TW201341046A - 高分子多孔質膜 - Google Patents
高分子多孔質膜 Download PDFInfo
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- TW201341046A TW201341046A TW101150530A TW101150530A TW201341046A TW 201341046 A TW201341046 A TW 201341046A TW 101150530 A TW101150530 A TW 101150530A TW 101150530 A TW101150530 A TW 101150530A TW 201341046 A TW201341046 A TW 201341046A
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- Prior art keywords
- copolymer
- solvent
- tetrafluoroethylene
- membrane
- porous
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Abstract
本發明係以提供一種透水性及親水性為優異的高分子多孔質膜為目的。本發明為關於一種高分子多孔質膜,其特徵係由共聚物(A)所構成,共聚物(A)具有乙烯醇單位及四氟乙烯單位,且乙烯醇單位與四氟乙烯單位之交互率為30%以上。
Description
本發明為關於高分子多孔質膜。
近年,多孔質膜在以淨水處理、廢水處理等之水處理領域、血液淨化等之醫療用途、食品工業領域等為首之領域,在帶電荷膜、電池用分隔器(separator)、燃料電池等各式各樣方面被利用著。
例如,在淨水處理用途或廢水處理用途等之水處理領域中,用來代替已往的砂過濾、凝聚沈澱過程,或是提昇處理水質,已為使用多孔質膜。如此般的水處理領域時由於處理水量為大,故要求著多孔質膜的透水性能優異。只要是透水性能優異,則可減少膜面積,故淨水裝置變得小型,可期待設備費用之低成本化。
作為如上述般的多孔質膜,已檢討著使用乙烯醇系聚合物之多孔質膜。例如於專利文獻1中揭示一種由下述共聚物所構成之含氟共聚物膜,其中該共聚物係四氟乙烯與乙酸乙烯酯之共聚物、或將前述共聚物中所含乙酸酯基之至少一部份皂化後之共聚物。
[專利文獻1]日本特開平5-261256號公報
然而,使用已往的乙烯醇系聚合物之多孔質膜,在透水性之點無法稱得上為充分,具有改善之餘地。又,為了使多孔質膜成為具有優異透水性能且不易被污染,對於多孔質膜亦要求著親水性。當多孔質膜之親水性高時,於膜表面不易產生污染物質之積蓄,又,該污染物質容易藉由洗淨而除去。因而,亦具有可壓低運轉壓力等之運轉成本面之優點、或所謂膜壽命變長之優點。
本發明為提供一種透水性及親水性為優異的高分子多孔質膜。
本發明團隊發現,當於具有乙烯醇單位及四氟乙烯單位之共聚物中,乙烯醇單位與四氟乙烯單位之交互率為30%時,能使高分子多孔質膜之透水性及親水性顯著地提昇。
即,本發明為一種高分子多孔質膜,其特徵係由共聚物(A)所構成,共聚物(A)具有乙烯醇單位及四氟乙烯單位,且乙烯醇單位與四氟乙烯單位之交互率為30%以上。
共聚物(A)較佳為乙烯醇單位及四氟乙烯單位之莫耳比(乙烯醇單位/四氟乙烯單位)為25~75/75~25。
本發明之高分子多孔質膜,較佳由共聚物(A)進而與偏二氟乙烯系樹脂所構成。
本發明之高分子多孔質膜,較佳藉由非溶劑誘發相分離法、熱誘發相分離法、或此等雙方之組合而製作者。
本發明之高分子多孔質膜,較佳為中空纖維膜。
本發明之高分子多孔質膜,較佳為水處理用。
由於本發明之高分子多孔質膜為上述之構成,故透水性及親水性為優異。
以下為詳細說明本發明。
本發明之高分子多孔質膜,其係由共聚物(A)所構成,共聚物(A)具有乙烯醇單位(-CH2-CH(OH)-)及四氟乙烯單位(-CF2-CF2-),且乙烯醇單位與四氟乙烯單位之交互率為30%以上。由於本發明之高分子多孔質膜係由乙烯醇單位與四氟乙烯單位為以高比例相互聚合之共聚物所構成,故透水性及親水性為優異。
作為乙烯醇系聚合物之製造方法,一般為使用如下述之方法:使以乙酸乙烯酯為代表的乙烯基酯單體聚合後,再將所得之聚合物進行皂化之方法。然而,在例如使四氟乙烯與乙酸乙烯酯共聚合時,由於乙酸乙烯酯之強均聚性而乙酸乙烯酯彼此容易鏈結,不易得到交互率為高的共聚
物。
本發明團隊為藉由如後述般地調整聚合條件,成功獲得乙烯醇單位與四氟乙烯單位之交互率為高的共聚物。然後,藉由使用上述交互率為高的共聚物時,發現可得到所謂透水性及親水性為高的高分子多孔質膜之新見解,遂而完成本發明。
