200530290 九、發明說明： 【發明所屬之技術領域】 本發明係相關於使用三環癸烷二甲醇作爲引發劑藉由使 內酯類被開環加成聚合後製得新穎內酯聚合物及其製法。 【先前技術】 先前，內酯聚合物非常適用於彈性體、合成皮革等聚胺 酯及塗料等的原料。 又，內酯聚合物亦可作爲使聚酯樹脂、聚碳酸酯樹脂、 Φ 聚氯乙烯樹脂、丙烯腈•苯曱酸類樹脂等具強韌性、加工 性等之改良劑及胺甲酸丙烯酸樹脂等之原料。 惟，先前使用乙二醇、二乙二醇、1，4 丁二醇、1，6己二 醇等作爲引發劑，使內酯類被開環加成聚合後製得的內酯 聚合物和有機異氰酸酯化合物進行反應製得的聚胺酯缺乏 耐熱性。 耐熱性的程度係以軟化溫度表示，先前的聚胺酯的軟化 溫度爲1 10°C〜〜1 15°C，爲要製得具更高軟化溫度的聚胺 φ 酯，通常，增加形成有機二異氰酸酯及鏈伸長劑等硬段成 分的比率’藉著提高玻璃轉變溫度以提昇耐熱性之方法。 惟’依據上述方法製得的聚胺酯不僅堅硬且彈性明顯降 低，有不具實用性能等缺點。 又，添加低軟化溫度的聚胺酯硬化劑，雖藉由三維元交 聯可提升軟化溫度，惟製得的聚胺酯的彈性低。 例如特開昭63 -23 923號公報中爲要提昇耐熱性，提議 2，2’-雙（4-羥苯基）丙烷的環氧化物加成物變性內酯聚合 物0 200530290 惟’上述特開昭63 -23923號公報提議的變性內酯聚合物 因具芳香族架構，雖可提升耐熱性惟耐天候性差。 本發明係提供一種新穎的內酯聚合物，其特徵係改良上 述缺點且不破壞其他特性，有助於作爲具優異耐熱性、耐 天候性、耐藥品性的聚胺酯用原料。 【發明內容】 本發明者們爲要改良上述缺點經硏究的結果，發現使用 三環癸烷二甲醇作爲引發劑藉由使內酯類進行開環加成聚 Φ 合製得新穎內酯聚合物，係一種可作爲具耐熱性、耐天候 性、耐藥品性的聚胺酯用原料之多醇成分。 亦即，本發明的第1方面係提供下述一般式（I )200530290 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to the use of tricyclodecane dimethanol as an initiator to obtain a novel lactone polymer by ring-opening addition polymerization of lactones and its production. System of law. [Previous Technology] Previously, lactone polymers were very suitable for raw materials such as polyurethanes and coatings such as elastomers and synthetic leather. In addition, lactone polymers can also be used as polyester resin, polycarbonate resin, Φ polyvinyl chloride resin, acrylonitrile and benzoic acid resin, etc. to improve toughness, processability and other modifiers, urethane acrylic resin, etc. raw material. However, lactone polymers and lactone polymers obtained after ring-opening addition polymerization of lactones and ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol were previously used as initiators. Polyurethanes prepared by reacting organic isocyanate compounds lack heat resistance. The degree of heat resistance is expressed by the softening temperature. The softening temperature of the previous polyurethane is 1 10 ° C ~~ 1 15 ° C. In order to obtain a polyamine φ ester with a higher softening temperature, it is generally increased to form an organic diisocyanate. And the ratio of the hard segment components such as chain extenders and the like to increase the heat resistance by increasing the glass transition temperature. However, the polyurethane produced according to the method described above is not only hard, and its elasticity is significantly reduced, but also has disadvantages such as lack of practical properties. In addition, by adding a polyurethane hardener having a low softening temperature, although the softening temperature can be increased by three-dimensional cross-linking, the elasticity of the obtained polyurethane is low. For example, in Japanese Patent Application Laid-Open No. 63-23-23923, in order to improve heat resistance, an epoxide adduct denatured lactone polymer of 2,2'-bis (4-hydroxyphenyl) propane is proposed. 