I 80:20 weight ratio of mixture physical properties are measured in accordance with JIS κ-630 1 and J IS K-640 1 Implementation &gt; Implementation The density in the comparative example refers to the overall density. Example 12 Seven components under mixed M Parts, to make a resin solution, polyenzyme C 60 parts by weight polymer polyol c 40 parts by weight water 3.0 parts by weight catalyst-1 0.5 parts by weight catalyst-2 0.1 parts by weight crosslinking agent-1 3.0 parts by weight foam stabilizer -1 1.0 parts by weight In the above resin solution, 07. 6 parts by weight, 3S 丨 parts by weight of isofluoro acid ester are mixed --------- © ^ 1 ---- „ltrJ ------ Therefore ( Please read the notes on the back before filling in this page) The paper printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economics is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -1 * Inject it into the pre-adjustment immediately In the mold with an internal size of 400 × 400 × 100mm, the cover is closed and the hair is held. After heating and hardening it in a hot-air electric furnace of 100Ό for 7 minutes, the foam was taken out of the mold. The physical properties of the obtained foam are shown in Table 5. The equivalent ratio of active hydrogen of isocyanate and resin liquid (NC0 / H) is 1.00. Examples 13 to 17 In these examples, except that the polyol C in Example 12 was changed to the polyols E, H, I, J, and KM, the rest of the implementation was the same as in Example 12 A7 B7 Central Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau 5. Description of the invention (3 0 (Table 5) 12 13 Example 14 15 16 17 fcfc Comparative Example 6 7 Polyol CEHIJKLM Polymer Polyol CCCCCCLM (physical properties) Density (kg / m3) 54.0 54.4 54.1 54.3 54.2 54.3 54.4 54.9 Hardness 25% ILD 18.0 18.5 19.1 17.5 16.4 19.2 18.6 18.2 (kg / 314cnf) Damp heat durability 5096 ¥ et Set (96) 7.5 7.7 8.0 7.4 7.4 7.9 14.1 18.0 (Please read the precautions on the back first (Fill in this page) Θ installed. ， 1T This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) • iu L-1020: Catalyst A7 B7 made by Biomaterial Chemical Company 5. Description of the invention (3S) In Examples 12 to 14, and 17, under the conditions of foam density = 54 to 55 kg / m3, 25% ILD = 18 to 201 ^ / 314 (: 1112, the tfet Set is 7 to 8 »; relative to Therefore, in Comparative Examples 6 to 7, it is approximately the same. Below the degree and hardness, the 50% Wet Set is 14 to 18%. From this result, it can be seen that the soft polyurethane shown in this example has effectively improved the resistance to humidity and heat. ※ Polymer polyol Evaluation 1. The raw materials, abbreviations, and analysis methods used in the production examples and comparative examples of polyoxyalkylene polyols are described below. Polyols A to E: Polyoxyalkylenes obtained in Production Examples 1 to 5. Polyol catalyst (1): Hydrogenated planing catalyst (2): Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of potassium hydroxide (Please read the precautions on the back before filling this page) Catalyst (3): Zinc A so-called complex alloy made of a cobalt compound, zinc chloride, water, and dimethoxyethanol. Cyanide complex catalyst P0: propylene oxide E0: ethylene oxide AN: acrylonitrile St: styrene TEA: triethylamine NEM: N-methylmorpholine AIBN: azobisisobutyronitrile AIVN: azobisisovaleronitrile polymer polyenzyme a ~ i: obtained in Examples 18-22, Comparative Examples 8-11 The polymer polyol of this paper is sized according to the Chinese National Standard (CNS) A4 (210 X 297 mm) j! Central Standard of the Ministry of Economic Affairs Cooperate with employees for printing. The paper size applies to Chinese National