又,由於本發明之高分子多孔質膜為由共聚物(A)所構成者,水等之處理液體之透過性能為優異之同時,拉伸強度、伸長特性、彎曲強度等之機械性強度、耐藥品性及耐鹼性亦為優異。又,本發明之高分子多孔質膜為藉由控制製膜條件,而能廣泛地製作出使徑10nm左右之微粒子分離者至使微米等級之微粒子分離者。
就提昇透水性之觀點而言,共聚物(A)較佳為乙烯醇單位與四氟乙烯單位之交互率為35%以上。更佳為40%以上、又佳為60%以上。交互率之上限為100%,較佳為95%、更佳為90%。
乙烯醇單位與四氟乙烯單位之交互率,係使用重丙酮等共聚物(A)為可溶解之溶劑來進行共聚物(A)之1H-NMR測定,並可藉由下述式而以3鏈結之交互率算出。
交互率(%)=C/(A+B+C)×100
A:如-V-V-V-般地,與2個V鍵結之V之個數
B:如-V-V-T-般地,鍵結於V與T之V之個數
C:如-T-V-T-般地,鍵結於2個T之V之個數
(T:四氟乙烯單位、V:乙烯醇單位)
A、B、C之V單位之數為藉由1H-NMR測定,算出鍵結於乙烯醇單位(-CH2-CH(OH)-)之三級碳的主鏈之H之強度比。
交互率亦較佳為35%以上85%以下,35%以上、未滿80%亦為佳。當共聚物(A)之交互率過高時,對於溶劑之溶解性會降低,有不易製造高分子多孔質膜之虞,可能無法得到親水性與機械性強度為優異的多孔質膜。
當交互率為95%以上時,作為膜材料之耐熱性為優異。
共聚物(A)為具有乙烯醇單位及四氟乙烯單位之共聚物(以下亦有稱為「乙烯醇/四氟乙烯共聚物」)。
乙烯醇/四氟乙烯共聚物,乙烯醇單位/四氟乙烯單位以莫耳比計較佳為25~75/75~25。當乙烯醇單位與四氟乙烯單位之莫耳比為上述範圍外時,有無法得到交互率為高的乙烯醇/四氟乙烯共聚物之虞。當乙烯醇單位過多時,使所製作的多孔質膜與熱水接觸時會有溶出現象產生,又有無法得到充分機械性強度之虞。當乙烯醇單位過少時,親水性會降低,有無法得到充分透水性之虞。共聚物(A),乙烯醇單位/四氟乙烯單位之莫耳比更佳為33~60/67~40,又更佳為38~60/62~40。
就提高上述交互率之觀點而言,共聚物(A)實質上較佳為僅由乙烯醇單位及四氟乙烯單位所構成之乙烯醇/
四氟乙烯共聚物。
在不損及本發明之效果之範圍內,共聚物(A)可具有乙烯醇單位及四氟乙烯單位以外的其他單體單位。作為其他單體單位,舉例如乙烯基酯單體單位、乙烯基醚單體單位、側鏈具有聚環氧乙烷之(甲基)丙烯基單體單位、側鏈具有聚環氧乙烷之乙烯基單體單位、具有長鏈烴基之(甲基)丙烯基單體單位、具有長鏈烴基之乙烯基單體單位、六氟丙烯單位、氯三氟乙烯單位、全氟乙烯基醚單位等。其他單體單位之合計較佳為0~50莫耳%、更佳為0~40莫耳%、又更佳為0~30莫耳%。
共聚物(A)亦可具有乙烯基酯單體單位。當共聚物(A)為具有乙烯基酯單體單位時,由於玻璃轉移溫度會變高,故高分子多孔質膜之機械性強度會變得更優異。更,由於高分子多孔質膜之耐酸性亦會變成優異者,即使是將高分子多孔質膜藉由酸來進行洗淨或消毒時,亦可防止高分子多孔質膜之損傷。具有乙烯基酯單體單位之共聚物(A),當本發明之高分子多孔質膜為藉由將具有乙烯基酯單體單位與四氟乙烯單位之共聚物以皂化而得到時,可藉由調整皂化度而製造。有關皂化如後述內容。
共聚物(A)之重量平均分子量,雖然會依本發明之高分子多孔質膜之用途而有所差異,惟就機械性強度及成膜性之觀點而言,較佳為10000以上。更佳為30000~2000000、又佳為50000~1000000。上述重量平均分子量可藉由凝膠滲透層析法(GPC)而求得。
以下為對於共聚物(A)之製造方法進行說明。通常,共聚物(A)為將乙酸乙烯酯等乙烯基酯單體與四氟乙烯予以共聚合,之後再將所得之共聚物藉由皂化而得到。就使共聚物(A)之交互率成為30%以上之觀點而言,較佳為使乙烯基酯單體與四氟乙烯之組成比以幾乎保持於一定之條件下來進行聚合。即,共聚物(A)較佳為藉由如下述製造方法而得到,前述製造方法係由下述步驟所構成:使乙烯基酯單體與四氟乙烯之組成比以幾乎保持於一定之條件下進行聚合,以得到具有乙烯基酯單體單位與四氟乙烯單位之共聚物之步驟;及,將所得到的共聚物皂化而得到具有乙烯醇單位及四氟乙烯單位之共聚物之步驟。
乙烯基酯單體與四氟乙烯之聚合,一般而言,由於乙烯基酯單體之強均聚性而乙烯基酯單體彼此容易鏈結,故乙烯基酯單體與四氟乙烯之交互率難以變高。