0 200530290 The denatured lactone polymer proposed in Japanese Patent Publication No. 63-23923 has an aromatic structure, and although it can improve heat resistance, it has poor weather resistance. The present invention provides a novel lactone polymer, which is characterized by improving the above-mentioned disadvantages without destroying other characteristics, and is useful as a raw material for polyurethanes having excellent heat resistance, weather resistance, and chemical resistance. [Summary of the Invention] In order to improve the above-mentioned shortcomings, the inventors have studied the results and found that using tricyclodecanedimethanol as an initiator, a novel lactone polymerization is obtained by ring-opening addition polymerization of lactones. The substance is a polyol component which can be used as a raw material for polyurethane having heat resistance, weather resistance and chemical resistance. That is, the first aspect of the present invention provides the following general formula (I)
〔一般式（I )中的Z1、Z2爲相同或相異。各Z1、Z2中X 個R1及R2表示爲各自獨立的H、CH3或C2H5，X係3〜7的 整數，依使用的內酯類之種類而異，m及η分別爲〇〜1〇〇 的整數，m + n表示爲1〜100的整數，又，Ζ1及Ζ2係分子的 兩末端鍵結成爲趨基。〕 表示的三環癸烷二甲醇變性內酯聚合物。 本發明的第2方面係提供如上述一般式（I )表示的三環 200530290 癸烷二甲醇變性內酯聚合物之製法，其特徵係於三環癸烷 二甲醇使碳數4〜8的內酯類開環加成聚合。 本發明的第3方面係提供如上述第2方面的三環癸烷二 甲醇變性內酯聚合物之製法，其中進行開環加成聚合時使 用催化劑。 本發明的第4方面係提供如上述第3方面的三環癸烷二 甲醇變性內酯聚合物之製法，其中催化劑係選自錫、鈦、 鋁、鎢、鉬、锆、鋅及其混合物之金屬化合物。 φ 本發明的第5方面係提供如上述第3方面的三環癸烷二 甲醇變性內酯聚合物之製法，其中催化劑係選自陽離子交 換樹脂、硫酸、高氯酸、BF3、對甲苯基磺酸、及其混合物 之酸催化劑。 本發明的第6方面係提供如上述第2方面的三環癸烷二 甲醇變性內酯聚合物之製法，其中內酯類係r - 丁內酯、3 -甲基- /3-丙內酯、<5-戊內酯、ε -己內酯、3 -甲基-ε -己內 酯、4·甲基-ε -己內酯、3,3,5-三甲基-ε -己內酯、3,5,5-三 φ 甲基-ε-己內酯、3-甲基-5-戊內酯或其混合物。 【實施方式】 實施發明之最佳型態 本發明的新穎內酯聚合物係如上述一般式（I )所表示。 一般式（I)中的ζ1、Ζ2爲各自獨立的聚內酯鏈，可爲相同 或相異。又，Ζ1、Ζ2結構中的一 c0 -係鍵結再三環癸烷二 甲醇的氧原子。各Zi、Z2中，X個R1及R2表示爲各自獨立 的Η、CH3或C2H5，R1及R2爲相同或相異，X係3〜7的整 數’依使用的內酯類之種類而異，m及n分別爲0〜1 〇〇的 200530290 整數，m + n表示爲1〜100的整數，表示爲開環加成聚合的 內酯類之總量。 本發明中使用的內酯類係丁內酯、己內酯、戊內酯、及 這些的或丙內酯的烷基化內酯等鏈的部分爲碳數4〜8之內 酯類，具體例例如r -丁內酯、3 -甲基-/3 -丙內酯（簡稱爲 /5-甲基丙內酯）、戊內酯、ε-己內酯、3-甲基-ε-己 內酯（簡稱爲3-甲基己內酯）、4-甲基-ε-己內酯（簡稱 爲4-甲基己內酯）、3,3,5-三甲基-ε-己內酯（簡稱爲3,3,5 • 三甲基己內酯）、3,5,5-三甲基-ε-己內酯（簡稱爲3,5,5-三甲基己內酯）、3-甲基-5-戊內酯（簡稱爲yS-甲基- (5-戊內酯）等，可爲單獨或2種以上任意比例混合使用。工 業上主要使用ε-己內酯、戊內酯、3-甲基己內酯、4-甲基己內酯，亦可因應其目的添加任意比例的3,3，5-三甲 基己內酯、3，5,5-三甲基己內酯或/3-甲基-5-戊內酯等。 本發明中使用的ε -己內酯、5-戊內酯、3 -甲基己內酯、 4 -甲基己內酯、3,3,5-三甲基己內酯、3,5,5-三甲基己內酯 φ 之製法，係分別使用過氧化的環己酮、環戊酮、甲基取代 環己酮、3，3,5 _三甲基環己酮，利用拜耳-維里格反應進行 氧化而製得。其中，又以工業上已量產的6_己內酯、 戊內醋、3 -甲基己內醋、4_甲基己內醋較理想。 使用於本發明的這些內酯類的另一種起始原料成分（引 發劑）亦即藉由使三環癸烷二甲醇進行開環加成聚合反 應’製得二環癸院一甲醇變性內酯聚合物。相對於1莫耳 三環癸烷二甲醇，內酯類的加成莫耳數〔一般式（I)中的 m + n〕爲1〜1〇〇，以1〜20較理想。若內酯類的加成莫耳數 200530290 大於1 ο ο，例如使用爲塗料時，樹脂的結晶性變高，無法聚 有充分的塗膜物性亦即伸長和撓性較不理想。相反地，若 內酯類的加成莫耳數小於1時，則無內酯類加成的效果。 爲要使引發劑三環癸烷二甲醇和內酯類的反應開始，且 連續地進行內酯類的開環加成聚合反應，需使含內酯類和 引發劑的反應系加熱至50〜220°C，以100〜200°C更佳。低 溫使反應速度變慢較不實用，溫度過高則引發熱分解較不 理想。 • 此反應中使用催化劑較理想。催化劑例如無機鹼、無機 酸、有機鹼金屬催化劑、錫化合物、鈦化合物、鋁化合物、 鋅化合物、鎢化合物、鉬化合物及锆化合物等。其中，考 量其操作容易性、低毒性、反應性、無著色性、耐安定性 等的平衡，以錫化合物、鈦化合物較適用。具體而言，可 適當使用四丁基鈦酸酯、四丙基鈦酸酯、四乙基鈦酸酯、 四甲基鈦酸酯等鈦化合物、辛酸錫、一丁基氧化錫、一丁 基三（2-乙基己酮酯）錫、二丁基氧化錫、二丁基月桂酸 φ 酯錫、二丁基二乙酸酯錫、一 丁基羥氧化錫等有機錫化合 物、及氧化亞錫、氯化亞錫、溴化亞錫、碘化亞錫等鹵化 錫、氯化鋁、鹼金屬的烷氧基金屬、丁基鋰、對甲苯基磺 酸、硫酸、昂伯系列1 5等陽離子交換樹脂、高氯酸、鋅、 BF3等鹼或酸催化劑。其中，氯化亞錫、辛酸錫、四丁基鈦 酸酯等因只要少量即具有高活性較理想。 除溶劑之外的起始原料亦即三環癸烷二甲醇和內酯類的 總計重量爲基準，催化劑的用量爲0.0 1〜2 0 0 p p m，又以 0.1〜5 0ppm較理想。若催化劑的用量多於200ppm，則樹脂 200530290 容易著色且對製品的安定性產生不良影響較不理 地，若催化劑的用量少於〇·01 ppm ’則內酯類的開 合的反應速度變得非常緩慢較不理想。 又，在空氣中進行反應容易造成著色’故於氮 氣體中進行反應較理想。 亦可於無溶劑的條件下進行反應，惟在甲苯、 甲基乙酮、甲基異丁酮等不具活性氫的惰性溶劑 應較理想。使用溶劑係可降低反應結束後反應系 液黏度，且容易控制反應的溫度。惟，含酯鍵結 不理想。因爲反應中聚己內酯的酯基和酯發生交 產生含三環癸烷二甲醇之外的物質之內酯聚合物 惰性溶劑的用量爲含溶劑的全起始原料基準的 % ，以0〜50重量％較理想。若溶劑用量多於80 則反應成分濃度降低，內酯類的開環加成聚合速 不理想。 通常，進行反應係將起始原料三環癸烷二甲醇 催化劑放入反應器，其次將溫度升高至上述的溫 使內酯類進行加成聚合。內酯類的加成聚合過程 色譜法測定反應液中殘留的內酯類的濃度，一般 的濃度小於1 %時作爲加成聚合的終點。即使使 加成聚合結束後亦不需一定從生成物中去除。 又，使用本發明新穎內酯聚合物之聚胺酯，藉 處理亦可作爲聚胺酯分散使用。 其次，舉實例及比較例更詳細地說明本發明， 不受限於此。又，各例中的「部」表示爲重量部 想。