TW201704542A - 具多層支撐基材的離子交換膜 - Google Patents

具多層支撐基材的離子交換膜 Download PDF

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Publication number
TW201704542A
TW201704542A TW105105492A TW105105492A TW201704542A TW 201704542 A TW201704542 A TW 201704542A TW 105105492 A TW105105492 A TW 105105492A TW 105105492 A TW105105492 A TW 105105492A TW 201704542 A TW201704542 A TW 201704542A
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Taiwan
Prior art keywords
ion exchange
support substrate
ion
layer
exchange membrane
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TW105105492A
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English (en)
Inventor
約翰 鮑伯
拉索 麥當勞
永昌 鄭
張凱
永紅 趙
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通用電機股份有限公司
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Publication of TW201704542A publication Critical patent/TW201704542A/zh

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    • B01D61/422—Electrodialysis
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Abstract

本文揭露離子交換膜，其包括浸有離子交換材料且從膜之一面至膜之相對面以使得支撐膜基材中之相對的層足以提供相同物理性質以實質避免於鹽溶液中時之不規則擴展的順序而設置的離子可透性層。該離子可透性層包含至少一非織物層以及至少一強化層。

Description

具多層支撐基材的離子交換膜
本揭示內容大致關於具有多層支撐基材的離子交換膜。
以下段落並非承認其中所討論的任何事物係屬先前技術或為本領域具通常知識者之知識的一部分。
離子交換膜係作為電解膜(electrolytic membrane)用於電透析(electrodialysis)(ED)、雙極式ED(bipolar ED)、逆電透析(reversed electrodialysis)(RED)、電去電離(electrodeionization)(EDI)、以及倒極式電透析(electrodialysis reversal)(EDR)。此等純化製程使離子在所施加之電位差(electric potential difference)作用下由一溶液通過離子交換膜而送至另一溶液。
可用於電透析的離子交換膜係包含離子交換材料(ion-exchange material)及用於該離子交換材料之支撐基材(supporting substrate)。於使用梭織物料 (woven fabric sheet)或非織物料(non-woven fabric sheet)作為支撐基材而製造之離子交換膜中，梭織物料或非織物料中的孔隙係被離子交換材料所填充。
以下概述係用以將讀者引導入此說明書而非用以界定任何發明。一或更多發明可在於在下文或此文件其他部分描述之裝置元件或方法步驟的組合或次組合。本案發明人並不會僅因未敘述其他發明於申請專利範圍中而放棄或不主張其對本說明書中所揭示之任何發明的權利。
在離子交換膜中使用非織物(non-woven fabric)是所希望的因為與使用梭織物(woven fabrics)所形成的膜相比，非織物中纖維的高度交錯結構(highly interlaced structure)可降低洩漏(leaking)、電阻(electrical resistance)、厚度或彼等之任何組合。然而，與使用梭織物所形成的膜相比，僅使用非織物所形成的膜通常具有不理想的物理性質。不理想的物理性質可為降低的強度、降低的尺寸穩定性(dimensional stability)、或降低的形狀穩定性(shape stability)。此外，若非織物內有不平整，膜可能具有離子交換材料的不均勻分布。此離子交換材料的不均勻分布可能導致離子交換膜有不一致的物理性質。
