TWI636068B - 聚合物、及包含其之離子交換膜與結構增強膜材 - Google Patents
聚合物、及包含其之離子交換膜與結構增強膜材 Download PDFInfo
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Abstract
本發明提供一種聚合物、及包含其之離子交換膜。該聚合物包含一第一重複單元、及一第二重複單元,其中該第一重複
單元係;該第二重複單元係,其中R+可為
、、、或;A-可為F-、
Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -、
或H2PO2 -;Y1及Y2可獨立為-O-、-S-、-CH2-、或-NH-;Ra及Rb可獨立為氫、或C1-8的烷基;R1可為C1-10的烷基或C5-6的環烷基;i、j、及k可獨立為0、或1-6的整數;以及,R2及R3可獨立為氫、C1-8的烷基、乙烯基、C6-12的芳基、或烯丙基。
Description
本發明關於一種聚合物、及包含其之離子交換膜與結構增強膜材。
離子交換膜目前被廣泛應用於電透析提純、燃料電池、以及其它電鍍及食品工業中。
離子交換膜具有與構成膜本體的聚合物材料連接的帶負電荷或正電荷的基團,可在電勢或化學勢下輸送陽離子或陰離子。陽離子交換膜具有固定的負電荷和移動的正電荷離子。同樣地,陰離子交換膜則具有固定的帶正電荷的基團和移動的帶負電荷的陰離子。離子交換膜的性質受固定的離子基團的數量、類型和分佈控制。然而,傳統作為陰離子交換膜的高分子材料,由於溶解度、機械強度、及溶劑選擇性較差,並不適用於離子交換膜燃料電池中。
根據本發明一實施例,本發明提供一種聚合物,包含一第一重複單元、及一第二重複單元,其中該第一重複單
元係;該第二重複單元係,其中R+可為
、、、或;A-可為F-、
Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -、或H2PO2 -;Y1及Y2可獨立為-O-、-S-、-CH2-、或-NH-;Ra及Rb可獨立為氫、或C1-8的烷基;R1可為C1-10的烷基或C5-6的環烷基;i、j、及k可獨立為0、或1-6的整數;以及,R2及R3可獨立為氫、C1-8的烷基、乙烯基、C6-12的芳基、或烯丙基。
根據本發明另一實施例,本發明提供一種離子交換膜,包含一聚合物或一交聯聚合物,其中,該聚合物為前述之聚合物,而該交聯聚合物則是前述聚合物與一交聯劑的反應產物,且該交聯劑為具有至少二個醯亞胺官能基的化合物;以及,該離子交換膜的膜厚介於15至200微米之間。
根據本發明其他實施例,本發明提供一種結構增強膜材,包含:一聚合物或一交聯聚合物,以及一基材。其中,
該聚合物為前述之聚合物,而該交聯聚合物則是前述聚合物與一交聯劑的反應產物,且該交聯劑為具有至少二個醯亞胺官能基的化合物;以及,該基材為一多孔材料。
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉出較佳實施例,並配合所附圖式,作詳細說明如下:
10‧‧‧結構增強膜材
11、13‧‧‧表面
12‧‧‧基材
12a‧‧‧混合層
14‧‧‧聚合物或交聯聚合物層
第1A圖為本發明實施例之基材之示意圖;第1B圖為本發明實施例之結構增強膜材之剖面示意圖;及,第2圖至第4圖為本發明其他實施例之結構增強膜材之剖面示意圖。
以下所揭示提供許多不同之實施例,例如提供不同揭示之特徵。所述之部分特定範例係在以下揭示,以簡化本發明。當然,此些實施例僅為範例,而不用以限制本發明。本發明所述之「一」表示為「至少一」。
本發明提供一種聚合物,所述聚合物可為一含陽離子基團及非離子基團的聚合物。在聚合物的設計上,為增加聚合物的導電性,本發明所述聚合物導入具有陽離子基團的重複單元。此外,為避免聚合物因為具有陽離子基團的重複單元導致在溶劑中的可溶性下降,本發明所述聚合物進一步導入具有非離子基團的重複單元。根據本發明實施例,本發明所述的聚合物除了在溶劑中具有較高的溶解度外,亦具有改善的機械
強度以及增加的溶劑選擇性。
根據本發明實施例,本發明所述聚合物包含一第一重複單元、及一第二重複單元。該第一重複單元可為
,其中R+可為、、、
、或;A-可為F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、