作為乙烯基酯單體,舉例如甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、戊酸乙烯酯、異戊酸乙烯酯、己酸乙烯酯、庚酸乙烯酯、醯辛酸乙烯酯、三甲基乙酸乙烯酯、壬酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、十四酸乙烯酯、十五酸乙烯酯、十六酸乙烯酯、十七酸乙烯酯、硬脂酸乙烯酯、辛酸乙烯酯、Veova-9(Shows Shell Sekiyu(股)製)、Veova-10(Showa Shell Sekiyu(股)製)、安息香酸乙烯酯、叔碳酸乙烯酯(vinyl versatate)等,之中就容易取得、廉價之點而言,較佳為使用乙酸乙烯酯、丙酸乙烯酯、叔碳酸乙烯酯
。又,此等亦可混合使用。
作為使乙烯基酯單體與四氟乙烯共聚合之方法,可舉例如溶液聚合、塊狀聚合、乳化聚合、懸濁聚合等之聚合方法,但就工業性容易實施之點而言,較佳為藉由乳化聚合或溶液聚合,但不限定於此。
在乳化聚合或溶液聚合中,可使用聚合起始劑、溶劑、鏈轉移劑、界面活性劑等,可分別使用已往公知者。
溶液聚合中所使用的溶劑,較佳為能溶解四氟乙烯與乙烯基酯單體、及共聚物(A)者,列舉例如乙酸丁酯、乙酸乙酯、乙酸甲酯、乙酸丙酯等之酯類;丙酮、甲基乙基酮、環己酮等之酮類;己烷、環己烷、辛烷等之脂肪族烴類;苯、甲苯、二甲苯等之芳香族烴類;甲醇、乙醇、tert-丁醇、異丙醇等之醇類;四氫呋喃、二噁烷等之環狀醚類;HCFC-225等之含氟溶劑;二甲基亞碸、二甲基甲醯胺;或此等之混合物等。
作為乳化聚合中所使用的溶劑,列舉例如水、水與醇之混合溶劑等。
作為上述聚合起始劑,可使用例如二異丙基過氧基二碳酸酯(IPP)、二-n-丙基過氧基二碳酸酯(NPP)等之過氧基碳酸酯類,或以t-丁基過氧基三甲基乙酸酯等為代表的油溶性自由基聚合起始劑,或例如過硫酸、過硼酸、過氯酸、過磷酸、過碳酸之銨鹽、鉀鹽、鈉鹽等之水溶性自由基聚合起始劑等。乳化聚合中特佳為過硫酸銨、過硫酸鉀。
作為上述界面活性劑,可使用公知的界面活性劑,可使用例如非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑等。又,亦可為含氟系界面活性劑。
作為上述鏈轉移劑,列舉例如乙烷、異戊烷、n-己烷、環己烷等之烴類;甲苯、二甲苯等之芳香族類;丙酮等之酮類;乙酸乙酯、乙酸丁酯等之乙酸酯類;甲醇、乙醇等之醇類;甲基硫醇等之硫醇類;四氯化碳、氯仿、二氯甲烷(methylene chloride)、氯甲烷等之鹵化烴等。雖添加量會依據使用的化合物之鏈轉移常數之大小而改變,但通常相對於聚合溶劑為以0.001~10質量%之範圍使用。
作為聚合溫度,只要是在反應中的乙烯基酯單體與四氟乙烯之組成比幾乎為一定之範圍內即可,可為0~100℃。
作為聚合壓力,只要是在反應中的乙烯基酯單體與四氟乙烯之組成比幾乎為一定之範圍內即可,可為0~10MPaG。
來自於乙酸乙烯酯之乙酸酯基之皂化為吾人所知,可藉由醇解或水解等已往公知的方法來進行。藉由此皂化,乙酸酯基(-OCOCH3)會變換成為羥基(-OH)。其他的乙烯基酯單體中亦相同地,可藉由已往公知的方法予以皂化而得到羥基。
將具有乙烯基酯單體單位與四氟乙烯單位之共聚物皂化而得到本發明之高分子多孔質膜時,皂化度只要是在不會損及透水性能及耐鹼性之範圍內即可,具體較佳為50
%以上、更佳為60%以上、又更佳為70%以上。
皂化度為藉由共聚物(A)之IR測定或1H-NMR測定,並以下述式所算出。
皂化度(%)=D/(D+E)×100
D:共聚物(A)中的乙烯醇單位數
E:共聚物(A)中的乙烯基酯單體單位數
本發明之高分子多孔質膜,構成該高分子多孔質膜之樹脂可僅為共聚物(A),亦可為由共聚物(A)與共聚物(A)以外之樹脂所構成者。
本發明之高分子多孔質膜,就透水性之觀點而言,共聚物(A)較佳為高分子多孔質膜整體之30質量%以上,更佳為40質量%以上。
作為共聚物(A)以外之樹脂,列舉例如熱可塑性樹脂。熱可塑性樹脂為藉由進行加熱及外力而變形或流動之樹脂。作為熱可塑性樹脂,舉例如偏二氟乙烯系樹脂、聚乙烯系樹脂、聚丙烯系樹脂、丙烯酸樹脂、聚丙烯腈、丙烯腈-丁二烯-苯乙烯(ABS)樹脂、聚苯乙烯樹脂、丙烯腈-苯乙烯(AS)樹脂、氯乙烯樹脂、聚對苯二甲酸乙二酯、聚醯胺樹脂、聚縮醛樹脂、聚碳酸酯樹脂、變性聚苯醚樹脂、聚苯硫樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂及此等之混合物或共聚物。亦可混合與此等為可混和之其他樹脂。
作為熱可塑性樹脂,就高耐藥品性而言,較佳為選自於由偏二氟乙烯系樹脂、聚乙烯系樹脂、聚丙烯系樹脂、及丙烯酸樹脂所構成之群之至少1種。更佳為偏二氟乙烯系樹脂。