Standards (CNS) M specifications (210 × 297 mm) A7 B7 V. Description of the invention (39) Water: ion-exchanged water L-1020: Catalyst X made by Biomaterials Chemical Company -DM: Catalyst KL-21 made by Living Material Chemica 1 0: Crosslinking agent L-530 made by Mitsui Toya Chemical Co., Ltd. 9: Surfactant TM-20 made by Vonika Japan: TD 1-80 / 20 (mixture of 80-to-20 weight ratio of 2,4-methylphenyl diisocyanate and 2,6-methylphenyl diisocyanate) and Cosmonate MDI-CR manufactured by Mitsui To pressure Co., Ltd. Physical properties of a mixture foam with a weight ratio of 80 to 20. Measured in accordance with JIS K-6301, J IS K-6401. 1. Production of polyoxyalkylene polyols Manufacturing Examples 1 to 4 The catalyst (1) or (2) was added to glycerin, and after dehydration at 100¾ for 6 hours, the ring was subjected to the conditions shown in Table 6. Addition polymerization of oxypropane, and then 15% by weight of ethylene oxide addition polymerization of the polyoxyalkylene polyol. After the reaction is completed, water and phosphoric acid are added to neutralize, and then dried under reduced pressure. The crystal M of the generated alkali metal phosphate was removed by filtration to obtain polyols A to D. The physical property values are shown in Table 6. Production Example 5 6.93 g of the catalyst (3) was added to glycerin, and propylene oxide was subjected to addition polymerization under the conditions shown in Table 6. Then, the catalyst (3) was extracted with ammonia water. After washing with water to refine the polyoxyl propyl polyenzyme, potassium hydroxide K was added in an amount of 0.23 mol relative to 1 mol of glycerol, which was reduced by 100 ¾. Dehydrate for 6 hours. Thereafter, ethylene oxide was subjected to addition polymerization under the conditions shown in Table 6. After the reaction is over, add water and phosphoric acid to neutralize, and then dry it under reduced pressure to produce 42 (please read the precautions on the back before filling this page) 丨 © installation ------------ line --- Printed by A7, B7, Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs. 5. Description of the invention (40) The crystal M of the alkali metal phosphate was removed. The obtained physical properties of the polyol are shown in Table 6. (Table 6) Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 Polysaccharide ABCDE Glycerol 1.00 1.00 1.00 1.00 1.00 1.00 Catalyst (1) Mol 0.23 0.23 ― ― One catalyst (2) Ear ― ― 0.37 0.37 0.23 Catalyst (3) g I. ― ―-6.93 P0 addition reaction temperature t 80 80 115 115 90 Maximum pressure kgf / cm2_ 3.5 3.5 4.0 4.0 4.0 Hydroxyl value (nigKOH / g) 37 28 37 28 28 E0 Addition reaction temperature 1C 80 80 115 115 90 Maximum pressure kgf / cnf 3.5 3.5 4.0 4.0 4.0 Hydroxyl valence (msKOH / s) 33.8 23.5 33.4 24.0 24.0 Monohydric alcohol content (mole%) 6.7 8.0 24.0 35.5 11.0 Head and tail ( Selectivity "96.8 96.4 96.3 96.4 86.4 Viscosity (cps / 2510) 1100 1650 900 1400 3300 This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) IL —-^ --- ^ ----- --.------ J line (Please read the precautions on the back before filling this page) A7 B7 V. Description of the invention (4!) 2. Manufacturing examples of polymer polyols 18 to 24, comparative examples 8 ~ 12 In the autoclave with a capacity of 1 liter, which is equipped with a thermometer, a stirring device, and a liquid feeding device, many The alcohol is fed into a full state, and while being stirred, the temperature is raised to 120 ° C. Then, the polyol, AIBN or AIVN, AN, St, TEA, or NEM, which are mixed in the ratio shown in Tables 7 and 8 in advance. The mixed liquid was continuously charged into the autoclave, and the polymer polyol was continuously obtained from the discharge port. At this time, the reaction pressure was S.Skg / cffl2 (440kPa), and the residence time was 50 minutes. After reaching a constant state, The obtained reaction solution M120 ° C and 20 mmHg were subjected to a reduced pressure suction treatment for 4 hours to remove unreacted monomers and TEA or NEM to obtain polymer polyols a to 1. The results are shown in Tables 7 and 8. .