SbF6 -、BF4 -、H2PO4 -、H2PO3 -、或H2PO2 -;Y1可為-O-、-S-、-CH2-、或-NH-;Ra及Rb可獨立為氫、或C1-8的烷基(例如:甲基(methyl)、乙基(ethyl)、丙基(propyl)、異丙基(isopropyl)、正丁基(n-butyl)、仲丁基(sec-butyl)、異丁基(isobutyl)、叔丁基(tert-butyl)、戊基(pentyl)、己基(hexyl)、庚基(heptyl)、或辛基(octyl));i及j可獨立為0、或1-6的整數;以及,R2及R3可獨立為氫、C1-8的烷基(例如:甲基(methyl)、乙基(ethyl)、丙基(propyl)、異丙基(isopropyl)、正丁基(n-butyl)、仲丁基(sec-butyl)、異丁基(isobutyl)、叔丁基(tert-butyl)、戊基
(pentyl)、己基(hexyl)、庚基(heptyl)、或辛基(octyl))、乙烯基、
C6-12的芳基、或烯丙基。該第二重複單元可為,其中
Y2可為-O-、-S-、-CH2-、或-NH-;k可為0、或1-6的整數;以及,R1可為C1-10的烷基(例如:甲基(methyl)、乙基(ethyl)、丙基(propyl)、異丙基(isopropyl)、丁基(butyl)、仲丁基(sec-butyl)、異丁基(isobutyl)、叔丁基(tert-butyl)、戊基(pentyl)、仲戊基(sec-pentyl)、異戊基(isopentyl)、新戊基(neopentyl)、己基(hexyl)、仲己基(sec-hexyl)、庚基(heptyl)、仲庚基(sec-heptyl)、辛基(octyl)、仲辛基(sec-octyl)、壬基(nonyl)、癸基(decyl)、1-乙基戊基(1-ethylpentyl)、2-乙基己基(2-ethylhexyl)、或2-丁基己基(2-butylhexyl))或C5-6的環烷基(例如:環戊基(cyclopentyl)或環己基(cyclohexyl))。
根據本發明之一些實施例,前述第一重複單元可
例如為、、、、
;其中A-係F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、
SbF6 -、BF4 -、H2PO4 -、H2PO3 -、或H2PO2 -;Ra及Rb係獨立為氫、或C1-8的烷基;i及j係獨立為0、或1-6的整數;以及,R2及R3係獨立為氫、C1-8的烷基、乙烯基、C6-12的芳基、或烯丙基。
根據本發明之一些實施例,前述第一重複單元可
例如為、、、、
;其中A-係F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、
SbF6 -、BF4 -、H2PO4 -、H2PO3 -、或H2PO2 -;Ra及Rb係獨立為氫、或C1-8的烷基;i及j係獨立為0、或1-6的整數;以及,R2及R3係獨立為氫、C1-8的烷基、乙烯基、C6-12的芳基、或烯丙基。
根據本發明之一些實施例,前述第一重複單元可
例如為、或;其中A-係F-、Cl-、Br-、
I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -、或H2PO2 -;Y1係-O-、-S-、-CH2-、或-NH-;Ra及Rb係獨立為氫、或C1-8的烷基;i及j係獨立為0、或1-6的整數;以及,R2及R3係獨立為氫、C1-8的烷基、乙烯基、C6-12的芳基、或烯丙基。
根據本發明之某些實施例,前述第二重複單元可
例如為、、、、、
或;其中k係獨立為0、或1-6的整數。
根據本發明實施例,該聚合物的該第一重複單元與該第二重覆單元的數量比例可依所需的聚合物性質來加以調整。舉例來說,為增加聚合物的導電性及陰離子的交換能力,可增加聚合物中第一重複單元的數量。另一方面,為增加聚合物的溶解度、機械強度、以及溶劑選擇性,可增加聚合物中第二重複單元的數量。該第一重複單元與該第二重覆單元的數量比例可介於約1:99至99:1之間,例如介於約10:90至90:10之間、介於約20:80至80:20之間、或介於30:70至70:30之間。另外,該聚合物的分子量(例如重量平均分子量)可介於約5,000至500,000之間,例如介於10,000至300,000之間。
藉由不同的合成方法,前述第一重複單元與第二重複單元可以無規或有規方式重複,或是形成嵌段式聚合物(block copolymer),合成方法可例如為可逆加成-斷裂鏈轉移(Reversible Addition-Fragmentation Transfer,RAFT)反應、氮氧調節自由基聚合反應(Nitroxide-mediated radical
polymerization,NMRP)、或原子轉移自由基聚合反應(Atom Transfer Radical Polymerization,ATRP)。當使用可逆加成-斷裂鏈轉移法進行聚合,可加入起始劑、鏈轉移劑等輔助聚合反應之進行,起始劑可例如為偶氮二異丁腈(azobisisobutyronitrile,AIBN),而鏈轉移劑可為二硫酯或三硫酯類鏈轉移劑,例如S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl
carbonotrithioate、結構為)。
根據本發明實施例,本發明所述聚合物可應用於製備一離子交換膜。該離子交換膜可直接由前述聚合物形成,或是由前述聚合物與一交聯劑進行交聯反應所得到的交聯聚合物形成。根據一些實施例,離子交換膜的製備方法可包含以下步驟:首先提供一組成物,該組成物包含上述聚合物以及一交聯劑。此外,該組成物亦可包含一溶劑,使得該組成物的固含量介於約5wt%至50wt%之間。在該組成物中,該交聯劑可具有一重量百分比介於約1wt%至30wt%之間(例如:介於約5wt%至30wt%之間、或介於約3wt%至25wt%之間),以該聚合物的總重為基準。接著,對該組成物進行混合及分散,將該組成物塗佈於一基材(如玻璃基板)上形成一塗層薄膜,於高溫下進行烘烤以除去大部分的溶劑後,再提高溫度持續烘烤,以除去剩餘之殘存溶劑,得到本發明所述之離子交換膜。根據另一實施例,離子交換膜的製備方法可包含先將上述聚合物溶解於溶劑中後,將聚合物溶液塗佈於一基材(如玻璃基板)上形成一塗層
薄膜,於高溫下進行烘烤以除去大部分的溶劑後,再提高溫度持續烘烤,以除去剩餘之殘存溶劑,得到本發明所述之離子交換膜。該離子交換膜的膜厚可介於約15至200微米之間,例如介於約30至100微米之間。
上述交聯劑可為具有至少二個醯亞胺官能基(例如作為末端基)的化合物,醯亞胺官能基可選自如鄰苯二甲醯亞胺、琥珀醯亞胺、N-溴代琥珀醯亞胺、戊二醯亞胺、或馬來醯亞胺。舉例來說,該交聯劑可為具有至少二個馬來醯亞胺官能基的化合物。根據本發明實施例,該具有二個馬來醯亞胺官能
基的化合物可為,其中Z可為、
、或,其中Y1係為單鍵、
-O-、-S-、-CH2-、或-NH-,R4係獨立為氫、或C1-4的烷基;以及,n≧1、x係介於1至12之間、y和z係獨立介於1至5之間。舉
例來說,該交聯劑可為、、
此外,根據本發明實施例,上述交聯劑亦可為具有至少二個馬來醯亞胺官能基的高分子型交聯劑。該高分子型交聯劑係起始物(a)與起始物(b)之反應產物,起始物(a)係
,其中Z係為、、
或,R4係獨立為氫、或C1-4的烷基;以
及,n≧1、x係介於1至12之間、y和z係獨立介於1至5之間;以及,該起始物(b)係具有式(III)或式(IV)所示之化合物
,其中R5係為氫、或C1-4的烷基,以及R6係為氫、或C1-4的烷基。該起
始物(b)可例如為、或。該高分子型交聯劑可與該
聚合物形成具化學交聯的互穿結構,強化該離子交換膜的機械強度及尺寸安定性。
根據本發明實施例,本發明所述聚合物或交聯聚合物可進一步用於結構增強膜材的製造,以形成具有複合結構的膜材。根據本發明一實施例,該結構增強膜材可包括前述聚合物或交聯聚合物以及一基材,該基材可為一多孔材料;其中,前述聚合物或交聯聚合物配置於該基材的至少一表面上,並填充於該基材的孔洞中。具體來說,該結構增強膜材的製造方式可包含以下步驟:首先,提供一基材12,其中該基材12可為一多孔材料,並具有一第一表面11,請參照第1A圖。接著,將上述聚合物或交聯聚合物塗佈於該基材12的該第一表面11上,形成一聚合物或交聯聚合物層14。其中,由於該基材12係為多孔材料,因此部份該聚合物或交聯聚合物可進一步滲入該基材12中,使被該聚合物或交聯聚合物滲入的基材12形成一混合層12a,得到本發明所述結構增強膜材10,請參照第1B圖。根據本發明另一實施例,若使用的基材12厚度較薄、或是用於塗佈的聚合物或交聯聚合物具有較低的黏度(例如將聚合物或交聯聚合物溶於一溶劑,製備一包含聚合物或交聯聚合物的塗佈溶液),該溶劑可例如為:二甲基乙醯胺(dimethylacetamide,DMAc)、二甲基亞碸(dimethyl sulfoxide,DMSO)、N-甲基吡咯烷酮(N-methyl-2-pyrrolidone,NMP)、甲醇(methanol,MeOH)、或丁醇(butanol,BuOH),部份該聚合物或交聯聚合物可滲入整個基材12中,使得整個基材12形成混合層12a,得到聚合物或交聯聚合物層14及混合層12a所構成的結構增強膜材