為了改善至少一個不理想的物理性質，以非織物製成之離子交換膜(ion-exchange membrane)亦可包 含強化層(reinforcing layer)。然而增加了強化層會提高膜的厚度且因而亦使膜的電阻(resistance)提高。具有附加至單一非織物層之單一強化層的離子交換膜在鹽溶液中亦可能不規則地擴展(expand)，其造成膜之起伏(undulation)。此不規則擴展(irregular expansion)係因在鹽溶液中時兩層間的擴展、或收縮的差異所致。
因此，仍需要具支撐基材的離子交換膜，其中該支撐基材包含(a)非織物層作為用於離子交換材料(ion-exchange material)的支撐材料、以及(b)強化層，其中，置於鹽溶液中時該離子交換膜展現減少的不規則擴展。尤其希望該離子交換膜至少薄如已知的具有非織物層及強化層之離子交換膜。
降低離子交換膜之厚度是所希望的(可以說此降低能導致較高的來自電解槽堆(electrolytic cell stack)之通量(throughput)(所有其他條件相當))，因為更多膜可被裝載入同樣裝置。降低離子交換膜之厚度可導致降低膜之給定面積的化學品消耗，因為較薄的膜於每膜表面積(per surface area of membrane)具有少的離子交換材料。降低離子交換膜之厚度可導致降低電解純化製程(electrolytic purification process)中的能量消耗(energy consumption)，若其對應於較薄之膜的電阻降低的話。
一或更多所述之實施態樣係欲解決或改善與由非織物及強化層形成之離子交換膜相關的一或更多缺 點。
一般而言，本揭示內容提供離子交換膜，其包括離子交換材料以及浸有該離子交換材料的支撐膜基材(supporting membrane substrate)。該支撐膜基材，文中亦稱為“支撐基材(supporting substrate)”，係包含離子可透性層(ion-permeable layer)設為使支撐基材中之相對的層足以提供相同物理性質以實質避免於鹽溶液中時之不規則擴展。
於本揭示之內容中，膜中之相對的層應理解為意指在該支撐基材截面(cross-section)中於相對處之層。舉例來說，在0.4mm厚的支撐基材中，於深度0.02mm之層係和於深度0.38mm之層相對，因為兩處皆離其各自表面0.02mm。
於一實施態樣中，離子交換膜包括在兩強化層之間的一非織物層(non-woven layer)。該兩強化層可由不同材料製成，只要彼等足以提供相同物理性質以實質避免於鹽溶液中時之不規則擴展(irregular expansion)即可。
於另一實施態樣中，離子交換膜包括在兩非織物層之間的一強化層。該兩非織物層可由不同材料製成，只要彼等足以提供相同物理性質以實質避免於鹽溶液中時之不規則擴展即可。
可影響擴展的層之物理性質的一實例為層之擴展(expansion)或收縮(contraction)趨勢。包括具有 實質相同之擴展趨勢(expansion tendency)的強化層之離子交換膜，與包括具有實質不相同之擴展趨勢的強化層之離子交換膜相比，會展現減少的不規則擴展。
可影響層之擴展或收縮趨勢的一物理性質為層之抗拉強度(tensile strength)。抗拉強度近似的層會以近似程度抵抗擴展或收縮。其支撐基材具有設為使層之抗拉強度(tensile strength)從膜之一面至膜之另一面為對稱的層的離子交換膜，比起具有不對稱抗拉強度之層的離子交換膜，會展現少的不規則擴展。
層之抗拉強度可在縱向(machine direction)(MD)上與在橫向(cross-machine direction)(CD)上不同。於特定實施態樣中，希望的是支撐基材所具有的層設為使層之抗拉強度在縱向上從膜之一面至膜層之另一面為對稱的，以及層之抗拉強度在橫向上從膜之一面至膜層之另一面為對稱的。
抗拉強度的範圍可由0.2MPa至40N/cm。例示的層包括：(A)聚酯熔噴層(polyester meltblown layer)，其具有MD抗拉強度為0.24N/cm及CD抗拉強度為1.04N/cm；(B)聚丙烯熔噴層(polypropylene meltblown layer)，其具有MD抗拉強度為1.8N/cm及CD抗拉強度為0.92N/cm；(C)聚酯紡黏層(polyester spunbond layer)，其具有MD抗拉強度為11.8N/cm及CD抗拉強度為12.2N/cm；(D)聚丙烯紡黏層(polypropylene spunbond layer)，其具有MD抗拉強度 為12.2N/cm及CD抗拉強度為11.4N/cm；以及(E)聚丙烯紡黏層，其具有MD抗拉強度為30.4N/cm及CD抗拉強度為10.5N/cm。只要於MD及CD方向上的抗拉強度各係從膜之一面至膜層之另一面為對稱的，該等層可包含上述例示的層之任何組合。
舉例言之，離子交換膜可具有含上述層(A)及(D)為相同厚度且順序為(D)-(A)-(D)的支撐基材。於此例中，第一及第三層於縱向上之抗拉強度係彼此相同。於另一例中，離子交換膜可具有含上述層(B)、(C)及(D)為相同厚度且順序為(C)-(B)-(D)的支撐基材。於此第二例中，第一及第三層於縱向上之抗拉強度為3.7%之差異，且於橫向上為6.7%之差異。在兩例示的膜中，該等層之MD及CD抗拉強度係從膜之一面至膜層之另一面為對稱的。