-,. 1 \ — / ^. »------- yi ------ ^ c-txΛ ------ record (please read the precautions on the back before filling this page) Economy Printed by the Central Consumers ’Cooperative of the Ministry of Standards of the People ’s Republic of China. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 × 297 mm). Printed by the Consumer ’s Cooperative of the Central Bureau of Standards of the Ministry of Economics. A7. _____B7. 19 Real face 20 21 22 23 24 Polyheteropoly adef J k Polyenzyme A (parts by weight) One 47.55 53.33 53.33 — one more Alcohol B (parts by weight) 77.60 — — 46.86 46.86 46.86 M (parts by weight) 22.40 41.96 37.34 30.34 42.51 30.34 30.34 St (parts by weight) — 10.49 9.33 16.33 10.63 16.33 16.33 TEA (parts by weight) — 4.00 1.00 1.00 4.00 — — NEM (parts by weight) One by one — — 2.00 2.00 AIBH (parts by weight) 0.35 0.26 0.26 0.26 0.26 0.26 — AIVN (parts by weight) 3.00 Hydroxyl value (msKOH / g) 19.5 19.7 18.6 18.6 15.3 18.9 19.1 Viscosity (cps / 25t: ) 4800 6600 6840 6500 13200 6300 6600 Polymer concentration (% by weight) 21.0 47.6 44.8 44.0 50.0 43.8 44.2 Tg ° C) — 99 115 118 99 112 111 Aggregated particles No No No No No No No iL-n-n II- -I n (Please read the notes on the back before filling in this page) ^^ 1 -----. &Gt; 彐 .... I, JKn m In · ί-^ _ * · --β% d -—, .------- This paper size is applicable to the Mid-week National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 8) Comparative Example 8 9 10 11 12 Polymer polyol b C h 1 2 Polyenzyme A (parts by weight) ― One 53.33 53.33 Polyenzyme C (parts by weight) One ― 53.33 ― ―Polyol D (parts by weight) 77.60 ― ― One-Polyol E (parts by weight) ― 75.97 One AN (parts by weight) 22.40 18.97 37.34 37.34 37.34 St ( Parts by weight)-5.07 9.33 9.33 9.33 TEA (parts by weight)----NEM (parts by weight)-----AIBN (parts by weight) 0.35 0.35 0.26 0.26-AIVN (parts by weight)-one--0.26 hydroxyl value ( ragKOH / g) 19.8 18.1 18.5 18.9 19.3 Viscosity (cps / 25 ° C) 4100 12000 14500 15000 15200 Polymer concentration (% by weight) 20.8 22.3 44.2 44.0 43.8 Tg (° C)-112 123 125 125 Aggregated particles None Yes Yes Yes (Please read the precautions on the back before filling this page) L --- ^ --- 5¾-- 'Order: ------ J line — ^ ------- This paper size is applicable to China National Standard (CNS) A4 Specification (210X297mm) Λ 印 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _B7___ V. Invention Description (44) 3. Manufacturing Example 25 of Polyurethane Foam 26. Comparing 13-14, polymer polyenzyme, polyol, Water, L-1020, X-DM, KL-210, and L-5309 are stirred and mixed according to the ratio shown in Table 9 * to make a prefabricated fat mixture, which is adjusted to 25 ° C. Then, by adjusting the amount of active hydrogen equivalent ratio of NCO group and resin premix to 1.00 to 25t: TM-20'M and the resin resin premix prepared earlier, M can obtain foam with the target density. Adjust the amount of use, then stir vigorously for 6 seconds, and then inject it into an aluminum test mold pre-coated with a commercially available release agent, which is preheated at 601C, and then close the lid. The K-clamp closes it and then foam-hardens it. After 3 minutes from the start of stirring, remove the mold clamps * demold the hardened soft polyurethane foam, and evaluate the strength of the foam when the foam is pressed by hand to evaluate its independent air bubbles. Then, 'the method of using a roller to compress the K thickness by 80%' is used for K rolling. After 24 hours, the physical properties were measured. The physical properties of the foam are shown in Table 9. (Please read the precautions on the back before filling this page) --------- r --- ¾ Installation ------ Ά ·; ΤΓ · ------ Line I ^- ----- This paper size applies to Chinese National Standard (CNS) Α4 size (210X297 male) 1 A7

