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TWI512038B - 穩定之聚（３，４－伸乙基二氧基噻吩）組成物及具有有限酸性之陰離子穩定劑 - Google Patents

穩定之聚（３，４－伸乙基二氧基噻吩）組成物及具有有限酸性之陰離子穩定劑 Download PDF

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TWI512038B
TWI512038B TW103137620A TW103137620A TWI512038B TW I512038 B TWI512038 B TW I512038B TW 103137620 A TW103137620 A TW 103137620A TW 103137620 A TW103137620 A TW 103137620A TW I512038 B TWI512038 B TW I512038B
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pedot
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methacrylate
aryl
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TW201533148A (zh
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Christophe Navarro
Wiljan Smaal
Muhammad Mumtaz
Eric Cloutet
Cyril Brochon
Georges Hadziioannou
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Arkema France
Centre Nat Rech Scient
Univ Bordeaux
Inst Polytechnique Bordeaux
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Description

穩定之聚(3,4-伸乙基二氧基噻吩)組成物及具有有限酸性之陰離子穩定劑
本發明關於具有有限酸度之聚(3,4-伸乙基二氧基噻吩)陰離子穩定劑的穩定組成物。
以縮寫PEDOT已知的聚(3,4-伸乙基二氧基噻吩)為1980年代末期於德國Bayer AG之實驗室中與AGFA集團共同研究發現的聚合物。該聚合物特別被用於有機電子應用中，尤其用於光伏打電池中，但是更普遍地用光電子應用中，因為其良好的導電率及特別因為其對氧化的穩定性和其透明性。
PEDOT為不可溶於一般溶劑中的聚合物。其通常與聚(苯乙烯-共-苯乙烯磺酸)(PSS)共聚物組合，使其有可能分散於水中。PSS充當為填充劑摻雜劑，形成由連結至PEDOT的PSS鏈之纏結物所組成的膠態粒子，具有以富含PSS之頂冠覆蓋的富含PEDOT之核心。在商業上可取 得具有不同的導電率之該等粒子。PEDOT：PSS可經由常見的方法輕易地以薄膜形式沉積，諸如旋轉澆注法或噴墨印刷法。在許多光電子裝置中，PEDOT：PSS層係排列在由氧化銦錫(ITO)所組成的電極層與活性有機材料層之間。PEDOT：PSS供給更好的電極功能、使粗糙的ITO表面平滑及因此限制了短路，且其保護活性有機層免受游離銦及氧的傷害，得到壽命延長的系統。
不幸地，PEDOT：PSS組成物的特有性質具有缺點。特別地，PEDOT：PSS之膠態分散液具有高酸性且為鄰近的層降解之可能原因。為了解決此問題，有必要以另一聚電解質代替非常酸性的PSS，且同時維持PEDOT：PSS的優點，特別為分散液的穩定性。
在許多試驗之後，申請者發現聚陰離子(Pan)穩定劑族群，其充當為電荷摻雜劑，能使具有PEDOT的膠態分散液有非常良好的穩定性，且同時限制該等膠態分散液的酸性。所得膜既容易製造又具有良好的導電率和良好的機械性質。
 本發明的概述：
本發明關於PEDOT：聚陰離子組成物，其中聚陰離子包含對應於下列式I之單體：