亦較佳者為層在MD方向上之抗拉強度係實質上相同於該層在CD方向上之抗拉強度。例如：層(D)具有在MD方向上之抗拉強度與在CD方向上之抗拉強度的差異為6.9%；以及，層(C)具有在MD方向上之抗拉強度與在CD方向上之抗拉強度的差異為3.3%。
可影響層之擴展或收縮趨勢的另一物理性質為層之密度(density)。不欲為理論所束縛，本揭示內容之作者相信層之密度影響在離子交換膜製造期間由該層所吸收之離子交換材料的量。其中吸收了不同量之離子交換材料的層會有不同的擴展或收縮，這是由於彼等接觸鹽溶 液時會吸收不同量之鹽與水所致。包含具不同密度之層的離子交換膜，比起含有具實質相同密度之強化層的離子交換膜，會展現更多不規則擴展。
在本揭示之內容中，實質上相同的密度或者抗拉強度應理解為意指密度或抗拉強度之值至少彼此相差在10%內。於特定實例中，實質相同的該等值係彼此相差在5%內。於特佳實例中，實質相同的該等值係彼此相差在2%內。兩值之間的百分比差異(percent difference)可藉由將兩值之差(difference)除以兩值之平均(average)來計算。例如，9.5g/cm3與10.5g/cm3之間的差為10%。
根據本揭示內容之離子交換膜的一實例中，在支撐基材截面之給定處的支撐基材密度係實質上相同於在支撐基材截面之相對處的支撐基材密度。例如，在0.4mm厚的支撐基材中，在深度0.02mm之支撐基材密度係與在深度0.38mm之支撐基材密度實質上相同，因為兩處皆離其各自表面0.02mm。
多個離子可透性層(ion-permeable layer)可由多個結合在一起的不同層形成。支撐基材可包含具有第一密度、結合於第二離子可透性層的一側之第一離子可透性層，該第二離子可透性層具有第二密度且結合於具有第三密度之第三離子可透性層的相對側。第二密度及第三密度實質上相同。第一密度可為約0.04g/cm3至約0.6g/cm3，且第二密度及第三密度可為約0.2g/cm3至約0.6 g/cm3。或者，第一密度可為約0.2g/cm3至約0.6g/cm3，且第二密度及第三密度可為約0.04g/cm3至約0.6g/cm3。
第一離子可透性層可為熔噴層(melt-blown layer)，而第二及第三離子可透性層可為紡黏層(spunbond layer)。或者，第一離子可透性層可為紡黏層，而第二及第三離子可透性層可為熔噴層。
於根據本揭示內容之一例示的離子交換膜中，離子交換膜包括作為支撐基材之至少一非織物層以及至少一強化層。該等層係從膜之一面至膜之另一面以對稱順序之層而設置。
於特定實例中，離子交換膜包括三層結構其具有一非織物層(non-woven layer)夾於兩強化層之間。於其他特定實例中，離子交換膜包括三層結構其具有一強化層(reinforcing layer)夾於兩非織物層之間。
當根據本揭示內容之離子交換膜包括多個非織物層時，該等非織物層較佳為相同的。當根據本揭示內容之離子交換膜包括多個強化層時，該等強化層較佳為相同的。較佳地，當根據本揭示內容之離子交換膜包括多個非織物層及多個強化層時，該等非織物層彼此相同且該等強化層彼此相同。
於特佳實例中，支撐基材中的所有層係由相同化學材料製成，儘管例如該非織物層可具有相較於該強化層之不同直徑纖維、不同密度、及/或不同抗拉強度。 支撐基材之該等層可由例如下列者製成：聚丙烯 (polypropylene)、聚酯(polyester)、或聚丙烯腈(polyacrylonitrile)。
10‧‧‧離子交換膜
12‧‧‧非織物層
14‧‧‧強化層
16‧‧‧強化層
18‧‧‧離子交換膜
20‧‧‧非織物層
22‧‧‧非織物層
24‧‧‧強化層
現將僅透過實施例參照所附圖式以闡述本揭示內容之實施態樣。
圖1係例示說明根據本揭示內容之離子交換膜的一實施態樣。
圖2係例示說明根據本揭示內容之離子交換膜的一實施態樣。
圖3係顯示於根據本揭示內容之例示的膜進行洩漏試驗(leak test)之結果的一組照片。
圖4係顯示於根據本揭示內容之例示的膜、及對比的膜進行洩漏試驗之結果的一組照片。
圖5係顯示於根據本揭示內容之例示的膜、及對比的膜進行洩漏試驗之結果的一組照片。
圖6係由兩層基材所製成之離子交換膜的照片。
圖7係根據本揭示內容的由例示之三層基材所製成之離子交換膜的照片。
大致上，本揭示內容提供具有支撐膜基材的離子交換膜，該支撐膜基材包含離子可透性層(ion- permeable layer)設為使得支撐基材中之相對的層足以提供相同物理性質以實質避免於鹽溶液中時之不規則擴展。
於一態樣中，本揭示內容提供離子交換膜其具有至少一非織物層、以及至少一強化層，其中該等層之設置為從膜之一面至膜之另一面係對稱的。
於另一態樣中，離子可透性層係設為使得在支撐基材截面之給定處的支撐基材密度係實質上相同於在支撐基材截面之相對處的支撐基材密度。
於又另一態樣中，離子可透性層係設為使得在支撐基材截面之給定處的支撐基材抗拉強度(tensile strength)為實質上相同於在支撐基材截面之相對處的支撐基材抗拉強度。
離子交換膜的層較佳載有離子交換材料。離子交換材料中的離子官能基(ionic functional group)可為磺酸(sulfonic acid)基團、羧酸(carboxylic acid)基團、磷酸(phosphoric acid)基團、四級銨(quaternary ammonium)基團、咪唑鎓(imidazolium)基團、吡啶鎓(pyridinium)基團、或彼等之鹽。