7 B 五、發明説明（45) 經濟部中央標隼局員工消費合作社印製 (表9) 實施例 比較例 實施例 比較例 25 13 26 14 聚合物多元醇a 40 — — — 聚合物多元醇b — 40 — — 聚合物多元醇e — — 28 — 聚合物多元醇h — — — 28 多元醇C (重量份） 60 60 72 72 水 （重量份） 3.3 3.3 3.5 3.5 L-1020 (重量份） 0.4 0.4 0.4 0.4 X-DM (重量份） 0.3 0.3 0.3 0.3 L-5309 (重量份） 1.0 1.0 1.0 1.0 KL-210 (重量份） 3,0 3.0 3.0 3.0 獨立氣泡性評估 小 小 小 大 碾壓後之發泡體龜裂 無 無 無 有 密度整體（kg/m3 ) 50 50 50 50 硬度 25% ILD(kg/314cnf ) 22 21 24 22 抗拉強度（kg/cm2 ) 1.52 1.37 1.15 1.04 伸度（％) 120 105 114 112 抗撕裂強度（kg/crn2) 0.60 0.53 0.64 0.58 濕熱耐久性50% wet(%) 9.3 11.3 16.2 20.6 反彈彈性（％)中心 74 71 76 73 (請先聞讀背面之注意事項再填寫本頁) —ο裝-- --ιϊ&gt;».ν-----'線--------- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） j b mmn a7 B7 五、發明説明U6) 〔發明之效果〕 (請先閎讀背面之注意事項再填寫本頁) 本發明聚氧伸烷基多元醇，係使用鹼金屬氫氧化物觸媒 製造，其一元醇含量低，又，與使用習用絡合金屬氰化物 觸媒等之方法比較，頭尾（Head-to-Tail)鐽结選擇率高， 因此，具有低粘度之特徵，在廣泛之聚胺甲酸酯之用途中 ，可造成物性之提高。 本發明之聚合物多元酵，係K 一元酵含量低，頭尾鍵结 選擇率高之聚氧伸烷基多元醇作為基體*因此，具有低粘 度之特徵，在廣泛之聚胺甲酸酯之用途中，可造成物性之 提高。又，即使是使聚合物濃度提高，也較習用為低粘度 ，而且也無粒子凝集之現象，可獲得分散安定性良好之聚 合物多元醇。 由依此所獲得之聚氧伸烷基多元醇及聚合物多元醇發泡 時之獨立氣泡性低，因此*在碾壓後在發泡體上不會產生 龜裂等之問題，可提供硬度、耐濕熱耐久性（Wet Set)、 反彈彈性等之物性優異的聚胺甲酸酯發泡體。 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐）7 B V. Description of the invention (45) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (Table 9) Examples Comparative Examples Examples Comparative Examples 25 13 26 14 Polymer polyol a 40 — — — Polymer polyol b — 40 — — Polymer polyol e — — 28 — Polymer polyol h — — — 28 Polyol C (parts by weight) 60 60 72 72 Water (parts by weight) 3.3 3.3 3.5 3.5 L-1020 (parts by weight) 0.4 0.4 0.4 0.4 X-DM (parts by weight) 0.3 0.3 0.3 0.3 L-5309 (parts by weight) 1.0 1.0 1.0 1.0 KL-210 (parts by weight) 3,0 3.0 3.0 3.0 Foam cracked with or without density Overall (kg / m3) 50 50 50 50 Hardness 25% ILD (kg / 314cnf) 22 21 24 22 Tensile strength (kg / cm2) 1.52 1.37 1.15 1.04 Elongation (%) 120 105 114 112 Tear strength (kg / crn2) 0.60 0.53 0.64 0.58 Damp heat durability 50% wet (%) 9.3 11.3 16.2 20.6 Rebound elasticity (%) center 74 71 76 73 (Please read the precautions on the back first (Fill in this page) —ο 装---ιϊ &gt; ». Ν ----- 'line --------- This paper size applies China National Standard (CNS) A4 specification (210X297 mm) jb mmn a7 B7 V. Description of the invention U6) [Effects of the invention] (Please read the notes on the back before filling this page) The polyoxyalkylene polyalkylene of the present invention Alcohols are manufactured using alkali metal hydroxide catalysts, and their monohydric alcohol content is low. Compared with the methods using conventional complex metal cyanide catalysts, the head-to-tail knot selection rate is higher. Therefore, it has the characteristics of low viscosity, which can cause the improvement of physical properties in a wide range of polyurethane applications. The polymer polyenzyme of the present invention is a polyoxyalkylene polyol having a low monomonomer content and a high selectivity of head-to-tail bonding as a substrate *. Therefore, it has the characteristics of low viscosity and is widely used in polyurethanes. In use, it can cause improvement of physical properties. Moreover, even if the polymer concentration is increased, it is lower in viscosity than conventional, and there is no phenomenon of particle agglomeration, and a polymer polyol having good dispersion stability can be obtained. The polyoxyalkylene polyols and polymer polyols obtained in this way have low closed cells when foaming, so * there are no problems such as cracks in the foam after rolling, and can provide hardness, Polyurethane foam with excellent physical properties such as wet heat resistance (Wet Set) and rebound elasticity. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm)

