201209072 六、發明說明： 【發明所屬之技術領域】 本發明係與連續式製造聚合物的方法有關，進一步而 言，尤指一種丙交酯系化合物之聚合物的連續式製造方 法，該方法係將丙交酯系化合物及觸媒化合物連續式注入 一反應裝置，在特定的聚合條件下進行開環聚合’據以得 到耐濕熱安定性佳的丙交酯系化合物之聚合物。 【先前技術】 一般而言，丙交酯系化合物之聚合物的製造，可由乳 酸(Lactic acid簡稱LA)化合物聚合成之乳酸寡聚物，經 裂解成為丙交酯系（Lactide)化合物，再由該丙交酯系化合 物進行開環聚合成為丙交酯系化合物之聚合物，該丙交酯 系化合物之聚合物具有生物可分解性之特性，為未來環保 塑膠之主力產品。 一般而言，丙交酯系化合物之聚合物的聚合製造係在 L-丙父醋（L-lactide)、D-丙交S旨（D-lactide)或内消旋-丙 交醋（Meso-lactide)等丙交酯系化合物及適量的觸媒化合 物存在下’進行開環聚合而得到丙交酯系化合物之聚合 物’聚合所得的該丙交酯系化合物之聚合物經後段熔融押 出、切粒、結晶等步驟，即可得到丙交酯系化合物之聚合 物的粒狀物。上述丙交酯系化合物進行開環聚合而成丙交 醋系化合物之聚合物的方法，一般係使用批式(Batch)方式 進行聚合’其係包括丙交酯系化合物及觸媒化合物一次或 分為多次注入反應器中，加熱聚合成為丙交酯系化合物之 聚合物’隨著聚合物分子量的增加’聚合物的黏度上升的 201209072 緣故’聚合過程中必需保持在高溫以降低反絲度，但高 溫聚合會降低丙交酯系化合物之聚合物的分子量，產生丙 父酯系化合物之寡聚物，導致無法商業化大量生產，並且 聚合物的耐濕熱安定性差的缺點。 【發明内容】 為解決上述先行技術的缺點，經發明人銳意研究而得 本發明。 本發明主要目的在於提供一種丙交酯系化合物之聚合 • 物的連續式製造方法，其主要係將丙交酯系化合物及觸媒 化合物連續式注入一反應裝置在特定的聚合條件下進行開 環聚合，該反應裝置包含至少一個栓塞流式反應器（Plug flow reactor)，該栓塞流式反應器内設有一擾拌裝置，藉 此得到耐濕熱安定性佳的丙交酯系化合物之聚合物。 本發明係一種丙交酯系化合物之聚合物的連續式製造 方法，主要係將丙交酯系化合物及觸媒化合物連續式注入 一聚合反應裝置進行開環聚合’俾供製得财濕熱安定性佳 Φ 的丙交S旨系化合物之聚合物； 其中’該聚合反應裝置包括至少一個栓塞流式反應 器’該栓塞流式反應器内部設有一攪拌裝置，該攪拌裝置 包括一垂直軸及由該垂直轴的周側向外延伸的複數根棒狀 攪拌葉； 所述開環聚合的聚合溫度為110°c〜30(Tc，聚合壓力 為〇· lkg/cm2〜50kg/cm2;該丙交酯系化合物與該觸媒化合 物的重量比=5, 000 : 1〜1〇〇, 〇〇〇 : 1。 【發明詳細說明】 201209072 本發明丙交酯系化合物之聚合物的連續式製造方法， 所使用的丙交酯系化合物具體例為：二個L-乳酸形成的L-丙交酯、二個D-乳酸形成的D-丙交酯、L-乳酸與D-乳酸形 成的内消旋-丙交醋（Meso-lactide，后稱Meso丙交S旨）等， 以及視需要而選之共聚合單體化合物，其中，視需要而選 之共聚合單體化合物的具體例為：丁二酸(succinicacid)、 己二酸(adipic acid)、壬二酸(azelaic acid)、癸二酸 (sebacic acid)、對苯二曱酸(Phthalic acid)、異苯二曱 籲 酸（Isophthalic acid)、對苯二甲酸（terephthalic acid)、乙二醇（ethylene glycol)、1，2-丙二醇 (1，2-propylene glycol)、1，2-丁二醇（1，2-butylene glycol)、1，2-戊二醇（l，2-Pentanediol)、己二醇 (Hexamethylene glycol)、辛二醇（Octanediol)、新異二 醇（Neopentyl glycol)、 環己基雙曱醇 (Cyclohexanedimethanol)等。 本發明的丙交酯系化合物之聚合物的連續式製造方法 # 主要係在丙交酯系化合物及適量的觸媒化合物存在下，視 情況加入添加劑及溶媒進行開環聚合；上述聚合使用之觸 媒化合物例如：週期表第IV、V、Μ金屬的氧化物(oxide)、 鹵化物(halogenide)或羧酸酯（carboxylate)，具體例如： 三氧化二銻Sb2〇3、氧化鍚(SnO)、二氣化錫(snCh)、雙-(2-乙基己基叛酸醋）錫 （Sn( Oct )2、Stannous bis(2-ethylhexyl carboxylate))等，觸媒化合物的使用 量係依據聚合反應情況而定，上述丙交酯系化合物與觸媒 化合物的重量比為5, 000 ·· 1〜1〇〇, 〇〇〇 : 1，較佳為1〇, 〇〇〇 : 201209072 ⑽〇 · 1 ’更佳為15, 000 : 1〜80, 000 : 1。上述聚合 加入的，谷媒，例如.乙基苯(的㈣benzene)、甲苯、乙己 炫(ethyl hexane)、丙酮等。 上述之聚合時加入添加劑的種類不限定，添加劑的種 類包括抗氧化劑、除水劑、分子量調節劑、結晶核劑等， 添加劑的添加量不限制，相對於丙交g旨系化合物，添加劑 佔10〜5G’ _ ppm為佳，更佳為5()〜3()，_卿。 本發明之丙交酯系化合物之聚合物的連續式製造方 法，主要係將丙交酿系化合物、觸媒化合物及視需要加入 的溶媒、添加解作為祕組成，將該進料組成連續式注 入-聚合反應裝置巾進行聚合，該進料组成的注入處並無 特別限定，可在該反應裝置之前段、在該反應裝置的中段， 亦可視需要將構成該進料組成的一部份，例如添加劑，選 擇在該反應裝置之後段注入。 本發明所使用之聚合反應裝置，包括至少一個检塞流 式反應器，且該栓塞流式反應器内部具有一攪拌裝置，如 第一圖所示，該攪拌裝置（1〇)包括一垂直軸(shaft)(12)及 由該垂直軸（12)的周側向外延伸的複數根棒狀（r〇d)撥拌 葉（14)，上述垂直軸（12)係由一運轉機構（圖中未示）所帶 動，該運轉機構並無特別限制，可包括馬達等，該運轉機 構的轉速依該反應器内部聚合物的黏度大小來決定，一般 而言，聚合物的黏度愈大則該運轉機構的轉速愈小，以該 運轉機構所能負荷為上限。本發明之攪拌裝置使用該 棒狀(rod)攪拌葉（14)，聚合時的觸媒用量少，得到高分子 量的聚合物較不易裂解。另外，各該棒狀搜拌葉（14)與該 201209072 垂直轴⑽可為一體成型，各該棒狀授拌葉（14)亦可藉由 銜接方式®)疋於該垂直軸（12)，所述的銜接方式可選擇銲 接、螺接或其他連結方式。上述棒狀授拌葉(14)的數目並 無特別_，依反應H的大小而定；各鱗紐摔葉（⑷ 的大小及職可為相同亦可不同，但依據該垂直抽⑽為 中心形成對稱的二棒狀攪拌葉⑽，彼此的大小及形狀相 间為佳’以利於在攪拌時，各該棒狀磐葉（⑷的授摔均 勻。各轉狀響葉（⑷的橫截面形狀不限制，可為圓形、 | 方^橢11$或其他幾何形狀或不規細嫌等，其中以圓 形為佳。另外，上述攪拌裝置⑽中，令該垂直轴（12)兩 側對稱狀向外延伸的二棒狀擾拌葉⑽的末端之間的距離 為L，且L係指依據該垂直軸⑽形成對稱向外延伸的兩棒 狀麟葉（14)的長度加上該垂直軸⑽直徑的總和，令各 該棒狀授拌葉⑽的直徑為D，（L/D)的比錄佳為5〜30, 更佳為6〜27 ’最佳為7〜25，當(L/D)之比值小於5或大 於30時’ 絲不佳；誠轉紐拌葉（⑷的直徑ρ 1 係4曰該棒狀攪拌葉（⑷的橫截面外徑，當該棒狀授摔葉（⑷ 的橫截面為圓形以外的其他幾何形狀(例如：三角形' 四邊 形、多邊形、麵形等）或不規卿狀時，_棒狀擾摔^ U4)的直㈣為該棒狀擾拌葉（14)喊面積換算為具有相 同面積的圓形的直徑。另外，令沿著該垂直軸⑽長軸延 伸方向上，彼此相鄰的二棒狀攪拌葉（14)的距離為p，則 (P/L)的比值較佳為0 〇5〜〇 5，更佳為〇丨〜⑴奶，最佳 為0.12〜〇, 4，當(Ρ/L)比值小於〇. 〇5時，相鄰二棒狀攪拌 葉（14)彼此的間隙太小’授拌負荷過重；若⑽^的比值大 201209072 於0.5時，相鄰二棒狀攪拌葉（14)的間隙太大，失去攪拌 效果不利聚合反應。上述相鄰二棒狀授拌葉（⑷的距離p 係私相鄰二棒狀攪拌葉（14)的橫截面中心點之間的距離。 本發明的聚合反應褒置包括至少一個栓塞流式反應 器，當該反應裝置包含二個或二個以上的柱塞流式反應器 時，各該反應器的排列方式可為串聯或並聯方式排列，亦 可選擇串聯及並聯方式並用，較佳為二個反應器串聯排 列。令一栓塞流式反應器為第一栓塞流式反應器，另一栓 鲁 塞式反應器為第·一检塞流式反應器，該第一检塞流式反 應器與該第二栓塞流式反應器串聯排列，由第一栓塞流式 反應器出口的聚合物溶液送入該第二栓塞流式反應器進行 開環聚合。 本發明之聚合反應條件為聚合溫度110〜300X：及聚合 壓力0. lkg/cm2〜50kg/cm2，較佳為聚合溫度120〜250。(：及 聚合壓力0. 2kg/cm2〜30kg/cm2下進行聚合反應，更佳為聚 合溫度130〜200°C及聚合壓力0.4kg/cm2〜15kg/cm2下進 瞻 行聚合反應。 本發明之聚合反應若以前述二個反應器串聯排列時的 較佳排列方式進行時，該第一栓塞流式反應器的聚合溫度 較佳為110〜200°C，更佳的聚合溫度為120〜180°C，最佳 的聚合溫度為130〜170°C，當第一栓塞流式反應器的聚合 溫度小於11 〇°C時，聚合物溶液之丙交S旨系化合物的轉化率 不足，聚合反應性差；若第一栓塞流式反應器的聚合溫度 大於200°C時，聚合反應黏度增加太快，則不利於生產的穩 定控制；第一栓塞流式反應器的聚合壓力較佳為〇. lkg/cm2 201209072 〜20kg/cm2，更佳的聚合壓力為〇· 3kg/cm2〜18kg/cm2。上 述第一栓塞流式反應器的攪拌裝置的攪拌速率並不限制， 視該第一栓塞流式反應器的容積大小、内部生成聚合物的 黏度大小等因素決定，攪拌速率以小於l〇〇rpm為較佳。上 述第一栓塞流式反應器出口之聚合物溶液的化合物的轉化 率為10重量％〜70重量％，更佳為15重量％〜60重量％，最 佳為20重量％〜50重量％，若該第一栓塞流式反應器出口的 聚合物溶液之化合物的轉化率小於1〇重量％時，聚合反應 # 不足；若聚合物溶液之化合物的轉化率大於70重量％時， 反應器中的聚合物黏度太高。 本發明的聚合反應若以前述二個反應器串聯排列時的 較佳排列方式進行時，該第二栓塞流式反應器的聚合溫度 較佳為120〜300°C，更佳的聚合溫度為15〇〜21(Tc，最佳 的聚合溫度為160〜200。(：，當該第二栓塞流式反應器的聚 合溫度小於120°C時，聚合物溶液之化合物的轉化率不足， 聚合反應性差；當該第二栓塞流式反應器的聚合溫度大於 _ 300°C時，聚合物易裂解；且該第二栓塞流式反應器的聚合 壓力較佳為2kg八:m2〜50kg/cm2’更佳聚合壓力為3kg/cm2 〜30kg/cm2;該第二栓塞流式反應器的搜拌裝置的擾拌速率 不限制，視該第二栓塞流式反應器的容積的大小、内部生 成聚合物的黏度大小等因素決定，其中，授拌速率以小於 20rpm為較佳。另外，上述第二栓塞流式反應器出口的聚合 物溶液之丙交酯系化合物的轉化率較佳為重量％〜98重 量％’更佳轉化率70重量％〜95重量％，最佳轉化率75重量 %〜90重量％。 201209072 當該第二栓塞流式反應器出口的聚合物溶液之丙交醋 系化合物的轉化率小於6〇重量％時，後置的脫揮裝置負擔 大，若聚合物溶液之丙交酯系化合物的轉化率大於重量 %時，聚合物容易裂解。 本發明的單體化合物及觸媒化合物或添加劑，較佳可 自該第一栓塞流式反應器的上方進入，並由其下方出口， 或者自該第一栓塞流式反應器下方進入，並由其上方出 口 ’其中，自該第一栓塞流式反應器的上方進入，並由其 • 下方出口為更佳。