離子交換材料可為例如離子交換樹脂(ion-exchange resin)其係透過離子性單體(ionic monomer)與交聯劑(crosslinker)之聚合而形成。該離子性單體及交聯劑可溶於溶劑浸透(saturating)該支撐基材。
於一些實例中，離子交換材料可為以下列者聚合而形成之陽離子交換聚合物(cation-exchange polymer)：2-丙烯醯胺基-2-甲基丙磺酸(2-acrylamido-2-methylpropane sulfonic acid)、2-丙烯醯胺基-2-甲基丙磺酸鈉(sodium 2-acrylamido-2-methylpropane sulfonate)、3-磺酸丙基丙烯酸鉀(potassium 3-sulfopropyl acrylate)、甲基丙烯磺酸鈉(sodium methallyl sulfonate)、乙烯基磺酸鈉(sodium vinyl sulfonate)、4-乙烯基苯磺酸鈉(sodium 4-vinylbenzenesulfonate)、4-乙烯基苯磺酸鋰(lithium 4-vinylbenzenesulfonate)、丙烯酸、2-乙基丙烯酸(2-ethylacrylic acid)、甲基丙烯酸、2-丙基丙烯酸(2-propylacrylic acid)、丙烯酸鈉(sodium acrylate)、甲基丙烯酸鈉(sodium methacrylate)、乙二醇甲基丙烯酸磷酸酯(ethylene glycol methacrylate phosphate)、乙烯基磷酸(vinylphosphonic acid)、或雙[2-(甲基丙烯醯氧基)乙基]磷酸鹽(bis[2-(methacryloyloxy)ethyl]phosphate)。於一些實例中，離子交換材料可為以下列者聚合而形成之陰離子交換聚合物(anion-exchange polymer)：N-三甲基胺基乙基甲基丙烯酸酯氯化物(N-trimethylaminoethylmethacrylate chloride)(TMAEMC)、[2-(丙烯醯氧基)乙基]三甲基氯化銨([2-(acryloyloxy)ethyl]trimethylammonium chloride)、[2-(甲基丙烯醯氧基)乙基]三甲基氯化銨([2-(methacryloyloxy)ethyl]trimethylammonium chloride)、(3-丙烯醯胺丙基)三甲基氯化銨((3-acrylamidopropyl)trimethylammonium chloride)、[3-(甲基丙烯醯胺基 )丙基]三甲基氯化銨([3-(methacryloylamino)propyl]trimethylammonium chloride)、二烯丙基二甲基氯化銨(diallyldimethylammonium chloride)、或(乙烯基苄基)三甲基氯化銨((vinylbenzyl)trimethylammonium chloride)、溴化-1-乙烯基-3-乙基咪唑(1-vinyl-3-ethylimidazolium bromide)、或三溴化-4-乙烯基吡啶(4-vinylpyridinium tribromide)。
或者，離子交換膜之層可透過非離子性單體(non-ionic monomer)與交聯劑(crosslinker)之聚合、然後處理以引入陰離子或陽離子基團而形成。例如，支撐基材可先以含有至少一種單體、至少一種交聯劑、及起始劑(initiator)的化學混合物浸透。浸透的(saturated)支撐基材可於高溫固化以聚合單體與交聯劑。接著可處理所得材料以引入例如磺酸基團或四級銨基團。此製備之一實例為聚合苯乙烯與二乙烯苯，然後磺酸化(sulfonation)。此製備之另一實例為聚合(polymerization)苯乙烯與二乙烯苯，然後氯甲基化(chloromethylation)且以三胺(triamine)胺化(amination)。
於另一另外的方法中，離子交換膜之層可透過將溶解之聚合物撒(cast)入支撐基材之層而形成。例如，帶正電荷或負電荷的聚合物可溶於有機溶劑以形成均質溶液(homogeneous solution)。所得溶液可隨後以刀(knife)撒(cast)入支撐基材。在浸透的基材中之有機 溶劑可隨後被移除，較佳係於真空、高溫下，以提供離子交換膜。負電聚合物可為例如：磺酸化聚碸(sulfonated polysulfone)、磺酸化聚醚碸(sulfonated polyethersulfone)、或磺酸化聚二氟亞乙烯(sulfonated polyvinylidene floride)。正電聚合物可為例如：四級化聚(乙烯苄基氯)(quaternized poly(vinyl benzyl chloride))、或四級化聚(苯醚)(quaternized poly(phenylene oxide))。有機溶劑可包括例如：1-甲基-2-吡咯啶酮(1-Methyl-2-pyrrolidinone)、N,N-二甲基甲醯胺(N,N-Dimethylformamide)、或N,N-二甲基乙醯胺(N,N-Dimethylacetamide)。
於一實施態樣中，說明於圖1，離子交換膜(10)包括非織物層(non-woven layer)(12)夾於兩強化層(reinforcing layer)(14，16)之間。該非織物層(12)及強化層(14，16)係浸以離子交換材料(ion-exchange material)。
於另一實施態樣中，說明於圖2，離子交換膜(18)包括兩非織物層(20，22)夾有一強化層(24)。非織物層(20，22)及強化層(24)係浸以離子交換材料。
在根據本揭示內容之離子交換膜的一實例中，支撐基材係由非織物層(12)及兩強化層(14，16)組成。支撐基材係以陰離子交換材料(anion-exchange material)浸透(saturate)。陰離子交換材料係由N-三甲 基胺基乙基甲基丙烯酸酯氯化物(N-trimethylaminoethylmethacrylate chloride)(TMAEMC)與乙二醇二甲基丙烯酸酯(ethylene glycol dimethacrylate)(EDGM)在自由基起始劑(radical initiator)諸如2,2'-偶氮雙(2-甲基丙酸)二甲酯(dimethyl 2,2'-azobis(2-methylpropionate))(V-601)的存在下聚合而形成。單體及起始劑係溶於二丙烯甘醇(dipropylene glycol)(DPG)，支撐基材係以所得溶液浸透。浸透的(saturated)支撐基材於高溫固化以聚合單體及交聯劑。當17.6克之TMAEMC、10.9g之EGDM及0.2g之V-601溶於15.2g之DPG且接著聚合於Tapyrus非織聚酯支撐基材時，所得之陰離子交換膜具有離子交換容量(ion exchange capacity)(IEC)為2.71meq/g以及含水量(water content)為42.8%。
於另一實例中，支撐基材係由非織物層(12)及兩強化層(14，16)組成，且支撐基材係以陽離子交換材料(cation-exchange material)浸透(saturate)。陽離子交換材料係由2-丙烯醯胺基-2-甲基丙磺酸(2-acrylamido-2-methylpropane sulfonic acid)(AMPS)與EGDM在自由基起始劑諸如過氧化2-乙基己基碳酸三級丁酯(tert-butylperoxy 2-ethylhexyl carbonate)(TPO)的存在下聚合而形成。單體及起始劑係溶於水和1-甲基-2-吡咯啶酮(NMP)之溶液，支撐基材係以所得溶液浸透。浸透的(saturated)支撐基材於高 溫固化以聚合單體及交聯劑。當34.2克之AMPS、33.06g之EGDM及1.05mL之TPO溶於3.6g水和38.9g之NMP的溶液且接著聚合於Tapyrus非織聚酯支撐基材時，所得之陽離子交換膜具有離子交換容量(IEC)為2.5meq/g以及含水量為40%。
在以上論述之實例中，該Tapyrus非織聚酯支撐基材為三層基材，具有兩強化層夾有一非織物層。三層皆由聚酯製成。強化層為紡黏(spunbond)且非織物層為熔噴(melt-blown)。非織物層為非織物料(non-woven fabric sheet)。三層係藉由例如令彼等透過加熱之軋輥(nip roller)輪壓(calendering)而彼此結合。加熱之軋輥可加熱至超過100℃。紡黏層比起熔噴層具有較大直徑纖維。紡黏纖維較佳具有直徑為15至35μm。熔噴纖維較佳具有直徑在2至4μm之範圍，儘管彼等可小至0.1μm、及大到10μm。與紡黏強化層相較，熔噴層中之較小直徑纖維提供非織物基材層較大的孔隙度(porosity)。非織物基材層之孔隙度可為大於70%。
在以上論述之例示的離子交換膜中，離子交換材料係與具有以下規格之三種不同非織物聚酯支撐基材進行測試： 聚酯支撐基材對電透析(ED)、雙極式ED、逆電透析(RED)、電去電離(EDI)、及倒極式電透析(EDR)中存在的酸性條件(acidic condition)是穩定的。
在以上論述之兩例示的膜中使用之離子交換聚合物(ion-exchange polymer)僅為可浸入支撐基材之樹脂的兩實例。可使用本領域已知的其他陽離子或陰離子聚合物。例如，可使用包含下列者的聚合物：磺酸基團(例如聚苯乙烯磺酸鈉(sodium polystyrene sulfonate))；羧酸基團；或四級胺基(quaternary amino group)(例如聚(丙烯醯胺基-N-丙基三甲基氯化銨)(poly(acrylamido-N-propyltrimethylammonium chloride)))。可使用之聚合物的具體實例包括使用(乙烯基苄基)三甲基氯化銨((vinylbenzyl)trimethylammonium chloride)、及苯乙烯磺酸鋰(lithium styrene sulfonate)形成之聚合物。
於根據本揭示內容之離子交換膜的另一實例中，支撐基材係由非織物層(12)及兩強化層(14，16)組成。支撐基材係以由(乙烯基苄基)三甲基氯化銨((vinylbenzyl)trimethylammonium chloride)(VBTAC)與 二乙烯苯(divinyl benzene)(DVB)在自由基起始劑諸如過氧化2-乙基己基碳酸三級丁酯(tert-butylperoxy 2-ethylhexyl carbonate)(TPO)的存在下聚合而形成之陰離子交換材料浸透(saturate)。單體及起始劑係溶於DPG，支撐基材係以所得溶液浸透。浸透的(saturated)基材於高溫固化以聚合單體及交聯劑。當28.9克之VBTAC、29.7g之DVB及0.9ml之TPO溶於38.5g之DPG且接著聚合於Tapyrus非織聚酯支撐基材時，所得之陰離子交換膜具有離子交換容量(IEC)為2.5meq/g以及含水量為35%。
於根據本揭示內容之離子交換膜的另一實例中，支撐基材係由非織物層(12)及兩強化層(14，16)組成。支撐基材係以陽離子交換材料(cation-exchange material)浸透(saturate)。陽離子交換材料係由苯乙烯磺酸鋰(lithium styrene sulfonate)(LiSS)與DVB在自由基起始劑諸如V-601的存在下聚合而形成。單體及起始劑係溶於NMP，三層皆以所得溶液浸透。浸透的(saturated)基材於高溫固化以聚合單體及交聯劑。當17.6g之LiSS、15.2g之DVB及0.2g之V-601溶於24.0g之NMP且接著聚合於Tapyrus非織聚酯支撐基材時，所得之陽離子交換膜具有離子交換容量(IEC)為2.5meq/g以及含水量為45%。
以上論述之離子交換材料係與具有以下規格之三種不同非織聚丙烯支撐基材進行測試： 聚丙烯支撐基材為疏水性(hydrophobic)，基材E和F係在以含有單體與交聯劑之溶液浸透前使用界面活性劑處理。聚丙烯支撐基材對電透析(ED)、雙極式ED、逆電透析(RED)、電去電離(EDI)、及倒極式電透析(EDR)中存在的腐蝕性條件(caustic condition)是穩定的。
雖然例示的離子交換膜係使用非織聚丙烯或聚酯層製成，但亦可使用其他的非織物層。例如可使用非織聚乙烯層、非織聚氯乙烯層、非織聚丙烯腈層、或非織聚醯胺層。
使用陰離子交換材料(樣品1-3)、或陽離子交換材料(樣品4-6)以Tapyrus三層聚酯支撐基材A-C製成之離子交換膜具有以下性質：
使用陰離子交換材料(樣品7-9)、或陽離子交換材料(樣品10-12)以Tapyrus三層聚丙烯支撐基材D-F製成之離子交換膜具有以下性質：
所得之膜於洩漏試驗(leak test)中進行測試，利用染料確認膜中的洩漏。陰離子交換膜的洩漏試驗使用5%亞甲藍(methylene blue)水溶液，而陽離子交換膜的洩漏試驗使用5%藻紅B(Erythrosin B)水溶液。使用Tapyrus三層聚酯基材所製之陰離子交換膜及陽離子交 換膜的照片示於圖3。陰離子交換膜展現：一洩漏(leak)及平滑(smooth)表面(樣品1)；無洩漏及一小粗糙(rough)區(樣品2)；以及無洩漏及平滑表面(樣品3)。具Tapyrus三層聚酯基材之陽離子交換膜展現：無洩漏但染料透過該膜(樣品4)；無洩漏(樣品5)；以及無洩漏(樣品6)。可用於電透析(ED)、雙極式ED、逆電透析(RED)、電去電離(EDI)、或倒極式電透析(EDR)的離子交換膜應較佳沒有洩漏(leak)。
膜係於Mullen破裂度機(Mullen burst machine)中測試，其量測擊穿該膜所需的壓力且為負載能力(load carrying capacity)之一指標(indicator)。樣品1於98psi破裂、樣品2於115psi破裂、樣品3於92psi破裂、樣品4於105psi破裂、樣品5於113psi破裂、以及樣品6於96psi破裂。
亦使用非接觸式電阻率測量裝置(non-contact resistance measurement device)量測膜於0.01N NaCl溶液中的電阻(resistance)，且使用螺旋測微計(spiral micrometer)測定膜的厚度。膜係具以下性質：
只要膜的厚度相同，預期離子交換膜的電阻實質上等同於對應之兩層離子交換膜的電阻。
例示之離子交換膜的各種物理性質係與以(a)0.15mm-厚的梭織聚丙烯支撐基材(woven polypropylene support substrate)(來自Tri-Ocean)、或(b)0.45mm-厚的丙烯酸系(acrylic)支撐基材製得之離子交換膜進行比較。三例示之離子交換膜(樣品13-15)分別使用Tapyrus支撐基材A-C，其係如上文所論述。Tri-Ocean支撐基材以及丙烯酸系支撐基材的透氣性約比Tapyrus支撐基材的透氣性大十倍。
陰離子交換材料(anion-exchange material)，藉由將58.0g之TMAEMC、24.6g之EDGM及0.4g之VA-601溶於13.03g之DPG和10.5g正丙醇(n-propanol)、以所得溶液浸透(saturating)該支撐基材、 以及聚合(polymerizing)單體與交聯劑，而聚合於支撐基材。目標離子交換容量(IEC)為3.14meq/g，且目標含水量為33.1%。
具丙烯酸系支撐基材的膜係具有粗糙表面、IEC為2.84meq/g、且WC為39.8%。如上文所述之洩漏試驗(leak testing)顯示洩漏通過具丙烯酸系支撐基材的膜。具0.15mm厚之Tri-Ocean梭織支撐基材的膜顯示嚴重洩漏。樣品13和14顯示粗糙表面及一些洩漏。樣品15顯示粗糙表面但無洩漏。洩漏試驗的拍照結果示於圖4。
Mullen破裂試驗(Mullen burst test)顯示具丙烯酸系支撐基材的離子交換膜於195psi破裂；具Tri-Ocean 0.15mm厚之支撐基材的離子交換膜於210psi破裂；而離子交換膜樣品13-15則分別於170psi、120psi及120psi破裂。
量測膜之厚度。電阻係於0.01N NaCl和0.5N NaCl進行量測。
製作另一例示的陰離子交換膜且將其物理性質與以(a)0.15mm厚的梭織支撐基材(來自Tri- Ocean)、(b)0.24mm厚的梭織(woven)支撐基材(來自Tri-Ocean)、或(c)0.45mm厚的丙烯酸系支撐基材製成之離子交換膜進行比較。此等支撐基材為來自多纖維絲(multifiber filiament)的梭織物，且極有組織(structured)與對稱(symmetrical)。例示之離子交換膜(樣品16)使用Tapyrus支撐基材A，其係如上文所論述。
陰離子交換材料(anion-exchange material)，藉由將17.6g之TMAEMC、10.9g之EDGM及0.2g之VA-601溶於15.2g之DPG、以所得溶液浸透(saturating)該支撐基材、以及聚合(polymerizing)單體與交聯劑，而聚合於支撐基材。目標離子交換容量(IEC)為2.71meq/g，且目標含水量為42.6%。
具丙烯酸系支撐基材的離子交換膜係具有平滑表面、IEC為2.42meq/g、且WC為42.6%。如上文所述之洩漏試驗(leak testing)顯示一洩漏。具0.15mm厚之Tri-Ocean梭織支撐基材的離子交換膜顯示嚴重洩漏。具0.24mm厚之Tri-Ocean梭織支撐基材的離子交換膜顯示嚴重洩漏，但比具0.15mm厚之Tri-Ocean梭織支撐基材的離子交換膜還少洩漏。樣品16顯示平滑表面及一洩漏。不希望為理論所束縛，本揭示內容之作者相信，比起使用梭織材料製成的支撐基材，非織物材料的高度交錯結構(highly interlaced structure)可降低膜洩漏的機會。洩漏試驗的拍照結果示於圖5。以非織物層所製之例示的膜 展現比以梭織物層製成之膜還少的洩漏。此可因在非織物層中增加的交錯纖維(interlacing fiber)量所致。
Mullen破裂試驗(Mullen burst test)顯示具丙烯酸系支撐基材的膜於200psi破裂；具Tri-Ocean 0.15mm厚之支撐基材的膜於210psi破裂；具Tri-Ocean 0.24mm厚之支撐基材的膜於240psi破裂；而膜樣品16則於118psi破裂。
量測膜之厚度。電阻係於0.01N NaCl和0.5N NaCl進行量測。
接觸鹽溶液對根據本揭示內容之例示的離子交換膜至鹽溶液的影響係和對以兩層支撐基材製成之離子交換膜的影響進行比較。具兩層支撐結構的離子交換膜係藉由將非織物層結合至強化層(透過加熱之軋輥(nip roller)輪壓該兩層)而成。如圖6所示，以兩層基材製成的離子交換膜展現顯著捲曲，表示於接觸鹽溶液時該兩層不同地擴展。相對地，如於圖3-5之樣品1-6及13-16的照片以及於圖7所示之樣品的照片所示，以根據本揭示內容之三層基材製成的離子交換膜展現減少的捲曲。
之前的敘述中，為了解釋之目的，提出許多 細節以供對實施態樣之徹底了解。然而，習此技藝之人士明顯知曉此等特定細節可非必須的。因此，已敘述者僅係例示所述實施態樣之應用，而鑑於以上教示可作許多修飾及變化。
由於以上敘述提供例示之實施態樣，熟習此技藝之人士咸瞭解可進行對特定實施態樣之修飾及變化。因此，申請專利範圍之範疇不應受文中所提之特定實施態樣所限制，而應以符合本說明書的方式作為整體以釋之。
10‧‧‧離子交換膜
12‧‧‧非織物層
14‧‧‧強化層
16‧‧‧強化層

Claims (15)

  1. 一種離子交換膜，包括：支撐基材，包含至少三個離子可透性層(ion-permeable layer)從膜之一面至膜之相對面以對稱順序而設置；以及離子交換材料；其中，該離子可透性層係浸以離子交換材料且包含：至少一非織物層；以及至少一強化層。
  2. 如申請專利範圍第1項之離子交換膜，其中，該支撐基材包含複數個非織物層且該複數個非織物層皆具有實質上相同的密度或實質上相同的抗拉強度，及/或其中，該支撐基材包含複數個強化層且該複數個強化層皆具有實質上相同的密度或實質上相同的抗拉強度。
  3. 如申請專利範圍第1或2項之離子交換膜，其中，該離子交換膜包括一強化層夾於兩非織物層之間，及/或其中，該離子交換膜包括一非織物層夾於兩強化層之間。
  4. 如申請專利範圍第1或2項之離子交換膜，其中，該離子交換材料為陽離子交換聚合物(cation-exchange polymer)，具有磺酸基團、羧酸基團、磷酸基團、或彼等之鹽。
  5. 如申請專利範圍第4項之離子交換膜，其中，該陽離子交換聚合物為以下列者聚合所形成之聚合物：2-丙 烯醯胺基-2-甲基丙磺酸(2-acrylamido-2-methylpropane sulfonic acid)、2-丙烯醯胺基-2-甲基丙磺酸鈉(sodium 2-acrylamido-2-methylpropane sulfonate)、3-磺酸丙基丙烯酸鉀(potassium 3-sulfopropyl acrylate)、甲基丙烯磺酸鈉(sodium methallyl sulfonate)、乙烯基磺酸鈉(sodium vinyl sulfonate)、4-乙烯基苯磺酸鈉(sodium 4-vinylbenzenesulfonate)、4-乙烯基苯磺酸鋰(lithium 4-vinylbenzenesulfonate)、丙烯酸、2-乙基丙烯酸(2-ethylacrylic acid)、甲基丙烯酸、2-丙基丙烯酸(2-propylacrylic acid)、丙烯酸鈉(sodium acrylate)、甲基丙烯酸鈉(sodium methacrylate)、乙二醇甲基丙烯酸磷酸酯(ethylene glycol methacrylate phosphate)、乙烯基磷酸(vinylphosphonic acid)、或雙[2-(甲基丙烯醯氧基)乙基]磷酸鹽(bis[2-(methacryloyloxy)ethyl]phosphate)。
  6. 如申請專利範圍第1或2項之離子交換膜，其中，該離子交換材料為陰離子交換聚合物(anion-exchange polymer)，具有四級銨基團、咪唑鎓(imidazolium)基團、或吡啶鎓(pyridinium)基團。
  7. 如申請專利範圍第6項之離子交換膜，其中，該陰離子交換聚合物為以下列者聚合所形成之聚合物：N-三甲基胺基乙基甲基丙烯酸酯氯化物(N-trimethylaminoethylmethacrylate chloride)(TMAEMC)、[2-(丙烯醯氧基)乙基]三甲基氯化銨([2-( acryloyloxy)ethyl]trimethylammonium chloride)、[2-(甲基丙烯醯氧基)乙基]三甲基氯化銨([2-(methacryloyloxy)ethyl]trimethylammonium chloride)、(3-丙烯醯胺丙基)三甲基氯化銨((3-acrylamidopropyl)trimethylammonium chloride)、[3-(甲基丙烯醯胺基)丙基]三甲基氯化銨([3-(methacryloylamino)propyl]trimethylammonium chloride)、二烯丙基二甲基氯化銨(diallyldimethylammonium chloride)、(乙烯基苄基)三甲基氯化銨((vinylbenzyl)trimethylammonium chloride)、溴化-1-乙烯基-3-乙基咪唑(1-vinyl-3-ethylimidazolium bromide)、或三溴化-4-乙烯基吡啶(4-vinylpyridinium tribromide)。
  8. 如申請專利範圍第1或2項之離子交換膜，其中，該至少一非織物層為下列的非織物料(non-woven fabric sheet)：聚丙烯、聚乙烯、聚氯乙烯、聚酯、聚丙烯腈、或聚醯胺。
  9. 一種離子交換膜，包括：離子交換材料；以及浸有該離子交換材料的支撐膜基材，該支撐基材包含離子可透性層，係設為使得在支撐基材截面之給定處的支撐基材密度為實質上相同於在支撐基材截面之相對處的支撐基材密度。
  10. 如申請專利範圍第9項之離子交換膜，其中：該離子可透性層為結合在一起的不同層，且該支撐基 材包含具有第一密度、結合於第二離子可透性層的一側之第一離子可透性層，該第二離子可透性層具有第二密度且結合於具有第三密度之第三離子可透性層的相對側，該第三密度與該第二密度實質上相同。
  11. 一種離子交換膜，包括：離子交換材料；以及浸有該離子交換材料的支撐膜基材，該支撐基材包含離子可透性層，係設為使得在支撐基材截面之給定處的支撐基材抗拉強度為實質上相同於在支撐基材截面之相對處的支撐基材抗拉強度。
  12. 如申請專利範圍第1、9及11項中任一項之離子交換膜，其中，該支撐基材具有厚度為小於0.5mm。
  13. 如申請專利範圍第1、9及11項中任一項之離子交換膜，其中，該支撐基材具有透氣性為至少0.5cc/cm2/s。
  14. 一種方法包括：以包含陰離子或陽離子單體以及交聯劑的溶液浸透(saturate)或浸漬(impregnate)包含至少三個離子可透性層(ion-permeable layer)從膜之一面至膜之相對面以對稱順序而設置的支撐膜基材；以及聚合(polymerize)該單體及交聯劑，其中，離子可透性層係包含：至少一非織物層；及至少一強化層。
  15. 一種方法包括： 以包含陰離子或陽離子單體以及交聯劑的溶液浸透或浸漬包含至少三個離子可透性層的支撐膜基材；以及聚合該單體及交聯劑；其中，在支撐基材截面之給定處的支撐基材密度為實質上相同於在支撐基材截面之相對處的支撐基材密度，及/或其中，在支撐基材截面之給定處的支撐基材抗拉強度為實質上相同於在支撐基材截面之相對處的支撐基材抗拉強度。
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