Claims (1)

Λ 六、申請專利範圍 390898 A8 B8 C8 D8 m. 88. 8. 3 1 修正本 rih 經濟部智慧財產局員工消費合作社印製 1. 一種聚氧伸烷基多元醇之製法，其特微為：對於該申 丙三醇及季戊四醇中之所選擇出之_至少一種活屢氫化合物 1莫耳，於至少一種選自純度9 0重量％ Μ ±之氮氧化絶及氧 氧化铷之鹼金屬氫氧也物禰媒0.0 5〜 _0. 5莫耳存在下*且 溫度為60〜98°€!及反應最大壓力為氣2之條件下，__將 撂氧、量為,70重量% Μ上之環氧烷類，加成聚合， 並且，羥_基價為10〜35mgK0H/g，一元醇最大含量為15莫 耳S：，藉環氧丙烷加-成聚合之頭尾（head-to-tail)鍵結之 最低選擇率為96%* Μ及聚氧伸、丙基含量為70重量％以上。 2. —種聚氧伸烷基多元_醛_，係為藉由申請專利範圍第1 項之製法而得到之聚氧伸烷基多元酵，其特徵為：羥基價 為10〜35mgK0H/g，一元酵最大含量為15莫耳％，並且，藉 環氧丙烷加成聚合之頭屋（head-to-tai 1)鍵結之最低選擇. , j 率為96«，K及聚氧伸丙基含量為70重量上。 3 . —種軟f聚胺基甲酸醅發泡體之製法，其特^徵為：對 於、該由丙三醇及季戊四酵中之所選擇出之至少一種活性氫. 张合物、1莫耳，於至少一種選自選自純度90重量ϋ上之 氫氧化鉋及氫氧化铷之鹼金屬氫氧化物觸媒〇.〇 5〜0.5莫 耳存在&quot;R，Κ及溫度為60〜98¾及反應最大壓力為4kg/cm2 -厂， Μ下之條件下，將環氧丙烷含量為70重量上之環氧烷 類，加成聚合*並且，將羥基價10〜35mgK0H/g、一元醇 最大含量15莫耳J!、及藉環氧丙烷加成聚合之頭尾（head-， to-tail)鍵结之最低選擇率96¾、以及聚氧伸丙基含量為 70重量上之環氧烷類，加成聚合，K製造聚氧柯踪基 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐） 1 (請先聞讀背面之注音？事項再填寫本頁) I 1/--I I I 訂 — — — — —----- Λ 六、申請專利範圍 390898 A8 B8 C8 D8 m. 88. 8. 3 1 修正本 rih 經濟部智慧財產局員工消費合作社印製 1. 一種聚氧伸烷基多元醇之製法，其特微為：對於該申 丙三醇及季戊四醇中之所選擇出之_至少一種活屢氫化合物 1莫耳，於至少一種選自純度9 0重量％ Μ ±之氮氧化絶及氧 氧化铷之鹼金屬氫氧也物禰媒0.0 5〜 _0. 5莫耳存在下*且 溫度為60〜98°€!及反應最大壓力為氣2之條件下，__將 撂氧、量為,70重量% Μ上之環氧烷類，加成聚合， 並且，羥_基價為10〜35mgK0H/g，一元醇最大含量為15莫 耳S：，藉環氧丙烷加-成聚合之頭尾（head-to-tail)鍵結之 最低選擇率為96%* Μ及聚氧伸、丙基含量為70重量％以上。 2. —種聚氧伸烷基多元_醛_，係為藉由申請專利範圍第1 項之製法而得到之聚氧伸烷基多元酵，其特徵為：羥基價 為10〜35mgK0H/g，一元酵最大含量為15莫耳％，並且，藉 環氧丙烷加成聚合之頭屋（head-to-tai 1)鍵結之最低選擇. , j 率為96«，K及聚氧伸丙基含量為70重量上。 3 . —種軟f聚胺基甲酸醅發泡體之製法，其特^徵為：對 於、該由丙三醇及季戊四酵中之所選擇出之至少一種活性氫. 张合物、1莫耳，於至少一種選自選自純度90重量ϋ上之 氫氧化鉋及氫氧化铷之鹼金屬氫氧化物觸媒〇.〇 5〜0.5莫 耳存在&quot;R，Κ及溫度為60〜98¾及反應最大壓力為4kg/cm2 -厂， Μ下之條件下，將環氧丙烷含量為70重量上之環氧烷 類，加成聚合*並且，將羥基價10〜35mgK0H/g、一元醇 最大含量15莫耳J!、及藉環氧丙烷加成聚合之頭尾（head-， to-tail)鍵结之最低選擇率96¾、以及聚氧伸丙基含量為 70重量上之環氧烷類，加成聚合，K製造聚氧柯踪基 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐） 1 (請先聞讀背面之注音？事項再填寫本頁) I 1/--I I I 訂 — — — — —----- Α8 Β8 C8 D8 390B9S 六、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) ，多元醇，然後將該聚氧伸烷基多元醇與聚異氟酸德化合物 ，在觸媒、整泡劑、發泡劑、交聯劑及其他助劑之存在^下 反應。 4 .如申請專利範圍第3項之軟、質聚γ瞭^基甲酸-酯發梅體之^ .....— 屬法，其中聚氧」申烷基~爹元醇之〜部份，為―藉著選自两遒 腈或者丙烯擔與苯乙烯之混合物之乙烯糸不飽.和單體之聚 舍而被改質之聚合物多元酵。 5.如申請專利範圍第3項之軟質聚胺基甲酸酯發泡體之 製法，其中使用水做為發泡劑。 6 . —種聚合物多元醇，其特徵為：係在聚氧伸烷基多斥 P中，分散有5重量上’但不到30重量％之乙烯系不裨 和單體聚合而成之聚合物粒子；其中該聚氣伸烷基多元醇 之特徵為羥基價為10〜35mgKQH/g，一元醇最大含量為15 莫耳|，释環展丙烷加-成聚合之頭尾Oiead-to-ta i 1)鍵結 之最低里擇率為96各，及聚氧伸丙基含量為重髯％以上； Μ及該乙歸糸不錐和單體選亩丙烯腈或f丙鲁腈與苯乙铺' 之混合物。 經濟部智慧財產局員工消費合作社印製 7. —種聚合物多元醇，其特徵為：係在聚氧悚烷基多元 醇中，分散有30重量！8以上，60重量％K下之玻璃轉移溫^ &lt;— 為9,0〜120U之乙烯备不飽和單體聚鱼而成之寧合物粒子 ;其中該聚氧伸烷基多元醇之特徵為羥基價為10〜、 3.5_..fflg_K0..H*/..g，...一.元、薦最大含量.為15拜、耳％ ’藉環氧.丙'.焼..加屬 聚合之頭尾（Rea、d-t〇-ta i 1)鐽結之最低選擇率為96¾，及 聚氧伸1棊含暈為J立雪量上Λ Μ及該乙稀系不飽和單 2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A8 B8 S90893_m______ 六、申請專利範圍 體騷自西#腈或者丙烯腈與苯乙烯之混合物。 g. —種聚合物多元醇之製法*其特徵為：藉申請專利範 圍第2項之方法製造聚氧伸烷基多元醇，該聚氧伸釋基多 元醇之羥基價為10〜35ragK0H/g，一元醇最大含量為15莫 耳丨，藉_環氧-丙院加成_聚-合之頭尾，.(-上々8&lt;^-1；0.-_1311)鍵結之 最低選擇率為96¾，及聚氧伸丙基含量為71重量％以上；在 該聚氧伸烷基多元醇中，於胺基化合物構成之鏈轉移劑存 ·&gt;、_〆 ' .在下，使選自丙締膀或者丙烯腈與苯乙輝之混合物之乙烯 〆’ 系4不飽和單體進行聚合。 9 . 申請專利範圍第8項之聚合物多元^酵之製法，其中 使用環氧丙烷含量為70-重量％以上之環氧烷類，Μ及用做 聚氧伸烷基多元醇之封端蓋之環氧乙烷為5重量％以上。 10. 如申請專利範圍第8項之聚合物多元醇之製法，其中 、胺基化合物為三乙基胺。 11. 如申請專利範圍第8項之聚合物多元醇之製法*其中 胺基化合物為Η-甲基嗎啉。 12 . —種軟質聚胺基^甲酸酯發泡體之製法，其特徵為： 藉由申請專利範圍第8項之方法，製得聚合物多元醇，f 將含.有前述之聚合物多元醇之多元醇與有機聚異氰避酯化 合物，在發泡劑、觸媒、整泡劑、交聯劑及其他肋劑之存 在下反應。 