相反 環加成聚 氣等惰性 二甲苯、 中進行反 內的反應 之溶劑較 換’可能 〇 〇~80重量 重量％ ’ 度變慢較 、內酯類、 度範圍， ，以氣相 以內酯類 用溶劑， 由水性化 惟本發明 ，％表示 -10- 200530290 爲重量％ 。 (實例1 ) 在具有攬拌機、溫度計、氮氣導入管及冷凝器的4 口可 拆式燒瓶中，放入3 92.6份三環癸烷二甲醇（Celanese Ud 製）、228.3份ε -己內酯、0.5份辛酸錫的庚烷溶液（1% 庚烷溶液），於200°C反應7小時，製得常溫爲液狀的內酯 聚合物（數平均分子量315) °ε·己內酯的反應率爲993 % 。 (實例2 ) 和實例1相同的裝置中放入3 9 2.6份三環癸烷二甲醇 (Celanese Ltd·製）、456.6份ε -己內酯、〇.4份辛酸錫的 庚烷溶液（1%庚烷溶液），於200°C反應7小時，製得常 溫爲液狀的內酯聚合物（數平均分子量425 ) 。ε -己內酯 的反應率爲99.1°/。。 (實例3 ) 和實例1相同的裝置中放入196.3份三環癸烷二甲醇 (Celanese Ltd·製）、803.7份ε -己內酯、0.8份辛酸錫的 庚烷溶液（1%庚烷溶液），於200°C反應8小時’製得常 溫爲液狀的內酯聚合物（數平均分子量1〇〇〇)。己內酯 的反應率爲99.6% 。 各實例中製得的聚合物（樹脂）的性狀如表1所示。 200530290 表1 實例1 實例2 實例3 比較例1 酸價 (KOHmg/g) 0.3 0.4 0.4 0.5 水分（％ ) 0.02 0.02 0.02 0.02 〇H價 (KOHmg/g ) 361.2 264.2 112.3 112.5 又，分析値係以JIS K1557-1970爲基準。 以下，比較例中使用2,2’-雙（4-羥苯基）丙烷的環氧化 物加成物爲引發劑。 (比較例1 ) 和實例1相同的裝置中放入324.3份2,2，-雙（4-羥苯基） 丙烷的環氧化物加成物（日本乳化劑股份公司製： Newcol-1900，〇H 價：346) 、675.7 份 e -己內酯、0.8 份辛 φ 酸錫的庚烷溶液（1%庚烷溶液），於20CTC反應8小時， 製得常溫爲液狀的內酯聚合物（數平均分子量1〇〇〇 )。ε -己內酯的反應率爲99.7% 。 以下’應用例及比較應用例係使用上述實例3及比較例 1製得的內酯聚合物，顯示應用於聚胺酯分散時對聚胺酯 物性的影響。 (應用例1 ) 在反應器中放入83.5份異佛酮二異氰酸酯、111.6份實 例3製得數平均分子量！〇〇〇的內酯聚合物、及54.9份含羧 -12- 200530290 基的聚酯二醇（大西化學工業公司製：PL AC CEL 2 06B A : 數平均分子量600 )，在氮氣流中進行攪拌的同時於80 °C 反應5小時，製得均勻透明的NCO基末端胺甲酸酯預聚 體。其次使溫度降至50°C添加9.24份三乙胺進行中和。 於其中緩慢地加入3 83.4份脫鹽水，作成水中油型的胺 甲酸酯預聚體分散液後，於l〇°C添加3 3.22份異佛酮二胺、 2 99.0份脫鹽水以延長預聚體的鏈長，製得固形分30% 、 黏度150mPa · s/2 5°C、平均顆粒徑5 // m的水性聚胺酯樹 • 脂。 將上述樹脂塗抹在玻璃板上使其厚度爲250 // m，於80 °C乾燥2小時後可得厚度約70 # m的均勻透明、柔軟的薄 膜。於23 °C、6 0% RH中放置1曰後於相同環境中進行拉引 試驗，結果顯示具有拉引強度4 8 Μ P a、伸長6 0 0 %等良好物 性。使1 %薄膜溶解於四氫呋喃，以GPC (凝膠滲透色譜 法）測定分子量的結果，以苯乙烯換算其數平均分子量爲 31000° φ (比較應用例1 ) 在反應器中放入83.5份異佛酮二異氰酸酯、111.6份比 較例1製得數平均分子量1000的內酯聚合物、及54.9份含 羧基的聚酯二醇（大西化學工業公司製：PL ACCEL 206B A : 數平均分子量600 )，在氮氣流中進行攪拌的同時於80°C 反應5小時，製得均勻透明的NCO基末端胺甲酸酯預聚 體。其次使溫度降至50t添加9.24份三乙胺進行中和。 於其中緩慢地加入3 8 3.4份脫鹽水，作成水中油型的胺 甲酸酯預聚體分散液後，於10°C添加3 3.22份異佛酮二胺、 200530290 29 9 ·0份脫鹽水以延長預聚體的鏈長，製得固形分30% 、 黏度140mPa · S/25°C、平均顆粒徑5 // m的水性聚胺酯樹 脂。 將上述樹脂塗抹在玻璃板上使其厚度爲250 // m，於80 °C乾燥2小時後可得厚度約7 〇 #㈤的均勻透明、柔軟的薄 膜。於23 °C、6 0% RH中放置1日後於相同環境中進行拉引 試驗，結果顯示具有拉引強度42MPa、伸長590%等良好物 性。使1 %薄膜溶解於四氫呋喃，以GPC (凝膠滲透色譜 φ 法）測定分子量的結果，以苯乙烯換算其數平均分子量爲 29000 ° 又，以下述的方法測定製得的薄膜之1 〇 〇 %應力、伸度保 持率及應力保持率。 (1 ) 100%應力：100%伸長時的應力 (2 )應力保持率：（耐溼熱性試驗後的斷裂應力/斷裂 應力）X 1 0 0 (3 ) 1〇〇%應力保持率：（耐溼熱性試驗後的1〇〇%應 φ 力 /100% 應力）X100 (4 ) 黃變著色性：以眼觀察 又，耐溼熱性試驗係使薄膜於1 00 °C、溼度1 〇 0 %的環境 下放置2 4小時。 -14- 200530290 表2 初期薄膜物性 耐溼熱性試驗後 強度 伸度 100% 應 強度 保持率 100% 應 保持率 黃變率 (MPa) (¾ ) 力（MPa) (MPa) (% ) 力（MPa) (°/〇 ) 應用例1 48 600 2 44 92 1.6 80 無著色 比較應用例1 42 590 2 38 90 1.5 75 有著色 【應用於產業的可能性】 使用三環癸烷二甲醇爲引發劑而製造的本發明的新穎內 酯聚合物係可作爲具優異耐熱性、耐天候性、耐藥品性的 聚胺酯用原料之化合物。聚胺酯的用途例如熱塑性聚胺酯 彈性體、熱硬化性聚胺酯彈性體、胺甲酸酯泡沬、黏著劑、 密封劑、塗料等，應用於這些用途時具良好物性。又，因 本發明的新穎內酯聚合物和三聚氰胺或聚異氰酸酯類反 應，可製得具優異塗膜物性之塗料組成物。[Z1 and Z2 in the general formula (I) are the same or different. The X R1 and R2 in each Z1 and Z2 are each independently represented by H, CH3 or C2H5, and X is an integer of 3 to 7, which varies depending on the type of the lactone used, and m and η are each 0 to 100. M + n is an integer from 1 to 100, and both ends of the Z1 and Z2 series molecules are bonded to each other. ] Is a tricyclodecane dimethanol denatured lactone polymer. The second aspect of the present invention provides a method for producing a tricyclic 200530290 decanedimethanol denatured lactone polymer represented by the general formula (I) described above, which is characterized