473482 經濟部中央標準局員工消費合作社印製 A7 五、發明説明（1 本發明係關於兩步聲聚合乳交@旨成爲聚乳交酯。更詳言 之，本發明係關於-種方法，在其第二步躁中，在避Μ 體混合和乳交醋蒸發之條件下，進行聚合至高轉化率/ 近年來，曰漸增加對生物可降解之聚合物，即，生 合物之重視，許多公司餐六I王^ 晃力耆手進仃包裝材料，衛生產品 袋和供農業目的用之薄膜及裝廢物之袋子等上市。尤其， 各種薄膜具ΐ重要性。迄今，使用乳酸的聚合物在此等應 用方面受到此等聚合物的高價格及其於技術加工間 易於破裂所限制。 聚靡可經由縮聚反應予以製備，在製備聚醋時，其 係典型’或經由自環狀内酯進行開環聚合予以製備。聚羥 基酸是熱塑性聚酯，其相似許多習見之聚合物。 二 局了、序义原因t礼又酯或以乳酸爲基準之縮聚物特別 引人注意，因爲其主要降解產物，乳酸是事實上普遍之— 種產物，它係無毒且經廣泛使用於食品和藥物工業中。合 分子量聚合物可經由自交酿之開環聚合最佳產生。乳酸: 旋光性，而因此，其二聚物以四種不同形式出現：以-乳 X酯，D , D -乳交S旨，L D - 51奁两匕,+卞 軋人g日（内消旋乳交酯）&l，l與 D，D-乳交㈣外消旋晶合物。經由聚合此等成爲純化合物 或以不同摻合比例聚合，獲得聚合物其具有不同之立體化 學結構影響其彈性和結晶度，而因此之故，亦影響其機械 和熱等性質。所獲得之聚合物通常是硬質且光學明亮。 羥基酸的環狀内醋之開環聚合，例如乳交酷，乙醇酸交 醋，ε-己内醋構成就其本身而論所熟知之工業技術。所熟 -4- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公f (請先閱讀背面之注意事項再填苟本頁}473482 Printed A7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (1 The present invention is about two-step acoustic polymerization of lactose @intent to become polylactide. More specifically, this invention is about a method, In the two-step process, polymerization is carried out to a high conversion rate under the conditions of avoiding the mixing of M-body and the evaporation of lactose vinegar. In recent years, increasing attention has been paid to biodegradable polymers, that is, biochemicals. I Wang ^ Marketed packaging materials, hygienic product bags, films for agricultural purposes and bags for waste, etc., in particular. Various films are of great importance. To date, polymers using lactic acid have been used in these applications. This aspect is limited by the high price of these polymers and their susceptibility to cracking in the technical processing room. Jumei can be prepared through polycondensation, which is typical when preparing polyacetate or through ring-opening polymerization from cyclic lactones. It is prepared. Polyhydroxy acid is a thermoplastic polyester, which is similar to many conventional polymers. The second round, the reason for the meaning of the ester or the polycondensate based on lactic acid is particularly noticeable, because Its main degradation product, lactic acid is in fact universal-a product that is non-toxic and widely used in the food and pharmaceutical industries. Polymers of molecular weight can be best produced through ring-opening polymerization of inbreeding. Lactic acid: optical activity , And therefore, its dimer appears in four different forms: -milk X ester, D, D-Lactation S purpose, LD-51 奁 two daggers, + 卞 rolling human g day (mesolactide) & amp l, l and D, D-lactate racemic crystals. By polymerizing these to become pure compounds or polymerizing at different blending ratios, the polymers obtained have different stereochemical structures that affect their elasticity and crystallinity, And for this reason, it also affects its mechanical and thermal properties. The polymers obtained are usually hard and optically bright. Ring-opening polymerization of cyclic internal vinegars of hydroxy acids, such as lactolactone, glycolic acid, ε-hexane Internal vinegar constitutes well-known industrial technology as far as it is concerned. Familiar 4- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 male f (Please read the precautions on the back before filling in this page})
2 8 34 7 經濟部中央標準局負工消費合作社印製 A7 __________B7 發明説明（2 ) 知又.?κ合方法是各式各樣，一些實例是美國專利案 5,378,80 i係關於擠壓聚合，歐洲專利案公告案〇6643〇9_α 係關於兩步驟聚合及歐洲專利案公告案〇499747-Α ,係敘 述在混合反應器中之聚合。 、先前所熟知之技藝中，其典型是殘餘乳交酯濃度高，其 妨礙水合物 < 加工處理，且在另—方面，其移除造成附加 之成本。 本發明的目的是尋求聚合乳交酯的方法，較佳達到接近 理論上最大値之轉化率。乳交酯之聚合速度以許多因素爲 基準，例如，所使用之引發劑，？丨發劑濃度，聚合溫度和 乳交酯濃度。 當乳交酯濃度係高於3〇重量％時，聚_合速度値得注意地 以乳交酯濃度爲基準。在此範圍以内，—在一般所使用之聚 合溫度下，聚合物-乳交酯摻合物的黏度亦相當低，而因 此，可將聚合在所需要之聚合溫度下，於攪拌式反應器中 有利進行。 在咸方法的發展期間，經觀察：聚合成高達大約3 〇重量 %乳又@旨濃度的有利方法是反應性攝壓_聚合，其中將單體 和催化劑連續餵供入擠壓機中。在有關之乳交酯濃度和溫 度範圍以内’單體迅速聚合典型在大約2分鐘以内達到 30重量％轉化率。 出人意料以外，現已觀察到：爲了聚合乳交酯至高轉化 率及低乳交酯濃度，最好在一種裝、置中進行更進一步聚 合，在此裝置中，將聚合物熔體在沒有物料轉移之條件下 _____-5- 本紙張尺度適用中國國家標準（CNS ) Α4規格（2l〇X：297公釐） (請先閱讀背面之注意事項再填寫本頁)2 8 34 7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 __________B7 Invention Description (2) Knowledge and Knowledge. The κ-combination methods are various, some examples are US patent 5,378,80 i is about extrusion polymerization The European Patent Case Announcement 06643〇9_α relates to two-step polymerization and the European Patent Case Publication 0499747-A, which describes the polymerization in a mixed reactor. In previously known techniques, it is typically high in residual lactide concentration, which hinders hydrate < processing, and in addition, its removal causes additional costs. The object of the present invention is to find a method for polymerizing lactide, preferably to achieve a conversion rate close to the theoretical maximum. The rate of polymerization of lactide is based on many factors, such as the initiator used?丨 Hair agent concentration, polymerization temperature and lactide concentration. When the lactide concentration is higher than 30% by weight, the polymerization rate is noticeably based on the lactide concentration. Within this range, at the polymerization temperature generally used, the viscosity of the polymer-lactide blend is also quite low. Therefore, the polymerization can be carried out at the desired polymerization temperature in a stirred reactor. get on. During the development of the salty process, it was observed that an advantageous method of polymerizing to a concentration of up to about 30% by weight of milk is a reactive pressure-polymerization, in which monomers and catalysts are continuously fed into an extruder. Within the relevant lactide concentration and temperature ranges, the 'monomer rapid polymerization typically reaches a 30% by weight conversion in about 2 minutes. Surprisingly, it has been observed that in order to polymerize lactide to high conversion and low lactide concentration, it is best to carry out further polymerization in a device and place. In this device, the polymer melt is transferred without material transfer. The following ___- 5- This paper size applies to Chinese National Standard (CNS) Α4 size (2l0X: 297 mm) (Please read the precautions on the back before filling this page)
473482 ft A7 B7 今/(473482 ft A7 B7 Today / (
第87103676號專利申請案 中文說明書修正頁(90年11月） 五、發明説明（3 ) 聚合至儘可能高之程度。進行努力以防止裝置中乳交酯蒸 發及乳交酯熔體之混合。聚合速度係十分的高且聚合之反 應熱低，以致可將乳交酯以受控制方式在短期内可聚合達 高轉化率。 圖示簡單說明 圖1為用於本發明方法的裝置之一具體實施態樣。 圖2為用於本發明方法的裝置之另一具體實施態樣。 根據本發明之較佳具體實施例，使用於第二聚合步驟中 之聚合裝置是一支經加熱之管，聚合物熔體在其中進行。 典型，將該管管壁加熱至1 80 -250 °C溫度而滯留時間是1 -1 0分鐘。該管中聚合物熔體的混合極輕微。根據此具體實 施例之裝置示於圖1中。 亦可能於聚合時，應用具有上述該型的聚合條件之其他 系統。其他_型式的較佳具體實施例包括一只加熱之傳送裝 置，其中將聚合物熔體在一片狀或金屬帶上傳送入經加熱 和經加熱之空間中，自該處，將它切屑以便更進一步處理 聚合物。此具體實施例之一個典型裝置示於圖2中。 經使用於根據本發明之方法中的第二反應器極為經濟。 典型，在第二聚合步驟期間聚合物之莫耳質量并不上 昇，甚至該乳交酯能與所存在之聚合物起反應及轉化達到 向級位。 根據本發明之聚合物或共聚物可自L -乳交酯，D -乳交 酯，或D，L -乳交酯或其摻合物予以製備。可使用適合於乳 交酯聚合之習用引發劑，例如各種錫與鐵化合物於該聚合 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 473482 五 第87103676號專利申請案 中文說明書修正頁(90年11月） A7 B7 發明説明（3a ) 中。聚合物之莫耳質量（Mw)是大約20000 - 500000，以 40000 - 300000較佳。該聚合物以自L -乳交酯製備較佳。 該聚合的第一步驟可經由擠壓聚合而有利進行。為了聚 -6a -Patent Application No. 87103676 Chinese Revised Sheet of Chinese Specification (November 1990) 5. Description of Invention (3) Polymerized to the highest possible degree. Efforts were made to prevent evaporation of lactide and mixing of lactide melt in the device. The polymerization rate is very high and the reaction heat of polymerization is low, so that lactide can be polymerized in a controlled manner in a short period of time to achieve high conversion. Brief description of the drawings Fig. 1 shows a specific embodiment of the device used in the method of the present invention. FIG. 2 shows another embodiment of the apparatus used in the method of the present invention. According to a preferred embodiment of the present invention, the polymerization device used in the second polymerization step is a heated tube in which the polymer melt is conducted. Typically, the tube wall is heated to a temperature of 1 80 -250 ° C and the residence time is 1-10 minutes. The mixing of the polymer melt in this tube is very slight. The device according to this specific embodiment is shown in FIG. It is also possible to apply other systems having the above-mentioned type of polymerization conditions during polymerization. Other preferred embodiments of the type include a heated transfer device in which the polymer melt is transferred on a sheet or metal strip into a heated and heated space, from where it is chipped so that The polymer is further processed. A typical device of this embodiment is shown in FIG. The second reactor used in the method according to the invention is extremely economical. Typically, the molar mass of the polymer does not increase during the second polymerization step, and even the lactide can react with the polymer present and convert to a directional position. The polymer or copolymer according to the present invention can be prepared from L-lactide, D-lactide, or D, L-lactide or a blend thereof. Custom initiators suitable for the polymerization of lactide, such as various tin and iron compounds, can be used in this paper. Chinese paper standard (CNS) A4 (210 X 297 mm) is applicable. Revised page (November 1990) A7 B7 invention description (3a). The molar mass (Mw) of the polymer is about 20,000-500000, preferably 40,000-300,000. The polymer is preferably prepared from L-lactide. The first step of the polymerization can be advantageously performed via extrusion polymerization. For poly-6a-
線 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 'd飞U乙五、 發明説明 A7 B7 合乳交醋，聚合物係經由加熱單體或單體摻合物而產生均 ，體及經由添加催化劑予以產生，於是環開敞。亦可能 有利地乘冷時，將催化劑和5 曰 , 孔人自日此3在一起而餵供接合 物至擠壓機中。 本發明將在下列實例之協助下另外更詳細敎述。 實例1 在大約2 0 0 C之溫度下，藉垃；毛也彳人 Λ 和溶姐泵舲仍含有引發劑之在擠 4機中予以聚合成大約7 〇重10/艟 i 里里/〇轉化率 < 聚合物熔體餵供 支管中（此管配有加熱夾套並具有2_3米之長度）。將 管壁藉油夾套加熱至大约22〇r之溫度，肖管之耐^程产 是1 000巴的等級。 、 “該聚合物熔體在高壓下，於管系統中聚合而無乳交醋之 蒸發’該溶體係、在層流條件下在管中進行。聚合之乳^旨 熔體在管系統中的平均滯留時間是大約2分鐘，聚合物中曰 之·乳又醋的濃度係低於1 〇重量％。 預聚合經由擠壓聚合進行至各種乳交酯濃度。第二聚人 的結果编列入表1中。 "" |衣-- (請先閱讀背面之注意事項再填寫本頁) I1TAw 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 473482 , A7 B7 五、發明説明（5 ) 表1 進料 聚合 產物 乳交酯濃 溫度 進料 莫耳重量 管長米 溫度 乳交S旨濃 莫耳重量 度，wt% °C Kg/h g/重量 °c 度,wt% g/重量 34,3 205 5 146500 3 220 8,0 105500 26,8 215 5 133000 3 220 10,9 90900 43,6 . 215 5 125200 2 210 10,1 118000 45,6 205 Λ 5 157000 2 220 6,4 109000 45,6 205 5 157000 2 220 10,4 123000 36,7 215 7 121500 2 210 9,6 109000 61,9 205 7 96600 2 220 8,6 101500 13,9 215 5 152000 2 220 10,0 108500 13,4 215 5 135500 2 210 5,9 113500 13,1 205 5 171000 2 210 6,8 106500 13,1 205 5 171000 2 220 5,4 105500 22,1 215 7 139500 2 210 8,2 105500 -8- 本纸張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） (請先閱讀背面之注意事項再填寫本頁)The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) 'd Fly U B. V. Description of the invention A7 B7 lactobacillus vinegar, the polymer is produced by heating monomers or monomer blends The body is produced by adding a catalyst, so the ring is open. It may also be advantageous to feed the catalyst to the extruder together with the catalyst and the pores when the cold is taken. The present invention will be described in more detail with the help of the following examples. Example 1 Borrowed at a temperature of about 200 ° C; Mao Yeren Λ and Rongjie Pump 舲 still contain initiators and polymerized in an extruder 4 to about 70 weight 10 / 〇i Li / Conversion rate < Polymer melt feed into branch pipe (this pipe is equipped with a heating jacket and has a length of 2-3 meters). The tube wall is heated to a temperature of about 22 Å by an oil jacket, and the resistance of the Xiao tube is 1 000 bar. "" The polymer melt is polymerized in a tube system under high pressure without evaporation of lactose. The solution is carried out in a tube under laminar flow conditions. The polymerized milk is intended to mean the average melt in the tube system. The residence time is about 2 minutes, and the concentration of milk and vinegar in the polymer is less than 10% by weight. The prepolymerization is performed by extrusion polymerization to various lactide concentrations. The results of the second polymer are compiled in Table 1. &Quot; " | Clothes-(Please read the precautions on the back before filling in this page) I1TAw Printed on the paper by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economy Applicable to China National Standard (CNS) A4 (210X297 mm) ) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 473482, A7 B7 V. Description of the invention (5) Table 1 Feed polymer product lactide concentration temperature Feed Mortal weight tube Long meter temperature Lactation S Molar weight, wt % ° C Kg / hg / weight ° c degrees, wt% g / weight 34,3 205 5 146500 3 220 8,0 105500 26,8 215 5 133000 3 220 10,9 90 900 43,6. 215 5 125 200 2 210 10,1 118000 45,6 205 Λ 5 157000 2 220 6,4 109000 45,6 205 5 157000 2 220 10,4 123000 36,7 215 7 121500 2 210 9,6 109000 61,9 205 7 96600 2 220 8,6 101500 13,9 215 5 152000 2 220 10,0 108500 13, 4 215 5 135500 2 210 5,9 113500 13,1 205 5 171000 2 210 6,8 106500 13,1 205 5 171000 2 220 5,4 105500 22,1 215 7 139500 2 210 8,2 105500 -8- present Paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling this page)