200530278 九、發明說明： 【發明所屬之技術領域】 本發明係有關於-種以掌性團聯共聚物 旋微結構及微孔柱，及-系列相關系統與物品之方^及更累 ==係關於一種以掌性團聯共聚合物製備奈米 螺㈣構與微孔柱，及其一連串相關系統與物品之方法。 【先前技術】 β本發明申請專利範圍主張美國暫時申請案優先權，案 10唬分別為60/454,764，申請曰為2003年3月14曰. 6〇/467,022,中請日為·3年4月％日；以及_72 377’， 申請日為2003年5月20日。上述内容係以參考方式合併 於本發明說明書。 pct專利申請案號WO00/02/99中揭示一種在三維空 15間構形中具有複數個重複出現獨立結構之聚合物的複雜製 備方法，其中至少有—第一與一第二結構，均有其拓樸連 績性並且在第一結構包含一可形成氧化陶瓷的無機物之聚 合物。因此開發其他可以減低成本的方法是需要的。 由於其特殊的相位變化，團聯共聚物的自組裝特性引 20起廣泛的注意。一些研究已報導於F.S. Bates in SCienee5 251，898 (1991)、F.S· Bates 與 G.H. Fredrickson in Phys.200530278 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to-a kind of microstructure and microporous columns of palm-linked copolymers, and-series of related systems and articles ^ and more tired == The invention relates to a method for preparing nano-spirostructures and microporous columns by palm group copolymers, and a series of related systems and articles. [Prior art] β The scope of the patent application of the present invention claims the priority of the US provisional application. The 10 cases are 60 / 454,764, and the application date is March 14, 2003. 6〇 / 467,022, and the Japanese date is 3 years 4 Month% Day; and _72 377 ', the application date is May 20, 2003. The foregoing is incorporated herein by reference. PCT patent application number WO00 / 02/99 discloses a complex preparation method of a polymer having a plurality of repeated independent structures in a three-dimensional space and a 15-dimensional configuration, at least one of which is a first structure and a second structure. It is topologically continuous and contains in the first structure a polymer that forms an inorganic material that can form an oxidized ceramic. Therefore, it is necessary to develop other methods that can reduce costs. Due to its special phase change, the self-assembly characteristics of the cross-linked copolymer attracted wide attention. Several studies have been reported in F.S. Bates in SCienee 5 251, 898 (1991), F.S. Bates and G.H. Fredrickson in Phys.
Today，32 (1990)中。自微觀相分離出的奈米級微結構，可 以藉由化學接合法將不互溶的聚合物鏈結一起，以形成團 200530278 塊聚合物。就熱動力學而言，已形成的微結構外型上利用 平衡混合作用的給損失（enthalpic penalty)及亂度驅動力 (entropic driving force)以達最低的Gibb自由能，並以χ N 表示，亦即Flory-Huggins片段交互作用參數X以及聚合反 5 應程度的N兩者之乘積。自組裝中型態之一維、二維、與 三維重複性結構整體如層板狀、圓柱狀與螺旋狀微結構已 經在所組成的團塊中被個別地鑑定出過。這些報導如下， 例 F.S. Bates in 251，898(1991); F.S. Bates and G.H. Fredrickson in Phys. Today, 32(1990); S. Forster, A. K. 10 Khandur，J· Zhao，F.S. Bates，I W. Hamley，A· J. Ryan，Bras W5 Macromolecules 27, 6922(1994); Vanessa Z.-H. Chan, J. Hoffman， V.Y. Lee, H. Iatrou, A Avgeropoulos, N. Hadjichritidis，R. D. Miller, E. L. Thomas, Science 286, 1716(1999); F.S. Bates and G.H. Fredrickson, Annu. Rev. 15 P/ζγ· 41，525(1990)。所定義的結構可以輕易的經由 利用奈米技術應用合成團塊聚合物之分子工程方式進行修 改。此項報導可以於 M. Park，C.K. Harison，ρ·Μ· Chaikin R.A. Register, D.H. Kddimson,Science 276, 1401 (1997);D.E. Fogg，L.H. Radzilowski，R. Balncki，R.R. Schrock，E.L. 20 Thomas, Macromolecules 30，417(1997);Y.N.C. Chan, R. R.Schrock, R.E.Cohen， chem" Mater· 4,24(1992); S. Fo,5rster? M. Antonietti, Adv. Mater. 10, 195 (1998); B.M. Discher，H. Bermudez，D.A. Hammer，D.E. Discher，Y.-Y.Won， F.S. Bates, J Phys. Chem. B 106, 2848(2002);A.-V.G.Ruzette, 25 P.P.Soo, D.R. Sadoway5A.M.Mayes, J. Eletrochem.Soc. 148, A537 (2001);N.Matsumi, K.Sugai5H.Ohno5 Macromolecules 200530278 35, 5731(2002); M. A. Hillmyer, P. M. Lipic, D. A. Hajduk, K. Almda, F.S. Bates, J. Am. Chem.Soc.119, 2749(1997); P. M. Lipic? F. S. Bates, M. A. Hillmyer, J. Am. Chem. Soc.120, 8963(1998); J.M. Dean, P.M..Lipic, R.B.Grubbs, R.F.Cook, 5 F.S. Bates, J. Polym.Sci., PartB:Polym.Phys.39,2996(2001); 與 M.R.Buchmeister，d/zgew.C/zem./zzi. £^.40，3795(2001) o 自然界亦利用化合物的自組裝特性做為形成結構要件 的工具。生物性結構可以經由空間性、疏水性、氫鍵與靜 電作用交互作用形成不同程度的組織。例：不同長度等級 10 型態。這些型態可以由較小的團塊組成，例如胺基酸，以 組成較高等級的組織。合成複雜分子的自組裝行為是在其 早期，利用生物性材料之二級交互反應而發生，並創造出 大量的奈米級結構。使用合成方式以完成類似生物性結構 之系統方法，是許多化學及物理領域研究者的重要目標， 15 並且這目標仍然存在。其中，經由不同螺旋鏈構型組合成 之不同長度的螺旋型態，從螺旋堆疊體到螺旋凝聚體是生 物系統中最為基礎也是最引發興趣的結構。由下列的文獻 可以發現此議題之相關討論，如 H_ Englkamp，S. Middelbeek，R.J.M. Nolte，Science 284，7785(1999); A.R.A. 20 Palmans, J.A.J.M. Vekemans, E.E. Havinga, E. W. Meijer, Angrw. Chem.? Int. Ed. Engl. 36,2648 (1997); T. Tachibana, H. Kambara, J. Am. Chem. Soc. 875 3015 (1965); R. J. H. Hafkamp, B. P. A. Kokke, I. M. Danke, Η. P. M. Geurts, A.E. Rowan, M.C. Feiters, R.J. M. Nolte, Chem. Commun.? 545 25 (1997); K.Hanabusa，M. Yamada，M· Kimura，H.Shirai，Today, 32 (1990). Nano-scale microstructures separated from the micro-phase can be used to link immiscible polymers together by chemical bonding to form clusters of 200530278 polymers. In terms of thermodynamics, enthalpic penalty and entropic driving force are used to achieve the lowest Gibb free energy on the formed microstructures, and are expressed as χ N. That is, the product of the Flory-Huggins fragment interaction parameter X and the aggregation reaction degree N. One-dimensional, two-dimensional, and three-dimensional repetitive structures in self-assembly, such as lamellar, cylindrical, and spiral microstructures, have been individually identified in the formed mass. These reports are as follows, eg FS Bates in 251, 898 (1991); FS Bates and GH Fredrickson in Phys. Today, 32 (1990); S. Forster, AK 10 Khandur, J. Zhao, FS Bates, I W. Hamley, A. J. Ryan, Bras W5 Macromolecules 27, 6922 (1994); Vanessa Z.-H. Chan, J. Hoffman, VY Lee, H. Iatrou, A Avgeropoulos, N. Hadjichritidis, RD Miller, EL Thomas, Science 286 , 1716 (1999); FS Bates and GH Fredrickson, Annu. Rev. 15 P / ζγ · 41,525 (1990). The defined structure can be easily modified by molecular engineering using nanotechnology to synthesize agglomerates. This report can be found in M. Park, CK Harison, ρ · M · Chaikin RA Register, DH Kddimson, Science 276, 1401 (1997); DE Fogg, LH Radzilowski, R. Balncki, RR Schrock, EL 20 Thomas, Macromolecules 30 417 (1997); YNC Chan, RRSchrock, RECohen, chem " Mater 4,24 (1992); S. Fo, 5rster? M. Antonietti, Adv. Mater. 10, 195 (1998); BM Discher, H. Bermudez, DA Hammer, DE Discher, Y.-Y. Won, FS Bates, J Phys. Chem. B 106, 2848 (2002); A.-VGRuzette, 25 PPSoo, DR Sadoway 5A.M. Mayes, J. Eletrochem.Soc. 148, A537 (2001); N. Matsumi, K. Sugai5H. Ohno5 Macromolecules 200530278 35, 5731 (2002); MA Hillmyer, PM Lipic, DA Hajduk, K. Almda, FS Bates, J. Am Chem. Soc. 119, 2749 (1997); PM Lipic? FS Bates, MA Hillmyer, J. Am. Chem. Soc. 120, 8963 (1998); JM Dean, PM. Lipic, RBGrubbs, RFCook, 5 FS Bates, J. Polym. Sci., PartB: Polym. Phys. 39, 2996 (2001); and MRBuchmeister, d / zgew.C / zem. / Zzi. £ ^ .40, 3795 (2001) o Nature also Self-organization using compounds Assembly characteristics are used as tools to form structural elements. Biological structures can form tissues to varying degrees through the interaction of steric, hydrophobic, hydrogen bonding, and electrostatic interactions. Example: Type 10 with different length grades. These forms can consist of smaller clumps, such as amino acids, to form higher grade tissues. The self-assembly behavior of synthesizing complex molecules occurred in its early stage, using secondary interactions of biological materials, and created a large number of nanoscale structures. The use of synthetic methods to achieve a systematic approach similar to biological structures is an important goal for many researchers in the chemical and physical fields, and this goal still exists. Among them, different lengths of helical patterns combined through different helical chain configurations, from helical stacks to helical aggregates, are the most basic and most interesting structures in biological systems. Related discussions on this subject can be found in the following literatures, such as H_ Englkamp, S. Middelbeek, RJM Nolte, Science 284, 7785 (1999); ARA 20 Palmans, JAJM Vekemans, EE Havinga, EW Meijer, Angrw. Chem.? Int Ed. Engl. 36, 2648 (1997); T. Tachibana, H. Kambara, J. Am. Chem. Soc. 875 3015 (1965); RJH Hafkamp, BPA Kokke, IM Danke, Η. PM Geurts, AE Rowan , MC Feiters, RJM Nolte, Chem. Commun.? 545 25 (1997); K. Hanabusa, M. Yamada, M. Kimura, H. Shirai,
Angew.Chem·，Int· Ed. Engl. 35，1949(1996); M. DeLoos，J. 200530278 vanEschJ.Stokroos, R. M. Kellog，B.M.Feringa，J.Am. Chem. Soc. 119, 12675 (1997); J.H. Van Esch, B. L. Feringa, Angew. Chem., Int. Ed. 39，2263 (2000); Y.Okamoto;K. Suzuki，K· Ohta，K. Hataa，H.Yuki，J.Am· Chem· Soc. 101， 5 4763 (1979)。其中所討論到之不對稱螺旋結構外型導致不 同之化學及物理特性，如分子辨識與光學活性特性。S· I· Stupp，V. LeBonheur, K. Walker, L. S. Li，K. E. Huggins，M. Keser，與 A. Amstutz，Science 276，384 (1997)中討論到在材料與生命科學領域中，已確認出用以 10 製備螺旋狀材料所需之較佳因素。 化合物之掌性已被視為形成螺旋狀結構的主要原因之 一，並且被用於二級反應以組合掌性分子與巨分子以成為 較大螺旋結構。這些已被廣泛的於下列論文中討論，例如 A.E.Rowan，R.J.M.Nolte，Angew.Chem.，Int.Ed·，37，63 15 (1998); and M.C. Feiters, R.J.M. Nolte, in Advances inAngew. Chem., Int. Ed. Engl. 35, 1949 (1996); M. DeLoos, J. 200530278 vanEsch J. Stokroos, RM Kellog, BMFeringa, J. Am. Chem. Soc. 119, 12675 (1997); JH Van Esch, BL Feringa, Angew. Chem., Int. Ed. 39, 2263 (2000); Y. Okamoto; K. Suzuki, K. Ohta, K. Hataa, H. Yuki, J. Am. Chem. Soc 101, 5 4763 (1979). The asymmetric helical structure discussed therein results in different chemical and physical properties, such as molecular identification and optically active properties. S. Stupp, V. LeBonheur, K. Walker, LS Li, KE Huggins, M. Keser, and A. Amstutz, Science 276, 384 (1997) have been identified in the field of materials and life sciences, which have been identified The 10 best factors needed to make spiral materials. The palmity of compounds has been considered as one of the main reasons for the formation of helical structures, and has been used in secondary reactions to combine palm molecules with macromolecules to form larger helical structures. These have been extensively discussed in, for example, A.E.Rowan, R.J.M.Nolte, Angew.Chem., Int. Ed., 37, 63 15 (1998); and M.C. Feiters, R.J.M. Nolte, in Advances in
Supramolecular Chemistry. Vol. 6. Chiral Self-assembled Structures of Biomolecules and Synthetic Analoggues; G.W. Gokel，Ed·; JAI PressInc.;Stamford，CV; Vol· 6，pp 41-156. 具有特定掌性的螺旋超結構可以藉由包含帶電螺旋團塊的 20 双性團塊聚合物緩衝液中製備得。根據Nolte與其同事的 研究，自緩衝液製備出團塊組成物的掌性，其双性與靜電 效應在溶液形成螺旋超結構中扮演了極為重要的角色。其 可參閱如 29.J.J.L.M. Cornelissen，M.Fischer, N.A.J.M. Sommerdijk，R.J.M. Nolte, Science 280, 1427(1998); 25 N.A.J.M. Sommerdijk，S.J· Holder，R.C. Hiorns，R.G. Jones， R.J.M. Nolte，Macromolecules 33，8289(2000)。Hillmyer 與 200530278 其同事研究聚（苯乙烯）·聚（左旋-乳酸）(PS-PLLA)時，並無 發現有螺旋狀構型的存在。見A.S.Zalusky，R. Olayo-Valles， C.J. Taylor, M.A. Hillmyer, J. Am. Chem. Soc. 123, 1519 (2001);與 A.S.Zalusky，R 01ayo-Valles，C.J. Taylor，M.A. 5 Hillmyer，J· Am. Chem. Soc. 124，1276(2002)。已知脂肪族 聚酯類如聚己内酯（polycaprolactone，PCL)與聚乳酸（PLA) 容易以水解方式被分解，是由於其具有酯類中不穩定的特 性。請參見 J· L. Kathleen，M. Edith, Biomaterials 19，1973 (1998); A. G6pferich，Biomaterials 17，103 (1996);與 W· Κ· 10 Lee，J.A. Gardella，Langmuir 16，3401 (2000)。 【發明内容】 本發明之目的係在提供一種製備奈米螺旋微結構與 微管柱之方法。更具體地，本發明之主要目的係在提供一 15 種以掌性團聯共聚合物製備奈米螺旋微結構與孔柱之方 法。 在本發明中，聚苯乙烯-聚左旋乳酸（PS-PLLA)，一包 含左手掌性螺旋骨架PLLA團塊的掌性團塊聚合物，在利用 連續的活性自由基與活性開環聚合反應進行製備時，觀察 20 到一種非預期的結果產生。合成團聯共聚物的「活性」聚 合反應係指連續性的加入單體。在大量合成自組裝 PS-PLLA時，左旋PLLA螺旋被發現具有奈米級直徑的螺距 長度與直徑。這些PLLA螺旋於PS基材中被塑形為六角型微 結構體。相較於PS-PLLA，螺旋體結構尚未被發現存在於 200530278 聚苯乙烯-聚（右旋，左旋-乳酸由於合成團聯共聚物的掌 性特性所形成的奈米級螺旋構型，創造出團聯共聚物熱動 力學新的領域與應用。就某種意義來說，本發明方法係模 仿自然界中存在之生物性機制，在一般二級反應之外的掌 5性特性，對於合成巨分子之自組裝過程中扮演著非常重要 的角色。本發明方法之主要優勢，係可藉由水解PLLA團塊 而形成奈米孔道。本發明開創出一個團塊共聚化合物於奈 米科學領域中應用的新機會。 於本發明中，只具有掌性與非掌性之二元團聯共聚物 10聚（苯乙烯聚（左旋乳酸）(PS-PLLA)，是合成出來用以鑑定 自組裝型態中之掌性效應。在大量合成PS_PLLA自組裝構 型時’非預期的形成了一自有序，六角，且具有左掌性螺 旋之PLLA奈米螺旋體，與其所組成之團塊特性相同。就我 們所知，到目前為止並沒有掌性團聯共聚物可於大量合成 15時形成掌性大分子結構，同時又可自組裝成三維之微結構 的記載。奈米螺旋微結構的形成是由於團聯共聚物的掌性 效應，凡得瓦力交互作用以及混合時的亂度所造成。如同 上述，本發明方法之主要優點係可藉由水解PLLA團塊就能 得到奈米級孔道。 20 一系列不同體積比例的聚（苯乙烯）-團塊-聚（左旋乳 酸）(PS-PLLA)共聚物可以透過使用兩步驟聚合反應進行製 備。苯乙烯自由基聚合反應使用4-羥-2,2,6,6-四曱基哌啶_ 氮-氧自由基，4-羥-ΤΕΜΡΟ(4·氫氧基-TEMPO)作為起始 物，在過氧化二苯（BPO)的存在下，形成聚苯乙烯的羥基 200530278 終端，此終端可進一步與[{/i3-EDBP}Li2]2[(/i3-nBu) Li(0.5Et2O)]2反應以形成一巨起始物。接著在巨起始物存 在下，控制L-乳酸的開環聚合反應以製備出PS-PLLA。利 用此步驟，可以得到不同PLLA量的PS-PLLA團聯共聚物。 5 多種團聯共聚物的自組裝型態係以穿透式電子顯微鏡Supramolecular Chemistry. Vol. 6. Chiral Self-assembled Structures of Biomolecules and Synthetic Analoggues; GW Gokel, Ed ·; JAI PressInc .; Stamford, CV; Vol · 6, pp 41-156. Spiral superstructures with specific palmity can Prepared from 20 amphoteric agglomerate polymer buffers containing charged spiral agglomerates. According to the research by Nolte and colleagues, the palmity of the agglomerate composition prepared from the buffer solution, its amphoteric and electrostatic effects play a very important role in the formation of the spiral superstructure from the solution. See, for example, 29. JJLM Cornelissen, M. Fischer, NAJM Sommerdijk, RJM Nolte, Science 280, 1427 (1998); 25 NAJM Sommerdijk, SJ Holder, RC Hiorns, RG Jones, RJM Nolte, Macromolecules 33, 8289 (2000 ). Hillmyer and 200530278 colleagues did not find the existence of a helical configuration when they studied poly (styrene) · poly (L-lactic acid) (PS-PLLA). See ASZalusky, R. Olayo-Valles, CJ Taylor, MA Hillmyer, J. Am. Chem. Soc. 123, 1519 (2001); and ASZalusky, R 01ayo-Valles, CJ Taylor, MA 5 Hillmyer, J. Am Chem. Soc. 124, 1276 (2002). It is known that aliphatic polyesters such as polycaprolactone (PCL) and polylactic acid (PLA) are easily decomposed by hydrolysis due to their unstable nature among esters. See J. Kathleen, M. Edith, Biomaterials 19, 1973 (1998); A. G6pferich, Biomaterials 17, 103 (1996); and W.K. 10 Lee, JA Gardella, Langmuir 16, 3401 (2000) . SUMMARY OF THE INVENTION The object of the present invention is to provide a method for preparing nano-helical microstructures and microtubules. More specifically, the main object of the present invention is to provide a method for preparing nano-helical microstructures and pore columns by palm group cross-copolymers. In the present invention, polystyrene-poly-L-lactic acid (PS-PLLA), a palm agglomerate polymer containing a left palm helix skeleton PLLA agglomerate, is performed by using continuous living free radicals and living ring-opening polymerization. When preparing, observe 20 to an unexpected result. The "living" polymerization reaction for synthesizing a crosslinked copolymer refers to the continuous addition of monomers. When a large number of self-assembled PS-PLLAs were synthesized, the left-handed PLLA helix was found to have a nanometer diameter pitch length and diameter. These PLLA spirals are shaped into hexagonal microstructures in PS substrates. Compared with PS-PLLA, the helix structure has not been found in 200530278. Polystyrene-poly (D-L-L-lactic acid, due to the palm-like properties of the synthesizing cross-linked copolymer, creates a nano-scale helix configuration, creating clusters New fields and applications of thermodynamics of cross-linked copolymers. In a sense, the method of the present invention mimics the biological mechanisms existing in nature, and possesses properties other than general secondary reactions. The self-assembly process plays a very important role. The main advantage of the method of the present invention is that nanopores can be formed by hydrolyzing PLLA agglomerates. The present invention creates a new application of agglomerate copolymer compounds in the field of nanoscience. Opportunity. In the present invention, a 10-poly (styrene poly (L-lactic acid) (PS-PLLA) binary-copolymer with only palm and non-palm is synthesized to identify the self-assembly type. Palm effect. When a large number of PS_PLLA self-assembled structures were synthesized, a self-ordered, hexagonal, and left palm spiral PLLA nanospira was formed unexpectedly, which has the same characteristics as the mass formed by it. As far as we know, there is no record that the palm group copolymer can form a palm macromolecular structure at the time of large-scale synthesis, and can also self-assemble into a three-dimensional microstructure. The formation of the nano-helical microstructure is Due to the palm-like effect of the cross-linked copolymer, van der Waals interaction and the disorder caused by mixing. As mentioned above, the main advantage of the method of the present invention is that nano-scale channels can be obtained by hydrolyzing PLLA agglomerates. 20 A series of poly (styrene) -lumps-poly (L-lactic acid) (PS-PLLA) copolymers with different volume ratios can be prepared by using a two-step polymerization reaction. 4-hydroxy-2 is used for styrene radical polymerization , 2,6,6-Tetrafluorenylpiperidine_ nitrogen-oxyl radical, 4-hydroxy-TEMPO (4 · hydroxy-TEMPO) as a starting material, in the presence of diphenyl peroxide (BPO), The hydroxyl terminal of polystyrene 200530278 is formed, and this terminal can further react with [{/ i3-EDBP} Li2] 2 [(/ i3-nBu) Li (0.5Et2O)] 2 to form a giant starting material. In the presence of the starting material, the ring-opening polymerization of L-lactic acid is controlled to prepare PS-PLLA. Using this step You can get different amounts of PS-PLLA PLLA group linked copolymer group with more than five kinds of patterns based copolymer self-assembly in a transmission electron microscope
(transmission electron microscopy，TEM)與小角度X光散射 儀（small-angle X-ray scattering，SAXS)觀察得知。團聯共 聚物的大量樣品可以在室溫中利用二氯乙烷（CH2C12)溶液 (0.5wt% 的 PS-PLLA)以溶液鑄膜（solution-casting)方式得 10 之。結晶效應顯著的存在於可結晶的團聯共聚物構型上。 為了消彌PLLA結晶作用於已形成之構型上的擾動，鑄膜樣 品可以於高於PLLA熔點但低於有序-無序之轉換溫度下進 行退火，並且於液態氮中迅速冷卻。測量PS-PLLA熱力學 行為可以透過微差式掃描熱卡計（differential scanning 15 calorimetry, DSC)進行。PS-PLLA的有序-無序轉換溫度係 藉由小角度X射線繞射觀察得知，高於分解溫度（〜170°C)。 非晶向PS-PLLA可於熱處理後，經過微分掃描熱量計與廣 角 X光繞射儀（wide-angle X-ray measurements, WAXD)測 量後取得。 20 在微觀相分離（microphase-separated)炼融迅速進行冷 卻後，熱處理後的樣品在Ru〇4染色後利用超薄切片機進行 切片。許多種不同的微結構如微膠粒（micelle)，六角柱形 (hexagonal cylinder)，層板結構（lamellae)係分別於/^1^為 0.17、0.30與0.56時，透過TEM與SAXS被鑑別出來。奈米 11 200530278 螺旋的螺距與直徑平均值分別為43 8nm與34 4nm。奈米螺 旋之螺距與半徑的比例（P/r=2.5)亦遵循自然界中螺旋形成 時P/r比率必須低於6·28的通常法則。完成定位之微結構於 ps基質所形成之六角形PLLA螺旋，可經由利用ΤΕΜ觀察禱 5膜樣品得知。PLLA團塊所佔據之體積比率經計算為 40vol%，此與經合成所計算之結果σρι^Αν=〇·37)接近一致。 接著進行SAXS之試驗以藉由更進一步的觀察確認構型。藉 由二維SAXS沿著其螺旋軸所明確界定之散射圖譜結果顯 示，結構具有六摺對稱，而相較於一般螺旋體，沿著其螺 10旋軸心所取得之散射結果只有兩摺對稱。方位角積分一維 SAXS圖譜更進一步可以自六面對稱圖譜中得之。繞射波峰 出現於相對q*值1:41/2:71/2:91/2，同時在約3.5q*時出現較寬 廣的繞射波峰。這些結果與六角微結構一致，這些奈米螺 旋體由於其特殊的Ρ/r值，因此可被視為圓柱管體。 15 在假設的圓柱結構中，根據TEM所觀察到沿著螺旋轴 心所投射出之直徑，可以確認3·5《*繞射波峰是因為類似柱 狀之構形所造成。此外，利用SAXS所決定出之長週期， 50.6nm，則與TEM所觀測到之間隔相符。由以上結果，可 以明顯的測定PS-PLLA結構的自組裝大量奈米級微結構螺 20旋體的二維幾何排序。並且’具左旋式螺旋的螺旋構形與 在TEM觀察下所組成團塊之構形一致。相較之下，奈米級 螺旋體彳放結構的形成則尚未被發現存在於團聯丘 物或疋PLLA早聚物中。因此’ PS-PLLA中螺旋體微*士構 的出現是因為所構成之團塊間不互溶而發生之掌性反靡， 12 200530278 以及混合時發生之亂度所造成之效應。 除PS-PLLA外，聚（4-乙烯基11比啶）_聚（左旋-乳 酸）(P4VP-PLLA)團聯共聚物亦經由上述實施例的類似製 程進行合成。在最佳實施例中，聚（左旋-乳酸）存在於（4-5 乙烯基吡啶）-聚（左旋-乳酸）團聯共聚物的體積比率經計算 後為23%(/PLLAv=0.23)。如所示之TEM微圖譜，可於其中觀 察到螺旋微結構。 由於團聯共聚物組成物中掌性體的存在’因此造成其 具有非常複雜的熱力學。這必定會造成傳統理論上處理團 10塊共聚物的影響。螺旋行為可以經由團聯共聚物的掌性特 性預測。在應用上，六角構形螺旋可以經由PLLA水解進行 處理。以原子力顯微鏡（atomic force microscope，AFM)觀 察，發現六角構形奈米孔洞陣列可以在水解後的溶液鑄膜 PS-PLLA樣品表面產生。為進一步確認PS-PLLA樣品水解 15 後的内部結構，利用場放射掃描式電子顯微鏡（field emission scanning electron microscopy，FESEM)於不同角 度來觀察樣品。自平行於螺旋軸之角度觀察，經由FESEM 可以觀察到排列有序的奈米孔洞陣列，且此結果與掃瞄式 探針顯微鏡觀察之結果雷同。自垂直於螺旋軸之角度觀 20 察，可以看到PLLA螺旋構形的分解遺跡。結果顯示，螺旋 孔柱可以簡單的經由水解PLLA螺旋體後得之。 【實施方式】 本發明將藉由下述之最佳實施例具體說明發明内 13 200530278 容。下述實施例僅係為了方便說明而舉例而已，本發明所 主張之權利範圍自應以申請專利範圍所述為準，而非僅限 於下述實施例。 實施例1 : 4-羥基-TEMPO-終端聚苯乙烯（PS-2)之合成 5 將一混合有苯乙烯（46ml，400mmol)、BPO(0.39g， 1.6mmol)以及 4-輕基-TEMPO(0.33g，1.92mmol)(4-羥基 TEMPO與BPO之莫耳比例為1·2)之混合物置於250ml圓底 燒瓶中，於氮氣氛圍中加熱至95°C，維持3小時，以使BPO 完全分解。接著再將整個系統加熱至130°C，維持4小時， 10 以形成PS-TEMPO-4-羥基；接著以甲醇（300ml)將聚苯乙烯 從THF(50ml)中沈澱出。 將產物置於二氣曱烷（40ml)/甲醇（200ml)混合液中再 結晶二次，並利用真空過濾方式收集白色固體；最後之固 體以100ml甲醇清洗，並置於真空中隔夜，以形成PS_2[產 15 物：32.6g(78%)· Mn=20900，PDI=1.17. 4 NMR(CDC13): 6.46-7.09 (br，5H，ArH)，1.84(br，1H，CH)，1.42(br，2H， CH2)]。所有過程均於一氮氣氛圍中進行。溶劑，過氧化苯 甲醯，苯乙烯，L-乳酸以及重氫化溶劑於使用前均先進行 純化。 20 實施例2 :聚（苯乙烯）-聚（左旋-乳酸）團聯共聚物（PS_b-PLA 或CP-4)之合成 藉著一典型之開環反應來合成CP-4。將 [g3-(EDBP)Li2]2[(g3-nBu)Li(0.5Et2O)]2(0.1 lg，〇· lmmol)於 0 °C，20ml甲苯中，加入4-羥基-TEMPO·聚苯乙烯（PS-2, 4.18g， 25 〇·2 mmol);混合物於室溫下攪拌2小時，並利用真空進行 200530278 乾燥。接著將用以作為起始劑的產物（鋰烷氧化合物）溶於 二氣曱烷（20ml)中，接著加入溶於二氯甲烷（10mi)的L-乳酸 (2_16g，15mmol);在攪拌混合物4小時的過程中，聚L-乳酸 將逐漸生成（74%)，接著再以iH NMR光譜進行分析。 5 加入一醋酸溶液（0.35N，20ml)於混合物中進行退 火，接著將混合液倒入正己烷（3〇〇ml)中，即開始形成白色 固體沈澱的聚合物。接著再將固體產物於二氣甲烷（30ml)/ 正己烷（150ml)中進行沈澱，以純化此固體產物。利用二氣 曱烷（30ml)/甲醇（l5〇ml)沈澱出最後之結晶產物，並於溫度 10 50-60°C的真空下進行隔夜乾燥，最後將生成3.02g的 PS-6-PLA(CP-4)(產率 48%)。(transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) observations. A large number of samples of the conjugated copolymer can be obtained by solution-casting using dichloroethane (CH2C12) solution (0.5 wt% PS-PLLA) at room temperature. The crystallization effect is significant in the crystallizable block copolymer configuration. In order to eliminate the disturbance of PLLA crystals on the formed configuration, the cast film samples can be annealed at a temperature higher than the melting point of PLLA but lower than the order-disorder transition temperature, and rapidly cooled in liquid nitrogen. The PS-PLLA thermodynamic behavior can be measured by differential scanning 15 calorimetry (DSC). The order-disorder transition temperature of PS-PLLA is higher than the decomposition temperature (~ 170 ° C) by observation of small-angle X-ray diffraction. Amorphous PS-PLLA can be obtained after heat treatment by differential scanning calorimeter and wide-angle X-ray measurements (WAXD). 20 After the microphase-separated smelting and rapid cooling, the heat-treated samples were sectioned with an ultra-thin microtome after Ru04 staining. Many different microstructures, such as micelles, hexagonal cylinders, and lamelae, were identified by TEM and SAXS at 0.17, 0.30, and 0.56, respectively. . Nano 11 200530278 The average pitch and diameter of the helix are 43 8nm and 34 4nm, respectively. The ratio of the pitch to the radius of the nano spiral (P / r = 2.5) also follows the general rule that the P / r ratio must be lower than 6.28 when the spiral is formed in nature. The hexagonal PLLA helix formed by the positioned microstructure in the ps matrix can be obtained by observing the P5 membrane sample with TEM. The volume ratio occupied by the PLLA mass is calculated to be 40 vol%, which is close to the calculated result σρι ^ Αν = 0.37). A test of SAXS was then performed to confirm the configuration by further observation. The results of the scattering pattern clearly defined by the two-dimensional SAXS along its spiral axis show that the structure has a six-fold symmetry, and compared with the general spiral body, the scattering results obtained along its spiral 10-axis center are only two-fold symmetrical. The azimuth integral one-dimensional SAXS spectrum can be further obtained from the six-sided symmetry spectrum. Diffraction peaks appear at a relative q * value of 1: 41/2: 71/2: 91/2, while a broader diffraction peak appears at about 3.5q *. These results are consistent with the hexagonal microstructure. These nano-spirals can be regarded as cylindrical tubes due to their special P / r values. 15 In the hypothetical cylindrical structure, based on the diameter projected along the axis of the spiral observed by the TEM, it can be confirmed that the 3 · 5 "* diffraction peak is caused by a column-like configuration. In addition, the long period determined by SAXS, 50.6nm, is consistent with the interval observed by TEM. From the above results, the two-dimensional geometric ordering of the self-assembled large number of nano-scale microstructure spiral 20 spins of the PS-PLLA structure can be clearly determined. And the spiral configuration of the left-handed spiral is consistent with the configuration of the mass formed under TEM observation. In contrast, the formation of nano-scale spirochondrial release structures has not been found in cluster mounds or erbium PLLA prepolymers. Therefore, the emergence of spirochondrial microstructure in ‘PS-PLLA’ is caused by incompatibility caused by the incompatibility between the formed masses, 12 200530278 and the effects caused by the chaos that occurs during mixing. In addition to PS-PLLA, poly (4-vinyl 11-pyridine) _poly (l-lactate) (P4VP-PLLA) block copolymers were also synthesized through a similar process to the above examples. In the preferred embodiment, the volume ratio of poly (L-lactic acid) present in (4-5 vinylpyridine) -poly (L-lactic acid) cross-linked copolymer is calculated to be 23% (/PLLAv=0.23). As shown in the TEM micrograph, the spiral microstructure can be observed therein. Due to the presence of palmitate in the crosslinked copolymer composition, it has a very complicated thermodynamics. This will inevitably cause the effect of traditionally processing 10 copolymers. Helix behavior can be predicted via the palm-like properties of the crosslinked copolymer. In application, the hexagonal configuration helix can be processed by PLLA hydrolysis. Observation by atomic force microscope (AFM) revealed that hexagonal nano-hole arrays can be produced on the surface of the PS-PLLA sample after solution hydrolysis. To further confirm the internal structure of the PS-PLLA sample after hydrolysis for 15 years, a field emission scanning electron microscopy (FESEM) was used to observe the sample at different angles. From an angle parallel to the helical axis, an ordered array of nanopore holes can be observed via FESEM, and this result is similar to that observed with a scanning probe microscope. Observed from an angle perpendicular to the spiral axis, the decomposition remains of the PLLA spiral configuration can be seen. The results show that the spiral-well column can be simply obtained by hydrolyzing the PLLA spiral body. [Embodiment] The present invention will be described in detail by the following preferred embodiments. The following embodiments are merely examples for the convenience of description. The scope of the rights claimed in the present invention shall be based on the scope of the patent application, rather than being limited to the following embodiments. Example 1: Synthesis of 4-hydroxy-TEMPO-terminated polystyrene (PS-2) 5 A mixture of styrene (46 ml, 400 mmol), BPO (0.39 g, 1.6 mmol) and 4-light-TEMPO ( 0.33 g, 1.92 mmol) (the molar ratio of 4-hydroxy TEMPO to BPO is 1.2) was placed in a 250 ml round bottom flask, heated to 95 ° C in a nitrogen atmosphere, and maintained for 3 hours to complete the BPO break down. The entire system was then heated to 130 ° C for 4 hours to form PS-TEMPO-4-hydroxyl; then polystyrene was precipitated from THF (50 ml) with methanol (300 ml). The product was recrystallized twice in a mixture of dioxane (40 ml) / methanol (200 ml), and a white solid was collected by vacuum filtration; the final solid was washed with 100 ml of methanol and placed in a vacuum overnight to form PS_2 [Product 15: 32.6 g (78%) · Mn = 20900, PDI = 1.17. 4 NMR (CDC13): 6.46-7.09 (br, 5H, ArH), 1.84 (br, 1H, CH), 1.42 (br, 2H, CH2)]. All processes were performed under a nitrogen atmosphere. Solvents, benzoylperoxide, styrene, L-lactic acid, and dehydrogenated solvents were all purified before use. 20 Example 2: Synthesis of poly (styrene) -poly (L-lactic acid) block copolymer (PS_b-PLA or CP-4) CP-4 was synthesized by a typical ring-opening reaction. [G3- (EDBP) Li2] 2 [(g3-nBu) Li (0.5Et2O)] 2 (0.1 lg, 0.1 mmol) in 0 ° C, 20 ml of toluene, and 4-hydroxy-TEMPO · polystyrene was added (PS-2, 4.18 g, 25.0 mmol); the mixture was stirred at room temperature for 2 hours and dried under vacuum for 200530278. The product (lithium alkoxide) used as a starter was then dissolved in dioxane (20 ml), and then L-lactic acid (2_16 g, 15 mmol) dissolved in dichloromethane (10 mi) was added; the mixture was stirred In the course of 4 hours, poly-L-lactic acid will be gradually formed (74%), and then analyzed by iH NMR spectrum. 5 Add an acetic acid solution (0.35N, 20 ml) to the mixture for annealing, then pour the mixture into n-hexane (300 ml), and a white solid precipitated polymer will begin to form. The solid product was then precipitated in methane (30 ml) / n-hexane (150 ml) to purify the solid product. The final crystalline product was precipitated with dioxane (30 ml) / methanol (150 ml) and dried overnight under vacuum at a temperature of 10 50-60 ° C. Finally, 3.02 g of PS-6-PLA ( CP-4) (yield 48%).
Mn=46700, PDI=1.17. NMR (CDC13): 6.46-7.09(br，5H， ArH)，5.16(q，1H，CH(CH3)，J=7.2Hz)，1.84(br，1H，CH)， 1.58(d，3H，CH(CH3))，J=7.2Hz)，1.42(br，2H，CH2)· 15 lU 以及13C NMR光譜結果係利用於 Varian Gemini-200(200 MHz 使用於 4，200 MHz 使用於 13C)光譜 儀作記錄，其中化學位移係以ppm為單位，由内部四曱基 矽烷（TMS)轉換至中心氣仿（CHC13)。凝膠滲透層析（GPC) 測定法則是利用具有BISCHOFF折射率檢測器（differential 20 Bischoff 8120 RI detector)的 Hitachi L-7100 系統，溶劑係 四氫呋喃（THF，HPLC等級）。分子量及分子量的分佈係利 用聚苯乙烯做為標準品計算之。 製備一數量之聚（苯乙烯）-聚（左旋-乳酸）(PS-PLLA)掌 性團聯共聚物。根據分子量及體積之比例，將這些 25 PS-PLLAs 以 PSxx-PLLAyy(/PLLAV=z)為標示，其中 XX 與 yy 15 200530278 分別代表量測自NMR之PS以及PLLA之分子量除以1000 之值，z則代表PLLA之體積分率。在這些計算中，PS以 及PLLA之密度係分別假設為1.02以及1.18g/cm3。 實施例3、穿透式電子顯微鏡（TEM)與小角度X光散射 5 (SAXS)研究 於實驗中發現，在PS-PLLA中進行PLLA之結晶，增加 了 PS-PLLA微觀相分離形態的明顯變化。破壞已形成之微 結構以形成結晶構形是可行的。微差掃瞄熱卡計係採用 Perkin-Elmer DSC 7。舉例說明，PS29-PLLA22(/PLlav=〇.37) 10 中PLLA團塊於約165°C時會熔化。PLLA團塊之最大結晶率 是在大約95°C時，伴隨著不同等溫結晶之放熱反應（即，結 晶化反應發生時）。然而，在快速冷卻過程中，並沒有明顯 的放熱反應發生。PLLA以及PS之玻璃轉換溫度分別約在 51.4°C 以及 99.2°C。 15 小角度X光散射實驗（SAXS)係於Brookhaven國家實 驗室中國家同步光源處（National Synchrotron Light Source in Brookhaven National Laboratory)，利用同步 X光束線 X3A2進行。X光束線之波長為0.154nm。小角度X光散射實 驗圖譜中之零點圖素係以silver behenate計算之，第一次散 20 射向量分*(分* = 4 λ -1sin 0，2 0即散射角）為1 ·076ηιη-1。時 析小角度X光散射實驗係於一加熱箱中，逐漸進行加熱。 裂解的溫度係以散射波峰消失時間為準。 微差掃瞄熱卡計（DSC)熱譜圖顯示在加熱過程中不會 產生内生性的熔融熱。廣角X光繞射圖（WAXD)的散射結果 16 200530278 顯示非晶相的繞射圖譜。含有繞射計的Siemens D5000 1.2Kw真空管X光產生器係用以進行WAXD粉體繞射實 驗。掃瞄的2 0角度係介於5 ° -40 °之間，每個掃瞄角度為 0·05°，持續3秒。繞射峰的位置與寬度係於WAXD實驗後， 5 利用已知結晶尺寸之矽結晶小心計算出。 穿透式電子顯微鏡（transmission electron microscopy) 在明視野係利用JEOL TEM-1200x穿透式電子顯微鏡；染色 步驟係將樣品置於4%Ru04水溶液氣霧中3小時。 溶液鑄膜之PS-PLLA樣品在水解後，其表面係利用原 10 子力顯微鏡（AFM)進行觀察。使用儀器為具有SEIKO SPI-3800N探針台之Seiko SPA-400AFM，於室溫下進行。 應用一長方形石夕製探頭於動態力模式（dynamic force mode， DFM)中進行檢測，使用一具有19ΝΠ1·1接觸彈簧力之 SI-DF20儀器，以1.0Hz之掃瞄頻率進行實驗。 15 利用場發射掃瞄電子顯微鏡於不同觀點下觀察 PS-PLLA樣品。所使用儀器是Hitachi S-900 FE-SEM，使用 之加速電壓為2-5keV。觀察之對象係溶液鑄膜樣品之表面 或是被水解破壞後的PS-PLLA截面薄膜。樣品係嵌合於銅 片中，以碳材做接合，再以旋轉塗布方式覆上一層2-3nm 20 之金粒子（金粒子塗覆厚度係以計算出之沈積速率以及實 驗出之沈積時間決定之）。 實施例4: TEM與SAXS實驗結果 圖 1A 係一 PS38-PLLA10(/pLLAv=0.17)之 TEM顯微照相 圖；圖 1B 係一 PS38-PLLA21(/pLLAv=0.30)之 TEM顯微照相 200530278 圖；圖 1C係一 PS13-PLLA22(/pllav=0.56)之 TEM顯微照相 圖；圖1D係PS38-PLLA10(/pLLAv=0.17)之奈米級微膠粒微結 構示意圖；圖1E係PS38-PLLA21(/pllav=0.30)之奈米級六角 形微結構示意圖；且圖1F係PS13-PLLA22(/pLLAv=0.56)之奈 5 米級層板形微結構示意圖。 各式團聯共聚物之自組裝型態係利用穿透式顯微鏡 (TEM)以及小角度X光散射儀（SAXS)進行研究。團聯共聚 物之批次樣品是以二氣乙烧（dichloroethane，CH2C12)溶液 (0.5wt%的PS-PLLA)於室溫下進行溶液鑄膜的方式製作。 10 結晶行為已被測定出明顯的發生於團聯共聚物之表面。要 降低PLLA於結晶形成時的干擾，鑄膜樣品需在溫度高於 PLLA熔點，但低於有序-無序轉換溫度之下進行退火，再 以液態氮將樣品迅速降溫。PS-PLLA之熱反應係利用微差 掃描熱卡分析儀進行量測。PS-PLLA之有序-無序轉換溫度 15 係如小角度X光散射儀量測值一樣，高於裂解溫度（〜17〇 °C )。在經過熱處理並進行DSC與WAXD量測後即得非晶相 PS-PLLA。 在微觀相分離熔點進行冷卻後，經過熱處理之樣品在 經過Ru〇4染色後，以超薄切片機切出薄片。即可利用TEM 20 以及SAXS分別觀測到不同型態的微結構，當/ρι^Αν分別為 0.17, 0.30以及0.56時，微結構型態依序為：微膠粒，六角 圓柱及層板等組織。這些微膠粒，六角圓柱及層板等微結 構請分別參見圖1D到圖1F。 圖 2A係一 PS29-PLLA22(/pllav=0.37)之 TEM 顯微照相 18 200530278 圖；圖2B係PS29-PLLA22(/pllav=0.37)之奈米級螺旋體微結 構不意圖。 在/plLAv=〇.37時進行TEM微結構觀察，意外的發現到 螺旋體微結構，如圖2A與2B所示。奈米級螺旋體的螺距以 5 及直徑分別量測出其平均值為43.8nm與34.4nm。此奈米級 螺旋體螺距與半徑的比例（P/r=2.5)亦遵循自然界中螺旋體 構形P/r值必須低於6.28的通常法則。 圖 3A係一 PS29-PLLA22(/pLLAv=0.37)溶液鑄膜樣品， 沿著xyz平面截面之三維TEM微結構圖；如圖所示，xy平面 10 是鑄膜基板之基本面，yz與zx平面對於鑄膜表面而言是屬 垂直平面。圖3B則是PS29-PLLA22(/pLLAv=0.37)鑄膜樣品在 不同方向下所呈現之二維SAXS散射圖譜。如圖3A與3ΒΚ 示，定位之微結構包括六角圓柱之PLLA，係交織於PS基材 中，利用TEM觀察鑄膜樣品。計算PLLA團塊所佔之體積分 15 率約為40%，此數值與合成後的結果(/pLLAv=(h37)幾乎是一 致的。 接著進行SAXS實驗以進一步觀測型態。二維SAXS結 果中，沿著螺旋軸之散射圖譜清楚的呈現出6摺對稱，相對 於此，一般螺旋體沿著螺旋軸只呈現出2摺對稱。更進一步 20 利用方位角積分之一維SAXS圖譜觀察6摺對稱之散射圖 譜，如圖4所示，係PS29-PLLA22(/pLLAv=0.37)鑄膜樣品之 方位角積分一維SAXS圖譜。繞射波峰出現於相對值的 1:41/2:71/2:91/2，以及一較寬之波峰出現於約3.5g*。這些結 果係包括六角圓柱微結構，而其中由於特定之P/r值，因此 19 200530278 奈米級螺旋體亦可視為圓柱管狀。 如同上述論點，根據投射出的管柱結構外形，3.5g* 繞射波可視為由於有類似圓柱之外形而造成，與TEM觀察 結果中，沿著螺旋軸推論出之直徑相符。此外，藉由SAXS 5 所測定出之長週期，50.6nm，則與TEM所觀測到之間隔相 符。由以上結果，可以明顯的測定自組裝PS-PLLA結構之 奈米級微結構螺旋體的三維幾何排序。同時，具左旋式螺 旋的螺旋構形與在TEM觀察下所組成團塊之構形一致。相 較之下，奈米級螺旋體微結構則尚未被發現存在於PS_PLA 10 團聯共聚物或是PLLA單聚物中。此所造成之結果， PS-PLLA中螺旋體微結構的出現是因為所構成之團塊間不 互溶而發生之掌性反應，以及混合時發生之亂度所造成之 效應。 團聯共聚物熱動力學的分析因為掌性體的存在而非 15 常複雜。這必定會對理論上團聯共聚物之傳統處理方式有 所影響。螺旋體行為係根據團聯共聚物之掌性來加以預測。 圖5A是PS29-PLLA22(/pLLAv=0_37)溶液鑄膜樣品水解 前之掃瞄式探針顯微鏡的顯微照相圖。圖5B則是 PS29_PLLA22(/pLLAv=0.37)溶液鑄膜樣品水解後之掃瞄式 20 探針顯微鏡的顯微照相圖。將PLLA進行水解來處理六角結 構螺旋體。以AFM進行觀察時發現，水解後的PS-PLLA溶 液鑄膜樣品之六角結構螺旋體，於其表面逐漸出現有奈米 孔洞陣列。 圖 6A 是 PS29-PLLA22(/pLLAv=0.37)樣品水解後之 200530278 FESEM顯微照相圖，其觀測點與螺旋軸平行。圖6B是 PS29-PLLA22(/pllav=0.37)樣品水解後之FESEM顯微照相 圖，其觀測點與螺旋軸垂直。為了更進一步鑑定水解後 PS-PLLA樣品之結構，本實施例使用場發射掃瞄式電子顯 5 微鏡於不同觀測點進行樣品之觀察。在進行平行於螺旋軸 向的觀察時，以FESEM所觀察到有序的奈米孔洞陣列結 果，與利用SPM觀察到的結果類似。而在進行垂直於螺旋 軸向的觀察時，可觀察到PLLA螺旋型態的裂解痕跡。因 此，PLLA螺旋結構經由簡單的水解處理即可形成螺旋體孔 10 道。 實施例7、流程圖 圖7是本發明合成聚（苯乙烯）-聚（左旋乳酸）(PS-PLLA) 掌性團聯共聚物的製程流程圖。流程圖中步驟已詳述於實 施例2中。 15 實施例8、PS280PLLA127團聯共聚物的合成 另一具有不同體積比例之PS-PLLA團聯共聚物系列 的製備，係利用相同之「活性」聚合順序進行。以分子量 以及體積比例為準，這些PS-PLLAs係標示為PSx-PLLAy (/ρι^Αν=ζ)，其中X與y係分別代表PS與PLLA團塊重複的次 20 數，z則代表PLLA之體積分率（假設PS與PLLA之密度分別 為1.02與1 · 18g/cm3來計算）。團聯共聚物之批次樣品是以二 氣乙烧（dichloroethane，CH2C12)溶液（10wt% 的 PS-PLLA)於 室溫下進行溶液鑄膜的方式製作。在微觀相分離熔融時進 行冷卻，10個經過熱處理之樣品以超薄切片機切出薄片。 21 200530278 即可利用TEM以及SAXS分別觀測到不同型態的自組裝微 結構，包括圓球，六角圓柱及層板結構。與非掌性團聯共 聚物聚（苯乙烯）-b-聚（左旋乳酸）(PS-PLA)類似的是，約u 個PS-PLLA樣品顯示出典型的相結構，就如同根據團聯丘 5 聚物熱動力學理論所預測的。 PS280PLLA127(/pllav=0.35)樣品的奈米螺旋體相結 構與圖2A、2B中呈現之結構很相似。螺距，投射出之直徑， 以及所測定出之奈米螺旋體直徑，其平均值分別約43 8、 31.9以及25.3nm。在適當的溶劑揮發速率下，可觀察到完 10成定位且在PS基材中具有三維PLLA螺旋體的微結構。以 TEM於不同角度來鑑定相之結構，可發現奈米螺旋體係位 於六角柱體晶格内。計算PLLA團塊所佔之體積分率約為 31%，此數值與合成後的結果乎是一致的。 接著利用同步輻射進行二維SAXS實驗以進一步觀測型 15態。當X光束沿著螺旋軸成一直線時，可以觀察到一界定 清楚，似六角型態繞射之散射圖譜。一維SAXS圖譜係根據 二維圖譜，利用方位角積分方式來獲取數據，如圖8所示。 繞射波峰出現於C值比例的1:4l/2:7l/2:9l/2:13l/2。這結果與 六角型態相結構一致，且其中奈米級螺旋體可視為圓柱管 20狀。然而，即使沿著螺旋軸所反射出之二維8八又8散射圖譜 暗不著此反射具有幾乎相同的間隔，此反射顯示出之強度 仍為2摺對稱，如圖8B所示。因此，此結果顯示微螺旋體 、、口構疋一異斜方體（ρ86ι1(1〇_〇ί1ι〇Γΐι〇ιη1*)結構（因為單一晶 格之空間中，a軸與!3軸比例近乎相同）而非一正六角形（接 22 200530278 近斜方體）。推測一接近正六角形結構之2摺對稱強度是來 自於奈米螺旋體結構被單軸向的毀壞，此毀壞方式就如同 1 (L乳Ssl )的α_螺旋結構以及plla的ο:形結晶。在TEM顯微 照相中，可發現奈米螺旋體係呈現一左手向性螺旋，與 5 PLLA團塊具有一 L型掌性中心之結果一致。直到本研究為 止，尚未有過於PS-PLA團聯共聚物以及PLLA單聚物中形 成有奈米螺旋相結構的報導。pS-plla中奈米螺旋體的出 現相信是由於掌性反應以及所組成之團塊間不互溶的效 應，而不像是非掌性三元共聚物或其混雜物之非中心對稱 10相結構。取而代之的是在彈性力與兩面之間能量的交互作 用，螺叙體彎曲的自組裝是由於PLLA鏈段因掌性體的交互 作用而形成特殊結構所誘發。與掌性液體結晶聚合物所形 成之螺旋體結晶相同的是，掌性強度足以與自有序步驟相 抗衡，且在此特殊構型之相結構中能穩定螺旋外型（例如， 15低液晶性狀態）。而其詳細機制之相關研究仍進行中。 實施例9、聚（4-乙烯基吡啶）_聚（左旋·乳酸）團聯共聚物 PS280PLLA127 的合成 聚（4-乙烯基吼啶）-聚（左旋_乳酸）團聯共聚物的合成 係藉由上述實施例中所描述之類似步驟進行。聚（左旋-乳 20酸）的體積分率經計算約為23%(/PLLAv=〇 23)。請參考圖9， 為一 TEM觀察螺旋體微結構之顯微照相。 上述本發明實施例之說明僅提供作為舉例與敘述。可 依據上述說明而有種種明顯之改變。本發明係藉由最佳實 施例說明内谷，但在不背離本發明之範_下，對本發明有 23 200530278 種種改變及修飾，均可由熟習本項技藝者加以進行，以適 用於種種用途與情況。根據本發明範疇所進行之種種改變 與修飾係在公平，合法公正的原則下與申請專利範圍一致。 5【圖式簡單說明】 圖 1A係PS38-PLLA10(/pLLAv=0.17)的 TEM顯微照相圖。 圖 1B係PS38_PLLA21(/pLLAv=0.30)的 TEM顯微照相圖。 圖 1C係PS38-PLLA22(/pllav=0.56)的 TEM顯微照相圖。 圖1D係形成PS38-PLLA10(/pLLAv=0.17)的奈米微膠粒微結 10 構之概要圖示。 圖1E係PS38-PLLA21(/pLLAv=0.30)的奈米六角構形微結構 之概要圖示。 圖1F係PS38_PLLA22(/pLLAv=0.56)的奈米層板微結構之概 要圖示。 15 圖 2A係 PS29-PLLA22(/pLLAv=0.37)的 TEM顯微照相圖。 圖2B係PS29-PLLA22(/pLLAv=0.37)的奈米螺旋微結構之概 要圖示。 圖3A係PS29-PLLA22(/pLLAv=0.37)溶液鑄膜樣品沿XYZ平 面切片之三維TEM顯微照相圖；如圖所示，xy平面是鑄膜 20 基材的基礎面，yz與zx平面則分別屬於相對於鑄膜表面的 垂直面。 圖3B係PS29-PLLA22(/pLLAv=0.37)沿鑄膜不同方向之二維 SAXS散射圖譜。 圖4係PS29-PLLA22(/pllav=0.37)溶液鑄膜樣品的方位角積 200530278 分一維SAXS資料點圖。 圖5A係PS29-PLLA22(/pLLAv=0.37)溶液鑄膜樣品水解前的 SPM顯微照相圖。 圖5B係為PS29-PLLA22(/pLLAv=0_37)溶液鑄膜樣品水解後 5 的SPM顯微照相圖。 圖6A係為已水解之PS29_PLLA22(/pllav=0.37)樣品平行於 螺旋軸心的FESEM顯微照相圖。 圖6B係為已水解之PS29_PLLA22(/pLLAv=0.37)樣品垂直於 螺旋軸心的FESEM顯微照相圖。 # 10 圖7係為本發明合成聚（苯乙烯）-聚（左旋-乳酸）（PS-PLLA) 掌性團聯共聚物之流程圖。 圖8A係表示PS280-PLLA127(/pllav=0.35)取自二維圖樣之 方位角積分一維SAXS數值圖；散射波峰出現於q*比例為 1:41/2:71/2:91/2:131/2 處。 15 圖8B係PS280_PLLA127(/pllav=〇.35)樣品沿螺旋軸觀察的 二維SAXS散射圖譜所投射出之反射像，顯示反射像具有幾 乎相等之空間；這些反射像顯現出2摺對稱之強度。 _ 圖9係為聚（4-乙烯基吡啶）-聚（左旋·乳酸）（/pLLAv=0.37)團 聯共聚物的TEM顯微照相圖，顯現出一螺旋微結構。 20 【主要元件符號說明】 無 25Mn = 46700, PDI = 1.17. NMR (CDC13): 6.46-7.09 (br, 5H, ArH), 5.16 (q, 1H, CH (CH3), J = 7.2Hz), 1.84 (br, 1H, CH), 1.58 (d, 3H, CH (CH3)), J = 7.2Hz), 1.42 (br, 2H, CH2) · 15 lU and 13C NMR spectrum results were used on Varian Gemini-200 (200 MHz used at 4,200 MHz Used in 13C) spectrometer for recording, in which the chemical shift is in ppm, and the internal tetramethylene silane (TMS) is converted to the central gas imitation (CHC13). The gel permeation chromatography (GPC) measurement method uses the Hitachi L-7100 system with a BISCHOFF refractive index detector (differential 20 Bischoff 8120 RI detector), and the solvent is tetrahydrofuran (THF, HPLC grade). The molecular weight and molecular weight distribution are calculated using polystyrene as a standard. A quantity of poly (styrene) -poly (l-lactic acid) (PS-PLLA) palm group copolymer was prepared. According to the ratio of molecular weight and volume, these 25 PS-PLLAs are marked with PSxx-PLLAyy (/ PLLAV = z), where XX and yy 15 200530278 represent the molecular weight of PS measured from NMR and PLLA divided by 1000, z represents the volume fraction of PLLA. In these calculations, the densities of PS and PLLA are assumed to be 1.02 and 1.18 g / cm3, respectively. Example 3. The study of transmission electron microscope (TEM) and small-angle X-ray scattering 5 (SAXS). It was found in experiments that crystallizing PLLA in PS-PLLA increased the apparent change of the micro-phase separation morphology of PS-PLLA. . It is feasible to destroy the formed microstructures to form a crystalline configuration. The differential scanning thermal card meter uses Perkin-Elmer DSC 7. For example, PSLA-PLLA22 (/PLlav=0.37) 10 melts at about 165 ° C. The maximum crystallization rate of PLLA agglomerates is an exothermic reaction accompanied by different isothermal crystallization (ie, when the crystallization reaction occurs) at about 95 ° C. However, no significant exothermic reaction occurred during the rapid cooling process. The glass transition temperatures of PLLA and PS are approximately 51.4 ° C and 99.2 ° C, respectively. 15 The small-angle X-ray scattering experiment (SAXS) was performed at the National Synchrotron Light Source in Brookhaven National Laboratory in the Brookhaven National Laboratory, using a synchronized X-ray beam X3A2. The X-ray beam has a wavelength of 0.154 nm. The zero-point pixels in the small-angle X-ray scattering experimental spectrum are calculated using silver behenate. The first scattered 20-ray vector score * (minutes * = 4 λ -1 sin 0, 2 0 is the scattering angle) is 1 · 076ηιη-1 . The time-lapse X-ray scattering experiment was performed in a heating box and gradually heated. The cracking temperature is based on the disappearance time of the scattering peak. The thermal scan of the DSC thermogram shows that no endogenous heat of fusion is generated during the heating process. Scattering results of wide-angle X-ray diffraction pattern (WAXD) 16 200530278 Shows the diffraction pattern of the amorphous phase. The Siemens D5000 1.2Kw vacuum tube X-ray generator with a diffractometer is used to perform WAXD powder diffraction experiments. The 20 angle of the scan is between 5 ° -40 °, and each scan angle is 0. 05 ° for 3 seconds. The position and width of the diffraction peaks are after the WAXD experiment. 5 Carefully calculated using silicon crystals of known crystal size. Transmission electron microscopy A JEOL TEM-1200x transmission electron microscope was used in the bright field system; the staining step was to place the sample in a 4% Ru04 aqueous solution aerosol for 3 hours. After hydrolysis of the PS-PLLA sample of the solution cast film, the surface was observed with an original force microscope (AFM). The instrument was a Seiko SPA-400AFM with a SEIKO SPI-3800N probe station and was performed at room temperature. A rectangular stone-made probe was used for detection in dynamic force mode (DFM). An SI-DF20 instrument with a contact force of 19NΠ1.1 · 1 was used to conduct the experiment with a scanning frequency of 1.0Hz. 15 Observe PS-PLLA samples from different perspectives using a field emission scanning electron microscope. The instrument used was Hitachi S-900 FE-SEM, and the acceleration voltage used was 2-5keV. The object to be observed is the surface of a solution casting film sample or a PS-PLLA cross-section film that has been damaged by hydrolysis. The sample is fitted in a copper sheet, bonded with carbon material, and then coated with a layer of 2-3nm 20 gold particles by spin coating (the thickness of the gold particle coating is determined by the calculated deposition rate and the experimental deposition time) Of). Example 4: TEM and SAXS experimental results Figure 1A is a TEM photomicrograph of PS38-PLLA10 (/pLLAv=0.17); Figure 1B is a TEM photomicrograph of PS38-PLLA21 (/pLLAv=0.30) 200530278; Fig. 1C is a TEM photomicrograph of PS13-PLLA22 (/pllav=0.56); Fig. 1D is a schematic diagram of the nano-grade micelle microstructure of PS38-PLLA10 (/pLLAv=0.17); Fig. 1E is PS38-PLLA21 ( /pllav=0.30) is a schematic diagram of nanometer-level hexagonal microstructures; and FIG. 1F is a schematic diagram of a nanometer 5-meter layer-shaped microstructure of PS13-PLLA22 (/pLLAv=0.56). The self-assembling forms of various types of cross-linked copolymers are studied using a transmission microscope (TEM) and a small-angle X-ray scattering (SAXS). Batch samples of the cross-linked copolymers were prepared by dichloroethane (CH2C12) solution (0.5 wt% PS-PLLA) at room temperature. 10 Crystallization behavior has been determined to occur clearly on the surface of the crosslinked copolymer. To reduce the interference of PLLA during crystal formation, the cast film samples need to be annealed at a temperature higher than the melting point of PLLA, but below the order-disorder transition temperature, and then the sample is rapidly cooled with liquid nitrogen. The thermal response of PS-PLLA was measured using a differential scanning thermal card analyzer. The order-disorder transition temperature 15 of PS-PLLA is higher than the cracking temperature (~ 17 ° C), as measured by a small-angle X-ray scattering instrument. The amorphous phase PS-PLLA was obtained after heat treatment and DSC and WAXD measurements. After cooling at the melting point of the micro-phase separation, the heat-treated sample was dyed with Ru04, and then sliced with an ultra-thin microtome. You can use TEM 20 and SAXS to observe different types of microstructures. When / ρι ^ Αν is 0.17, 0.30, and 0.56 respectively, the microstructure types are: microcolloids, hexagonal cylinders, and laminates. . Please refer to Figure 1D to Figure 1F for these microstructures, such as micelles, hexagonal cylinders, and laminates. Fig. 2A is a TEM photomicrograph of PS29-PLLA22 (/pllav=0.37). 18 200530278; Fig. 2B is a nano-scale spiral structure of PS29-PLLA22 (/pllav=0.37). TEM microstructure observation was performed at / plLAv = 0.37, and the spiral microstructure was unexpectedly found, as shown in Figs. 2A and 2B. The pitch of the nano-scale helix was measured by 5 and diameter, respectively, and the average values were 43.8 nm and 34.4 nm. The ratio of the pitch and radius of this nano-scale spiral body (P / r = 2.5) also follows the general rule that the spiral body configuration P / r value must be lower than 6.28 in nature. Figure 3A is a three-dimensional TEM microstructure diagram of a PS29-PLLA22 (/pLLAv=0.37) solution cast film sample along the xyz plane cross section; as shown, xy plane 10 is the basic plane of the cast film substrate, and the yz and zx planes It is a vertical plane for the surface of the cast film. Figure 3B is a two-dimensional SAXS scattering pattern of the PS29-PLLA22 (/pLLAv=0.37) cast film sample in different directions. As shown in Figs. 3A and 3BK, the positioned microstructure includes a hexagonal cylindrical PLLA, which is interwoven in a PS substrate, and the cast film sample is observed by TEM. Calculate the volume fraction of PLLA clumps, which is about 40%. This value is almost consistent with the result after synthesis (/ pLLAv = (h37). Then perform SAXS experiments to further observe the pattern. In the two-dimensional SAXS results, The scatter pattern along the spiral axis clearly shows a 60% symmetry. In contrast, the spiral body generally shows only a 2-fold symmetry along the spiral axis. Further, use the one-dimensional SAXS pattern of the azimuth integral to observe the 60% symmetry. The scattering pattern, as shown in Figure 4, is the azimuth-integrated one-dimensional SAXS pattern of the cast film sample of PS29-PLLA22 (/pLLAv=0.37). The diffraction peaks appear at the relative value of 1: 41/2: 71/2: 91 / 2, and a broader peak appears at about 3.5g *. These results include hexagonal cylindrical microstructures, and because of the specific P / r value, 19 200530278 nano-scale spirals can also be considered cylindrical. As above The argument, according to the projected shape of the column structure, the 3.5g * diffraction wave can be considered to be caused by the similar cylindrical outer shape, which is consistent with the diameter inferred along the spiral axis in the TEM observation results. In addition, by SAXS 5 The measured long period, 50.6nm, It is consistent with the interval observed by TEM. From the above results, the three-dimensional geometric ordering of the nano-scale microstructure spirals of the self-assembled PS-PLLA structure can be clearly determined. At the same time, the spiral configuration with a left-handed spiral and the observation with TEM The structure of the clumps formed below is the same. In contrast, the nano-scale spiral body microstructure has not been found in PS_PLA 10 group copolymers or PLLA monopolymers. As a result, PS-PLLA The appearance of the mesospiral microstructure is due to the palm reaction due to the immiscibility of the formed masses, and the effect caused by the disorder that occurs when mixing. The thermodynamic analysis of the group-linked copolymer is due to the existence of the palm body Instead of 15, it is often complicated. This will certainly have an impact on the traditional treatment of the block copolymer in theory. The spiral behavior is predicted based on the palmity of the block copolymer. Figure 5A is PS29-PLLA22 (/ pLLAv = 0_37 ) Scanning probe microscope photomicrograph of solution cast film sample before hydrolysis. Figure 5B is a photomicrograph of scan type 20 probe microscope after hydrolysis of PS29_PLLA22 (/pLLAv=0.37) solution cast film sample. . The hexagonal structure spiral body was treated with PLLA by hydrolysis. When observed with AFM, it was found that the hexagonal structure spiral body of the hydrolyzed PS-PLLA solution cast film sample gradually appeared with nano-hole arrays on its surface. Figure 6A is PS29-PLLA22 ( (/pLLAv=0.37) The FESEM photomicrograph of the sample after hydrolysis was 200530278, and its observation point was parallel to the spiral axis. Figure 6B is the FESEM photomicrograph of the PS29-PLLA22 (/pllav=0.37) sample after hydrolysis. The spiral axis is vertical. In order to further identify the structure of the PS-PLLA sample after hydrolysis, the present embodiment uses a field emission scanning electronic display micromirror to observe the sample at different observation points. When observed parallel to the helical axis, the ordered nanohole array results observed with FESEM are similar to those observed with SPM. When observed perpendicular to the axis of the spiral, cracks of the PLLA spiral pattern were observed. Therefore, the PLLA spiral structure can form 10 spiral body pores through a simple hydrolysis process. Example 7: Flow chart FIG. 7 is a process flow chart of synthesizing a poly (styrene) -poly (l-lactic acid) (PS-PLLA) palm group copolymer according to the present invention. The steps in the flowchart have been described in detail in the second embodiment. 15 Example 8. Synthesis of PS280PLLA127 block copolymers Another PS-PLLA block copolymer series with different volume ratios was prepared using the same "living" polymerization sequence. Based on molecular weight and volume ratio, these PS-PLLAs are marked as PSx-PLLAy (/ ρι ^ Αν = ζ), where X and y represent the 20th repetition of PS and PLLA clumps respectively, and z represents the number of PLLAs. Volume fraction (assuming that the densities of PS and PLLA are 1.02 and 1.18g / cm3, respectively). Batch samples of the concatenated copolymer were made by dichloroethane (CH2C12) solution (10% by weight of PS-PLLA) at room temperature. Cooling was performed during the melting of the microscopic phase separation, and the 10 heat-treated samples were cut into thin slices using an ultra-thin microtome. 21 200530278 Different types of self-assembled microstructures can be observed using TEM and SAXS, including spherical, hexagonal cylindrical and laminate structures. Similar to the non-palmated cross-linked copolymer poly (styrene) -b-poly (L-lactic acid) (PS-PLA), about u PS-PLLA samples show a typical phase structure, just as according to Tuanlianqiu 5 Predicted by polymer thermodynamic theory. The structure of the nanospiral phase of the PS280PLLA127 (/pllav=0.35) sample is very similar to that shown in Figures 2A and 2B. The average of the pitch, the projected diameter, and the measured diameter of the nano-spiral are about 43 8, 31.9, and 25.3 nm, respectively. At an appropriate solvent volatilization rate, it is possible to observe the microstructure of 10% localization and a three-dimensional PLLA helix in the PS substrate. TEM was used to identify the structure of the phases at different angles. It was found that the nano helix system was located in the hexagonal cylinder lattice. The volume fraction of the PLLA mass is calculated to be about 31%, which is consistent with the result after synthesis. Then use synchrotron radiation to conduct a two-dimensional SAXS experiment to further observe the type 15 state. When the X-ray beam is aligned along the spiral axis, a well-defined, hexagonal-like diffraction pattern can be observed. The one-dimensional SAXS atlas is based on the two-dimensional atlas and uses azimuth integration to obtain data, as shown in Figure 8. Diffraction peaks appear at 1: 4l / 2: 7l / 2: 9l / 2: 13l / 2 at the C value ratio. This result is consistent with the hexagonal phase structure, and the nano-scale spiral body can be regarded as a cylindrical tube 20 shape. However, even if the two-dimensional eight-eight-eight scattering pattern reflected along the spiral axis does not show that the reflection has almost the same interval, the intensity shown by the reflection is still 2-fold symmetrical, as shown in FIG. 8B. Therefore, this result shows that the micro-spiral body, the mouth structure, and an isosceles (ρ86ι1 (1〇_〇ί1ι〇Γΐι〇ιη1 *) structure (because the space of a single lattice, the a-axis and! 3-axis ratios are almost the same ) Instead of a regular hexagon (continued from 22 200530278 near cuboid). It is speculated that the 2-fold symmetry strength of a near-hexagonal structure is due to the uniaxial destruction of the nano-spiral structure. This destruction method is like 1 (L 乳 Ssl ) Α-helix structure and ο: -shaped crystal of plla. In the TEM photomicrograph, it can be found that the nano-helix system exhibits a left-handed helix, which is consistent with the result that the 5 PLLA mass has an L-shaped palm center. Up to this study, no nano-helical phase structure has been reported in PS-PLA cross-linked copolymers and PLLA monopolymers. The appearance of nano-spirals in pS-plla is believed to be due to the palm reaction and the composition The immiscibility effect between the clusters is not like the non-centrally symmetrical 10-phase structure of the non-palladium terpolymer or its hybrid. Instead, the interaction between the elastic force and the energy between the two sides is curved, Self-assembly The PLLA segment is induced by the formation of a special structure due to the interaction of palmar bodies. Like the spiral crystals formed by palmar liquid crystalline polymers, palmarity is strong enough to compete with self-ordered steps, and is special here The phase structure of the configuration can stabilize the spiral shape (for example, 15 low-liquid crystallinity). The detailed mechanism is still being studied. Example 9. Poly (4-vinylpyridine) _poly (L-L-lactic acid) ) Synthetic poly (4-vinylrole) -poly (L-lactic acid) group copolymer of PS280PLLA127 is synthesized by similar steps as described in the above examples. Poly (L-R-20 The volume fraction of acid) is calculated to be about 23% (/ PLLAv = 〇23). Please refer to FIG. 9 for a TEM microphotograph of the microstructure of the spiral body. The above description of the embodiment of the present invention is only provided as an example and description There can be various obvious changes according to the above description. The present invention describes the inner valley by the best embodiment, but without departing from the scope of the present invention, there are 23 200530278 various changes and modifications to the present invention, all of which can be familiarized The artist performed it to apply to various uses and situations. Various changes and modifications made in accordance with the scope of the present invention are consistent with the scope of patent application under the principles of fairness, legality and fairness. 5 [Schematic description of the diagram] Figure 1A TEM photomicrograph of PS38-PLLA10 (/pLLAv=0.17). Fig. 1B TEM photomicrograph of PS38_PLLA21 (/pLLAv=0.30). Fig. 1C TEM photomicrograph of PS38-PLLA22 (/pllav=0.56) Fig. 1D is a schematic illustration of a nano-micelle microstructure 10 forming PS38-PLLA10 (/pLLAv=0.17). Fig. 1E is a schematic illustration of a nano-hexagonal configuration microstructure of PS38-PLLA21 (/pLLAv=0.30). Figure 1F is a schematic illustration of the nano-layer microstructure of PS38_PLLA22 (/pLLAv=0.56). 15 Figure 2A is a TEM photomicrograph of PS29-PLLA22 (/pLLAv=0.37). Figure 2B is a schematic illustration of the nano-helical microstructure of PS29-PLLA22 (/pLLAv=0.37). Figure 3A is a three-dimensional TEM photomicrograph of a PS29-PLLA22 (/pLLAv=0.37) solution cast film sample sliced along the XYZ plane; as shown in the figure, the xy plane is the base surface of the cast film 20 substrate, and the yz and zx planes are Each belongs to a vertical plane with respect to the surface of the cast film. Figure 3B is a two-dimensional SAXS scattering pattern of PS29-PLLA22 (/pLLAv=0.37) along different directions of the cast film. Fig. 4 is the azimuth product of PS29-PLLA22 (/pllav=0.37) solution casting film sample 200530278 points one-dimensional SAXS data point diagram. Fig. 5A is a photomicrograph of SPM of a cast film sample of PS29-PLLA22 (/pLLAv=0.37) solution before hydrolysis. Fig. 5B is a photomicrograph of SPM of a cast film sample of a solution of PS29-PLLA22 (/ pLLAv = 0_37). Figure 6A is a FESEM photomicrograph of the hydrolyzed PS29_PLLA22 (/pllav=0.37) sample parallel to the axis of the spiral. Fig. 6B is a FESEM micrograph of the hydrolyzed PS29_PLLA22 (/pLLAv=0.37) sample perpendicular to the axis of the spiral. # 10 FIG. 7 is a flow chart of synthesizing poly (styrene) -poly (l-lactic acid) (PS-PLLA) palm group copolymer according to the present invention. Figure 8A shows the one-dimensional SAXS value diagram of the azimuth integral of PS280-PLLA127 (/pllav=0.35) taken from a two-dimensional pattern; the scattering peaks appear at a q * ratio of 1: 41/2: 71/2: 91/2: 131/2. 15 Figure 8B is a reflection image projected from a two-dimensional SAXS scattering spectrum of a PS280_PLLA127 (/ pllav = 0.35) sample viewed along the spiral axis, showing that the reflection images have almost equal spaces; these reflection images show a 2-fold symmetrical strength . _ Figure 9 is a TEM micrograph of a poly (4-vinylpyridine) -poly (L-lactic acid) (/pLLAv=0.37) cross-linked copolymer, showing a spiral microstructure. 20 [Description of main component symbols] None 25