10,請參照第2圖。除此之外,根據本發明實施例,該基材12具有一第二表面13於該第一表面11的對向側,且前述聚合物或交聯聚合物同時塗佈於該第一表面11及該第二表面13之上,分別在該第一表面11及該第二表面13上形成一聚合物或交聯聚合物層14,得到本發明所述結構增強膜材10,請參照第3圖及第4圖。值得注意的是,在該第一表面11上的聚合物或交聯聚合物層14以及在該第二表面13上的聚合物或交聯聚合物層14之材質可為相同或不同。上述基材12之材質可為聚四氟乙烯(polytetrafluoroethene,PTFE)、聚醯亞胺(polyimide,PI)、聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)、聚醚醚酮(Polyether ether ketone,PEEK)、聚丙烯(polypropylene,PP)、聚乙烯(polyethylene,PE)、聚偏氟乙烯(polyvinylidene fluoride,PVDF)、或上述之組合。上述結構增強膜材可應用於燃料電池作為複合離子交換膜,或於鋰離子電池作為單離子傳導膜,或於電解產氫領域作為離子傳導膜與隔膜之用,或是應用於水處理作為離子傳導膜或分離膜等。
以下藉由下列實施例來說明本發明所述之聚合物的製備方式,用以進一步闡明本發明之技術特徵。
聚合物之製備
實施例1
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-甲基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[MVBIM]Cl,結構為
)(10.01g,42.66mmole)、乙烯苄基丁基醚
(vinylbenzylbutyl ether,簡稱[VBOBu],結構為)(0.90g,
4.74mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可
得到聚合物(1)。(具有重複單元及重複單元
,其中重複單元及重複單元
的數量比例約為90:10)。經量測,該聚合物(1)之重
量平均分子量(Mw)約為25,345。
利用核磁共振光譜分析聚合物(1),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 10.02(br),7.76(br),6.62-7.45(br),6.40(br),5.42(br),4.28(br),3.84(br),0.78(br)。
實施例2
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-甲基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[MVBIM]Cl)(6.67g,28.44mmole)、乙烯苄基丁基醚(vinylbenzylbutyl ether,簡稱[VBOBu])(3.61g,18.97mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得到聚合物(2)。(具有重複單元
及重複單元,其中重複單元
及重複單元的數量比例約為60:40)。
經量測,該聚合物(2)之重量平均分子量(Mw)約為75,040。
利用核磁共振光譜分析聚合物(2),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.92(br),7.76(br),6.63-7.54(br),6.39(br),5.42(br),4.33(br),3.85(br),0.82(br)。
實施例3
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-甲基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[MVBIM]Cl)(2.78g,11.85mmole)、乙烯苄基丁基醚(vinylbenzylbutyl ether,簡稱[VBOBu])(6.75g,35.55mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,
進行減壓乾燥後即可得到聚合物(3)。(具有重複單元
及重複單元,其中重複單元
及重複單元的數量比例約為25:75)。
經量測,該聚合物(3)之重量平均分子量(Mw)約為62,787。
利用核磁共振光譜分析聚合物(3),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.43(br),7.68(br),6.96(br),6.41(br),5.30(br),4.31(br),3.82(br),0.81(br)。
實施例4
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-甲基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[MVBIM]Cl)(1.11g,4.74mmole)、乙烯苄基丁基醚(vinylbenzylbutyl ether,簡稱[VBOBu])(8.11g,42.62mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,