A=H,CH3 或芳基，R=烷基或芳基，R1=CF3 ,CH3 ,F,R' =芳基
詳細說明：
在本發明組成物中所使用之PAn係藉由單體I在隨意的離子或非離子共單體存在下的自由基聚合反應或經控制之自由基聚合反應而獲得。
與I隨意地共聚合之單體係選自乙烯基、亞乙烯基、 二烯、烯烴、烯丙基和(甲基)丙烯酸系單體。該等單體更特別地選自乙烯基芳族單體，諸如苯乙烯或經取代之苯乙烯，尤其為α-甲基苯乙烯，丙烯酸系單體，諸如丙烯酸或其鹽，丙烯酸烷酯、環烷酯或芳酯，諸如丙烯酸甲酯、乙酯、丁酯、乙基己酯或苯酯，丙烯酸羥烷酯，諸如丙烯酸2-羥乙酯，醚丙烯酸烷酯，諸如丙烯酸2-甲氧基乙酯，聚伸烷二醇丙烯酸烷氧酯或芳氧酯，諸如聚乙二醇丙烯酸甲氧酯、聚乙二醇丙烯酸乙氧酯、聚丙二醇丙烯酸甲氧酯、聚乙二醇-聚丙二醇丙烯酸甲氧酯或其混合物，丙烯酸胺基烷酯，諸如丙烯酸2-(二甲基胺基)乙酯(DAMEA)，丙烯酸氟酯、丙烯酸矽烷酯、磷丙烯酸酯，諸如伸烷二醇磷酸基丙烯酸酯，丙烯酸縮水甘油酯或二環戊烯氧基乙酯，甲基丙烯酸系單體，諸如甲基丙烯酸或其鹽，甲基丙烯酸烷酯、環烷酯、烯酯或芳酯，諸如甲基丙烯酸甲酯(MMA)，甲基丙烯酸月桂酯、環己酯、烯丙酯、苯酯或萘酯，甲基丙烯酸羥烷酯，諸如甲基丙烯酸2-羥乙酯或甲基丙烯酸2-羥丙酯，醚甲基丙烯酸烷酯，諸如甲基丙烯酸2-乙氧基乙酯，聚伸烷二醇甲基丙烯酸烷氧酯或芳氧酯，諸如聚乙二醇甲基丙烯酸甲氧酯、聚乙二醇甲基丙烯酸乙氧酯、聚丙二醇甲基丙烯酸甲氧酯、聚乙二醇-聚丙二醇甲基丙烯酸甲氧酯或其混合物，甲基丙烯酸胺基烷酯，諸如甲基丙烯酸2-(二甲基胺基)乙酯(DAMEMA)，甲基丙烯酸氟酯，諸如甲基丙烯酸2,2,2-三氟乙酯，甲基丙烯酸矽烷酯，諸如3-甲基丙烯醯基丙基三甲基矽烷，磷甲基丙烯酸酯， 諸如伸烷二醇磷酸基甲基丙烯酸酯，羥乙基咪唑烷酮甲基丙烯酸酯、羥乙基咪唑啶酮甲基丙烯酸酯、甲基丙烯酸2-(2-酮基-1-咪唑啶基)乙酯、丙烯腈、丙烯醯胺或經取代之丙烯醯胺、4-丙烯醯基嗎啉、N-羥甲基丙烯醯胺、甲基丙烯醯胺或經取代之甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺、氯化甲基丙烯醯胺基丙基三甲基銨(MAPTAC)、甲基丙烯酸縮水甘油酯或二環戊烯氧基乙酯、伊康酸、順丁烯二酸或其鹽、順丁烯二酸酐、聚伸烷二醇順丁烯二酸或半順丁烯二酸烷酯或烷氧酯或芳氧酯、乙烯基吡啶、乙烯基吡咯啶酮、(烷氧基)聚(伸烷二醇)乙烯醚或二乙烯醚，諸如甲氧基聚(乙二醇)乙烯醚、聚(乙二醇)二乙烯醚，烯烴單體，其中所述及為乙烯、丁烯、己烯和1-辛烯，二烯單體，包括丁二烯、異戊二烯，及氟烯烴單體，及亞乙烯基單體，其中所述及為亞乙烯基氟化物，或該等單體之組合。
PAn之聚合反應較佳地藉由經控制之自由基聚合反應(不論是否經由氮氧化物)、RAFT(可逆性加成斷裂轉移(reversible addition fragmentation transfer)或ATRP(原子轉移自由基聚合反應)來進行。
根據本發明的第一個態樣，經控制之自由基聚合反應係以自穩定的自由基(1)所衍生之烷氧基胺開始進行。
其中RL 基具有大於15.0342克/莫耳之莫耳質量。RL 基可為鹵素原子，諸如氯，溴或碘，直鏈、支鏈或環、飽和或不飽和烴為底質之基團，諸如烷基或苯基，或酯基團-COOR或烷氧基-OR或膦酸基團-PO(OR)2 ，先決條件為其具有大於15.0342之莫耳質量。單價RL 基可稱在相對於氮氧化物基的氮原子之β位置上。在式(1)中的碳原子及氮原子之其餘價位置可與各種基鍵結，諸如氫原子、以烴為底質之基，諸如包含從1至10個碳原子之烷基、芳基或芳基烷基。不排除將式(1)中的碳原子及氮原子經由二價基連結在一起，以便形成環。然而，式(1)的碳原子及氮原子之其餘價位置較佳地連結至單價基。RL 基較佳地具有大於30克/莫耳之莫耳質量。RL 基可具有例如介於40與450克/莫耳之間的莫耳質量。以實例說明的RL 基可為包含磷醯基的基，該RL 基可能以下式代表：
其中可相同或不同的R3 和R4 可選自烷基、環烷基、烷氧基、芳氧基、芳基、芳烷氧基、全氟烷基和芳烷基，且可包含從1至20個碳原子。R3 及/或R4 亦可為鹵素原子，諸如氯或溴或氟或碘原子。RL 基亦可包含至少一個 芳族環，如苯基或萘基，後者可能例如經包含從1至4個碳原子之烷基取代。
更特別地，自以下穩定的基所衍生之烷氧基胺較佳：- N-三級丁基-1-苯基-2-甲基丙基氮氧化物，- N-三級丁基-1-(2-萘基)-2-甲基丙基氮氧化物，- N-三級丁基-1-二乙膦基-2,2-二甲基丙基氮氧化物，- N-三級丁基-1-二苯甲膦基-2,2-二甲基丙基氮氧化物，- N-苯基-1-二乙膦基-2,2-二甲基丙基氮氧化物，- N-苯基-1-二乙膦基-1-甲基乙基氮氧化物，- N-(1-苯基-2-甲基丙基)-1-二乙膦基-1-甲基乙基氮氧化物，- 4-酮基-2,2,6,6-四甲基-1-哌啶氧基，- 2,4,6-三-三級丁基苯氧基。
在經控制之自由基聚合反應中所使用之烷氧基胺必須能良好控制單體的順序。不是所有的烷氧基胺皆能以此方式良好控制特定的單體。例如，自TEMPO所衍生之烷氧基胺有可能僅控制有限數量的單體，且這同樣為自2,2,5-三甲基-4-苯基-3-氮雜己烷3-氮氧化物(TIPNO)所衍生之烷氧基胺的例子。另一方面，自對應於式(1)的氮氧化物所衍生之其他的烷氧基胺，特別為那些自對應於式(2)的氮氧化物所衍生者，及甚至更特別為那些自N-三級丁基-1-二乙膦基-2,2-二甲基丙基氮氧化物所衍生者有可能擴大到 大量的單體以進行該等單體的經控制之自由基聚合反應。
此外，烷氧基胺之初始溫度對經濟因素亦有影響。使用低溫較佳，使工業困難度減至最低。因此，優先選擇為自對應於式(1)的氮氧化物所衍生之烷氧基胺，特別為那些自對應於式(2)的氮氧化物所衍生之烷氧基胺，及甚至更特別為那些自N-三級丁基-1-二乙膦基-2,2-二甲基丙基氮氧化物所衍生之烷氧基胺而不為那些自TEMPO或2,2,5-三甲基-4-苯基-3-氮雜己烷3-氮氧化物(TIPNO)所衍生之烷氧基胺。
根據本發明的第二形式，經控制之自由基聚合反應係經由RAFT發生，及更特別地以對應於下列式II之RAFT劑：
其中R代表包含1至22個碳原子，較佳為10至18個碳原子，及更佳為12個碳原子之烷基。
本發明主題之PEDOT：PAn組成物可被用於分散奈米填充劑，諸如碳奈米管(不論為單壁或多壁)、石墨烯或銀奈米紗。以該等組成物所獲得的膜具有良好的透明性及良好的導電率。本發明組成物亦可含有添加劑，特別為乙二醇。
圖1為實施例1之聚合物的質子NMR光譜。
圖2為實施例1之聚合物的19-氟NMR光譜。
圖3為自實施例1之PEDOT：聚合物分散液所獲得的膜之AFM形貌圖。
圖4為從如實施例3中所製備之含有碳奈米管的分散液而製得之薄膜經且測量導電率和透射率後標繪的曲線圖。
 實施例1：
4-苯乙烯磺醯基(三氟甲基磺醯基)醯胺鉀經由RAFT與2-(十二烷基-硫烷基-硫羰基-硫烷基)-2-甲基丙酸之聚合反應：
已知為STFSIK的單體4-苯乙烯磺醯基(三氟甲基磺醯基)醯胺鉀之合成係依照文獻進行且說明於R.Meziane等人之Electrochimica Acta,2011,57,14-19的文件中。
RAFT劑(2-(十二烷基-硫烷基-硫羰基-硫烷基)-2-甲基丙酸)係依照文獻合成且說明於J.T.Lai等人之Macromolecules,2002,35,6754-6756的文件中。
將2克(5.66毫莫耳)4-苯乙烯磺醯基(三氟甲基磺醯基)醯胺鉀、36.4毫克(0.1毫莫耳)2-(十二烷基-硫烷基-硫羰基-硫烷基)-2-甲基丙酸、3.28毫克(0.02毫莫耳) AIBN(偶氮雙異丁腈)及4毫升二甲基甲醯胺(DMF)放入無水Schlenk管中。接著使Schlenk管呈現惰性且放入65℃之油浴中。在全部轉化(24小時)之後，將Schlenk管插入液態氮中。將聚合物PSTFSIK(聚(4-苯乙烯磺醯基(三氟甲基磺醯基)醯胺)鉀)以沉澱清洗兩次且接著以醚過濾。接著將聚合物在真空下於60℃之烘箱中乾燥。聚合物的結構係由質子NMR(圖1)和19-氟NMR(圖2)確定。
藉由以聚苯乙烯標準物的SEC所測量之數量平均分子量為20 000克/莫耳，及多分散性指數為1.1。
實施例2：EDOT在PSTFSIK存在下的聚合反應：
將溶解在150毫升去離子水中的1.65克(Mn 20 000克/莫耳)PSFTSIK、0.3毫升(2.81毫莫耳)EDOT(Sigma-Aldrich)以攪拌放入單頸圓底燒瓶中。接著引入過硫酸銨(640毫克，2.81毫莫耳)與氯化鐵(136毫克，0.84毫莫耳)之混合物。將反應混合物在氮氛圍下於25℃下劇烈攪拌48小時。這得到深藍色分散液。將所得PEDOT與PSTFSIK之分散液以再生纖維素微孔薄膜NMWL：100 000(分子量截留)在去離子水的存在下超過濾而清洗，以移除源自於氧化劑之鹽及未鍵結至PEDOT的PSTFSIK。最終的固體產率為85%。膜係以此分散液藉由旋轉塗佈而製得且進行AFM成像。圖3顯示在從40至50奈米之範圍內的粒徑。
將實施例1中所製備之PEDOT-聚苯乙烯-共-聚苯乙 烯磺酸酯乳膠與市售乳膠(PEDOT-聚苯乙烯-共-聚苯乙烯磺酸酯)比較。
將該等材料分散在去離子水(1質量%)中且使用IKA T18 Ultra-turrax摻合機在不同的速度下(15 500、20 000、24 000rpm)進行剪切，每一速度進行5分鐘。
不論為市售乳膠或本發明主題的乳膠在該等條件下皆不可能觀察到絲毫聚結物，證明該兩種乳膠非常良好的穩定性。
實施例3：在實施例2之分散液中的單壁碳奈米管之分散液：
將來自Arkema公司的Graphistrength® 多壁碳奈米管藉助於實施例2之分散液以強大的超聲波激發經數分鐘分散於水中。將殘餘聚集物以超離心移除。以含有0.26重量%之PEDOT：PSTFSIK配對的水溶液中至多0.15重量%之碳奈米管濃度觀察到穩定的分散液。
實施例4：整體PEDOT：PSTFSIK配對之導電率
PEDOT：PSTFSIK之樣品的導電率係在壓製成1毫米厚度及13毫米直徑之碟片形式的PEDOT：PSTFSIK之樣品上經由〝4-探針〞方法測量。碟片係使用10-噸液壓機而獲得。將各種實驗條件下所製得的該等碟片之質量導電率記述於表1中。
最好的導電率係由1：0.3之比的APS/FeCl3 氧化配對在EDOT對STFSIK之莫耳比為0.6：1時獲得。當在水/異丙醇混合物中或在水/乙二醇混合物鐘進行合成時，未觀察到導電率。
實施例5：PEDOT：PSTFSIK配對及在PEDOT：PSTFSIK分散液中的碳奈米管分散液之導電率
PEDOT：PSTFSIK之薄膜係藉由放置在加熱至100℃之熱板上的玻璃板上噴霧塗佈具有10質量%之乙二醇的PEDOT：PSTFSIK分散液而製得。電阻係經由4-探針技術測量及透射率係使用Shimadzu UV-Vis-NIR UV-3600分光光度計在550奈米下測量。
在相同的方式中，薄膜係自如實施例3中所製備之含有碳奈米管的分散液而製得且測量導電率和透射率。
標繪的曲線圖可見於圖4中。
特別提出含有碳奈米管(CNT)之調配物與來自Clevios公司之PEDOT：PSS PH1000(註明為PEDOT：PSS)相比的滿意表現。

Claims (11)

  1. 一種PEDOT：聚陰離子組成物，其中聚陰離子包含對應於下列式I之單體： A=H,CH3 或芳基，R=烷基或芳基，R1=CF3 ,CH3 ,F,R' =芳基。
  2. 根據申請專利範圍第1項之組成物，其中該聚陰離子係藉由經控制之氮氧化物的自由基聚合反應來聚合。
  3. 根據申請專利範圍第2項之組成物，其中該氮氧化物為N-三級丁基-1-二乙膦基-2,2-二甲基丙基氮氧化物。
  4. 根據申請專利範圍第1項之組成物，其中該聚陰離子係藉由經控制之RAFT型的自由基聚合反應來聚合。
  5. 根據申請專利範圍第4項之組成物，其中該RAFT劑對應於下列式II： 其中R代表包含1至22個碳原子之烷基。
  6. 根據申請專利範圍第1項之組成物，其亦含有添加劑。
  7. 根據申請專利範圍第6項之組成物，其中該添加劑為乙二醇。
  8. 一種導電性透明膜，其係從如申請專利範圍第1至7項中任一項之組成物所獲得。
  9. 一種如申請專利範圍第1至7項中任一項之組成物的用途，其係用於分散奈米填充劑。
  10. 根據申請專利範圍第9項之用途，其中該奈米填充劑係由碳奈米管所組成。
  11. 一種導電性透明膜，其係從如申請專利範圍第1 至7項中任一項之組成物及碳奈米管所獲得。
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