13. —種軟質聚胺基甲酸酯發泡體之製法，其特徵為： g含有申請專利範圍第7項之聚合物多元醇之多元醇與有 機聚肩氰酸酯化合物，在發泡劑、觸媒、整泡劑、交聯劑 紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I~~I (請先閱讀背面之注意事項再填寫本頁) .Γ--------訂---------. 經濟部智慧財產局員工消費合作社印製 390893 § D8 六、申請專利範圍 及其他肋劑之存在Έ反應。 14. 一種聚合物多元醇，其特徵為：係在藉申請專利範 ................ .圍第1項之方法製得之聚氧伸院篇多元醇中*分散有30重 量％以上，60重量J：Μ下之4皮—璃轉移溫度為90〜1 20$之乙 烯糸不飽和單體聚合而成之聚合物粒子；其中該聚氧伸焼, 夸多元醇之特_|為羥基償為10〜351^〇1/^，一元醇最大 含量為15莫耳％，藉環氧丙烷加成聚合之頭尾（Read-to- 〆— &quot; ta i 1 )鍵結之最低選擇.率為9』％ *及聚氧伸丙基含量為70重 量上；Μ及該乙烯系不飽和單體選自丙烯腈或者丙烯 腈與苯乙烯之混合物。 (請先聞讀背面之注意事項再填寫本I) 裝.--II 訂---------《 經濟部智慧財產局員工消費合作社印製 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Λ 6. The scope of patent application is 390898 A8 B8 C8 D8 m. 88. 8. 3 1 Amend this rih Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. A method for producing polyoxyalkylene polyols, the characteristics of which are: For the selected one of the glycerol and pentaerythritol, at least one molybdenum compound is 1 mole, at least one alkali metal hydroxide selected from the group consisting of nitrogen oxides and oxygen oxides with a purity of 90% by weight. Under the conditions of 0.0 5 ~ _0. 5 moles * and a temperature of 60 ~ 98 ° € and a maximum reaction pressure of 2 gas, __ will be oxygen, the amount is 70% by weight of epoxy on Μ Alkanes, addition polymerization, and the hydroxyl group is 10 ~ 35mgK0H / g, the maximum content of monohydric alcohol is 15 mol S: by the head-to-tail bond of propylene oxide addition-polymerization The minimum selection rate of the knot is 96% * M, and the polyoxyethylene and propyl content are above 70% by weight. 2. A kind of polyoxyalkylene polyhydric aldehyde, which is a polyoxyalkylene polyvalent enzyme obtained by the manufacturing method of item 1 of the scope of patent application, which is characterized by a hydroxyl value of 10 ~ 35mgK0H / g, The maximum monovalent yeast content is 15 mol%, and the lowest choice of head-to-tai 1 bonding by propylene oxide addition polymerization., J rate is 96 «, K and polyoxypropylene The content is 70% by weight. 3. A method for producing a soft f polyurethane foam, characterized by: for, at least one active hydrogen selected from glycerol and pentaerythritol. 1 mole, at least one kind of alkali metal hydroxide catalyst selected from the group consisting of a hydroxide planer and a rhenium hydroxide having a purity of 90% by weight. 0.05 ~ 0.5 Moore exists &quot; R, K, and a temperature of 60 ~ 98¾ and the maximum reaction pressure is 4kg / cm2-factory, under the conditions of M, propylene oxide content of 70 weight of alkylene oxides, addition polymerization *, and the hydroxyl value of 10 ~ 35mgK0H / g, monohydric alcohol The maximum content is 15 moles J !, and the minimum selection rate of head-, to-tail bonding by propylene oxide addition polymerization is 96¾, and the alkylene oxide with a polyoxypropylene content of 70 weight Type, addition polymerization, K made of polyoxybenzol basic paper size applicable to Chinese national standards (CNS> A4 size (210 X 297 mm) 1 (please read the note on the back? Matters before filling out this page) I 1 / --III Order — — — — —----- Λ 6. Application scope 390898 A8 B8 C8 D8 m. 88. 8. 3 1 Amend this rih Economy Printed by the Ministry of Intellectual Property Bureau ’s Consumer Cooperatives 1. A method for making polyoxyalkylene polyols, the special feature of which is: for the selected glycerol and pentaerythritol _ at least one living hydrogen compound 1 mole, In the presence of at least one alkali metal hydroxide selected from the group consisting of nitrogen oxides and oxygen oxides with a purity of 90% by weight Μ ± in the presence of 0.0 5 to 0. 