偏二氟乙烯系樹脂為聚偏二氟乙烯或由具有偏二氟乙烯單位之共聚物所構成之樹脂。
聚偏二氟乙烯之重量平均分子量,就高分子多孔質膜之機械性強度及加工性之觀點而言,較佳為50000~1000000。
作為具有偏二氟乙烯單位之共聚物,舉例如偏二氟乙烯/四氟乙烯共聚物、偏二氟乙烯/六氟丙烯共聚物等。就機械性強度及耐鹼性之觀點而言,較佳為具有偏二氟乙烯單位之共聚物,特佳為偏二氟乙烯/四氟乙烯共聚物。
就成膜性及耐鹼性之觀點而言,偏二氟乙烯/四氟乙烯共聚物之偏二氟乙烯單位及四氟乙烯單位之莫耳比(偏二氟乙烯單位/四氟乙烯單位)較佳為50~99/50~1。作為如此般的聚合物,列舉例如大金工業(股)製的Neoflon VT50、VP50、VT100、VP100、VP101、VP100X等。偏二氟乙烯/四氟乙烯共聚物,偏二氟乙烯單位/四氟乙烯單位之莫耳比更佳為50~90/50~10。又,偏二氟乙烯/四氟乙烯共聚物,除了僅由偏二氟乙烯單位及四氟乙烯單位所構成的偏二氟乙烯/四氟乙烯共聚物外,在不損及特性之範圍內,偏二氟乙烯單位及四氟乙烯單位以外,亦可具有六氟丙烯單位、氯三氟乙烯單位、全氟乙烯基醚單位等之三元
共聚物。
具有偏二氟乙烯單位之共聚物之重量平均分子量,雖然會依本發明之高分子多孔質膜之用途而有所差異,惟就機械性強度及成膜性之觀點而言,較佳為10000以上。更佳為50000~1000000、又更佳100000~800000。上述重量平均分子量可藉由凝膠滲透層析法(GPC)而求得。
聚乙烯系樹脂係由乙烯均聚合物或乙烯共聚物所構成的樹脂。聚乙烯系樹脂可由複數種類的乙烯共聚物所構成者。作為乙烯共聚物,舉例由丙烯、丁烯、戊烯等之直鏈狀不飽和烴中所選出之1種以上與乙烯之共聚物。
聚丙烯系樹脂係由丙烯均聚合物或丙烯共聚物所構成的樹脂。聚丙烯系樹脂可由複數種類的丙烯共聚物所構成者。作為丙烯共聚物,舉例由乙烯、丁烯、戊烯等之直鏈狀不飽和烴中所選出之1種以上與丙烯之共聚物。
丙烯酸樹脂,主要為包含丙烯酸、甲基丙烯酸及此等之衍生物之例如丙烯醯胺、丙烯腈等之聚合物的高分子化合物。特佳為丙烯酸酯樹脂或甲基丙烯酸酯樹脂。
若本發明之高分子多孔質膜為由共聚物(A)與共聚物(A)以外之樹脂所構成時,藉由調整共聚物(A)以外之樹脂之種類及量,可調整高分子多孔質膜之膜強度、透水性能、阻擋性能等。特別是,當共聚物(A)以外之樹脂為偏二氟乙烯系共聚物時,高分子多孔質膜除了具有優異的透水性外,亦具有高的機械性強度及耐鹼性。
本發明之高分子多孔質膜,就親水化之觀點、或控制
相分離之觀點、或提昇機械性強度之觀點而言,可進而含有聚乙烯吡咯啶酮、聚甲基丙烯酸甲酯樹脂、聚環氧乙烷、蒙特石、SiO2、CaCO3、聚四氟乙烯等之添加劑。又,本發明之高分子多孔質膜,就提昇透水性之觀點而言,亦可以鹼進行處理。所謂的鹼,例如NaOH水溶液、KOH水溶液、氰水、胺溶液等。此等亦可包含乙醇、甲醇等之醇或有機溶劑。特佳為包含醇之鹼,惟並不限定於此等。
本發明之高分子多孔質膜,孔徑較佳為2nm~1.0μm、更佳為5nm~0.5μm。當孔徑過小時,氣體或液體之透過率有變得不足之虞;當孔徑過大時,有阻擋性能降低、或機械性強度降低而變得容易破損之虞。
孔徑為利用細孔為可明確確認之倍率,使用SEM等來拍攝高分子多孔質膜之表面之照片,並測定細孔之直徑。當孔為橢圓形狀時,細孔之直徑為將短徑定為a、長徑定為b,可藉由(a×b)0.5而求得。又,可從微粒子阻擋率求得大約的孔徑。意即,例如,阻擋95%以上的50nm聚苯乙烯微粒子等之多孔質膜,可認為其具有50nm以下之孔徑。
本發明之高分子多孔質膜,例如具有阻擋95%以上的50nm微粒子之性能時,純水透過係數較佳為1.0×10-9m3/m2/Pa/s以上,更佳為2.0×10-9m3/m2/Pa/s以上。雖純水透過係數之上限未特別限定,但在保持目的之阻擋率及強度之範圍內,宜為越高值越好。
純水透過係數為在溫度25℃,將離子交換水視所需地
以泵或氮加壓至0.01MPa以上,並藉由使用已製作的中空纖維膜或平膜來進行過濾而可求得。具體由下述式所求得之值。
純水透過係數[m3/m2/Pa/s]=(透過水量)/(膜面積)/(透過時間)/(評估壓力)
本發明之高分子多孔質膜,100nm或50nm之微粒子阻擋率較佳為90%以上,更佳為95%以上。
微粒子阻擋率係將粒徑為已控制的聚苯乙烯乳膠微粒子以離子交換水稀釋成100ppm左右的分散溶液來作為評估原液,並以進行過濾,使用下式所求得之值。
微粒子阻擋率(%)=((評估原液吸光度)-(透過液吸光度))/(評估原液吸光度)×100
本發明之高分子多孔質膜,就機械強度之觀點而言,最大點破斷強度較佳為1.0MPa以上,更佳為2.0MPa以上。
最大點破斷強度為在夾頭間距離50mm、拉伸速度200mm/分之條件下測定試片之破斷強度,並將拉伸試驗前的斷面積作為單位測定面積而求得之值。
本發明之高分子多孔質膜,就機械強度之觀點而言,最大點伸度較佳為90%以上,更佳為200%以上。
最大點伸度為在夾頭間距離50mm、拉伸速度200mm/分之條件下測定試片之破斷強度,並將夾頭間距離50mm作為基準藉由最大點之伸長率而求得之值。
本發明之高分子多孔質膜之構造未特別限定。例如,可為固形分以三次元地擴展成為網絡狀的三次元網絡狀構造,或多數的球狀或接近於球狀形狀之固形分,直接地或藉由筋狀的固形分而連結成球狀構造等。又,亦可具有此等雙方之構造。
本發明之高分子多孔質膜之形狀,較佳為平膜形狀或中空纖維膜形狀。
若為平膜形狀時,本發明之高分子多孔質膜可為由共聚物(A)所構成的氟聚合物層及由多孔質基材所構成的複合膜。複合膜之情形時,可為多孔質基材表面為被覆有由共聚物(A)所構成的氟聚合物層者,亦可為將多孔質基材與由共聚物(A)所構成的氟聚合物層予以層合者。又,亦可為由多孔質基材、氟聚合物層、及由共聚物(A)以外之樹脂所構成之樹脂層而構成的複合膜。作為形成上述樹脂層之樹脂,舉例如上述熱可塑性樹脂。
作為多孔質基材,舉例如聚酯纖維、尼龍纖維、聚胺酯纖維、丙烯酸纖維、嫘縈纖維、綿、絹等由有機纖維所構成的織物、編物或不織布。又,亦可舉例玻璃纖維、金屬纖維等由無機纖維所構成的織物、編物或不織布。就伸縮性、成本之觀點而言,較佳由有機纖維所構成的多孔質基材。
多孔質基材之表面之孔徑,可依用途而自由選擇,但較佳為5nm~1.0μm、更佳為8nm~0.5μm。
若為平膜形狀時,高分子多孔質膜之厚度較佳為10μm~1mm、更佳為30μm~500μm。若為使用上述多孔質基材之複合膜之情形時,包含多孔質基材之厚度較佳為位於上述範圍內。
本發明之高分子多孔質膜,就每單位面積、每單位體積之處理水量之觀點而言,更佳為中空纖維膜形狀。
若為中空纖維膜形狀時,中空纖維膜之內徑較佳為100μm~10mm、更佳為150μm~8mm。中空纖維膜之外徑較佳為120μm~15mm、更佳為200μm~12mm。
高分子多孔質膜之膜厚,較佳為20μm~3mm、更佳為50μm~2mm。又,中空纖維膜之內外表面之孔徑可依用途而自由選擇,惟較佳為2nm~1.0μm、更佳為5nm~0.5μm之範圍。
本發明之高分子多孔質膜,可藉由各種的方法製造。例如可使用:相分離法、熔融萃取法、蒸氣凝固法、延伸法、蝕刻法、將高分子薄片藉由燒結以製成多孔質膜之方法、將含有氣泡的高分子薄片藉由壓碎而得到多孔質膜之方法、使用靜電紡絲之方法等的成型方法。
熔融萃取法,係將無機微粒子及有機液狀體熔融混練於混合物中,並以共聚物(A)之融點以上的溫度由金屬口押出或藉由壓製機等成型後,冷卻固化,之後藉由萃取有機液狀體及無機微粒子而形成多孔構造之方法。
蒸氣凝固法,係在由良溶劑中為溶解有共聚物(A)之氟聚合物溶液所構成的薄膜狀物之至少一側之表面上,強制地供給與上述良溶劑為具有相溶性,但不溶解共聚物(A)之弱溶劑的飽和蒸氣或含噴霧之蒸氣之方法。
本發明之高分子多孔質膜之製造方法,就容易控制細孔尺寸而言,較佳為相分離法。作為相分離法,列舉例如熱誘發相分離法(TIPS)、非溶劑誘發相分離法(NIPS)等。
由於較容易生成三次元網絡狀構造,以非溶劑誘發相分離法所製作的多孔質膜之機械強度為強,又,適合使用於非對稱構造之膜之製作。以熱誘發相分離法所製作的多孔質膜,由於較易生成球狀構造,故具有透水性優異之傾向,又,藉由提高製膜時聚合物溶液之濃度,可提昇機械強度。較佳為考量此等內容來選擇膜之製作方法。
使用熱誘發相分離法時,藉由經下述二步驟所構成之製造方法可製造本發明之高分子多孔質膜:「將共聚物(A)以相對為高之溫度溶解於弱溶劑或良溶劑之溶劑中,而得到氟聚合物溶液之步驟;以及,將此氟聚合物溶液冷卻固化之步驟」。
溶劑中為溶解有共聚物(A)之氟聚合物溶液,若維持於較被稱呼為曇點(cloud point)之溫度為更高之溫度時,會成為均勻單相之液體,但曇點以下時,會產生相分離,分離成為聚合物濃縮相及溶劑濃縮相之二相,進而成為結晶化溫度以下時,聚合物基質會固定化,而形成多孔
質膜。
使用熱誘發相分離法時,相對於共聚物(A)與溶劑之合計,上述氟聚合物溶液較佳為共聚物(A)為10~60質量%。更佳為15~50質量%。
藉由將氟聚合物濃度調整於適當之範圍,可將氟聚合物溶液之黏度調整於適宜之範圍。當氟聚合物溶液之黏度非為適宜之範圍時,有無法成型為高分子多孔質膜之虞。
上述弱溶劑係指:「在未滿60℃之溫度時,無法溶解共聚物(A)5質量%以上,但在60℃以上且為樹脂之融點以下時,可溶解5質量%以上之溶劑」。相對於弱溶劑,將即使是以未滿60℃之溫度亦可溶解樹脂5質量%以上之溶劑稱為良溶劑。在樹脂之融點或液體之沸點仍無法使樹脂溶解或膨潤之溶劑,稱其為非溶劑。
作為弱溶劑,舉例如環己酮、異佛酮、γ-丁內酯、甲基異戊基酮、鄰苯二甲酸二甲酯、鄰苯二甲酸二乙酯、乙醇、丙醇、脂肪族多元醇、丙二醇甲醚、碳酸丙烯酯、二丙酮醇、三乙酸甘油酯等中鏈長度的烷基酮、酯、二醇酯及有機碳酸酯等,以及此等之混合溶劑。亦可舉例如HFC-365等之含氟溶劑、二苯基碳酸酯、甲基苯甲酸酯、二乙二醇乙酸乙酯、二苯基酮等。尚,即使是非溶劑與弱溶劑之混合溶劑,只要是滿足上述弱溶劑定義之溶劑,則為弱溶劑。
使用熱誘發相分離法時,作為氟聚合物溶液之溶劑,較佳為弱溶劑,但不限於此,由檢討氟聚合物之相分離舉
動,亦有使用良溶劑之情形。
作為良溶劑,舉例如HCFC-225等之含氟溶劑、N-甲基-2-吡咯啶酮、二甲基亞碸、二甲基乙醯胺、二甲基甲醯胺、甲基乙基酮、丙酮、甲醇、四氫呋喃、四甲基尿素、磷酸三甲酯等之低級烷基酮、酯、醯胺等及此等之混合溶劑等。
作為非溶劑,列舉例如水、己烷、戊烷、苯、甲苯、四氯化碳、o-二氯苯、三氯乙烯、乙二醇、二乙二醇、三乙二醇、丙二醇、丁二醇、戊二醇、己二醇、低分子量之聚乙二醇等之脂肪族烴、芳香族烴、芳香族多元醇、氯化烴、或其他的氯化有機液體及其混合溶劑等。
使用熱誘發相分離法時,在得到氟聚合物溶液之步驟,較佳為將共聚物(A)以20~220℃溶解於弱溶劑或良溶劑之溶劑中。使溶解之溫度更佳為30~200℃。以相對高溫來溶解時,可提高共聚物(A)之濃度,因此,可得到具有高機械性強度之高分子多孔質膜。當共聚物(A)之濃度過高時,所得到的高分子多孔質膜之空隙率會變小,透水性能有降低之虞。又,當調製的氟聚合物溶液之黏度非位於適當範圍時,有無法成型為多孔質膜之虞。
作為將氟聚合物溶液冷卻固化之方法,較佳例如將上述氟聚合物溶液由金屬口吐出至冷卻浴中之方法。高分子多孔質膜為平膜之情形時,予以澆鑄並使浸漬於冷卻浴中之方法,亦可舉例作為較佳之方法。
可作為冷卻浴使用的冷卻液體,以較氟聚合物溶液為
低溫者,例如可使用溫度為5~80℃,並含有濃度為60~100質量%之弱溶劑或良溶劑之溶劑之液體。又,冷卻液體中,亦可使用非溶劑、或含有弱溶劑或良溶劑之非溶劑。
在得到本發明之高分子多孔質膜之製造方法中,氟聚合物溶液之濃度、溶解氟聚合物之溶劑之組成、構成冷卻浴之冷卻液體之組成,為重要的。藉由調整此等組成,亦可控制高分子多孔質膜之多孔質構造。
例如,在高分子多孔質膜之一側之面與另一側之面,藉由變更氟聚合物溶液之組成組合或冷卻液體之組成組合,亦可將高分子多孔質膜一側之面之構造與另一側之面之構造設定為相異者。
若本發明之高分子多孔質膜為藉由非溶劑誘發相分離法來製造時,較佳例如藉由下述二步驟所構成之製造方法來得到高分子多孔質膜:「將共聚物(A)溶解於溶劑中而得到氟聚合物溶液之步驟;以及,將所得到的氟聚合物溶液由金屬口吐出至含有非溶劑之凝固浴中之步驟。」。
藉由將上述氟聚合物溶液浸漬於含有非溶劑之凝固浴中,並以該氟聚合物溶液與凝固浴中的溶劑及非溶劑之濃度梯度作為驅動力,可使生成非溶劑誘發型之相分離。藉由此方法,起初因為溶劑與非溶劑之取代,而在產生相分離之外表面會形成緻密的表皮層,隨著時間之經過之同時相分離現象會朝向膜內部方向進行。其結果亦可製造:「繼表皮層之後,在朝向膜內部方向孔徑會連續變大之非對
稱膜」。
使用非溶劑誘發相分離法時,上述氟聚合物溶液較佳由共聚物(A)及溶劑所構成。上述氟聚合物溶液,除了共聚物(A)及溶劑外,進而由非溶劑所構成者亦為較佳型態之一。
氟聚合物溶液,相對於共聚物(A)、溶劑及非溶劑之合計(若氟聚合物溶液不含非溶劑時,以共聚物(A)及溶劑之合計),共聚物(A)較佳為5~40質量%。更佳為10~35質量%。
氟聚合物溶液,相對於共聚物(A)、溶劑及非溶劑之合計,非溶劑較佳為0.1~10質量%。更佳為0.5~8質量%。
藉由將氟聚合物濃度調整至於適當之範圍,可將氟聚合物溶液之黏度調整於適宜之範圍。當氟聚合物溶液之黏度非為適宜之範圍時,有無法成型為高分子多孔質膜之虞。
氟聚合物溶液可為常溫或被加熱者。例如,較佳為10~35℃。
在非溶劑誘發相分離法中,作為上述溶劑,可使用在熱誘發相分離法中所示例的溶劑。上述溶劑可為弱溶劑或良溶劑,較佳為良溶劑。
作為上述非溶劑,可使用在熱誘發相分離法中所示例的非溶劑。
作為在上述凝固浴為可使用的凝固液體方面,較佳為
使用含有非溶劑之液體來使固化,亦可含有弱溶劑、良溶劑。作為上述非溶劑,可使用在熱誘發相分離法中所示例的非溶劑。例如,可合適地使用水。
製造本發明之高分子多孔質膜時,亦可併用上述熱誘發相分離法及非溶劑誘發相分離法。
非溶劑誘發相分離法及熱誘發相分離法時,將溶劑中為溶解有共聚物(A)之氟聚合物溶液由金屬口予以吐出後,藉由使固化而可得到多孔質膜。作為上述金屬口,可使用例如隙縫金屬口、雙層管式金屬口、三層管式金屬口等。
使高分子多孔質膜之形狀成為中空纖維膜時,上述金屬口方面,較佳為使用中空纖維膜紡絲用的雙層管式金屬口、三層管式金屬口等。
使用雙層管式金屬口時,將氟聚合物溶液由雙層管式金屬口之外側管吐出,並將離子交換水等之中空部形成流體由內側管同時吐出,藉由在凝固浴或冷卻浴中進行固化,而可設定為中空纖維膜。
中空部形成流體,通常可使用氣體或液體。熱誘發相分離法時,較佳可採用與冷卻液體為相同,即含有濃度為60~100%之弱溶劑或良溶劑之液體,但亦可使用非溶劑、或含有弱溶劑或良溶劑之非溶劑。非溶劑誘發相分離法時,作為上述中空部形成流體,較佳為使用上述非溶劑,較佳例如離子交換水等之水。又,上述非溶劑亦可含有弱溶劑、良溶劑。
藉由變更中空部形成流體及冷卻液體或凝固液體之組成,亦可形成具有雙層構造的中空纖維膜。中空部形成流體,可於冷卻後再進行供給,惟,僅以冷卻浴之冷卻能力即足夠使中空纖維膜固化時,亦可不將中空部形成流體冷卻即進行供給。
三層管式金屬口,適合於使用二種類的樹脂溶液之情形。例如,將二種類的氟聚合物溶液由三層管式金屬口之外側管及中間管吐出,並將中空部形成液體由內側管同時吐出,藉由在凝固浴或冷卻浴中進行固化,而可設定為中空纖維膜。又,將氟聚合物溶液由三層管式金屬口之外側管吐出,並將由共聚物(A)以外之樹脂所構成的樹脂溶液由中間管吐出,另將中空部形成液體由內側管同時吐出,藉由在凝固浴或冷卻浴中進行固化,而可設定為中空纖維膜。
作為共聚物(A)以外之樹脂,舉例如上述者。之中,較佳為上述熱可塑性樹脂,更佳為偏二氟乙烯系樹脂或丙烯酸樹脂。
如上述般地,若中空纖維膜為使用雙層管式金屬口或三層管式金屬口之製造方法來製造時,由於凝固液體或冷卻液體之量可較製造平膜時更為降低之點,故宜。
若本發明之高分子多孔質膜之形狀為中空纖維膜時,在以上述方法所得之中空纖維膜之外表面或內表面,亦可進而形成氟聚合物層或由共聚物(A)以外之樹脂所構成之樹脂層。
氟聚合物層或樹脂層可藉由將氟聚合物溶液或樹脂溶液塗布於中空纖維膜之外表面或內表面而形成。作為將氟聚合物溶液或樹脂溶液塗布於中空纖維膜之外表面之方法,較佳為使用將中空纖維膜浸潰於該溶液中,或將該溶液滴下於中空纖維膜之方法等。作為將上述溶液塗布於中空纖維膜之內表面之方法,較佳為使用將該溶液注入於中空纖維膜內部之方法等。
作為控制溶液之塗布量之方法,除了控制該溶液之塗布量本身以外,在使多孔質膜浸漬於該溶液中或將該溶液塗布於多孔質膜後,亦較佳為利用將該溶液之一部分刮取或使用氣刀吹掉之方法。
若使本發明之高分子多孔質膜之形狀成為平膜時,可藉由澆鑄氟聚合物溶液,並使浸漬於冷卻浴或凝固浴中來予以製造。又,使用隙縫金屬口,並將氟聚合物溶液吐出至冷卻浴或凝固浴中亦可製造。
若本發明之高分子多孔質膜為由多孔質基材所構成之複合膜時,亦可藉由如下述般之方法而得到本發明之高分子多孔質膜:使多孔質基材浸漬於氟聚合物溶液之方法、使氟聚合物溶液塗布於多孔質基材之至少單面之方法等。
藉由上述製造方法可得到具有優異透水性的高分子多孔質膜,惟當透水性能不充分時,亦可將以上述製造方法所得之多孔質膜進而予以延伸而製成本發明之高分子多孔質膜。
作為控制本發明之高分子多孔質膜之孔徑之方法,可
採用例如,將用來控制孔徑的添加劑添加於氟聚合物溶液中,並於利用共聚物(A)來形成多孔質構造之際或於形成多孔質構造後,藉由溶出添加劑而控制高分子多孔質膜之孔徑之方法。又,亦可使添加劑留滯於多孔質膜內。
於非溶劑誘發相分離法及熱誘發相分離法中,氟聚合物溶液皆可含有添加劑。於形成多孔質構造後,藉由溶出添加劑而可控制高分子多孔質膜之孔徑。添加劑可視所需地留滯於多孔質膜內。
作為添加劑,可舉例如有機化合物及無機化合物。作為有機化合物,較佳為能溶解或均勻地分散於構成氟聚合物溶液之溶劑中者。更佳為:「非溶劑誘發相分離法時,為可溶解於凝固液體中所含有的非溶劑中者;熱誘發相分離法時,為可溶解於冷卻液體中所含有的溶劑中者」。
作為有機化合物,列舉例如聚乙烯吡咯啶酮、聚乙二醇、聚乙烯醇、聚伸乙亞胺、聚丙烯酸、聚葡萄糖等之水溶性聚合物、界面活性劑、甘油、糖類等。
作為無機化合物,較佳為使用水溶性化合物,可列舉例如氯化鈣、氯化鋰、硫酸鋇等。
以未使用添加劑,而採用藉由凝固液之非溶劑之種類、濃度及溫度來控制相分離速度,亦可控制表面之平均孔徑。一般而言,當相分離速度快時,表面平均孔徑為小;慢時則會變大。又,藉由在氟聚合物溶液中添加非溶劑,對於相分離速度之控制亦為有效。