另外，聚合物溶液由該第一栓塞流式反 應器出口後，流入該第二栓塞流式反應器時，可自該第二 检塞流式反應器下方進入，並由其上方出口，或者，自該 第一检塞流式反應器上方進入，並由其下方出口，但以自 5亥第一栓塞流式反應器下方進入，並由其上方出口為較 佳。第一栓塞流式反應器及第二栓塞流式反應器的管路間 可視情況加入一泵浦幫助聚合物溶液的輸送。 本發明丙交酯系化合物之聚合物的連續式製造方法， • 在聚合反應裝置後，置一脫揮裝置將未反應的丙交酯系化 合物進行回收的步驟’該脫揮裝置並不限制，可為脫揮槽 或附排氣口之押出機等設備，脫揮槽可以抽真空方式使槽 内形成負壓，其真空度較佳為0.5〜200torr，使脫揮後聚 合物中的殘留單體較佳小於〇. 5重量％;該脫揮裝置再經一 回收設備回收未聚合反應的丙交酯系化合物重覆使用，該 回收設備可選用蒸餾設備或冷凝器（trap)設備；脫揮後聚 合物則經切粒、結晶、乾燥等步驟後，製得數量平均分子 量60, 000〜170, 000之丙交酯系化合物之聚合物。 201209072 本發明所製得之丙交醋系化合物以凝勝渗透層析儀器 (GPC)測得數量平均分子4Mnl ;並且將該丙交g旨系化合物 之聚合物放置在溫度8GT：及相對濕度観的環境條件下24 小時，再只上述凝膠渗透層析儀器測定其數量平均分子量201209072 VI. Description of the Invention: [Technical Field] The present invention relates to a method for continuously producing a polymer, and more particularly to a continuous method for producing a polymer of a lactide compound, which is a method The lactide-based compound and the catalyst compound are continuously injected into a reaction apparatus, and ring-opening polymerization is carried out under specific polymerization conditions to obtain a polymer of a lactide-based compound excellent in moisture and heat stability. [Prior Art] In general, a polymer of a lactide-based compound can be polymerized into a lactic acid oligomer by a lactic acid (Lactic acid abbreviated as LA) compound, which is cleaved into a lactide-based compound, and then The lactide-based compound is subjected to ring-opening polymerization to a polymer of a lactide-based compound, and the polymer of the lactide-based compound has biodegradable properties and is a main product of environmentally friendly plastics in the future. In general, the polymerization of polymers of lactide-based compounds is carried out in L-lactide, D-lactide or meso-propanine (Meso-). In the presence of a lactide-based compound such as lactide and an appropriate amount of a catalyst compound, a polymer obtained by polymerizing a polymer obtained by ring-opening polymerization to obtain a lactide-based compound is melted and cut in a subsequent stage. A pellet of a polymer of a lactide compound can be obtained by a step of granules, crystals, and the like. The method for ring-opening polymerization of the above-mentioned lactide-based compound to form a polymer of a propylene-based vinegar compound is generally carried out by a batch method, which comprises a lactide-based compound and a catalyst compound once or divided. In the case of multiple injection into the reactor, the polymer which is polymerized into a lactide-based compound 'as the molecular weight of the polymer increases', the viscosity of the polymer rises, 201209072. In the polymerization process, it is necessary to maintain the high temperature to reduce the anti-filament degree. However, high-temperature polymerization lowers the molecular weight of the polymer of the lactide-based compound, and produces an oligomer of the propylene-based ester compound, resulting in a failure to commercialize mass production, and the polymer has poor heat and humidity stability. SUMMARY OF THE INVENTION In order to solve the above disadvantages of the prior art, the present invention has been intensively studied by the inventors. The main object of the present invention is to provide a continuous method for producing a polymerization product of a lactide-based compound, which is mainly characterized in that a lactide-based compound and a catalyst compound are continuously injected into a reaction apparatus to be opened under a specific polymerization condition. In the polymerization, the reaction apparatus comprises at least one Plug Flow reactor, and a plugging device is provided in the plug flow reactor, thereby obtaining a polymer of a lactide-based compound excellent in moisture and heat stability. The present invention relates to a continuous method for producing a polymer of a lactide-based compound, which is mainly characterized in that a lactide-based compound and a catalyst compound are continuously injected into a polymerization reaction device for ring-opening polymerization to obtain a wet heat stability. Preferably, the Φ is a polymer of a compound; wherein 'the polymerization device comprises at least one plug flow reactor'. The plug flow reactor is internally provided with a stirring device, the stirring device comprising a vertical axis and a plurality of rod-shaped stirring blades extending outwardly from the circumferential side of the vertical axis; the polymerization temperature of the ring-opening polymerization is 110 ° C to 30 (Tc, the polymerization pressure is 〇 · lkg / cm 2 ~ 50 kg / cm 2 ; the lactide The weight ratio of the compound to the catalyst compound = 5,000 : 1 to 1 〇〇, 〇〇〇: 1. [Detailed Description of the Invention] 201209072 The continuous production method of the polymer of the lactide compound of the present invention, Specific examples of the lactide-based compound to be used are: L-lactide formed from two L-lactic acids, D-lactide formed from two D-lactic acids, and meso formed by L-lactic acid and D-lactic acid -交 vinegar (Meso-lactide, later called Meso C And the like, and optionally a copolymerized monomer compound, wherein specific examples of the copolymerized monomer compound, if desired, are: succinic acid, adipic acid, adipic acid Acid (azelaic acid), sebacic acid, Phthalic acid, isophthalic acid, terephthalic acid, ethylene glycol ), 1,2-propylene glycol, 1,2-butylene glycol, 1,2-pentanediol (1,2-Pentanediol), hexanediol (Hexamethylene glycol), Octanediol, Neopentyl glycol, Cyclohexanedimethanol, etc. Continuous production method of the polymer of the lactide compound of the present invention# Mainly In the presence of a lactide compound and an appropriate amount of a catalyst compound, an additive and a solvent are optionally added to carry out ring-opening polymerization; and the catalyst compound used in the above polymerization is, for example, an oxide of a metal of the IV, V, and a base of the periodic table. Halogenide or carboxylate e), for example: antimony trioxide Sb2〇3, antimony oxide (SnO), disodium tin oxide (snCh), bis-(2-ethylhexyl retinoic acid) tin (Sn( Oct) 2, Stannous bis (2-ethylhexyl carboxylate)), etc., the amount of the catalyst compound used depends on the polymerization reaction, and the weight ratio of the above-mentioned lactide-based compound to the catalyst compound is 5,000 ··1 to 1 〇〇, 〇〇 〇: 1, preferably 1 〇, 〇〇〇: 201209072 (10) 〇 · 1 'More preferably 15,000: 1~80, 000 : 1. The above-mentioned polymerization is added to a grain medium such as ethylbenzene (benzene), toluene, ethyl hexane, acetone or the like. The type of the additive to be added during the above polymerization is not limited, and the type of the additive includes an antioxidant, a water removing agent, a molecular weight modifier, a crystal nucleating agent, etc., and the additive amount is not limited, and the additive accounts for 10% of the compound. ~5G' _ ppm is better, more preferably 5 () ~ 3 (), _ Qing. The continuous production method of the polymer of the lactide-based compound of the present invention mainly comprises a continuous injection of the feed composition by using a blending compound, a catalyst compound, and a solvent to be added as needed, as a secret component. - the polymerization device is subjected to polymerization, and the injection portion of the feed composition is not particularly limited, and a part of the composition of the feed may be formed in the middle stage of the reaction apparatus or in the middle of the reaction apparatus as needed, for example The additive is selected to be injected in the latter stage of the reaction apparatus. The polymerization reaction apparatus used in the present invention comprises at least one plug flow reactor, and the plug flow reactor has a stirring device inside, as shown in the first figure, the stirring device (1〇) includes a vertical axis (shaft) (12) and a plurality of rod-shaped (r〇d) dialing blades (14) extending outward from a circumferential side of the vertical axis (12), wherein the vertical axis (12) is operated by a running mechanism (Fig. The operating mechanism is not particularly limited, and may include a motor or the like. The rotational speed of the operating mechanism is determined by the viscosity of the polymer inside the reactor. Generally, the greater the viscosity of the polymer, the greater the viscosity of the polymer. The smaller the rotational speed of the operating mechanism, the upper limit of the load that can be used by the operating mechanism. In the stirring apparatus of the present invention, the rod stirring blade (14) is used, and the amount of the catalyst used in the polymerization is small, and the polymer obtained by obtaining a high molecular weight is less likely to be cleaved. In addition, each of the rod-shaped search leaf (14) and the 201209072 vertical shaft (10) may be integrally formed, and each of the rod-shaped mixing leaves (14) may be attached to the vertical shaft (12) by means of a joint method. The connection manner can be selected from welding, screwing or other joining methods. The number of the above-mentioned rod-shaped mixing leaves (14) is not particularly _, depending on the size of the reaction H; the size of the scales of the scales (4) may be the same or different, but centered on the vertical pumping (10) The two rod-shaped stirring blades (10) are formed symmetrically, and the size and shape of each other are better between each other to facilitate the uniformity of each of the rod-shaped leaves ((4) when stirring. The cross-sectional shape of each of the rotating leaves ((4) is not The limitation may be a circle, a square ellipse 11$ or other geometric shapes or irregularities, etc., wherein a circle is preferred. In addition, in the stirring device (10), the vertical axis (12) is symmetrical on both sides. The distance between the ends of the outwardly extending two rod-shaped scrambled leaves (10) is L, and L is the length of the two rod-like lobes (14) extending symmetrically outward according to the vertical axis (10) plus the vertical axis (10) The sum of the diameters, so that the diameter of each of the rod-shaped mixing leaves (10) is D, and the ratio of (L/D) is preferably 5 to 30, more preferably 6 to 27', preferably 7 to 25, when (L) /D) When the ratio is less than 5 or greater than 30, the silk is not good; the turntable leaves ((4) diameter ρ 1 is 4 曰 the rod-shaped stirring blade ((4) cross-sectional outer diameter, when the rod When the cross-section of the (4) is a geometric shape other than a circle (for example, a triangle 'quadrilateral, a polygon, a polygon, a surface, etc.) or an irregular shape, the straight (four) of the rod-shaped disturbing ^ U4) is The rod-shaped scrambled leaf (14) is converted into a circular diameter having the same area, and the distance between the two rod-shaped stirring blades (14) adjacent to each other along the longitudinal axis of the vertical axis (10) For p, the ratio of (P/L) is preferably 0 〇5~〇5, more preferably 〇丨~(1) milk, preferably 0.12~〇, 4, when (Ρ/L) ratio is less than 〇. 〇 At 5 o'clock, the gap between adjacent two rod-shaped stirring blades (14) is too small, and the mixing load is too heavy; if the ratio of (10)^ is large at 201209072 at 0.5, the gap between adjacent two rod-shaped stirring blades (14) is too large. Loss of the stirring effect is unfavorable for the polymerization reaction. The distance between the adjacent two rod-shaped mixing leaves ((4) is the distance between the center points of the cross-sections of the privately adjacent two rod-shaped stirring blades (14). The polymerization reaction of the present invention Including at least one plug flow reactor, when the reaction apparatus comprises two or more plug flow reactors, each of the reactors The arrangement may be arranged in series or in parallel, or may be selected in series and in parallel, preferably two reactors are arranged in series. One plug flow reactor is the first plug flow reactor, and the other plug is ruse. The reactor is a first plug flow reactor, and the first plug flow reactor is arranged in series with the second plug flow reactor, and is fed by a polymer solution at the outlet of the first plug flow reactor. The second plug flow reactor is subjected to ring-opening polymerization. The polymerization reaction conditions of the present invention are a polymerization temperature of 110 to 300 X: and a polymerization pressure of 0.1 kg / cm 2 to 50 kg / cm 2 , preferably a polymerization temperature of 120 to 250. The polymerization reaction is carried out at a polymerization pressure of 0.2 kg/cm 2 to 30 kg/cm 2 , more preferably at a polymerization temperature of 130 to 200 ° C and a polymerization pressure of 0.4 kg/cm 2 to 15 kg/cm 2 . When the polymerization reaction of the present invention is carried out in a preferred arrangement when the two reactors are arranged in series, the polymerization temperature of the first plug flow reactor is preferably 110 to 200 ° C, and the polymerization temperature is preferably 120. ～180°C, the optimum polymerization temperature is 130~170°C. When the polymerization temperature of the first plug flow reactor is less than 11 〇°C, the conversion rate of the compound of the polymer solution is insufficient. Poor polymerization reactivity; if the polymerization temperature of the first plug flow reactor is greater than 200 ° C, the viscosity of the polymerization reaction increases too fast, which is not conducive to stable control of production; the polymerization pressure of the first plug flow reactor is preferably 〇 Lkg/cm2 201209072 ~ 20kg/cm2, more preferably a polymerization pressure of kg·3kg/cm2~18kg/cm2. The stirring rate of the stirring device of the first plug flow reactor is not limited, and is determined according to factors such as the volume of the first plug flow reactor and the viscosity of the internally generated polymer, and the stirring rate is less than 10 rpm. It is better. The conversion rate of the compound of the polymer solution at the outlet of the first plug flow reactor is 10% by weight to 70% by weight, more preferably 15% by weight to 60% by weight, most preferably 20% by weight to 50% by weight, if When the conversion rate of the compound of the polymer solution at the outlet of the first plug flow reactor is less than 1% by weight, the polymerization reaction is insufficient; if the conversion rate of the compound of the polymer solution is more than 70% by weight, the polymerization in the reactor The viscosity of the object is too high. When the polymerization reaction of the present invention is carried out in a preferred arrangement when the two reactors are arranged in series, the polymerization temperature of the second plug flow reactor is preferably 120 to 300 ° C, and the polymerization temperature is preferably 15 〇~21 (Tc, the optimum polymerization temperature is 160 to 200. (: When the polymerization temperature of the second plug flow reactor is less than 120 ° C, the conversion of the compound of the polymer solution is insufficient, and the polymerization reactivity is poor. When the polymerization temperature of the second plug flow reactor is greater than _300 ° C, the polymer is easily cracked; and the polymerization pressure of the second plug flow reactor is preferably 2 kg 八: m 2 〜 50 kg / cm 2 ' The polymerization pressure is preferably from 3 kg/cm 2 to 30 kg/cm 2 ; the scavenging rate of the second plug flow reactor is not limited, depending on the volume of the second plug flow reactor and the internal polymer formation The viscosity is determined by factors such as the viscosity, and the mixing rate is preferably less than 20 rpm. Further, the conversion ratio of the lactide compound of the polymer solution at the outlet of the second plug flow reactor is preferably from weight to 98% by weight. %' better conversion rate 70% by weight 95% by weight, the optimum conversion rate is 75% by weight to 90% by weight. 201209072 When the conversion rate of the propylene-based compound of the polymer solution at the outlet of the second plug flow reactor is less than 6% by weight, the latter The devolatilizer has a large burden, and if the conversion ratio of the lactide compound of the polymer solution is more than % by weight, the polymer is easily cleaved. The monomer compound and the catalyst compound or additive of the present invention are preferably from the first plug. Above the flow reactor enters and exits from below, or from below the first plug flow reactor, and exits from above, where it enters from above the first plug flow reactor and is Preferably, the lower outlet is further provided. Further, after the polymer solution is discharged from the first plug flow reactor, it flows into the second plug flow reactor and enters from below the second plug flow reactor. And exiting from above, or from above the first plug flow reactor, and exiting from below, but entering from below the first plug flow reactor of 5 hai, and exiting from above A pump may be added between the first plug flow reactor and the second plug flow reactor to facilitate the transport of the polymer solution. The continuous manufacturing method of the polymer of the lactide compound of the present invention, After the polymerization apparatus, a step of recovering the unreacted lactide-based compound by a devolatilizer is used. The devolatilizer is not limited, and may be a device such as a devolatilizer or an extruder with an exhaust port. The slewing device can be vacuumed to form a negative pressure in the groove, and the degree of vacuum is preferably 0.5 to 200 torr, so that the residual monomer in the polymer after devolatilization is preferably less than 0.5% by weight; The recycling device recovers the unpolymerized lactide-based compound for repeated use, and the recycling device may be a distillation apparatus or a trap device; after the devolatilization, the polymer is subjected to a step of dicing, crystallization, drying, etc. A polymer of a lactide-based compound having a number average molecular weight of 60,000 to 170,000. 201209072 The vinegar-based compound prepared by the present invention has a number average molecule of 4Mnl measured by a gas chromatography instrument (GPC); and the polymer of the compound is placed at a temperature of 8 GT: and relative humidity. 24 hours under ambient conditions, and only the above gel permeation chromatography instrument to determine its number average molecular weight
Mn2，且(Mn2/Mnl)^5〇%，當 Mn2/Mnl <50%時，所製得丙交 酯系化合物之聚合物的耐濕熱安定性差；上述溫度刖它及 相對濕度80%的環境條件可包括在具有溫度及濕度控制的 保溫箱（Oven)中進行。 φ 本發明聚合時所使用的添加劑’可以在進行開環聚合 的反應前、聚合反應中，或在聚合反應後添加，本發明所 使用的添加劑種類可包括抗氧化劑、紫外線吸收劑、熱安 定劑、醇類及其他添加劑；其中’抗氧化劑的具體例：2, 6-雙-第三-丁基-4-曱基盼 (2,6-di-t-buty卜4-methylphenol ; BHT)、四[3-(3, 5-二 叔丁基-4-經笨基）丙酸]季戊醇@旨 pentaerythritol-tetrakis(3-(3, 5-di-t-butyl-4-hydro _ xyphenyl) propionate)、四[3-(3, 5-二叔丁基-4-羥苯基） 丙酸] 十八醋 octadecy1-3-(3,5-d i-t-buty1-4-hydroxypheny1) propionate、填酸三苯酯（triphenyl phosphate)、亞填酸 三壬苯酯（trinonylphenyl phosphate)、叔丁基羥基茴香 醚(butyl hydroxyanisole ; BHA)等；紫外線吸收劑的具體 例：水揚酸衍生物（salicylic acid)、二苯曱酮化合物 (benzophenone compounds)、苯並三嗤衍生物 (benzotriazole derivatives)等；熱安定劑的具體例：磷 。 [△ } 201209072 酸酯（phosphoric esters)、異氰酸酯化合物（isocyanate compounds)、碳二亞胺（carbodiimide)、酸酐 (anhydrides)、醯氣（acylchlorides)等；醇類的具體例 為：C1〜C18醇，較佳為C4〜C16醇、更佳為C6〜C14醇， 例如Η 醇、正十二烧醇(C12H250H)、十三醇等；其他添 加劑的具體例：1，2-環氧-7-辛烯（1，2-6卩〇又7-7-〇〇^61^)、 丙烯酸缩水甘油酯（glycidyl acrylate)、甲基丙烯酸缩水 甘油酯（glycidyl methacrylate)、十一碳烯酸鹽缩水甘油 φ 酯（glycidyl undecylenate)、環氧大豆油（Epoxidized Soybean Oil)及環氧塔爾油（Epoxidized Tall Oil)。上述 在進行開環聚合反應後添加添加劑的狀況，包括在聚合物 溶液離開聚合反應裝置後，且在進入脫揮裝置前加入，或 在脫揮裝置後的押出機中加入。另外，本發明為了促進結 晶化’丙交醋系化合物之聚合物可進一步添加結晶核劑形 成熔融物，一般而言’加入結晶核劑會使高分子結晶變微 細，具有結晶速度變快的優點；結晶核劑的具體例為：滑 鲁 石（Talc)、二氧化欽(Ti〇2)粒子、碳酸碳CaC〇3粒子、氮化 硼、脂肪族羧酸胺、芳香基磺酸鹽衍生物（Aromatic sulfonate derivative)、苯基礙酸酯鋅（zinc Phenyl phosphonate)等0 另外，為增加丙交g旨系化合物之聚合物的可塑性，本 發明可在聚合物中，混練適當的可塑劑提高聚合物的可塑 性’可塑劑的具體例為：二辛基己二酸酯（dioctyl adipate)、二辛基癸二酸酯（dioctyl sebacate)、二辛基 鄰苯二曱酸酯（dioctyl phthalate)、聚丙烯己二酸酉旨 201209072 (polypropylene adipate)及丁二醇己二酸酯（butanediol adipate) ’可塑劑與丙交酯系化合物之聚合物的相容性佳。 本發明之丙交酯系化合物之聚合物可與其他熱可塑性 樹脂混練形成樹脂組成物，可改善聚合物之物性，其他熱 可塑性樹脂，例如：高衝擊性聚苯乙烯(HIPS)、丙烯腈-丁 二稀-笨乙烯樹脂(ABS)、丙烯腈-丙烯酸系橡膠-苯乙烯樹 脂(AAS)、丙烯腈-(乙烯-丙烯橡勝)—苯乙烯樹脂(aes)等橡 膠變性之苯乙烯系樹脂、聚苯乙烯(PS)、苯乙烯-丙稀腈共 聚物(AS)、苯乙烯-曱基丙烯酸甲酯共聚物(MS)、聚曱基丙 烯酸甲酯（PMMA)、聚碳酸酯（PC)、聚醯胺(pa)、聚氯乙烯 (PVC)、聚對苯二甲酸丁二酯（PBT)、聚對苯二曱酸乙二醋 (PET)等，但不以前述所列舉的熱可塑性樹脂為限。 為了說明本發明之效果，特以下列實施例說明，惟其 僅為本發明之較佳可行實施例，舉凡熟悉此項技藝的人 仕，其依本發明精神範疇所作的修飾或變更，均理應包含 在本案發明申請專利範圍内。 【物性測定方法】 1、丙交酯系化合物之聚合物之耐濕熱安定性測定： 先取丙交酯系化合物之聚合物樣品以凝膠滲透層析 (GPC)儀器測定數量平均分子量Mnl :另外，將此丙交 酯系化合物之聚合物樣品放置在恆溫（8(rc)恆濕（相對 濕度80%)的環境條件下24辦，取出樣品後再以凝膠 滲透層析（GPC)儀器測定數量平均分子量此2。 Mn2/Mnl250%，财濕熱安定性佳，以◎表示。 Mn2/Mnl<50%，耐濕熱安定性差，以X表示。 201209072 【實施方式】 〔實施例1〕 在串聯排列的1 〇〇公升第一栓塞流式反應器（攪拌裝置 具有棒狀攪拌葉）及100公升的第二栓塞流式反應器（攪拌 裝置具有棒狀攪拌葉）進行丙交酯化合物開環聚合反應；其 中，該第一栓塞流式反應器的攪拌裝置，（L/D)的比值為 21 ’（P/L)的比值為〇. 16，該第二栓塞流式反應器的攪拌裝 置，（L/D)的比值為21，（P/L)的比值為〇· 16，該第一栓塞 流式反應器的入口在上方，出口在下方；將1〇〇重量份丙 交酯化合物(L-丙交酯95重量％以上）以40公斤/小時連續 地注入该第一栓塞流式反應器上方入口，另外，取相對於 丙交酯化合物使用量為4〇ppm的觸媒化合物雙_(2_乙基己 基羧酸酯）錫連續地注入該第一栓塞流式反應器的上方入 口’丙交酯化合物與觸媒化合物的重量比=25〇〇〇 : 1。該 第一栓塞流式反應器的聚合溫度為15(rc、聚合壓力為2. 〇 kg/cm2、攪拌速率6〇 rpm，反應滯留時間為2. 5小時，測 得該第一反應器出口的聚合物溶液之丙交酯化合物的轉化 率為38重量％，該第一拴塞流式反應器出口的聚合聚合物 溶液以泵浦繼續泵入該第二栓塞流式反應器的下方入口， 該第二栓塞流式反應器的聚合溫度為19〇。〇、聚合壓力為 20kg/cm2、攪拌速率1〇 rpm ’反應滯留時間為2 5小時， 該第二反應器的上方出口的聚合物溶液之丙交酯化合物的 最後轉化率為85重量％，聚合完成後的聚合物經一脫揮槽 (真空度<10 torr)脫揮（聚合物中的丙交酯化合物含量小 於0.5重量％)，再經一回收設備冷凝器回收未聚合反應的 201209072 丙交能化合物再伽；峨觸下柿崎合物 結晶、乾燥等步驟後得到本發明之丙交g旨化合物丄 物。實施例1 _料_、反應條件如表-卿，所= 的丙交1旨化合物之聚合物特性如表—所示。 表件 〔實施例2〕 如實施例1的聚合方式’並絲—的聚合反應條 作得到本發明之丙錢化合物之聚合物，聚合物的特性如 表一所示。Mn2, and (Mn2/Mnl)^5〇%, when Mn2/Mnl < 50%, the polymer obtained by preparing the lactide-based compound has poor moist heat stability; the above temperature is 80% relative humidity Environmental conditions can be included in an incubator with temperature and humidity control (Oven). φ The additive used in the polymerization of the present invention may be added before, during or after the polymerization of the ring-opening polymerization. The types of additives used in the present invention may include an antioxidant, an ultraviolet absorber, and a heat stabilizer. , alcohols and other additives; specific examples of 'antioxidants: 2,6-bis-tert-butyl-4-indolyl (2,6-di-t-buty) 4-methylphenol; BHT, Tetrakis[3-(3,5-di-tert-butyl-4-pyridyl)propanoic acid]-pivalol@pentaerythritol-tetrakis(3-(3, 5-di-t-butyl-4-hydro _ xyphenyl) Propionate), tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] octadecyl octadecy1-3-(3,5-d it-buty1-4-hydroxypheny1) propionate, Triphenyl phosphate, trinonylphenyl phosphate, butyl hydroxyanisole (BHA), etc.; specific examples of ultraviolet absorbers: salicylic acid derivatives (salicylic) Acid), benzophenone compounds, benzotriazole derivatives, etc.; specific examples of thermal stabilizers: phosphorus. [△} 201209072 Phosphoric esters, isocyanate compounds, carbodiimides, anhydrides, acylchlorides, etc.; specific examples of alcohols are: C1 to C18 alcohols, Preferred are C4 to C16 alcohols, more preferably C6 to C14 alcohols, such as decyl alcohol, n-dodecyl alcohol (C12H250H), tridecyl alcohol, etc.; specific examples of other additives: 1,2-epoxy-7-octyl Alkene (1,2-6卩〇 and 7-7-〇〇^61^), glycidyl acrylate, glycidyl methacrylate, undecylenate glycidol φ Glycidyl undecylenate, Epoxidized Soybean Oil and Epoxidized Tall Oil. The above-mentioned addition of the additive after the ring-opening polymerization reaction is carried out after the polymer solution leaves the polymerization reactor, and is added before entering the devolatilizer or in the extruder after the devolatilizer. Further, in order to promote the crystallization of the polymer of the propylene vinegar-based compound, the nucleating agent may be further added to form a melt, and generally, 'the addition of the nucleating agent causes the polymer crystal to be fine, and has the advantage that the crystallization rate becomes faster. Specific examples of the crystal nucleating agent are: Talc, Ti〇2 particles, carbonic acid CaC〇3 particles, boron nitride, aliphatic carboxylic acid amines, aryl sulfonate derivatives (Aromatic sulfonate derivative), zinc Phenyl phosphonate, etc. In addition, in order to increase the plasticity of the polymer of the propylene-based compound, the present invention can knead a suitable plasticizer in the polymer to increase polymerization. Specific examples of the plasticity of the plasticizer are: dioctyl adipate, dioctyl sebacate, dioctyl phthalate, poly The propylene adipate 201209072 (polypropylene adipate) and butanediol adipate 'plasticizers have good compatibility with the polymer of the lactide compound. The polymer of the lactide compound of the present invention can be kneaded with other thermoplastic resin to form a resin composition, which can improve the physical properties of the polymer, and other thermoplastic resins such as high impact polystyrene (HIPS), acrylonitrile- Rubber-denatured styrene resin such as butyl diene-stupid vinyl resin (ABS), acrylonitrile-acrylic rubber-styrene resin (AAS), acrylonitrile-(ethylene-propylene rubber)-styrene resin (aes) , polystyrene (PS), styrene-acrylonitrile copolymer (AS), styrene-methyl methacrylate copolymer (MS), polymethyl methacrylate (PMMA), polycarbonate (PC) , polyamine (pa), polyvinyl chloride (PVC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), etc., but not the aforementioned thermoplasticity Resin is limited. The invention is described in the following examples, which are merely preferred embodiments of the present invention, and those skilled in the art should be modified or modified in accordance with the spirit of the present invention. Within the scope of the patent application of the present invention. [Measurement method of physical properties] 1. Determination of moisture and heat stability of a polymer of a lactide-based compound: First, a polymer sample of a lactide-based compound is measured by a gel permeation chromatography (GPC) instrument to determine a number average molecular weight Mnl: The polymer sample of the lactide compound was placed under constant temperature (8 (rc) constant humidity (80% relative humidity) environment, and the sample was taken out and then measured by a gel permeation chromatography (GPC) instrument. The average molecular weight is 2. Mn2/Mnl is 250%, and the wet heat stability is good, expressed by ◎. Mn2/Mnl < 50%, poor heat and humidity stability, expressed by X. 201209072 [Embodiment] [Example 1] 1 〇〇 liter first plug flow reactor (stirring device with rod stirring blade) and 100 liter second plug flow reactor (stirring device with rod stirring blade) for ring-opening polymerization of lactide compound; Wherein, the stirring device of the first plug flow reactor has a ratio of (L/D) of 21 '(P/L) to 〇. 16, the stirring device of the second plug flow reactor, (L) /D) ratio is 21, (P/L) The value is 〇·16, the inlet of the first plug flow reactor is above, and the outlet is below; 1 〇〇 parts by weight of the lactide compound (L-lactide 95% by weight or more) is continuously 40 kg/hr. Injecting into the upper inlet of the first plug flow reactor, and further injecting the catalyst compound bis(2-ethylhexylcarboxylate) tin in an amount of 4 〇ppm relative to the lactide compound. The weight ratio of the lactide compound to the catalyst compound at the upper inlet of a plug flow reactor = 25 〇〇〇: 1. The polymerization temperature of the first plug flow reactor was 15 (rc, polymerization pressure was 2.拴kg/cm2, stirring rate of 6 rpm, reaction residence time of 2.5 hours, the conversion rate of the lactide compound of the polymer solution at the outlet of the first reactor was measured to be 38% by weight, the first sputum The polymerized polymer solution at the outlet of the flow reactor is pumped continuously into the lower inlet of the second plug flow reactor, and the polymerization temperature of the second plug flow reactor is 19 Torr. The polymerization pressure is 20 kg/ Cm2, stirring rate 1 rpm 'reaction retention time is 25 hours The final conversion of the lactide compound of the polymer solution at the upper outlet of the second reactor was 85% by weight, and the polymer after completion of the polymerization was subjected to a devolatilization tank (vacuum degree < 10 torr) devolatilization (polymer The content of the lactide compound is less than 0.5% by weight, and then the unpolymerized 201209072 propylene cross-linking compound is recovered by a recovery device condenser; the bismuth of the persimmonate is crystallized, dried, etc., and the C of the present invention is obtained. The compound of the present invention is as shown in Table 1. The reaction conditions are as shown in Table-Q. Table [Example 2] A polymerization reaction strip of the polymerization method of Example 1 was prepared as a polymer of the propanol compound of the present invention, and the properties of the polymer are shown in Table 1.
〔實施例3〕 如實施例1的聚合方式，並依表一的聚合反應條件操 作得到本發明之丙錢化合物之聚合物，聚合物的特性如 表一所示。 〔比較例1〕 在串聯排列的第一管狀反應器（無攪拌葉）2〇公升及第 一管狀反應器（無授拌葉）2〇公升進行丙交酯化合物開環聚 合反應；將100重量份的丙交酯化合物(L_丙交酯95重量％ 以上）以40公斤/小時連續地注入該第一管狀反應器，另 外，取相對於丙交酯化合物使用量為2〇〇ppm的觸媒化合物 雙-(2-乙基己基羧酸酯）錫連續地注入該第一管狀反應器 的上方入口’丙交醋化合物與觸媒化合物的重量比= 5000 : 1。該第一管狀反應器的聚合溫度為n(^c、聚合壓 力為20kg/cm2，反應滯留時間為〇· 5小時，測得該第一管 狀反應器出口的聚合物溶液之丙交酯化合物的轉化率為5〇 重量％ ’該第一管狀反應器出口的聚合物溶液以泵浦繼續系 入該第二管狀反應器，該第二管狀反應器的聚合溫度為190 t S] 15 201209072 °C、聚合壓力為60kg/cm2 ’反應滯留時間為〇 5小時，該 第二管狀反應器出口的聚合物溶液之丙交酯化合物的最後 轉化率為85重量％ ’聚合完成後的聚合物經一脫揮槽（真空 度<10 torr)脫揮，再經一回收設備冷凝器回收未聚合反 應的丙交酯化合物，供再次使用；而脫揮槽下方熔融聚合 物基押出、結晶、乾燦專步驟。比較例1的進料組成、反 應條件如表一所示，所製得的丙交酯化合物之聚合物特性 如表一所示。 〔比較例2〕 如比較例1的聚合方式，但改為串聯排列的8〇公升第 一連續攪拌槽式反應器（具有螺旋狀攪拌葉）及8〇公升的第 二連續攪拌槽式反應器（具有螺旋狀攪拌葉）進行丙交酯化 合物開環聚合反應，並依表一的聚合反應條件操作得到丙 交酯化合物之聚合物，所製得的丙交酯化合物之聚人 性如表一所示。 °奇 【附表說明】 表-係本發明實關及比較例㈣合反祕件及 合物特性。 付^ 【圖式簡單說明】 第一圖係本發明所使用攪拌裴置之結構示意圖。 【主要元件符號說明】 攪拌裝置（10) 垂直轴（12) 棒狀攪拌葉（14) 201209072[Example 3] The polymer of the present invention was obtained by the polymerization method of Example 1, and the polymer of the present invention was obtained according to the polymerization conditions of Table 1. The properties of the polymer are shown in Table 1. [Comparative Example 1] Ring-opening polymerization of lactide compound was carried out in 2 liters of a first tubular reactor (without stirring blades) arranged in series and 2 liters of a first tubular reactor (without feeding leaves); a portion of the lactide compound (L_lactide 95% by weight or more) was continuously injected into the first tubular reactor at 40 kg/hr, and further, a contact amount of 2 〇〇 ppm relative to the lactide compound was used. The bis-(2-ethylhexylcarboxylate) tin is continuously injected into the upper inlet of the first tubular reactor. The weight ratio of the propylene compound to the catalyst compound = 5000:1. The polymerization temperature of the first tubular reactor is n (c, the polymerization pressure is 20 kg/cm 2 , the reaction residence time is 〇·5 hours, and the lactide compound of the polymer solution at the outlet of the first tubular reactor is measured. The conversion rate is 5% by weight 'The polymer solution at the outlet of the first tubular reactor is pumped into the second tubular reactor, and the polymerization temperature of the second tubular reactor is 190 t S] 15 201209072 °C The polymerization pressure is 60 kg/cm 2 'the reaction residence time is 〇5 hours, and the final conversion rate of the lactide compound of the polymer solution at the outlet of the second tubular reactor is 85% by weight. The vortex (vacuum degree <10 torr) devolatilization, and then the unpolymerized lactide compound is recovered by a recovery equipment condenser for reuse; and the molten polymer base is liquefied, crystallized, dried, and dried under the devolatilization tank The composition of the feed of Comparative Example 1 and the reaction conditions are shown in Table 1. The polymer properties of the obtained lactide compound are shown in Table 1. [Comparative Example 2] The polymerization method of Comparative Example 1, but Changed to tandem 8 liter liter first continuous stirred tank reactor (with spiral stirring blade) and 8 liter liter second continuous stirred tank reactor (with spiral stirring blade) for ring-opening polymerization of lactide compound The polymerization conditions of Table 1 were carried out to obtain a polymer of a lactide compound, and the polyglycolic compound obtained by the polymerization was as shown in Table 1. ° [Scheduled Table] Table - The present invention and comparative examples (4) The characteristics of the anti-secret and the compound. [Full description of the drawings] The first figure is a schematic diagram of the structure of the stirring device used in the present invention. [Description of main components] Stirring device (10) Vertical axis (12) Stirring leaves (14) 201209072
※通寐：滩-(2-6^01妒綦琛SI)翁 -力：亦獅；ίίι^^^ϋ (plug flow rsctor) CSTR :择兹港#-it^^>is^(continuous stirred tank rsctor ) Tube "^^^舞甜(="reactor) (Mn2/Mnl)w50% -犀詾濟唞M^^-e©^^。 (Mn2/Mnl)<50% ' 皂餡濟唞 Mt±^- αχ>^'。※ 通寐:Bang-(2-6^01妒綦琛SI) Weng-Li:Yi lion; ίίι^^^ϋ (plug flow rsctor) CSTR : 泽兹港#-it^^>is^(continuous Stirred tank rsctor ) Tube "^^^ Dance sweet (="reactor) (Mn2/Mnl)w50% - rhinoceros 唞 M^^-e©^^. (Mn2/Mnl) <50% 'soap fillings Mt±^-αχ>^'.
1 聚合物 ‘14-1.1 應條件 1聚合反1 耐濕熱安定性(Mn2/Mnl) 未經相對濕度條件下數量平均分子量Mill 反應 1» 反應 組成 進料 轉化率 滯留時間 攪拌速率 聚合壓力 聚合溫度 攪拌裝置P/L 攪拌裝置L/D 1 攪拌葉形狀 反應器大小 反應器型式 轉化率 滯留時間 !攪拌速率 聚合壓力 聚合溫度 攪拌裝置P/L 攪拌裝置L/D 攪拌葉形狀 反應器大小 反應器型式 丙交酯/觸媒 觸媒量 丙交酯進料量 (重量％) (小時） (rpm) o' 〇° Nw^ (公升） (重量％) (小時） (rpm) o' 〇° (公升） (重量比） (ppm) (kg/hr) ◎ 99000 00 L^l K) ΪΛ s Μ a-* s 0.16 Κ) 棒狀 〇 PFR CO 〇〇 DO g IND 0.16 NJ 棒狀 〇 PFR 25000 實施例 ◎ 101400 U) UJ g 0.23 棒狀 100 PFR DO CO CO CO g G CJl 〇 0.23 棒狀 〇 PFR 50000 to ◎ 95000 1 1 1 | 1 I 1 | 1 | | 1 On U» ♦CO CO s UJ 0.16 to 棒狀 〇 PFR 20000 CJl ο CO ><1 85000 00 L/1 〇 Ιλ 1 g 190 1 1 1 N) 〇 Tube cn o c 1 DO CD 170 1 1 1 Μ Tube 5000 200 - 比較例 !χί 88700 00 hJ - 螺旋狀 00 CSTR CJl o •CO Ξ2 〇 cn § ] 螺旋狀 CSTR 8333 N-— g C0 CO s 171 Polymer '14-1.1 Condition 1 Polymerization inverse 1 Moisture and heat stability (Mn2/Mnl) No average relative molecular weight Mill reaction without relative humidity 1» Reaction composition Feed conversion rate Retention time Stirring rate Polymerization Pressure polymerization temperature stirring Device P/L Stirrer L/D 1 Stirring Leaf Shape Reactor Size Reactor Type Conversion Rate Retention Time! Stirring Rate Polymerization Pressure Polymerization Temperature Stirring Device P/L Stirring Unit L/D Stirring Leaf Shape Reactor Size Reactor Type C LAC/catalyst amount of lactide feed (% by weight) (hours) (rpm) o' 〇° Nw^ (liters) (% by weight) (hours) (rpm) o' 〇° (liters) (weight ratio) (ppm) (kg/hr) ◎ 99000 00 L^l K) ΪΛ s Μ a-* s 0.16 Κ) Rod 〇 PFR CO 〇〇 DO g IND 0.16 NJ Rod 〇 PFR 25000 Example ◎ 101400 U) UJ g 0.23 rod 100 PFR DO CO CO CO g G CJl 〇 0.23 rod 〇 PFR 50000 to ◎ 95000 1 1 1 | 1 I 1 | 1 | | 1 On U» ♦CO CO s UJ 0.16 to rod 〇PFR 20000 CJl ο CO >< ;1 85000 00 L/1 〇Ιλ 1 g 190 1 1 1 N) 〇Tube cn oc 1 DO CD 170 1 1 1 Μ Tube 5000 200 - Comparative example!χί 88700 00 hJ - Helical 00 CSTR CJl o •CO Ξ2 〇cn § ] Spiral CSTR 8333 N-- g C0 CO s 17