5 moles * and a temperature of 60 to 98 ° €; and Under the condition that the maximum pressure of the reaction is gas 2, the alkylene oxides on the basis of 70% by weight of arsenic oxygen are subjected to addition polymerization, and the hydroxyl value is 10 to 35 mgK0H / g, and the maximum alcohol is The content is 15 mol S: The minimum selection rate for head-to-tail bonding by propylene oxide addition-polymerization is 96% * Μ and polyoxygen and propyl content is above 70% by weight 2. —A kind of polyoxyalkylene polyhydric aldehyde is a polyoxyalkylene polyenzyme obtained by the method of applying for the first item in the scope of patent application. It is characterized by a hydroxyl value of 10 ~ 35mgK0H / g. , The maximum content of monovalent yeast is 15 mol%, and the lowest choice of head-to-tai 1 bonding by propylene oxide addition polymerization., J It is 96 «, and the content of K and polyoxypropylene is 70% by weight. 3. A method for preparing a soft f polyurethane foam, the characteristics of which are: for glycerol and pentapentyl The selected at least one active hydrogen in the four fermentations. Tensile compound, 1 mole, at least one selected from the group consisting of a hydroxide hydroxide planer having a purity of 90% by weight and an alkali metal hydroxide catalyst of rhenium hydroxide. 〇5 ~ 0.5 Moore &quot; R, K and temperature is 60 ~ 98¾ and the maximum reaction pressure is 4kg / cm2-factory, under the conditions of M, the propylene oxide content is 70 weight of alkylene oxides, Addition polymerization * And the lowest selectivity of the head-to-tail bonding of hydroxy valence 10 ~ 35mgKOH / g, the maximum monohydric alcohol content of 15 mol J !, and the addition polymerization of propylene oxide 96¾, and alkylene oxides with a content of 70% by weight of polyoxyalkylene, addition polymerization, K-made polyoxykepan basic paper size applicable to Chinese national standards (CNS> A4 specifications (210 X 297 mm) 1 ( Please read the Zhuyin on the back first? Matters need to be completed on this page) I 1 /-III Order — — — — ———- Α8 Β8 C8 D8 390B9S VI. Scope of patent application (please read the notes on the back before filling this page), polyol, The polyoxyalkylene polyol is then reacted with a polyisofluoride compound in the presence of a catalyst, a foam stabilizer, a foaming agent, a cross-linking agent, and other auxiliary agents. 4. If the soft and high-quality poly-gamma-carboxylic acid-ester hair plum body of item 3 of the scope of the patent application is applied ...... It is a polymer polyenzyme that has been modified by the polymerization of ethylene, which is selected from the group consisting of two nitriles or a mixture of propylene and styrene. 5. The method for producing a soft polyurethane foam as claimed in claim 3, wherein water is used as a foaming agent. 6. A polymer polyol characterized by being polymerized by polyoxyalkylene doped P, dispersed by 5 wt.%, But less than 30 wt.% Of ethylene based polymer and monomer polymerization The polyhydric alkylene polyol is characterized by a hydroxyl valence of 10 to 35 mgKQH / g and a maximum monohydric alcohol content of 15 mol |. Oiead-to-ta i 1) The minimum selectivity of the bond is 96 each, and the content of polyoxypropylene is above 髯%; Μ and the ethyl acetate and monomers are selected from acrylonitrile or f-propionitrile and phenethyl shop. 'A mixture. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 7. A polymer polyol characterized by being dispersed in a polyoxyl alkyl polyol with 30 weights! Above 8 and glass transition temperature at 60% by weight K ^ &lt;-Nyrate particles of polyunsaturated ethylenically unsaturated monomers of 9,0 ~ 120U; characteristics of the polyoxyalkylene polyol The hydroxyl value is 10 ~, 3.5 _ .. fflg_K0..H * / .. g, ... one yuan, the recommended maximum content is 15 Bayes, ear% 'borrow epoxy. C'. 