進行減壓乾燥後即可得到聚合物(4)。(具有重複單元
及重複單元,其中重複單元
及重複單元的數量比例約為10:90)。
利用核磁共振光譜分析聚合物(4),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.25(br),7.63(br),6.98(br),6.40(br),5.28(br),4.30(br),3.80(br),0.81(br)。
實施例5
在氮氣系統下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基丁基醚(vinylbenzylbutyl ether,簡稱[VBOBu])(6.75g,35.55mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL四氫呋喃進行溶解,將反應溫度提高到100度,反應72小時後,以甲醇析出固體並清洗殘留單體,進行減壓乾燥後,得到poly([VBOBu])聚合物,接著加入乙烯苄基-甲基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[MVBIM]Cl)(2.78g,11.85mmole)與AIBN(9.72mg,0.059
mmole)至於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後,即可得到聚合物(5)(具有聚合物嵌段
及聚合物嵌段,其中第一重複單元
及第二重複單元的莫耳比例約為
25:75)。經量測,該聚合物(5)之重量平均分子量(Mw)約為42,700。
利用核磁共振光譜分析聚合物(5),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.63(br),7.75(br),6.97(br),6.40(br),5.27(br),4.29(br),3.82(br),0.78(br)。
實施例6
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-甲基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[MVBIM]Cl)(6.67g,28.44mmole)、乙烯苄基辛基醚(vinylbenzyloctyl ether,簡稱
[VBOOc]、結構為)(4.67g,18.96mmole)與AIBN
(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得到聚合物(6)。(具
有重複單元及重複單元,其中重複
單元及重複單元的數量比例約為
60:40)。經量測,該聚合物(6)之重量平均分子量(Mw)約為
153,507。
利用核磁共振光譜分析聚合物(6),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.83(br),7.75(br),7.22(br),6.39(br),5.42(br),4.33(br),3.86(br),3.26(br),0.76(br)。
實施例7
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-甲基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[MVBIM]Cl)(7.79g,33.18mmole)、乙烯苄基(2-乙基)己基醚(vinylbenzyl-(2-ehtyl)hexyl ether,簡稱[VBOEH]、結構為
)(3.5g,14.22mmole)與AIBN(9.72mg,0.059mmole)
置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得到聚合物(7)。(具有重複單元
及重複單元,其中重複單元
及重複單元的數量比例約為
70:30)。經量測後,該聚合物(7)之重量平均分子量(Mw)約為74,648。
利用核磁共振光譜分析聚合物(7),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.74(br),7.73(br),7.29(br),6.37(br),5.43(br),4.33(br),3.86(br),3.23(br),0.75(br)。
實施例8
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-丁基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[BVBIM]Cl、結構為