in that tricyclodecanedimethanol has a carbon number of 4 to 8 Ester ring-opening addition polymerization. A third aspect of the present invention provides the method for producing a tricyclodecanedimethanol denatured lactone polymer as described in the second aspect, wherein a catalyst is used for the ring-opening addition polymerization. A fourth aspect of the present invention provides the method for producing a tricyclodecane dimethanol lactone polymer as described in the third aspect, wherein the catalyst is selected from the group consisting of tin, titanium, aluminum, tungsten, molybdenum, zirconium, zinc, and mixtures thereof. Metal compounds. φ The fifth aspect of the present invention is a method for producing a tricyclodecanedimethanol denatured lactone polymer as described in the third aspect above, wherein the catalyst is selected from the group consisting of cation exchange resin, sulfuric acid, perchloric acid, BF3, and p-tolylsulfonic acid. Acid catalysts for acids, and mixtures thereof. A sixth aspect of the present invention provides the method for producing a tricyclodecane dimethanol denatured lactone polymer as described in the second aspect above, wherein the lactones are r-butyrolactone and 3-methyl- / 3-propiolactone. ≪ 5-valerolactone, ε-caprolactone, 3-methyl-ε-caprolactone, 4.methyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone Lactone, 3,5,5-tri-φ methyl-ε-caprolactone, 3-methyl-5-valerolactone or a mixture thereof. [Embodiment] The best mode for carrying out the invention The novel lactone polymer of the present invention is represented by the general formula (I) described above. Ζ1 and Z2 in the general formula (I) are independent polylactone chains, and may be the same or different. In addition, one c0-system in the structure of Z1 and Z2 is bonded to the oxygen atom of tricyclodecanedimethanol. In each of Zi and Z2, X R1 and R2 are each independently represented by Η, CH3 or C2H5, R1 and R2 are the same or different, and the integers X of 3 to 7 vary depending on the type of lactones used, m and n are 200530290 integers of 0 to 100 respectively, m + n is an integer of 1 to 100, and it is expressed as the total amount of lactones of ring-opening addition polymerization. The lactones used in the present invention are butyrolactone, caprolactone, valerolactone, and these or alkylated lactones such as propiolactone, and the chain parts are lactones having 4 to 8 carbon atoms, specifically Examples such as r-butyrolactone, 3-methyl- / 3-propiolactone (referred to as / 5-methylpropiolactone), valerolactone, ε-caprolactone, 3-methyl-ε-caprolactone Lactone (3-methylcaprolactone for short), 4-methyl-ε-caprolactone (4-methylcaprolactone for short), 3,3,5-trimethyl-ε-caprolactone Esters (abbreviated as 3,3,5 • trimethylcaprolactone), 3,5,5-trimethyl-ε-caprolactone (abbreviated as 3,5,5-trimethylcaprolactone), 3-methyl-5-valerolactone (abbreviated as yS-methyl- (5-valerolactone), etc., can be used singly or in a mixture of two or more of any ratio. Industrially, ε-caprolactone and valerate are mainly used. Lactone, 3-methylcaprolactone, 4-methylcaprolactone, 3,3,5-trimethylcaprolactone, 3,5,5-trimethyl Caprolactone or / 3-methyl-5-valerolactone, etc. ε-caprolactone, 5-valerolactone, 3-methylcaprolactone, 