TWI627264B - 導電性聚合物用高分子化合物及其製造方法 - Google Patents
導電性聚合物用高分子化合物及其製造方法 Download PDFInfo
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Abstract
本發明之課題為提供可溶於有機溶劑,適用為燃料電池用或導電性材料用之摻混劑的導電性聚合物用高分子化合物。
解決方法為,含有一種以上的下述一般式(1)所示之重覆單位a的導電性聚合物用高分子化合物,且重量平均分子量為1,000~500,000之範圍的導電性聚合物用高分子化合物。
(式中,R1為氫原子或甲基,R2為單鍵、酯基,或可具有醚基、酯基中任一方或雙方的碳數1~12之直鏈狀、支鏈、環狀之烴基中任一種。R3為碳數1~4之直鏈狀、
支鏈狀之烷基,R3中1個以上之氫原子可被氟原子取代。Z為單鍵、伸苯基、伸萘基、醚基、酯中任一種。a為0<a≦1.0)。
Description
本發明係有關導電性聚合物用高分子化合物及其製造方法。
先前燃料電池或導電性高分子之摻混劑聚合物係使用含有磺基之聚合物。燃料電池係廣泛使用登記商標為Nafion所代表之乙烯基全氟烷基醚磺酸,導電性高分子廣泛使用之摻混劑聚合物為乙烯基磺酸或苯乙烯磺酸之聚合物(專利文獻1)。又,專利文獻2曾提案,以質子被陽離子取代之氟化酸聚合物作為摻混劑聚合物用,其中曾揭示具有雙氟烷基磺醯亞胺之鋰鹽的苯乙烯衍生物摻混劑。
乙烯基全氟烷基醚磺酸具有較高之化學安定性而具有優良耐久性,但玻璃化溫度較低,因此使用其之燃料電池曝露於高溫下會使聚合物發生熱流動而有降低離子傳導性之問題。具有雙氟烷基硫醯亞胺之苯乙烯衍生物
也具有相同問題。為了提高離子傳導性,α位被氟化之磺基所代表的超強酸聚合物具有效果,但未隨之發現可提高玻璃化溫度而具有化學安定性之材料。
又,聚噻吩、聚苯胺、聚吡咯等之具有共軛雙鍵的導電性高分子本身不具有導電性,但摻混磺酸等之強酸時會展現導電性。所使用之摻混劑最佳為聚苯乙烯磺酸(PSS)。其因為,摻混PSS時可得最高導電率。
PSS為水溶性樹脂,幾乎無法溶解於有機溶劑。因此摻混PSS所得之聚噻吩也為水溶性。
摻混PSS所得之聚噻吩因具有高導電性及高透明性,故被期待取代ITO(銦-錫氧化物)作為有機EL照明用之導電膜用。但有機EL之發光體會因水分而發生化學變化而無法發光。即,有機EL使用水溶性樹脂之導電膜時,會有樹脂含有水而有縮短有機EL之發光壽命的問題。
專利文獻1:日本特開2008-146913號公報
專利文獻2:日本特許第5264723號
有鑑於上述事情,本發明之目的為,提供可溶於有機溶劑,適用為燃料電池用或導電性材料用之摻混
劑的導電性聚合物用高分子化合物。又目的為,提供該類導電性聚合物用高分子化合物之製造方法。
為了解決上述課題,本發明係提供含有一種以上的下述一般式(1)所示之重覆單位a的導電性聚合物用高分子化合物,且重量平均分子量為1,000~500,000之範圍的導電性聚合物用高分子化合物。
(式中,R1為氫原子或甲基,R2為單鍵、酯基,或可具有醚基、酯基中任一方或雙方的碳數1~12之直鏈狀、支鏈狀、環狀之烴基中任一種。R3為碳數1~4之直鏈狀、支鏈狀之烷基,R3中1個以上之氫原子可被氟原子取代。Z為單鍵、伸苯基、伸萘基、醚基、酯基中任一種。a為0<a≦1.0)。
該類導電性聚合物用高分子化合物可得,可溶於有機溶劑,適用為燃料電池用或導電性材料用之摻混劑的具有特定之超強酸的硫醯亞胺基之導電性聚合物用高
分子化合物。
此時前述導電性聚合物用高分子化合物較佳為,另具有下述一般式(2)所示之重覆單位b之物。
(式中,b為0<b<1.0)。
前述重覆單位a為,可與聚苯乙烯磺酸之重覆單位b共聚合之物,可作為導電性較高之摻混劑聚合物用。
又,此時前述一般式(1)所示之重覆單位a較佳為,含有下述一般式(3)所示之重覆單位a1之物。
(式中,R1及R3與前述相同,a1為0<a1≦1.0)。
該類重覆單位更適用作為燃料電池用或導電性材料用之摻混劑用。
又,本發明係提供含有下述一般式(1)所示之重覆單位a的導電性聚合物用高分子化合物之製造方法中,
使用具有由硫醯亞胺基與鋰、鈉、鉀或氮化合物所形成之鹽的結構之單體進行聚合反應,聚合後藉由離子交換將由前述硫醯亞胺基與鋰、鈉、鉀或氮化合物所形成之鹽的結構轉換為硫醯亞胺基的導電性聚合物用高分子化合物之製造方法。
(式中,R1為氫原子或甲基,R2為單鍵、酯基,或可具有醚基、酯基中任一方或雙方的碳數1~12之直鏈狀、支鏈狀、環狀之烴基中任一種,R3為碳數1~4之直鏈狀、支鏈狀之烷基,R3中1個以上之氫原子可被氟原子取代。Z為單鍵、伸苯基、伸萘基、醚基、酯基中任一種。a為0<a≦1.0)。
藉由該類製造方法易製造含有上述一般式(1)
所示之重覆單位a之導電性聚合物用高分子化合物。
又,此時使用具有由前述硫醯亞胺基與鋰、鈉、鉀或氮化合物所形成之鹽的結構之單體進行聚合反應所得的聚合物較佳為,含有下述一般式(4)所示之重覆單位之物。
(式中,R1、R2、R3、Z及a與前述相同,X為鋰、鈉、鉀,或下述一般式(5)所示之氮化合物)。
(式中,R101d、R101e、R101f、R101g各自表示氫原子,或碳數1~12之直鏈狀、支鏈狀或環狀之烷基、鏈烯基、羰基烷基或羰基烯基、碳數6~20之芳基,或碳數7~12之芳烷基或芳基羰基烷基,該等基之部分或全部氫原子可被烷氧基取代。R101d與R101e、R101d與R101e與R101f可形成環,形成環時R101d與R101e及R101d與R101e與R101f表示
碳數3~10之伸烷基,或環中具有式中之氮原子的雜芳香族環)。
該類重覆單位易藉由離子交換而轉換為上述一般式(1)所示之重覆單位a。
如上述本發明之導電性聚合物用高分子化合物可得,可溶於有機溶劑,適用為燃料電池用或導電性材料用之摻混劑的具有特定之超強酸的硫醯亞胺基之導電性聚合物高分子化合物。
燃料電池使用該導電性聚合物用高分子化合物時,可形成高介電係數之燃料電池用材料。又,作為共軛雙鍵聚合物之摻混劑時,可形成高透明,高導電性下具有高耐久性之導電膜。又,本發明之導電性聚合物用高分子化合物具有特定之超強酸的硫醯亞胺基,該硫醯亞胺基為,單側具有鍵結被氟化之烷基的磺酸基,另一側具有磺酸酯基之結構。藉由兩側之基的電子吸引效果,可提高該硫醯亞胺基之酸性度,得到與α位被氟化之磺酸同程度的超強酸。
因此本發明之導電性聚合物用高分子化合物可藉由來自該超強酸之強離子鍵結而得提高作為摻混劑用之能力,及提高作為離子用之安定性之物。故以其作為導電性材料用時可得較高之導電性及安定性。另外因相對於有機溶劑具有優良溶解性,故使用於有機EL照明用之導電膜時,可防止有機EL元件劣化。
又,藉由本發明之製造方法易製造該類本發明之導電性聚合物用高分子化合物。
如上述般需求開發可溶於有機溶劑,適用為燃料電池用或導電性材料用之摻混劑的導電性聚合物用高分子化合物。
本發明者們為了使導致有機EL元件劣化的含有水之水溶性導電性聚合物成為水分含量極少之有機溶劑可溶型而可防止元件劣化,因此嘗試由水溶性而相對於有機溶劑缺乏溶解性之摻混劑的聚苯乙烯磺酸,開發出相對於有機溶劑具有高溶解性之摻混劑用的聚合物。因導入長鏈烷基或氟原子可有效提升相對於有機溶劑之溶解性,故檢討導入氟原子,但導入長鏈烷基或過量之氟原子會降低導電率而不宜,故目標為藉由導入少量氟原子以構築強酸性單元。上述雙氟烷基磺醯亞胺雖具有較高酸性度,但因兩側具有氟烷基,因此作為摻混劑聚合物時之導電率較低。故本發明者們發現使雙氟烷基磺醯亞胺之單側為磺酸酯基時,可藉由磺酸酯基之高電子吸引性而以少量氟原子得到具有充分高度之酸性度的硫醯亞胺基,因此具有其之重覆單位所形成之高分子化合物可達成上述課題,而完成本發明。
即,本發明為,含有一種以上的下述一般式
(1)所示之重覆單位a的導電性聚合物用高分子化合物中,重量平均分子量為1,000~500,000之範圍的導電性聚合物用高分子化合物。
(式中,R1為氫原子或甲基,R2為單鍵、酯基,或可具有醚基、酯基中任一方或雙方的碳數1~12之直鏈狀、支鏈狀、環狀之烴基中任一種。R3為碳數1~4之直鏈狀、支鏈狀之烷基,R3中1個以上之氫原子可被氟原子取代。Z為單鍵、伸苯基、伸萘基、醚基、酯基中任一種。a為0<a≦1.0)。
下面將詳細說明本發明,但本發明非限定於該等。
本發明之導電性聚合物用高分子化合物為,含有一種以上的下述一般式(1)所示之重覆單位a的聚合物。本發明之導電性聚合物用高分子化合物因含有一般式(1)所示之重覆單位a,故為特別是具有高透明性之物。
(式中,R1為氫原子或甲基,R2為單鍵、酯基,或可具有醚基、酯基中任一方或雙方的碳數1~12之直鏈狀、支鏈狀、環狀之烴基中任一種。R3為碳數1~4之直鏈狀、支鏈狀之烷基,R3中1個以上之氫原子可被氟原子取代。Z為單鍵、伸苯基、伸萘基、醚基、酯基中任一種。a為0<a≦1.0)。
一般式(1)中,R1為氫原子或甲基。
R2為單鍵、酯基,或可具有醚基、酯基中任一方或雙方的碳數1~12之直鏈狀、支鏈狀、環狀之烴基中任一種,烴基如,伸烷基、伸芳基(例如伸苯基、伸萘基等)、伸烯基等。
Z為單鍵、伸苯基、伸萘基、醚基、酯基中任一種。
a為0<a≦1.0。
又,上述一般式(1)所示之重覆單位a較佳為,含有下述一般式(3)所示之重覆單位a1之物。
(式中,R1及R2與前述相同。a1為0<a1≦1.0)。
該類重覆單位更適合作為燃料電池用或導電性材料用之摻混劑用。
又,本發明之導電性聚合物用高分子化合物較佳為,另具有下述一般式(2)所示之重覆單位b之物。前述重覆單位a為,可與聚苯乙烯磺酸之重覆單位b共聚合之物時,可作為導電性較高之摻混劑聚合物用。
(式中,b為0<b<1.0)。
又,如後述本發明之導電性聚合物用高分子化合物可具有重覆單位a、重覆單位b以外之重覆單位c。
又,本發明之導電性聚合物用高分子化合物
為,重量平均分子量係1,000~500,000,較佳為2,000~200,000之物。重量平均分子量未達1,000時會成為耐熱性較差之物。又,重量平均分子量超過500,000時會提升黏度,使作業性惡化而降低相對於有機溶劑或水之溶解性。
又,重量平均分子量(Mw)為,以水、二甲基甲醯胺(DMF)、四氫呋喃(THF)作為溶劑,之來自凝膠滲透色譜(GPC)的聚苯乙烯換算測定值。
上述般本發明之導電性聚合物用高分子化合物可得,可溶於有機溶劑,適用為燃料電池用或導電性材料用之摻混劑的具有特定之超強酸的硫醯亞胺基之導電性聚合物用高分子化合物。
又,本發明係提供製造該類本發明之導電性聚合物用高分子化合物之方法。
即,本發明之製造方法為,含有下述一般式(1)所示之重覆單位a之導電性聚合物用高分子化合物之製造方法中,使用具有由硫醯亞胺基與鋰、鈉、鉀或氮化合物所形成之鹽的結構之單體進行聚合反應,聚合後藉由離子交換將前述由硫醯亞胺基與鋰、鈉、鉀或氮化合物所形成之鹽的結構轉換為硫醯亞胺基之導電性聚合物用高分子化合物的製造方法。
(式中,R1為氫原子或甲基,R2為單鍵、酯基,或可具有醚基、酯基中任一方或雙方的碳數1~12之直鏈狀、支鏈狀、環狀之烴基中任一種。R3為碳數1~4之直鏈狀、支鏈狀之烷基,R3中1個以上之氫原子可被氟原子取代。Z為單鍵、伸苯基、伸萘基、醚基、酯基中任一種。a為0<a≦1.0)。
其中具有由硫醯亞胺基與鋰、鈉、鉀或氮化合物所形成之鹽的結構之單體進行聚合反應所得之聚合物較佳為,含有下述一般式(4)所示之重覆單位之物。
(式中,R1、R2、R3、Z及a與前述相同,X為鋰、鈉、鉀,或下述一般式(5)所示之氮化合物)。
(式中,R101d、R101e、R101f、R101g各自表示氫原子,或碳數1~12之直鏈狀、支鏈狀或環狀之烷基、鏈烯基、羰基烷基或羰基烯基、碳數6~20之芳基,或碳數7~12之芳烷基或芳基羰基烷基,該等基之部分或全部氫原子可被烷氧基取代。R101d與R101e、R101d與R101e與R101f可形成環,形成環時R101d與R101e及R101d與R101e與R101f表示碳數3~10之伸烷基,或環中具有式中之氮原子的雜芳香族環)。
該類重覆單位易藉由離子交換而轉換為上述一般式(1)所示之重覆單位a,故為佳。
本發明之製造方法所使用的具有由硫醯亞胺基與鋰、鈉、鉀或氮化合物所形成之鹽的結構,製造重覆單位a用之單體的具體例可為下述之物。
(式中,R1與前述相同,X為鋰、鈉、鉀或氮化合物)。
又,如上述般一般式(1)所示之重覆單位a較佳為,含有上述一般式(3)所示之重覆單位a1。即,上述所列舉之單體中,特佳為製造重覆單位a1用之單體。
又,如上述般本發明之導電性聚合物用高分子化合物較佳為,具有一般式(2)所示之重覆單位b之物,製造該類重覆單位b用之單體的具體例如可為下述之物。
(式中,X2為氫原子、鋰、鈉、鉀、氮化合物或鋶化合物)。
上述X2為氮化合物時,可為下述一般式(5)所示之化合物。
(式中,R101d、R101e、R101f、R101g各自表示氫原子,
或碳數1~12之直鏈狀、支鏈狀或環狀之烷基、鏈烯基、羰基烷基或羰基烯基、碳數6~20之芳基,或碳數7~12之芳烷基或芳基羰基烷基,該等基之部分或全部氫原子可被烷氧基取代。R101d與R101e、R101d與R101e與R101f可形成環,形成環時,R101d與R101e及R101d與R101e與R101f表示碳數3~10之伸烷基,或環中具有式中之氮原子的雜芳香族環)。
又,如上述般本發明之導電性聚合物用高分子化合物可具有重覆單位a、重覆單位b以外之重覆單位c,該重覆單位c如,苯乙烯系、乙烯基萘系、乙烯基矽烷系、苊烯、茚、乙烯基咔唑等。
製造重覆單位c用之單體的具體例可為下述之物。
合成本發明之導電性聚合物用高分子化合物的方法如,溶劑中加入自由基聚合引發劑,使上述單體中所希望之單體進行加熱聚合,得共聚物之高分子化合物的方法。
聚合時所使用之溶劑如,水、甲醇、乙醇、n-丙醇、異丙基醇、甲氧基乙醇、乙氧基乙醇、n-丁醇、乙二醇、丙二醇、甘油、二乙二醇、二甲基甲醯胺、二甲基乙醯胺、丙酮、二甲基亞碸、N-甲基吡咯烷酮、甲苯、苯、四氫呋喃、二乙基醚、二噁烷、環己烷、環戊烷、甲基乙基酮、γ-丁內酯等。
自由基聚合引發劑如,二-t-丁基過氧化物、二枯基過氧化物、t-丁基枯基過氧化物、苯醯過氧化物、二月桂基過氧化物、枯烯氫過氧化物、t-丁基氫過氧化物、t-丁基過氧基異丁酸酯、過硫酸鉀、過硫酸銨、過氧化氫水、2,2’-偶氮雙異丁腈(AIBN)、2,2’-偶氮雙(2,4-二甲基戊腈)、二甲基2,2-偶氮雙(2-甲基丙酸酯)、月桂醯過氧化物、2,2’-偶氮雙(2-脒基丙烷)二鹽酸鹽、或4,4’-偶氮雙(4-氰基戊酸)之鹼金屬鹽或銨鹽等。
反應溫度較佳為50~80℃,反應時間較佳為2~100小時,更佳為5~20小時。
本發明之導電性聚合物用高分子化合物中,形成一般式(1)所示之重覆單位a的單體可一種或二種以上組合使用,但為了提高聚合性較佳為組合使用甲基丙烯酸基型與苯乙烯型之單體。
又,形成重覆單位a的二種以上之單體可為無規共聚合,或各自嵌段共聚合。以嵌段共聚合聚合物(嵌段共聚物)作為導電膜用時,藉由凝聚由二種以上之重覆單位a所形成之重覆單位部分相互間凝集而形成海島結構,故具有期待提升導電性之優點。
又,製造重覆單位a~c用之單體可無規共聚合,或各自嵌段共聚合。此時與上述重覆單位a時相同,形成嵌段共聚物可具有期待提升導電率之優點。
以自由基聚合進行無規共聚合時,一般係藉由混合進行共聚合用之單體及自由基聚合引發劑後再加熱以進行聚合之方法。於第一種單體與自由基聚合引發劑存在下開始聚合後添加第二種單體時,可得聚合物分子之單側聚合第一種單體之結構,而另一側聚合第二種單體之結構。但此時中間部分會混在第一與第二種單體之重覆單位,因此形態不同於嵌段共聚物。以自由基聚合形成嵌段共聚物時,較佳為使用活性自由基聚合。
稱為RAFT聚合(Reversible Addition Fragmentation chain Transfer polymerization)之活性自由基聚合方法中,聚合物末端常生成自由基,因此以第一種單體開始聚合後,藉由消耗該等之階段中添加第二種單體時,可由第一種與第二種重覆單位形成嵌段共聚物。又,以第一種單體開始聚合後,於消耗其之時間點添加第二種單體,再加入第三種單體時可形成三嵌段共聚物。
進行RAFT聚合時會有形成分子量分布(分散
度)較窄之窄分散聚合物的特性,特別是一起添加單體進行RAFT聚合時,可形成分子量分布更窄之聚合物。
又,本發明之導電性聚合物用高分子化合物中,分子量分布(Mw/Mn)較佳為1.0~2.0,特佳為1.0~1.5之窄分散狀。其為窄分散高,可防止使用高分子化合物合成所得之導電性聚合物的導電率不均勻。
進行RAFT聚合時需具有鏈轉移劑,具體例如2-氰基-2-丙基苯并硫酸酯、4-氰基-4-苯基碳基硫醯硫戊酸、2-氰基-2-丙基十二烷基三硫碳酸酯、4-氰基-4-[(十二烷基磺醯硫羰基)磺醯]戊酸、2-(十二烷基硫碳基硫醯硫基)-2-甲基丙酸、氰基甲基十二烷基硫碳酸酯、氰基甲基甲基(苯基)胺基甲硫酸酯、雙(硫苯醯)二硫化物)、雙(十二烷基磺醯硫羰基)二硫化物。其中特佳為2-氰基-2-丙基苯并硫酸酯。
此時重覆單位a~c之比例為0<a≦1.0、0≦b<1.0、0≦c<1.0,較佳為0.1≦a≦0.9、0.1≦b≦0.9、0≦c≦0.8,更佳為0.2≦a≦0.8、0.2≦b≦0.8、0≦c≦0.5。