)(5.9g,21.33mmole)、乙烯苄基丁基醚
vinylbenzylbutyl ether,簡稱[VBOBu])(3.61g,18.96mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得到聚合物 (8)。(具有重複單元及重複單元,
其中重複單元及重複單元的數量
比例約為45:55)。經量測,該聚合物(8)之重量平均分子量(Mw)約為117,200。
利用核磁共振光譜分析聚合物(8),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.86(br),7.83(br),
6.99(br),6.42(br),5.37(br),4.32(br),4.10(br),3.17(br),0.87(br)。
實施例9
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-丁基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[BVBIM]Cl)(7.87g,28.44mmole)、乙烯苄基丁基醚(vinylbenzylbutyl ether,簡稱[VBOBu])(3.61g,18.96mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得到聚合物(9)。(具有重複單元
及重複單元,其中重複單元
及重複單元的數量比例約為
60:40)。經量測,該聚合物(9)之重量平均分子量(Mw)約為135,966。
利用核磁共振光譜分析聚合物(9),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 9.96(br),7.84(br),6.68-7.57(br),6.43(br),5.42(br),4.33(br),4.18(br),0.80(br)。
實施例10
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-丁基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[BVBIM]Cl)(9.18g,33.18mmole)、乙烯苄基丁基醚(vinylbenzylbutyl ether,簡稱[VBOBu])(2.71g,14.22mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得到聚合物(10)。(具有重複單元
及重複單元,其中重複單元
及重複單元的數量比例約為
70:30)。經量測,該聚合物(10)之重量平均分子量(Mw)約為262,100。
利用核磁共振光譜分析聚合物(10),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 10.08(br),7.86(br),6.70-7.58(br),6.37(br),5.44(br),4.33(br),4.16(br),0.79(br)。
實施例11
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、乙烯苄基-丁基咪唑氯鹽(vinylbenzylimidazolium chloride,簡稱[BVBIM]Cl)(9.18g,33.18mmole)、乙烯苄基(2-乙基)己基醚(vinylbenzyl-(2-ehtyl)hexyl ether,簡稱[VBOEH])(3.5g,14.22mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得
到聚合物(11)。(具有重複單元及重複單元
,其中重複單元及重複單元
的數量比例約為70:30)。經量測,該聚合物(11)之
重量平均分子量(Mw)約為138,010。
利用核磁共振光譜分析聚合物(11),所得之光譜資訊如下:1H NMR(DMSO-d6,500MHz)δ 10.03(br),7.85(br),6.66-7.57(br),6.35(br),5.43(br),4.34(br),4.18(br),3.23(br),0.75(br)。
實施例12
在氮氣環境下,將S’-十四烷基-S”-1-苯乙基-三硫代碳酸酯(1-phenylethyl tetradecyl carbonotrithioate)(0.0973g,0.237mmole)、2-(乙烯苄基異丙基醚)-2-(N,N’-二甲基)咪唑氯鹽(1,3-dimethyl-2-(2-((4-vinylbenzyl)oxy)propan-2-yl)-1H-imida
zol-3-ium chloride,簡稱[MVBCIM]Cl,結構為)
(10.18g,33.18mmole)、乙烯苄基丁基醚(vinylbenzylbutyl ether,簡稱[VBOBu])(2.71g,14.22mmole)與AIBN(9.72mg,0.059mmole)置於一雙頸瓶中,加入20mL甲醇進行溶解,將反應溫度提高到100度,反應72小時後,以乙醚析出固體並清洗殘留單體,進行減壓乾燥後即可得到聚合物(12)。(具有重複單
元及重複單元,其中重複單元
及重複單元的數量比例約為70:30)。經
量測,該聚合物(12)之重量平均分子量(Mw)約為16,172。
利用核磁共振光譜分析聚合物(12),所得之光譜資
訊如下:1H NMR(DMSO-d6,500MHz)δ 7.75(br),6.10-7.52(br),5.09(br),4.34(br),3.98(br)。
交聯劑之製備
製備例1
將2.73g之、以及0.37g的
加入一反應瓶中,並加入97g二甲基乙醯胺(DMAc)中。充分攪拌後,在100-150℃下反應5-10小時,得到高子型交聯劑(1)。
(與莫耳比例為2:1)。
陰離子交換膜之製備
實施例13
將100重量份之聚合物(2)(由實施例2所製備)加入一反應瓶中,並加入567重量份之二甲基乙醯胺(dimethylacetamide、DMAc)加以溶解。接著,將10重量份之高分子交聯劑(1)(由製備例1所製備)加入反應瓶中。接著,以高速均質機進行混合分散,並進行除泡,得到一溶液。接著,將該溶液以旋轉塗佈方式塗佈於一玻璃基板上,形成一塗層。接著,於40~150℃下進行烘烤以除去大部分的溶劑。接著,再於120~200℃下烘烤1~6小時,以除去剩餘之殘存溶劑。最後,得到陰離子交換膜(1)。量測該陰離子交換膜之離子導電度、尺寸變化率,尺寸變化率的測試方法係參照(Journal of Materials Chemistry A Materials for Energy and Sustainability 3(23)
(2015)12284-12296),在25℃下浸泡24小時後觀察尺寸變化率。結果如表1所示。
實施例14-17
實施例14-17如實施例13所述的方式進行,除了分別將聚合物(2)以聚合物(7)、(9)、(10)、(11)取代,得到陰離子交換膜(2)-(5)。接著,量測該陰離子交換膜之離子導電度、尺寸變化率,尺寸變化率的測試方法係參照(Journal of Materials Chemistry A Materials for Energy and Sustainability 3(23)(2015)12284-12296),在25℃下浸泡24小時後觀察尺寸變化率。結果如表1所示。
實施例18
將100重量份之聚合物高分子(8)加入一反應瓶中,並加入567重量份之二甲基亞碸(Dimethyl sulfoxide、DMSO)加以溶解,進行除泡,得到一溶液。接著,將該溶液以旋轉塗佈方式塗佈於一玻璃基板上,形成一塗層。接著,於40~150℃下進行烘烤以除去大部分的溶劑。接著,再於120~200℃下烘烤1~6小時,以除去剩餘之殘存溶劑。最後,得到陰離子交換膜(6)。量測該陰離子交換膜之離子導電度、尺寸變化率,尺寸變化率的測試方法係參照(Journal of Materials Chemistry A Materials for Energy and Sustainability 3(23)(2015)12284-12296),在25℃下浸泡24小時後觀察尺寸變化率。結果如表1所示。
表1
由表1可知,本發明所述陰離子交換膜,隨著離子性
重複單元(即具有結構為的重複單元)比例的增加,所
得之陰離子交換膜也隨之具較高之離子導電度。此外,本發明所述之陰離子交換膜亦具有不錯的尺寸安定性。
基於上述,本發明所述聚合物除了具有穩定的陽離子基團來增加聚合物的離子傳導能力外,亦在聚合物的設計上導入非離子基團,以提高聚合物的溶解度、機械強度、以及溶劑選擇性。
雖然本發明的實施例及其優點已揭露如上,但應該瞭解的是,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作更動、替代與潤飾。此外,本發明之保護範圍並未侷限於說明書內所述特定實施例中的製程、機器、製造、物質組成、裝置、方法及步驟,任何所屬技術領域中具有通常知識者可從本發明揭示內容中理解現行或未來所發展出的製程、機器、製造、物質組成、裝置、方法及步驟,只要可以
在此處所述實施例中實施大抵相同功能或獲得大抵相同結果皆可根據本發明使用。因此,本發明之保護範圍包括上述製程、機器、製造、物質組成、裝置、方法及步驟。另外,每一申請專利範圍構成個別的實施例,且本發明之保護範圍也包括各個申請專利範圍及實施例的組合。