4-methylcaprolactone, 3,3,5-trimethylcaprolactone, 3,5,5-trimethyl Caprolactone φ is produced by the oxidation of cyclohexanone, cyclopentanone, methyl-substituted cyclohexanone, and 3,3,5 _trimethylcyclohexanone by Bayer-Villig reaction. And it is obtained. Among them, 6-caprolactone, valerolactone, 3-methylcaprolactone, and 4-methylcaprolactone which have been industrially mass-produced are more preferable. These lactones used in the present invention Another kind of starting material component (initiator) is to produce tricyclodecane dimethanol lactone polymer by ring-opening addition polymerization reaction of tricyclodecane dimethanol. Compared to 1 mole For tricyclodecane dimethanol, the number of moles of addition of lactones [m + n in general formula (I)] is 1 to 100, preferably 1 to 20. If the addition of lactones is The number of ears 200530290 is greater than 1 ο ο. For example, when used as a coating, the crystallinity of the resin becomes high, and the physical properties of the coating film cannot be aggregated, that is, the elongation and flexibility are not ideal. On the contrary, if the addition of lactones is When the number of ears is less than 1, there is no effect of lactone addition. In order to start the reaction of the initiator tricyclodecanedimethanol and lactone, the reaction proceeds continuously. The ring-opening addition polymerization of lactones needs to heat the reaction system containing lactones and initiators to 50 ~ 220 ° C, preferably 100 ~ 200 ° C. Low temperature makes the reaction rate slower, which is not practical. If the temperature is too high, thermal decomposition is less desirable. • Catalysts are preferred for this reaction. Catalysts such as inorganic bases, inorganic acids, organic alkali metal catalysts, tin compounds, titanium compounds, aluminum compounds, zinc compounds, tungsten compounds, molybdenum compounds And zirconium compounds, etc. Among them, considering the balance of ease of operation, low toxicity, reactivity, non-coloring, and stability, tin compounds and titanium compounds are more suitable. Specifically, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraethyl titanate, and tetramethyl titanate, tin octoate, monobutyl tin oxide, and monobutyl can be suitably used. Organotin compounds such as tris (2-ethylhexanone ester) tin, dibutyltin oxide, dibutyl laurate φ, tin dibutyl diacetate, monobutyltin oxyhydroxide, and suboxide Tin, stannous chloride, stannous bromide, stannous iodide and other tin halides, aluminum chloride, alkali metal alkoxy metal, butyl lithium, p-tolyl sulfonic acid, sulfuric acid, Amber series 1 5 etc. Cation exchange resins, alkali or acid catalysts such as perchloric acid, zinc, BF3. Among them, stannous chloride, tin octoate, tetrabutyl titanate, and the like are preferable because they have high activity in a small amount. The total weight of the starting materials other than the solvent, that is, tricyclodecanedimethanol and lactones, is based on the total weight of the catalyst. The amount of the catalyst used is preferably from 0.01 to 2 0 p p m, and preferably from 0.1 to 50 ppm. If the amount of the catalyst is more than 200ppm, the resin 200530290 is easy to be colored and adversely affects the stability of the product. Regardless, if the amount