焼 .. plus It belongs to the polymerization head and tail (Rea, dt〇-ta i 1), the minimum selection rate is 96¾, and the polyoxygen 1 is contained in the amount of J, and the ethylenically unsaturated single 2 copies The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) A8 B8 S90893_m______ 6. Scope of patent application Tisao Zixi # nitrile or a mixture of acrylonitrile and styrene. g. —A method for producing a polymer polyol *, which is characterized in that a polyoxyalkylene polyol is manufactured by the method of the second item of the patent application, and the hydroxyl value of the polyoxy extended polyol is 10 ~ 35ragK0H / g , The maximum content of monohydric alcohol is 15 moles, and the lowest selection rate of (-上 .8 &lt;^-1; 0 .-_ 1311) bonding 96¾, and the content of polyoxyalkylene is 71% by weight or more; in the polyoxyalkylene polyol, the chain transfer agent composed of the amine compound is stored in the following: Ethylene fluorene 'series 4 unsaturated monomers which are a mixture of acrylonitrile and acetofluorene are polymerized. 9. The method for preparing polymer polysaccharide fermentation according to item 8 of the scope of patent application, in which alkylene oxides having a propylene oxide content of 70-wt% or more are used, and M is used as a cap for polyoxyalkylene polyols. The ethylene oxide is 5% by weight or more. 10. For example, a method for preparing a polymer polyol according to item 8 of the application, wherein the amine compound is triethylamine. 11. The method for preparing a polymer polyol according to item 8 of the patent application *, wherein the amine compound is fluorene-methylmorpholine. 12. A method for producing a soft polyurethane urethane foam, characterized in that: by applying the method in the scope of patent application No. 8 to obtain a polymer polyol, f will contain the aforementioned polymer polyol Alcohol polyols react with organic polyisocyanate compounds in the presence of blowing agents, catalysts, foam stabilizers, cross-linking agents, and other rib agents. 13. A method for producing a soft polyurethane foam, which is characterized by: g. A polyol containing a polymer polyol of the scope of application for patent No. 7 and an organic polyscylate compound in a foaming agent; Paper size of catalyst, foam stabilizer, cross-linking agent is applicable to China National Standard (CNS) A4 (210 X 297 mm) I ~~ I (Please read the precautions on the back before filling this page). Γ-- ------ Order ---------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 390893 § D8 VI. The scope of patent application and the existence of other cost agents have reacted. 14. A polymer polyol, characterized in that it is based on the method of patent application... * In the alcohol, more than 30% by weight and 60% by weight of J: 4 skins under M: polymer particles obtained by polymerizing ethylene / unsaturated monomers with a glass transition temperature of 90 to 120 dollars; The special feature of the polyhydric alcohol is that the hydroxyl compensation is 10 ~ 351 ^ 〇1 / ^, the maximum content of the monohydric alcohol is 15 mol%, and the head and tail of the propylene oxide addition polymerization (Read-to-〆— &quot; ta i 1) The lowest choice of bonding. The ratio is 9 ′% * and the content of polyoxypropylene is 70% by weight; M and the ethylenically unsaturated monomer are selected from acrylonitrile or a mixture of acrylonitrile and styrene. (Please read the precautions on the back before filling in this I) Packing.-Order II ---------- Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 4 This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm)