1251601 玖、發明說明： 【發明所屬之技術領域】 本發明有關一種生物可分解性材料之製法，詳言之，有關 一種聚乳酸之製造方法、乳酸共聚物之製法、聚乳酸之熔融聚 合製程、及乳酸共聚物之熔融聚合製程。 【先前技術】 聚乳酸具生物可分解性，可應用於纖維領域及其他日常 用塑膠品，亦因為具生物吸收性，可做為生醫高分子材料方面 之應用，例如，加工製成纖維可做手術縫線和心導管，或製成 骨釘、骨板、牙科填充材及生物支架。 目前許多報導正集中於以熔融聚合法合成聚乳酸之製 程，例如 Cargill Dow 或 Cargill 公司所揭露（WO 2002100921 及美國專利第5,357,035號系列）之製程，其須先以乳酸（lactic acid)製得寡聚合之聚乳酸（oligomeric PLA)，再由寡聚合之PLA 蒸餾純化後製得丙交酯，再利用丙交酯聚合成PLA。 另外目前有以乳酸直接進行聚合反應而得到PLA之製程 之報導，例如·· Ajioka M.、Enomoto K.、Suzuki K.、Yamaguchj A.等人所著之 5w//. C/zem. Soc· ，西元 1995 年，第 68 期， 第 2125 至 2131 頁，Moon SI、Lee CW、Miyamoto M·、及 Kimura Υ·等 k 所著之 J. Polym. Sci· , Part A, Polym. Chem·,西元 200Q 年，第38期，第1673至1679頁，以及汪朝陽等人所著之合 成纖維西元2002年，第31卷，第2期，第11頁。此種製程之 優點為··價格低，製程也較簡單，但是其缺點是得到之PLA得 率很低，僅30%至60%，且PLA分子量也低，Mw僅6,000至 50,000。依據作者之解釋，主要原因為：聚合反應生成之水， 對生成之PLA進行水解逆反應，故須利用長時間之低壓反應製 1251601 如养聚乳酸（oligomeric 被抽出，導致聚合槽内 程以除水，但是如此也造成大量反應物， PLA)及相伴生成之丙交酯（lacti㈣等， PLA量大幅降低，而分子量上升也有限 【發明内容】 因此，本發明之目的是提供一種製造聚乳酸之方法，苴係 -種新穎的熔融聚合製法，以相對低廉的乳酸為主要原料，藉 由低壓反應製程，可獲得高產率及高分子量之聚乳酸，解決^ 述相關技術之缺失。 依據本發明之製造聚乳酸之方法之特徵，本發明之另一目 的是提供一種製造乳酸共聚物之方法。 又依據本發明之製造聚乳酸之方法之特徵，本發明之又一 目的是提供一種聚乳酸之熔融聚合製程。 仍依據本發明之製造聚乳酸之方法之特徵，本發明之再一 目的是提供一種乳酸共聚物之熔融聚合製程。 本發明之製造聚乳酸之方法，包括以乳酸為原料，在第一 催化劑之存在下，於丨20至220〇C之間之反應溫度下，進行脫 水聚合反應，得到寡聚乳酸（oligolneric p〇lylactic acid);以及 加入無水丙交酯及第二催化劑於該寡聚乳酸中，於12〇至22〇〇c 之間之反應溫度下，及〇·1至1〇〇托耳（t〇rr)之間之壓力下或常 壓下之惰性氣體流中，進行反應，更有效地獲得高分子量及高 得率之聚乳酸之步驟。 本發明之製造乳酸共聚物之方法，包括以乳酸為原料，在 第一催化劑之存在下，於120至220oC之間之溫度下，進行脫 水來合反應，得到寡聚乳酸；加入無水丙交酯及第二催化劑於 該寡聚乳酸中，於120至220〇C之間之溫度下，及至1〇〇 托耳之間之壓力下或是常壓之高溫惰性氣體流中，進行反應， 1251601 獲知聚乳酸，及在上述進行脫水聚合反應以獲得聚乳酸之步驟 之後，加入可與聚乳酸或丙交酯進行共聚合反應之單體及第三 催化劑於该聚乳酸中，於12〇至220°C之間之溫度下，進行聚 合反應，藉以獲得乳酸共聚物之步驟。 本發明之聚乳酸之熔融聚合製程包括在第一反應槽中，於 120至220°C之反應溫度下，使乳酸在第一催化劑之存在下進 行脫水聚合反應，得到包括寡聚乳酸之混合產物；將該包括寡 聚乳酸之混合產物傳送至第二反應槽；在該第二反應槽反應初 始階段’由系統外添加無水丙交酯或乳酸之酯化衍生物、第二 催化劑、及視情況而定之添加劑至該第二反應槽中，將該第二 反應槽抽氣’使得該第二反應槽壓力保持為〇·丨至1〇〇托耳或 是惰性氣體流之常壓下，及外部溫度為12〇至220°C進行反 應；將該第二反應槽抽氣所抽出之化合物傳送至一分離裝置， 其中該化合物包括水及丙交酯及寡聚合物等；使該分離裝置進 行分離’得到無水丙交酯；及在第二反應槽之後續反應時，在 溫度為120至220°C下，及壓力為〇·ι至ι〇〇托耳下或是常壓 之惰性氣體流中，添加來自分離裝置之無水丙交酯之步驟。 本發明之乳酸共聚物之熔融聚合製程包括在一第一反應 槽中，於120至220°C之反應溫度下，使乳酸在第一催化劑之 存在下進行脫水聚合反應，得到包括募聚乳酸之混合產物；將 該包括寡聚乳酸之混合產物傳送至一第二反應槽；在該第二反 應槽反應初始階段，由系統外添加無水丙交g旨、第二催化劑、 及視情況而定之添加劑至該第二反應槽中，將該第二反應槽抽 氣，使得該第二反應槽壓力保持為〇· 1至100托耳下或是常壓 之惰性氣體流中，及外部溫度為120至220QC下，進行反應； 將該第二反應槽抽氣所抽出之化合物傳送至一分離裝置，其中 該化合物包括水及丙交酯及募聚合物等；使該分離裝置進行分 1251601 離，得到無水丙交酯；及在第二反應槽之後續反應時，在溫度 為120至220°C下及壓力為0.1至100托耳下或是常壓之惰性 氣體流中，添加來自分離裝置之無水丙交酯之步驟；及將可與 聚乳酸或丙交酯進行共聚合反應之單體及第三催化劑添加至 該第二反應槽之聚乳酸中，於120至220°C之間之溫度下，進 行聚合反應，獲得乳酸共聚物之步驟。 本發明之製造聚乳酸、乳酸共聚物之方法、聚乳酸之熔融 聚合製程、及乳酸共聚物之熔融聚合製程均具有下列優點： 1.與上述之Kimura Y.及汪朝陽等人揭示之脫水縮合反應 (Dehydration Condensation)技術（其係直接以乳酸為原料）比 較，本發明也是直接以乳酸為原料之脫水縮合反應，但是本發 明之方法及製程可得到較高之分子量及較高之產物得率。 2·與上述之WO 2002100921 (Cargill Dow公司）揭示之既 有技術製程（須先以乳酸製得寡聚合之PLA，再由寡聚合之PLA 製得丙交酯，再由丙交酯聚合形成PLA)比較，本發明之製程較 簡單，價格較貴之丙交酯之使用量較少，且可將丙交酯回收再 添加使用。 3.本發明也可以使用上述Kimura Y.及WO 2002100921等 所揭示之技術所使用之相似設備。 【實施方式】 本發明之方法，係先以乳酸進行聚合反應，且以低壓狀態 進行聚合反應，低壓反應期間，分次添加丙交酯或丙交S旨/催化 劑，能得到高得率及高分子量之聚乳酸。本發明之方法，有別 於習知技術於聚合反應中抽氣蒸餾取出丙交酯，乃獨特的反而 在聚合反應中添加無水丙交酯。在本發明中，添加無水丙交酯 之作用與效果如下：使得部分丙交酯與反應中生成之微量水反 1251601 應，生成乳酸，此既消耗殘存水量，又能增加乳酸單體反應濃 度，故有利反應向所欲之聚乳酸產物方向進行，增加聚乳酸產 率。再者，在低壓反應或在高溫常壓之惰性氣流中之反應條件 下，存在之尚未反應之丙交酯又可與殘存水一起被抽帶出，更 有效地降低存在之水量，使得聚乳酸之水解逆反應減少，而大 幅提高聚合物之分子量，另外，聚乳酸分子量也可以因為丙交 酯之不斷加入而不斷地提高。而所加入之部分丙交酯在製程中 被抽出成為抽出物後，可經過進行回收/脫水/分離後，成為無 水丙乂 g曰，再添加於聚合槽反應液中，回收再利用，可以節省 所需之無水丙交酯。 下列簡示本發明之主要反應：BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a biodegradable material, and more particularly to a method for producing a polylactic acid, a method for producing a lactic acid copolymer, a process for melting a polylactic acid, and And a melt polymerization process of a lactic acid copolymer. [Prior Art] Polylactic acid is biodegradable and can be applied to the fiber field and other daily plastic products. It is also bioavailable and can be used as a biomedical polymer material. For example, it can be processed into fiber. Surgical sutures and cardiac catheters are made, or bone nails, bone plates, dental fillers, and biological stents are made. Many reports are currently focused on the process of synthesizing polylactic acid by melt polymerization, such as the process disclosed by Cargill Dow or Cargill (WO 2002100921 and U.S. Patent No. 5,357,035), which must first be made with lactic acid. The polymerized polylactic acid (oligomeric PLA) is further purified by distillation of the oligomerized PLA to obtain lactide, which is then polymerized into PLA by using lactide. In addition, there are reports on the process of obtaining a PLA by direct polymerization of lactic acid, for example, Ajioka M., Enomoto K., Suzuki K., Yamaguchj A., etc. 5w//. C/zem. Soc· , 1995, No. 68, pp. 2125 to 2131, Moon SI, Lee CW, Miyamoto M., and Kimura Υ· et al. J. Polym. Sci·, Part A, Polym. Chem·, AD 200Q, No. 38, pp. 1673 to 1679, and Wang Chaoyang et al., Synthetic Fibers, 2002, Vol. 31, No. 2, p. 11. The advantages of this process are low price and simple process, but the disadvantage is that the yield of PLA is very low, only 30% to 60%, and the molecular weight of PLA is also low, and the Mw is only 6,000 to 50,000. According to the author's explanation, the main reason is: the water generated by the polymerization reaction, the hydrolysis reaction of the generated PLA, so it is necessary to use a long time low pressure reaction to make 1251601 such as polylactic acid (oligomeric is extracted, resulting in the inner tank of the polymerization tank to remove water However, this also causes a large amount of reactants, PLA) and the accompanying lactide (lacti (iv), etc., the amount of PLA is greatly reduced, and the molecular weight rise is also limited. [Invention] Therefore, the object of the present invention is to provide a method for producing polylactic acid. , a novel melt polymerization process, which uses relatively low-cost lactic acid as a main raw material, and obtains high-yield and high-molecular-weight polylactic acid by a low-pressure reaction process, and solves the defects of the related art. Another object of the present invention is to provide a method for producing a lactic acid copolymer. Further, according to a feature of the method for producing a polylactic acid of the present invention, it is still another object of the present invention to provide a melt polymerization of polylactic acid. Process. Still according to the features of the method for producing polylactic acid of the present invention, a further object of the present invention is to provide A method for producing a polylactic acid according to the present invention, comprising the steps of: carrying out dehydration polymerization using lactic acid as a raw material in the presence of a first catalyst at a reaction temperature of 丨20 to 220 〇C; Reacting to obtain oligolneric p〇lylactic acid; and adding anhydrous lactide and a second catalyst in the oligomeric lactic acid at a reaction temperature between 12 〇 and 22 〇〇c, and 〇·1 The step of carrying out the reaction to obtain a high molecular weight and high yield polylactic acid in a flow of inert gas under a pressure between 1 Torr (t〇rr) or under normal pressure is more effective. The method of copolymer comprises the steps of: dehydrating and reacting with lactic acid as a raw material in the presence of a first catalyst at a temperature between 120 and 220 ° C to obtain an oligomeric lactic acid; adding anhydrous lactide and a second catalyst In the oligolactic acid, the reaction is carried out at a temperature between 120 and 220 ° C and at a pressure between 1 Torr and a high temperature inert gas flow at normal pressure, 1251601 is known as polylactic acid, and Take the above After the step of polymerizing to obtain polylactic acid, a monomer which can be copolymerized with polylactic acid or lactide and a third catalyst are added to the polylactic acid at a temperature between 12 Torr and 220 ° C. a polymerization reaction to obtain a lactic acid copolymer. The melt polymerization process of the polylactic acid of the present invention comprises dehydrating lactic acid in the presence of a first catalyst at a reaction temperature of 120 to 220 ° C in a first reaction tank. Polymerization to obtain a mixed product comprising oligomeric lactic acid; transferring the mixed product including oligomeric lactic acid to a second reaction tank; adding an anhydrous lactide or an ester of lactic acid from outside the system in the initial stage of the second reaction tank reaction a derivative, a second catalyst, and optionally an additive to the second reaction tank, and pumping the second reaction tank to maintain the pressure of the second reaction tank to 〇·丨 to 1 Torr or The reaction is carried out under a normal pressure of an inert gas stream at an external temperature of 12 Torr to 220 ° C; and the compound extracted by pumping the second reaction tank is sent to a separation device, wherein the compound includes Water and lactide and oligopolymer; etc.; separating the separation device to obtain anhydrous lactide; and in the subsequent reaction of the second reaction tank, at a temperature of 120 to 220 ° C, and the pressure is 〇· The step of adding anhydrous lactide from the separation unit is carried out in an inert gas stream under ι to ι〇〇Torr or atmospheric pressure. The melt polymerization process of the lactic acid copolymer of the present invention comprises performing dehydration polymerization of lactic acid in the presence of a first catalyst at a reaction temperature of 120 to 220 ° C in a first reaction tank to obtain a lactic acid-containing polymer. Mixing the product; transferring the mixed product including the oligomeric lactic acid to a second reaction tank; adding an anhydrous propylene, a second catalyst, and optionally an additive from the outside of the system in the initial stage of the second reaction tank reaction In the second reaction tank, the second reaction tank is evacuated, so that the pressure of the second reaction tank is maintained at 〇 1 to 100 Torr or an inert gas flow at normal pressure, and the external temperature is 120 to The reaction is carried out at 220QC; the compound extracted by pumping the second reaction tank is sent to a separation device, wherein the compound comprises water and lactide, and the polymer is collected; and the separation device is separated into 1251601 to obtain anhydrous Lactide; and in the subsequent reaction of the second reaction tank, at a temperature of 120 to 220 ° C and a pressure of 0.1 to 100 Torr or an inert gas flow at normal pressure, added from the separation device a step of water lactide; and adding a monomer copolymerizable with polylactic acid or lactide and a third catalyst to the polylactic acid of the second reaction tank at a temperature between 120 and 220 ° C Next, a polymerization reaction is carried out to obtain a lactic acid copolymer. The method for producing polylactic acid, lactic acid copolymer, the melt polymerization process of polylactic acid, and the melt polymerization process of lactic acid copolymer of the present invention all have the following advantages: 1. Dehydration condensation revealed by Kimura Y. and Wang Chaoyang et al. The reaction (Dehydration Condensation) technology (which is directly based on lactic acid), the present invention is also a dehydration condensation reaction directly using lactic acid as a raw material, but the method and the process of the present invention can obtain a higher molecular weight and a higher product yield. . 2. The prior art process disclosed in WO 2002100921 (Cargill Dow) (the oligo-polymerized PLA is first prepared from lactic acid, the lactide is obtained from the oligo-polymerized PLA, and the lactide is polymerized to form the PLA. Comparing, the process of the invention is simpler, the more expensive lactide is used less, and the lactide can be recycled and used. 3. The present invention can also use similar devices used in the techniques disclosed in the above-mentioned Kimura Y. and WO 2002100921. [Embodiment] In the method of the present invention, the polymerization reaction is carried out by lactic acid, and the polymerization reaction is carried out in a low pressure state. During the low pressure reaction, the lactide or the acrylic acid/catalyst is added in portions, and high yield and high can be obtained. Polylactic acid of molecular weight. The method of the present invention is different from the conventional technique in which the lactide is extracted by distillation in a polymerization reaction, and it is uniquely added to the polymerization reaction to add anhydrous lactide. In the present invention, the effect and effect of adding anhydrous lactide are as follows: a part of lactide is reacted with a trace amount of water generated in the reaction to generate lactic acid, which consumes both residual water and lactic acid monomer reaction concentration. Therefore, the favorable reaction proceeds in the direction of the desired polylactic acid product, increasing the yield of polylactic acid. Furthermore, under the reaction conditions of the low pressure reaction or the inert gas flow under high temperature and normal pressure, the unreacted lactide may be taken out together with the residual water, thereby more effectively reducing the amount of water present, so that the polylactic acid The hydrolysis reverse reaction is reduced, and the molecular weight of the polymer is greatly increased. In addition, the molecular weight of the polylactic acid can be continuously increased by the continuous addition of lactide. After the portion of the lactide added is extracted into the extract in the process, it can be recovered, dehydrated/separated, and then becomes anhydrous propionate, and then added to the polymerization tank reaction solution for recycling and reuse. The desired anhydrous lactide. The following is a brief summary of the main reactions of the present invention:
下列詳述本發明。本發明之製造聚乳酸之方法，係以乳酸 為主要原料’加入第一催化劑，如：苯績酸、填酸、亞磷酸、 次磷酸或其相對應之衍生物或Mhx，其中M1為Sn、Ti、或 Zr;X為1至3之整數；用量為1%至0 05% (重量比）。 首先，於120至220，較佳為120至180，及更佳為160 1251601 =180。〇：之間之反應溫度下，進行脫水聚合反應，反應時間約 :、、、j至12小呀，較佳之時間為4至6小時，得到寡聚乳酸， 斤得到之任何为子畺之券聚乳酸均能適用於本發明，但較易庐 得重量平均分子量為_至2〇，_之寡聚乳酸。 又 接著，在所獲得之寡聚乳酸中加入無水丙交酯及第二催化 J於120至220，較佳為12〇至180，及更佳為16〇至18〇〇c 之間之反應溫度及〇_1至1〇〇，較佳為2至3〇，及更佳為2至 2〇托耳之間之壓力下，進行反應，反應時間為2至8小時，較 =為3至5小時，而獲得聚乳酸。所獲得之聚乳酸之重量平均 刀子里叙可為20,000至20〇,〇〇〇，但不限於此。 上述反應中，無水丙交酯可分次添加，添加之次數並無特 ，限制用畺亦無限制，一旦添加，即能達到增進產率及分子 量之功效，在所欲獲得之聚乳酸性質及經濟上考量，使丙交酯 總使用量與乳酸之總使用量之莫耳比為咖至4/1，但並不限 於此，此莫耳比數越大，生成之聚乳酸分子量越大。同時，於 相同之丙交S旨添加總量之條件下，分次添加之次數越多，生成 之聚乳酸分子量也越大。丙交酯在聚合反應初始階段添加之量 最佳為1/30至1/20，但並無特定之限制。 另者，可使用溫度為120至220。(：之常壓惰性氣體流之反 應條件替代（U至_托耳之低壓反應條件。所使用之惰性氣 體可為例如氮氣、氬氣、或氦氣等。 另者，可以乳酸之酯化衍生物替代丙交酯，添加至聚合反應 中，該乳酸之酯化衍生物可為乳酸甲酯、乳酸乙酯、乳 酸丙酯、或乳酸丁酯，但不限於此等。 所使用之第二催化劑可為M2(OOCR)m4 M2(〇R)m，其中Μ為 Sn、Zr、Tl、P、或Si ; m為1至4之整數；及R為苯 基或-(CH2)nCH3，n為〇至9之整數。用量為1%至〇 〇5% 1251601 (重量比）。 在此步驟中，可視情況而定加入添加劑，加入添加劑可使 反應時間縮短及分子量增加，所使用之添加劑可為一般習用之 乳酸聚合添加劑如：焦磷酸類、苯磺酸或其酯類、M2(〇R)m、 及其組合所組成之族群，其中Μ2為Sn、Zr、Ti、P、或Si ; m 為1至4之整數；及R為苯基或兴CH2)nCH3，n為〇至9之整 數。其中，焦磷酸類並具有可以與水反應，消耗反應中生成之 殘餘水置及催化縮合反應之功能。添加劑之用量為所使用之單 體總重量之5/100至1/1000，較佳為1/2〇〇至1/5〇〇。 對於本發明之製造乳酸共聚物之方法，在上述本發明之製 造聚乳酸之方法進行聚合反應以製備聚乳酸之後，加入可與聚 乳酸或丙交酯進行共聚合反應之單體及第三催化劑，於12〇至 2^0,較佳為120至18〇,及更佳為16〇至18〇。〇之間之溫度及 常壓下，進行共聚合反應，反應時間為丨至6小時，較佳時間 為2至3小時，從第二反應器2下料，即可獲得乳酸共聚物。 所獲得之乳酸共聚物，可由乳酸單體使用量、丙交酯添加 畺〜共象物之單體使用量等控制組成共聚物之單體量或比率， 乂獲付所欲之共1物。共聚物中通常乳酸單體與另一共聚單體 之莫耳比A 99 : 1 1 : 99 ’但此並無特別限制，使用本發明 之方法可依所需，獲得所欲之共聚物。 本發明之製造乳酸共聚物之方法，在製造聚乳酸之步驟 上所使用之反應條件、添加之物質均可適用上述有關本發明 之製造聚乳酸之敘述。此外，在可與聚乳酸或丙交酯進行反應 之共單體方面，可舉例為（但不限於）：環烷内酯 (cycl〇alkyllactone)、碳酸亞烴酯（alkylene 咖—刪、乙交酯 (glycolide)、環氧化物（epoxides)、環烷内醯胺 (cycloalkyllactam)、烧二醇（alkylene giyc〇1)、脂肪雙元酸或相 12 1251601 對應之_ (alkatiedicarbonic acid or ester)、及其組合。此共單體 在la中之使用里可$ 1%至99% (以所有單體總重量為剛％ 計之）。 3、所添加以進行共聚合之第三催化劑可為，其中 Μ 為 Sn Zr、Ti , m 為 1 至 4 之整數；及 R 為_(CH2)nCH3，n 為〇至9之整數。 ^對於依據本發明之特徵之聚乳酸之熔融聚合製程，請參閱 第1圖，說明如下： 在一第一反應槽1中，於120至220,較佳為12〇至18〇, 更佳為160 s 180 C之反應溫度下，使乳酸在第一催化劑之 存在下進行脫水聚合反應，反應時間為2 i 8小時，較佳為3 至5小時’得到包括寡聚乳酸之混合產物。將該包括寡聚乳酸 之此a產物傳送至一第二反應槽2 ;或者，可僅以單一反應槽 取代第一與第二反應槽進行反應。 、在該第二反應槽2反應初始階段，由系統外添加無水丙交 酯或乳酸之酯化衍生物、第二催化劑、及視情況而定之添加劑 ，該第=反應槽中，添加量與種類如上述。將該第二反應槽抽 氣使得》亥第—反應槽壓力保持為〇丨至1 ，較佳為2 及更佳為2至2〇托耳及外部溫度為m至跡較佳為12〇至 及更佳為160 s 180°c ’在此情況下，使丙交醋或乳酸之 酉旨化衍生物與上述包括寡聚乳酸之產物進行反應。 第二反應槽2抽氣所抽出之化合物包括水及丙交酯及寡聚 合物’將所抽出之化合物傳送至分離脫水設備3，如此，留在 第二^槽2之水量減少’對聚乳酸產生之水解逆反應效應降 低’有助於聚合物鏈之增長。在分離脫水設備3對送到之含有 水及丙交醋之物質進行分離，以習用之方式即可達成，例如基 顧’而得到無水丙交酯，可傳送至第二反應槽2中，繼續參與 13 1251601 t乳酸之反應。或者可進一步將氣體中所含之寡聚乳酸分離 出，再循環至第一反應槽1中繼續參與反應。 在第二反應槽2之後續反應時’添加來自分離脫水設備之 無水丙父S旨’在溫度為120至220 ’較佳為120至180，及更 佳為160至180°C及壓力為0·1至1〇〇，較佳為2至％，及更 佳為2至20托耳之情況下，使該丙交酯與上述包括募聚乳酸 之產物進行反應，反應時間為2至8小時，較佳為3至5小時， 產生聚乳酸。 其中所使用之低壓反應條件亦可使用常壓之高溫惰性氣 體流代替。 其中所使用之丙交酯量、催化劑、添加劑種類、乳酸之酯 化衍生物、惰性氣體等，均可適用如上述之本發明之製造聚乳 酸之方法中所使用者。 在上述之本發明之聚乳酸之熔融聚合製程中，若將可與聚 乳酸或丙交酯進行共聚合反應之單體及第三催化劑添加至該 第二反應槽之聚乳酸中，於120至220,較佳為12〇至18〇, 及更佳為160至180°C之間之温度及常壓下，進行聚合反應， 反應時間為1至6小時，較佳時間為2至3小時，獲得乳酸共 聚物。 其中，可與聚乳酸或丙交酯進行共聚合反應之單體及催化 劑，如上述對本發明之製造乳酸共聚物之方法所敘述者。 【實施例】 實施例1 (丙交酯一次全部加入） 於2L不銹鋼反應器中加入乳酸823g (含15% Η:⑺，在氮 氣下將反應器外溫升至15〇〇c，維持在15〇QC進行除水5小時， 然後加入4.5ml之HJO2,並維持外溫在16〇〇c攪拌〇·5 於15分鐘内將系統由常壓抽至真空度1〇1〇打以下，外溫維持 14 1251601 在^160〇C。反應2小時後，將外溫升至185。〇。反應3小時後 以氮氣破真空，取樣分析，所得到之聚乳酸寡聚合物之分子量 為5,000。接著於此反應液中加入丙交酯35〇g、乙醯丙酮鍅 (znxonium acetylacet〇nate) 3 7〇g、及 2_ 乙基己酸錫（仙 2-ethylhexanoate) 3.07g，且將内溫控制在175〇c以上。反應5 小時後下料切粒。Tm (熔點）=185〇c。聚乳酸（lH nmr， CDC13) : 3·8; 2.0 (ppm)。結果如表 1 所示。 實施例2(丙交酯及P(OCH2CH3)3 一次全部加入） 於2L不銹鋼反應器中加入乳酸823g (含15% H20)，在氮 軋下將反應器外溫升至15〇。〇,維持在15〇〇c進行除水5小時， 然後加入4.5ml之HsPO2,並維持外溫在16〇γ攪拌〇·5小時。 於15分鐘内將系統由常壓抽至真空度1〇托耳以下，外溫維持 在160 C。反應2小時後，將外溫升至丨85cC。反應3小時後 以氮氣破真空，加入丙交酯15〇g後於外溫185cC反應i小時， 然後於15分鐘内將系統由常壓抽氣至真空度10托耳以下，外 溫維持185。〇反應1小時後以氮氣破真空，加入丙交酯200g、 乙醯丙3.70g、及2-乙基己酸錫3 07g，及p(〇CH2CH3)3 12g，且將内溫控制在175。〇以上。反應4小時後下料切粒。 Tm= 191°C。結果如表1所示。 實施例3(丙交酯分兩次加入） 产於2L不銹鋼反應器中加入乳酸823g (含15% Ηβ)，在氮 氣下將反應器外溫升至15〇cC，維持在15〇c>c進行除水5小時， 然後加入4.5ml之HJO2,並維持外溫在16〇cC攪拌〇·5小時。 於15分鐘内將系統由常壓抽至真空度1〇托耳以下，外溫維持 在斤160。(：。反應2小時後，將外溫升至185〇c。反應3小時後 以氮氣破真空，加入丙交酯15〇g後於外溫185。〇反應i小時， 然後於15分鐘内將系統由常壓抽氣至真空纟10托耳以下，外 15 1251601 咖維持185〇C。反應1小時後以氮氣破真空，加入丙交酯2〇〇g、 乙醯丙酮錯3.7〇m-乙基己酸錫3 07g’且將内溫控制在 175 C以上。反應4小時後下料切粒。Tm = 189〇c。結果如 1所示。 比較例（未添加丙交酯）（仿照文獻上已知技術之製程） 於2L不銹鋼反應器中加入乳酸823g (含15% h2〇)，在氮 氣下將反應器外溫升至15〇。(：，維持在150cC進行除水5小 時，然後加入4.5ml之HJO2並維持外溫16〇〇c攪拌〇·5小時。 於15分鐘内將系統由常壓抽氣至真空度1〇托耳以下，外溫維 持在160QC。反應2小時後，將外溫升至185〇c。内溫控制在 175 C以上。反應5小時後下料切粒。Tm = 174°C。結果如表 1所示。 實施例4丙交酯-共-己内酯（PLA_c〇_cpL)共聚物之合成 於2L不銹鋼反應器中加入乳酸823g (含15%出〇)，在氮 氣下將反應器外溫升至15〇°C，維持在i5〇°C進行除水5小 日守’然後加入4.5ml之HsPO2，並維持外溫i60°C，攪拌0.5小 時。於15分鐘内將系統由常壓抽氣至真空度1 〇托耳以下，外 溫維持在160QC。反應2小時後，將外溫升至185cc。反應3 小時後以氮氣破真空，加入丙交酯35〇g、乙醯丙酮錯37〇g、 及2-乙基己酸錫3.07g，且將内溫控制在175〇c以上。反應2 小時後’加入己内酯（capr〇lactone) 22〇g (乳酸/己内酯=3/1， 莫耳/莫耳）、乙醯丙酮鍅3.70g、及2-乙基己酸錫3.07g，且將 内溫控制在175CC。反應4小時後下料切粒。Tm = 147°C。結 果如表1所示。 理論值：乳酸單體單元/己内酯單體單元=3〇/1〇 (由ιΗ NMR疋里出來的聚合物的單體單元（m〇n〇meric unit)的莫耳 比）。 16 1251601 實驗值：（巾 NMR，CDC13): 3·8; 2.0 (ppm)(聚乳酸）；3.4; 2.3; 1.6 (ppm)(聚己内酯）。乳酸莫耳單體單元/己内酯莫耳單體單元 =2.3/1.0 。 表1The invention is detailed below. The method for producing polylactic acid of the present invention comprises the following steps of adding lactic acid as a main raw material, such as: benzoic acid, acid, phosphorous acid, hypophosphorous acid or its corresponding derivative or Mhx, wherein M1 is Sn, Ti, or Zr; X is an integer from 1 to 3; and the amount is from 1% to 05% by weight. First, at 120 to 220, preferably 120 to 180, and more preferably 160 1251601 = 180. 〇: Under the reaction temperature between them, the dehydration polymerization reaction is carried out, and the reaction time is about:,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Polylactic acid can be suitably used in the present invention, but it is easier to obtain an oligomeric lactic acid having a weight average molecular weight of _ to 2 Å. Further, a reaction temperature of anhydrous lactide and a second catalyst J of from 120 to 220, preferably from 12 to 180, and more preferably from 16 to 18 ° C, is added to the obtained oligomeric lactic acid. And reacting with 〇_1 to 1〇〇, preferably 2 to 3〇, and more preferably between 2 and 2 Torr, the reaction time is 2 to 8 hours, and the ratio is 3 to 5 Hours, while obtaining polylactic acid. The obtained polylactic acid may have a weight average knife of 20,000 to 20 inches, 〇〇〇, but is not limited thereto. In the above reaction, anhydrous lactide can be added in several stages, and the number of additions is not special, and the limit is not limited. Once added, the effect of improving the yield and molecular weight can be achieved, and the polylactic acid property to be obtained and Economically, the ratio of the total amount of lactide used to the total amount of lactic acid used is 4/1, but it is not limited thereto. The larger the molar ratio, the larger the molecular weight of the produced polylactic acid. At the same time, under the condition that the same total amount of S is added, the more the number of times of addition, the larger the molecular weight of the produced polylactic acid. The amount of lactide added in the initial stage of the polymerization is preferably from 1/30 to 1/20, but is not particularly limited. Alternatively, the temperature can be used from 120 to 220. (: The reaction conditions of the atmospheric pressure inert gas stream are replaced by the low pressure reaction conditions of U to _Torr. The inert gas used may be, for example, nitrogen, argon, helium or the like. Alternatively, it may be derived by esterification of lactic acid. The lactide derivative may be methyl lactate, ethyl lactate, propyl lactate or butyl lactate instead of lactide, but is not limited thereto. It may be M2(OOCR)m4 M2(〇R)m, wherein Μ is Sn, Zr, Tl, P, or Si; m is an integer from 1 to 4; and R is phenyl or -(CH2)nCH3, n is 〇 to an integer of 9. The amount is from 1% to 〇〇5% 1251601 (weight ratio). In this step, additives may be added as needed, and the addition of additives may shorten the reaction time and increase the molecular weight. Commonly used lactic acid polymerization additives such as pyrophosphoric acid, benzenesulfonic acid or its esters, M2(〇R)m, and combinations thereof, wherein Μ2 is Sn, Zr, Ti, P, or Si; m An integer from 1 to 4; and R is phenyl or CH2)nCH3, and n is an integer from 〇 to 9. Among them, pyrophosphate has Reacts with water, consuming the residual water formed in the reaction and catalyzing the condensation reaction. The amount of the additive is from 5/100 to 1/1000, preferably 1/2 to 1/ of the total weight of the monomers used. For the method for producing a lactic acid copolymer of the present invention, after the above-described method for producing a polylactic acid of the present invention is subjected to a polymerization reaction to prepare a polylactic acid, a monomer which can be copolymerized with polylactic acid or lactide is added. And the third catalyst is copolymerized at a temperature between 12 Torr and 2 Torr, preferably 120 to 18 Torr, and more preferably 16 Torr to 18 Torr. The reaction time is 丨. Up to 6 hours, preferably 2 to 3 hours, from the second reactor 2, the lactic acid copolymer can be obtained. The obtained lactic acid copolymer can be used by the amount of lactic acid monomer, lactide added 共The monomer amount or ratio of the constituents of the image is controlled to control the amount or ratio of the monomers constituting the copolymer, and the desired total amount is obtained. The molar ratio of the lactic acid monomer to another comonomer in the copolymer is usually A 99 : 1 1 : 99 ' However, there is no particular limitation, and the method of the present invention can be used as needed. The copolymer of the present invention. The method for producing a lactic acid copolymer of the present invention, the reaction conditions used in the step of producing the polylactic acid, and the added matter can be applied to the above-mentioned description of the production of polylactic acid according to the present invention. The comonomer which is reacted with polylactic acid or lactide can be exemplified by, but not limited to, cycl〇alkyllactone, alkylene carbonate (alkylene coffee-deletion, glycolide). , epoxides, cycloalkyllactam, alkylene giyc〇1, fatty dibasic acid or phase 12 1251601 corresponding to _ (alkatiedicarbonic acid or ester), and combinations thereof. This comon can be used in la to be from 1% to 99% (based on the total weight of all monomers). 3. The third catalyst added for copolymerization may be wherein Μ is Sn Zr, Ti, m is an integer from 1 to 4; and R is _(CH 2 ) nCH 3 , n is an integer from 〇 to 9. For the melt polymerization process of polylactic acid according to the features of the present invention, please refer to FIG. 1 and the following description is as follows: In a first reaction tank 1, 120 to 220, preferably 12 to 18, more preferably At a reaction temperature of 160 s 180 C, lactic acid is subjected to dehydration polymerization in the presence of a first catalyst for a reaction time of 2 i 8 hours, preferably 3 to 5 hours 'to obtain a mixed product comprising oligomeric lactic acid. The a product including the oligomeric lactic acid is transferred to a second reaction tank 2; alternatively, the first and second reaction tanks may be replaced by a single reaction tank. In the initial stage of the reaction of the second reaction tank 2, an anhydrous lactide or an esterified derivative of lactic acid, a second catalyst, and optionally an additive are added from outside the system, and the amount and type of the first reaction tank are added. As above. Pumping the second reaction tank to maintain the pressure of the Hei-reaction tank to 11, preferably 2 and more preferably 2 to 2 Torr, and the external temperature is m to 12 turns to And more preferably 160 s 180 °c 'In this case, a propylene or lactic acid derivative is reacted with the above-mentioned product including oligolactic acid. The compound extracted by the second reaction tank 2 is pumped, including water and lactide, and the oligomer polymer 'transfers the extracted compound to the separation and dewatering apparatus 3, so that the amount of water remaining in the second tank 2 is reduced' to the polylactic acid. The resulting reduction in the effect of the hydrolysis reverse reaction ' contributes to the growth of the polymer chain. The separation and dehydration device 3 separates the substances which are sent to the water and the vinegar, and can be obtained by a conventional method. For example, anhydrous lactide can be obtained according to ', and can be transferred to the second reaction tank 2, and continue. Participate in the reaction of 13 1251601 t lactic acid. Alternatively, the oligolactic acid contained in the gas may be further separated and recycled to the first reaction tank 1 to continue to participate in the reaction. In the subsequent reaction of the second reaction tank 2, 'addition of water-free propanol from the separation and dehydration apparatus is at a temperature of 120 to 220', preferably 120 to 180, and more preferably 160 to 180 ° C and a pressure of 0. · 1 to 1 Torr, preferably 2 to %, and more preferably 2 to 20 Torr, the lactide is reacted with the above-mentioned product including polylactic acid for a reaction time of 2 to 8 hours Preferably, it is from 3 to 5 hours to produce polylactic acid. The low pressure reaction conditions used therein may also be replaced by a high temperature inert gas stream at atmospheric pressure. The amount of the lactide to be used, the catalyst, the type of the additive, the esterified derivative of lactic acid, the inert gas, and the like can be applied to the user of the method for producing a polylactic acid of the present invention as described above. In the above-described melt polymerization process of the polylactic acid of the present invention, if a monomer which can be copolymerized with polylactic acid or lactide and a third catalyst are added to the polylactic acid of the second reaction tank, at 120 to 220, preferably 12 to 18 Torr, and more preferably between 160 and 180 ° C, and at a normal pressure, the polymerization is carried out for a period of from 1 to 6 hours, preferably from 2 to 3 hours. A lactic acid copolymer is obtained. Among them, a monomer and a catalyst which can be copolymerized with polylactic acid or lactide are as described above for the method for producing a lactic acid copolymer of the present invention. EXAMPLES Example 1 (All the lactide was added at once) 823 g of lactic acid (containing 15% hydrazine: (7) was added to a 2 L stainless steel reactor, and the external temperature of the reactor was raised to 15 〇〇c under nitrogen, maintained at 15 〇QC is dehydrated for 5 hours, then 4.5ml of HJO2 is added, and the external temperature is maintained at 16〇〇c. 5·5. Within 15 minutes, the system is pumped from atmospheric pressure to a vacuum of 1〇1. Maintain 14 1251601 at ^160 ° C. After 2 hours of reaction, the external temperature was raised to 185. 反应 After 3 hours of reaction, the vacuum was broken under nitrogen, and the molecular weight of the obtained polylactic acid oligo polymer was 5,000. 35 〇g of lactide, znxonium acetylacetacetate (3 7 〇g), and 2_ethylhexanoate 3.07 g were added to the reaction solution, and the internal temperature was controlled at 175. 〇c or more. After 5 hours of reaction, the pellet was cut. Tm (melting point) = 185 〇 c. Polylactic acid (1H nmr, CDC13): 3·8; 2.0 (ppm). The results are shown in Table 1. Example 2 (Lactide and P(OCH2CH3)3 are added all at once) Add 823g of lactic acid (containing 15% H20) to the 2L stainless steel reactor, and the reactor is under nitrogen rolling. The temperature rises to 15 〇. 〇, maintain water at 15 ° C for 5 hours, then add 4.5 ml of HsPO2, and maintain the external temperature at 16 〇 γ stir 〇 · 5 hours. The system is under normal pressure within 15 minutes. The vacuum was below 1 Torr, and the external temperature was maintained at 160 C. After 2 hours of reaction, the external temperature was raised to 丨85 cC. After 3 hours of reaction, the vacuum was broken with nitrogen, and 15 〇g of lactide was added to the external temperature. 185cC reacted for 1 hour, then pumped the system from atmospheric pressure to a vacuum of 10 Torr or less in 15 minutes, and the external temperature was maintained at 185. After 1 hour of reaction, the vacuum was broken with nitrogen, and lactide 200 g, acetonitrile C 3.70 was added. g, and tin 2-ethylhexanoate 3 07g, and p (〇CH2CH3) 3 12g, and the internal temperature is controlled above 175. 。. After 4 hours of reaction, the pellet is cut. Tm = 191 ° C. The results are as follows Table 1 shows Example 3 (Lactide is added in two portions) 823g (containing 15% Ηβ) of lactic acid is added to a 2L stainless steel reactor, and the external temperature of the reactor is raised to 15 〇cC under nitrogen, and maintained at 15〇c>c was dehydrated for 5 hours, then 4.5 ml of HJO2 was added, and the external temperature was maintained at 16 °c C for 5 hours. The system was pumped from atmospheric pressure to vacuum in 15 minutes. The degree is below 1 Torr, and the external temperature is maintained at 1600. (: After 2 hours of reaction, the external temperature is raised to 185 〇c. After 3 hours of reaction, the vacuum is broken with nitrogen, and 15 〇g of lactide is added. Temperature 185. 〇 reaction for 1 hour, then pump the system from atmospheric pressure to vacuum 纟 10 Torr in 15 minutes, outside 15 1251601 coffee maintained 185 〇 C. After reacting for 1 hour, the mixture was evacuated with nitrogen, and 2 g of lactide, acetonitrile of 3.7 〇m-ethylhexanoate 3 07 g' was added, and the internal temperature was controlled to 175 C or more. After 4 hours of reaction, the pellet was cut. Tm = 189〇c. The result is shown in 1. Comparative Example (without adding lactide) (By the process of the known technique in the literature) 823 g of lactic acid (containing 15% h2 〇) was added to a 2 L stainless steel reactor, and the external temperature of the reactor was raised to 15 Torr under nitrogen. (:, maintain water at 150cC for 5 hours, then add 4.5ml of HJO2 and maintain the external temperature of 16〇〇c for 5 hours. The system will be pumped from atmospheric pressure to a vacuum of 1 Torr in 15 minutes. Hereinafter, the external temperature was maintained at 160 Q C. After the reaction for 2 hours, the external temperature was raised to 185 ° C. The internal temperature was controlled to be 175 C or more. After 5 hours of reaction, the pellet was cut. Tm = 174 ° C. The results are shown in Table 1. Example 4 Synthesis of lactide-co-caprolactone (PLA_c〇_cpL) copolymer In a 2L stainless steel reactor, 823 g of lactic acid (containing 15% of cerium) was added, and the temperature outside the reactor was raised under nitrogen. To 15 ° ° C, maintain water at 5 ° C ° ° ° ° then add 4.5 ml of HsPO2, and maintain the external temperature i60 ° C, stirring for 0.5 hours. The system is pumped from atmospheric pressure within 15 minutes The vacuum is below 1 Torr, and the external temperature is maintained at 160 QC. After 2 hours of reaction, the external temperature is raised to 185 cc. After 3 hours of reaction, the vacuum is broken with nitrogen, and lactide 35 〇g and acetamidineacetate 37 加入 are added. g, and tin 2-ethylhexanoate 3.07g, and the internal temperature is controlled above 175〇c. After 2 hours of reaction 'add caprolactone (capr〇lactone) 22〇g (lactic acid / hexane Lactone = 3/1, Mohr/mole), acetonitrile acetone oxime 3.70 g, and tin 2-ethylhexanoate 3.07 g, and the internal temperature was controlled at 175 cc. After 4 hours of reaction, the pellet was cut. Tm = 147 ° C. The results are shown in Table 1. Theoretical value: lactic acid monomer unit / caprolactone monomer unit = 3 〇 / 1 〇 (monomer unit of polymer derived from ιΗ NMR ( (m〇n 〇meric unit) Mohrby. 16 1251601 Experimental value: (towel NMR, CDC13): 3·8; 2.0 (ppm) (polylactic acid); 3.4; 2.3; 1.6 (ppm) (polycaprolactone). Lactic acid molar monomer unit / caprolactone molar monomer unit = 2.3 / 1.0. Table 1
Mw 得率 PLA寡聚物（加入丙交S旨之前） 5,000 75% 實施例1 (丙交S旨全部一次加入） 41,000 80% 實施例2(丙交酯及P(OCH2CH3)3 一次全部加入） 51,000 89% 實施例3 (丙交酯分兩次加入） 50,000 85% 比較例（未加入丙交酯）（仿照 文獻上已知技術之製程） 20,000 25% 實施例4 共聚合物 PLA-co-CPL 之合成 48,000 90%Mw yield PLA oligo (before adding the propylene exchange S) 5,000 75% Example 1 (All the ones are added) 41,000 80% Example 2 (Lactide and P(OCH2CH3)3 all added at once) 51,000 89% Example 3 (Lactide is added in two portions) 50,000 85% Comparative Example (without the addition of lactide) (similar to the process known in the literature) 20,000 25% Example 4 Copolymer PLA-co- Synthesis of CPL 48,000 90%
Mw :重量平均分子量，由凝膠渗透層析法（Gel Permeable Chromatography，GPC)儀器測試，以聚乙稀苯（Polystyrene) 為參考值。 表1顯示，在比較例中，未如本發明之方法添加丙交酯時， 聚乳酸產率只有25%及重量平均分子量只達20,000。在實施例 1至4，依據本發明之方法進行聚乳酸之製造時，能獲得80% 17 1251601 乂上之產率及重量平均分子量達4〇,〇〇〇以上之聚乳酸或乳酸 共聚物。 雖然本發明已以較佳實施例揭露如上，然其並非用以限定 本發明。任何熟習此技藝者，在不脫離本發明之精神和範圍 内，當可作些許之更動與潤飾。因此本發明之保護範圍當視後 附之申請專利範圍所界定者為準。Mw: weight average molecular weight, as measured by Gel Permeable Chromatography (GPC) instrument with reference to Polystyrene. Table 1 shows that, in the comparative example, when lactide was not added as in the method of the present invention, the yield of polylactic acid was only 25% and the weight average molecular weight was only 20,000. In Examples 1 to 4, when polylactic acid was produced in accordance with the method of the present invention, a polylactic acid or a lactic acid copolymer having a yield of 80% of 17 1251601 Å and a weight average molecular weight of 4 Å or more was obtained. While the invention has been described above in the preferred embodiments, it is not intended to limit the invention. Anyone skilled in the art can make some changes and refinements without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.
18 1251601 【圖式簡單說明】 第1圖為依據本發明之聚乳酸之熔融聚合製程之一實例 示意圖。 【圖式符號說明】 1〜第一反應槽 2〜第二反應槽 3〜分離脫水設備 4〜丙交S旨添加供應槽 5〜寡聚乳酸或乳酸傳送管線 6〜抽氣傳送管線 7〜丙交酯回收再使用傳送管線 1918 1251601 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a melt polymerization process of polylactic acid according to the present invention. [Description of Symbols] 1 to 1st Reaction Tank 2 to 2nd Reaction Tank 3 to Separation and Dehydration Apparatus 4 to Propylene S Add Supply Tank 5 to Oligolactic Acid or Lactic Acid Transfer Line 6 to Pumping Transmission Line 7 to C The lactide recovery and reuse transfer line 19