of the catalyst is less than 0.01 ppm, the reaction rate of opening and closing of lactones will change. Going very slowly is less desirable. Further, the reaction in air is liable to cause coloring, so the reaction is preferably performed in a nitrogen gas. The reaction can also be performed in the absence of a solvent, but inert solvents such as toluene, methyl ethyl ketone, methyl isobutyl ketone and the like which do not have active hydrogen should be preferred. The use of a solvent system can reduce the viscosity of the reaction system liquid after the reaction is completed, and it is easy to control the reaction temperature. However, ester-containing bonds are not ideal. Because the ester group of the polycaprolactone and the ester cross-linked during the reaction to produce a substance other than tricyclodecane dimethanol, the amount of the lactone polymer inert solvent is% of the total starting material containing solvent, based on 0 ~ 50% by weight is preferable. When the amount of the solvent is more than 80, the concentration of the reaction component decreases, and the rate of ring-opening addition polymerization of lactones is not satisfactory. Generally, the reaction is carried out by placing a tricyclodecanedimethanol catalyst as a starting material into a reactor, and then increasing the temperature to the above-mentioned temperature to effect addition polymerization of lactones. Additive polymerization process of lactones Chromatography measures the concentration of lactones remaining in the reaction solution. Generally, the concentration is less than 1% as the end point of addition polymerization. It is not necessary to remove the product from the product even after the addition polymerization is completed. In addition, the polyurethane using the novel lactone polymer of the present invention can also be dispersed as a polyurethane by treatment. Next, the present invention will be described in more detail with examples and comparative examples, without being limited thereto. In addition, the "part" in each example is expressed as a weight part. On the other hand, inert xylenes such as cycloaddition polygas, and the reaction of the internal reaction in the reaction may be changed to 'possible 〇0 ～ 80% by weight%', the degree is slower, the lactones, the degree range, and the gas phase is the lactones. In the present invention, a solvent is used, and the present invention is represented by%. -10- 200530290 is% by weight. (Example 1) In a 4-neck separable flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a condenser, 3 92.6 parts of tricyclodecanedimethanol (manufactured by Celanese Ud) and 228.3 parts of ε-caproline were placed. Ester, 0.5 part of tin octoate in heptane solution (1% heptane solution), reacted at 200 ° C for 7 hours to prepare a lactone polymer (number average molecular weight 315) at room temperature ° ε · caprolactone The response rate was 993%. (Example 2) In the same apparatus as in Example 1, 3 9 2.6 parts of tricyclodecane dimethanol (manufactured by Celanese Ltd.), 456.6 parts of ε-caprolactone, and 0.4 parts of tin octoate in heptane solution (1 % Heptane solution), and reacted at 200 ° C for 7 hours to prepare a lactone polymer (number average molecular weight: 425) at room temperature. The