Claims (14)
- 如申請專利範圍第1項所述之聚合物,其中該第一重複單元與該第二重複單元的比係介於1:99至99:1之間。
- 如申請專利範圍第1項所述之聚合物,其中R1係甲基(methyl)、乙基(ethyl)、丙基(propyl)、異丙基(isopropyl)、丁基(butyl)、仲丁基(sec-butyl)、異丁基(isobutyl)、叔丁基(tert-butyl)、戊基(pentyl)、仲戊基(sec-pentyl)、異戊基(isopentyl)、新戊基(neopentyl)、環戊基(cyclopentyl)、己基(hexyl)、仲己基(sec-hexyl)、環己基(cyclohexyl)、庚基(heptyl)、仲庚基(sec-heptyl)、辛基(octyl)、仲辛基(sec-octyl)、壬基(nonyl)、癸基(decyl)、1-乙基戊基(1-ethylpentyl)、2-乙基己基(2-ethylhexyl)、或2-丁基己基(2-butylhexyl)。
- 一種離子交換膜,包含一聚合物或一交聯聚合物,其中,該聚合物係申請專利範圍第1-7項所述之聚合物;該交聯聚合物係該聚合物與一交聯劑的反應產物,且該交聯劑係具有至少二個醯亞胺官能基的化合物;以及,該離子交換膜的膜厚係介於15至200微米之間。
- 如申請專利範圍第8項所述之離子交換膜,其中該醯亞胺官能基係馬來醯亞胺官能基。
- 一種結構增強膜材,包含:一聚合物或一交聯聚合物,其中該聚合物係申請專利範圍第1-7項所述之聚合物,而該交聯聚合物係該聚合物與一交聯劑的反應產物,且該交聯劑係具有至少二個醯亞胺官能基的化合物;以及一基材,該基材係一多孔材料。
- 如申請專利範圍第12項所述之結構增強膜材,其中該聚合物或該交聯聚合物係配置於該基材的至少一表面上,並填充於該基材的孔洞中。
- 如申請專利範圍第12項所述之結構增強膜材,其中該基材係聚四氟乙烯(polytetrafluoroethene,PTFE)、聚醯亞胺(polyimide,PI)、聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)、聚醚醚酮(Polyether ether ketone,PEEK)、聚丙烯(polypropylene,PP)、聚乙烯(polyethylene,PE)、聚偏氟乙烯(polyvinylidene fluoride,PVDF)、或上述之組合。
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- 2017-05-04 US US15/587,045 patent/US20180030187A1/en not_active Abandoned
- 2017-07-28 JP JP2017146151A patent/JP6407371B2/ja active Active
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CN102206386A (zh) * | 2011-04-02 | 2011-10-05 | 厦门大学 | 一种基于咪唑阳离子的聚合物阴离子交换膜及其制备方法 |
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TWI717789B (zh) * | 2019-07-22 | 2021-02-01 | 財團法人工業技術研究院 | 聚合物、包含其之離子交換膜、結構增強膜材 |
US11702490B2 (en) | 2019-07-22 | 2023-07-18 | Industrial Technology Research Institute | Polymer, ion-exchange membrane, and structure-enhanced membrane employing the same |
Also Published As
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US20180030187A1 (en) | 2018-02-01 |
CN107663260A (zh) | 2018-02-06 |
TW201803911A (zh) | 2018-02-01 |
CN107663260B (zh) | 2020-06-09 |
JP6407371B2 (ja) | 2018-10-17 |
JP2018028065A (ja) | 2018-02-22 |
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