又以a+b+c=1為佳。
本發明之導電性聚合物用高分子化合物之製造方法中,如上述聚合單體後,藉由離子交換可將由硫醯亞胺與鋰、鈉、鉀或氮化合物所形成之鹽的結構轉換為硫醯亞胺基。
此時之離子交換例如可使用離子交換樹脂進行。
上述般之方法中,易製造含有上述一般式(1)
所示之重覆單位a的導電性聚合物用高分子化合物。
如上述本發明之導電性聚合物用高分子化合物可得,可溶於有機溶劑中,適用為燃料電池用或導電性材料用之摻混劑的具有特定之超強酸的硫醯亞胺基之導電性聚合物用高分子化合物。
燃料電池使用該導電性聚合物用高分子化合物時,可形成高介電係數之燃料電池用材料。又,作為共軛雙鍵聚合物用之摻混劑用時,可形成高透明、高導電性下耐久性較高之導電膜。本發明之導電性聚合物用高分子化合物因具有特定之超強酸的硫醯亞胺基,故可藉由較強之離子鍵結而提高作為摻混劑用之能力,又,可得離子安定性較高之物。因此作為導電性材料用時,可具有較高導電性與安定性。另外因相對於有機溶劑具有優良溶解性,故使用於有機EL照明用之導電膜時可防止有機EL元件劣化。
又,本發明之製造方法易製造該類本發明之導電性聚合物用高分子化合物。
下面將舉實施例具體說明本發明,但本發明非限定於該等。
下面為實施例之合成用的單體。
苄基三甲基銨=甲基丙烯醯氧基乙基-N-[(三氟甲基)磺醯]胺基磺酸酯。
於氮環境下,以4小時將溶解有49.1g之單體1與5.13g之2,2’-偶氮雙(異丁酸)二甲酯的甲醇112.5g所得之溶液滴入64℃下攪拌之甲醇37.5g中。64℃下再攪拌4小時。冷卻至室溫後,滴入激烈攪拌之乙酸乙酯1,000g中,過濾取出所生成之固體物後,於50℃下真空乾燥15小時,得白色聚合物26.2g。
將所得之白色聚合物溶解於純水912g中,使用離子交換樹脂將苄基三甲基銨鹽轉換為硫醯亞胺基。測定所得聚合物之19F-NMR、1H-NMR及GPC,得下述分析結果。
重量平均分子量(Mw)=46,000
分子量分布(Mw/Mn)=1.59
以該高分子化合物為(聚合物1)。
於氮環境下,以4小時將溶解有24.6g之單體1與9.5g之苯乙烯磺酸鋰與5.13g之2,2’-偶氮雙(異丁酸)二甲酯的甲醇112.5g所得之溶液,滴入再於64℃下攪拌之甲醇37.5g中。再於64℃下再攪拌4小時。冷卻至室溫後滴入激烈攪拌之乙酸乙酯1,000g中。過濾取出所生成之固體物後,50℃下真空乾燥15小時,得白色聚合物28.3g。
將所得之白色聚合物溶解於純水912g中,使用離子交換樹脂各自將苄基三甲基銨鹽與鋰鹽轉換為硫醯亞胺基與磺基。測定所得聚合物之19F-NMR、1H-NMR及GPC,得下述分析結果。
共聚合組成比(莫耳比)單體1:苯乙烯磺酸=1:1
重量平均分子量(Mw)=41,000。
分子量分布(Mw/Mn)=1.63
以該高分子化合物為(聚合物2)。
上述所合成之聚合物1、2可溶於水、甲醇、乙醇、異丙基醇、丙二醇單甲基醚、四氫呋喃、二甲基甲醯胺。
藉由該類本發明之製造方法易製造可溶於有機溶劑,具有特定之超強酸的硫醯亞胺基之本發明之導電性聚合物用高分子化合物。
又,本發明非限定於上述實施形態。上述實施形態為例示,實質上具有與本發明專利申請範圍所記載之技術性思想相同之架構下,可得相同作用效果之物均可包含於本發明之技術範圍內。
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