reaction rate of ε-caprolactone was 99.1 ° /. . (Example 3) In the same apparatus as in Example 1, 196.3 parts of tricyclodecanedimethanol (manufactured by Celanese Ltd.), 803.7 parts of ε-caprolactone, and 0.8 parts of tin octoate in a heptane solution (1% heptane solution) ) And reacted at 200 ° C. for 8 hours to prepare a lactone polymer (number average molecular weight 1000) which is liquid at normal temperature. The reaction rate of caprolactone was 99.6%. The properties of the polymer (resin) obtained in each example are shown in Table 1. 200530290 Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Acid value (KOHmg / g) 0.3 0.4 0.4 0.5 Moisture (%) 0.02 0.02 0.02 0.02 OH value (KOHmg / g) 361.2 264.2 112.3 112.5 In addition, the analysis is based on JIS K1557-1970 is the benchmark. Hereinafter, in the comparative example, an epoxide adduct of 2,2'-bis (4-hydroxyphenyl) propane was used as an initiator. (Comparative Example 1) In the same apparatus as in Example 1, 324.3 parts of 2,2, -bis (4-hydroxyphenyl) propane epoxide adduct (manufactured by Japan Emulsifier Corporation: Newcol-1900, H valence: 346), 675.7 parts of e-caprolactone, 0.8 parts of a heptane solution of tin octoate (1% heptane solution), and reacted at 20CTC for 8 hours to prepare a lactone polymer in a liquid state at normal temperature ( (Number average molecular weight 1000). The reaction rate of ε-caprolactone was 99.7%. The following 'Application Examples and Comparative Application Examples' show the effects of the lactone polymers obtained in the above Examples 3 and 1 on the physical properties of the polyurethane when applied to polyurethane dispersion. (Application Example 1) A number average molecular weight was prepared by putting 83.5 parts of isophorone diisocyanate and 111.6 parts of Example 3 in a reactor! 〇〇〇lactone polymer and 54.9 parts of carboxyl-12-200530290-containing polyester diol (manufactured by Daisai Chemical Industry Co., Ltd .: PL AC CEL 2 06B A: number average molecular weight 600), and stirred in a nitrogen stream At the same time at 80 ° C for 5 hours, a uniform and transparent NCO-terminated urethane prepolymer was obtained. Secondly, the temperature was lowered to 50 ° C, and 9.24 parts of triethylamine was added for neutralization. 3 83.4 parts of desalinated water was slowly added thereto to prepare an oil-in-water urethane prepolymer dispersion solution, and then 3 3.22 parts of isophoronediamine and 2 99.0 parts of desalted water were added at 10 ° C to extend the pretreatment. The chain length of the polymer is 30% solid, the viscosity is 150mPa · s / 2 5 ° C, and the average particle diameter is 5 // m. Apply the above resin to a glass plate to a thickness of 250 // m. After drying at 80 ° C for 2 hours, a uniform transparent and soft film with a thickness of about 70 # m can be obtained. After being placed at 23 ° C and 60% RH for 1 day, the tensile test was performed in the same environment, and the results showed that it had good physical properties such as tensile strength of 48 MPa and elongation of 60%. As a result of dissolving a 1% film in tetrahydrofuran and measuring the molecular weight by GPC (gel permeation chromatography), the number average molecular weight in terms of styrene was 31,000 ° φ (Comparative Application Example 1) 83.5 parts of isophor were placed in a reactor Ketone diisocyanate, 111.6 parts of Comparative Example 1 and a lactone polymer having a number average molecular weight of 1,000, and 54.9 parts of a carboxyl group-containing polyester diol (manufactured by Daisai Chemical Industry Co., Ltd .: PL ACCEL 206B A: number average molecular weight of 600). The reaction was carried out at 80 ° C. for 5 hours while stirring in a nitrogen stream to prepare a uniform and transparent NCO-terminated urethane prepolymer. Secondly, the temperature was lowered to 50 t and 9.24 parts of triethylamine was added for neutralization. 3 8 3.4 parts of desalinated water was slowly added thereto to prepare an oil-in-water urethane prepolymer dispersion solution, and then 3 3.22 parts of isophoronediamine and 200530290 29 9 · 0 parts of desalted water were added at 10 ° C. In order to extend the chain length of the prepolymer, an aqueous polyurethane resin having a solid content of 30%, a viscosity of 140 mPa · S / 25 ° C, and an average particle diameter of 5 // m was prepared. The above resin was applied on a glass plate to a thickness of 250 // m, and after drying at 80 ° C for 2 hours, a uniform transparent and soft film with a thickness of about 70 ° was obtained. The tensile test was performed in the same environment after being left to stand at 23 ° C and 60% RH for 1 day. The results showed good physical properties such as tensile strength of 42 MPa and elongation of 590%. As a result of dissolving a 1% film in tetrahydrofuran and measuring the molecular weight by GPC (gel permeation chromatography φ method), the number average molecular weight in terms of styrene was 29,000 °, and 100% of the obtained film was measured by the following method. Stress, elongation retention and stress retention. (1) 100% stress: stress at 100% elongation (2) Stress retention rate: (fracture stress after damp heat resistance test / fracture stress) X 1 0 0 (3) 100% stress retention rate: (resistant 100% after the moist heat resistance test φ force / 100% stress) X100 (4) Yellowing discoloration: visually, the moist heat resistance test is performed on the film at 100 ° C and humidity 100%. Leave in the environment for 2 4 hours. -14- 200530290 Table 2 Strength elongation after initial moisture and heat resistance test of film properties 100% Strength retention rate 100% Retention rate Yellow rate (MPa) (¾) Force (MPa) (MPa) (%) Force (MPa ) (° / 〇) Application example 1 48 600 2 44 92 1.6 80 No coloring Comparative application example 1 42 590 2 38 90 1.5 75 Coloring [Possibility of application in industry] Tricyclodecanedimethanol is used as the initiator. The novel lactone polymer of the present invention is a compound that can be used as a raw material for polyurethane having excellent heat resistance, weather resistance, and chemical resistance. Applications of polyurethanes include thermoplastic polyurethane elastomers, thermosetting polyurethane elastomers, urethane foams, adhesives, sealants, coatings, and the like, and have good physical properties when applied to these applications. Further, the novel lactone polymer of the present invention reacts with melamine or polyisocyanate to obtain a coating composition having excellent coating film properties.