氟聚合物溶液,就親水化之觀點、或相分離控制之觀
點、提昇機械性強度之觀點而言,可進而含有聚乙烯吡咯啶酮、聚甲基丙烯酸甲酯樹脂、蒙特石、SiO2、CaCO3、聚四氟乙烯等之添加劑。
本發明之高分子多孔質膜適合作為在飲料水製造、淨水處理、廢水處理等水處理中所使用的精密過濾膜或超過濾膜。又,在超純水製造領域中,亦可作為用來提高離子排除性及提高所得到的純水之純度的帶電荷性多孔質膜使用。由於本發明之高分子多孔質膜為高透過性且耐藥品性優異,故較佳為作為水處理用之高分子多孔質膜。
又,本發明之高分子多孔質膜亦適合於醫療領域、食品領域、電池領域等中使用。
在醫療領域中,血液淨化,特別是用來代替腎機能的血液透析、血液過濾、血液過濾透析等,作為藉由體外循環來將血液中老化廢棄物除去為目的之血液淨化用膜,可使用本發明之高分子多孔質膜。
在食品領域中,作為發酵時使用的酵母之分離除去或液體之濃縮為目的,可使用本發明之高分子多孔質膜。
在電池領域中,作為用來使電解液透過惟不使電池反應所生成之生成物透過的電池用分隔器(separator),或作為高分子固體電解質之基材,可使用本發明之高分子多孔質膜。
以下為列舉實施例來說明本發明,惟本發明並不僅限定於此等實施例。
乙烯醇單位與四氟乙烯單位之交互率為使用重丙酮溶劑來進行共聚物之1H-NMR測定(重丙酮溶劑),並藉由下述式而以3鏈結之交互率算出。
交互率(%)=C/(A+B+C)×100
A:如-V-V-V-般地,與2個V鍵結之V之個數
B:如-V-V-T-般地,鍵結於V與T之V之個數
C:如-T-V-T-般地,鍵結於2個T之V之個數
(T:四氟乙烯單位、V:乙烯醇單位)
A、B、C之V單位之數為藉由1H-NMR測定,算出鍵結於乙烯醇單位(-CH2-CH(OH)-)之三級碳的主鏈之H之強度比。
1H-NMR(核磁共振法)測定為使用JNM-EX270(JEOL公司製:270MHz)。溶劑為使用重丙酮。
純水透過係數為在溫度25℃,將離子交換水視所需地以泵或氮加壓至0.01MPa以上,並藉由使用已製作的中空
纖維或平膜進行過濾而求得。
純水透過係數[m3/m2/Pa/s]=(透過水量)/(膜面積)/(透過時間)/(評估壓力)
微粒子阻擋率為將粒徑為已控制的聚苯乙烯乳膠微粒子,以離子交換水稀釋成為100ppm左右的分散溶液來作為評估原液,進行過濾並藉由下式而求得。
微粒子阻擋率%=((評估原液吸光度)-(透過液吸光度))/(評估原液吸光度)×100
最大點破斷強度為在夾頭間距離50mm、拉伸速度200mm/分之條件下,來測定試片的破斷強度,並將拉伸試驗前的斷面積作為單位測定面積而求得。
最大點伸度為在夾頭間距離50mm、拉伸速度200mm/分之條件下,來測定試片的破斷強度,並將夾頭間距離50mm作為基準,藉由最大點之伸長率而求得。
鹼處理為藉由將中空纖維浸漬於1N NaOH的甲醇/水(50/50(體積%))之水溶液中來進行。
接觸角測定(25℃)為使用協和界面化學(股)製的DropMaster701,並以純水作為測定溶劑來進行測定。
於3L不銹鋼製高壓釜中置入純水1000g、乙酸乙烯酯23.2g、Neocol P(二辛基磺基琥珀酸鈉之76.4質量%異丙基醇溶液:第一工業製藥(股)製),以氮取代並加入四氟乙烯37g,將槽內昇溫至80℃。之後,加入四氟乙烯30g。此時槽內之壓力為0.809MPa。將此於攪拌下加入過硫酸銨(APS)之1質量%水溶液22g,使開始反應。反應開始時開始追加乙酸乙烯酯,花費6小時追加283g的乙酸乙烯酯。反應中為使乙酸乙烯酯/四氟乙烯之比率成為一定之方式,使用電磁閥連續供給四氟乙烯。攪拌速度為500rpm。
具體而言,當四氟乙烯被消耗而槽內變成0.800MPa時,電磁閥會自動開啟供給四氟乙烯,當變成0.775MPa時,電磁閥會自動關閉停止四氟乙烯之供給,以循環來一邊控制四氟乙烯之供給及壓力,一邊配合四氟乙烯之消耗量而追加乙酸乙烯酯。
自反應開始6小時後停止四氟乙烯及乙酸乙烯酯之供給。之後,使反應1小時後,將槽內回復至常溫常壓並停止聚合,得到乙酸乙烯酯/四氟乙烯共聚物之乳化液1661g(固形分濃度38.5質量%)。
所得到的乙酸乙烯酯/四氟乙烯共聚物之玻璃轉移溫度為40℃,粒子徑為116nm。藉由氟之元素分析而求得乙酸乙烯酯/四氟乙烯共聚物之組成為49/51(莫耳比)。
使乙酸乙烯酯/四氟乙烯共聚物(乙酸乙烯酯/四氟乙烯=49/51(莫耳比))22.5g溶解於四氫呋喃150ml中。於此溶液中加入26質量%NaOH溶液(水/甲醇=50/50(質量%))8g並予以攪拌。將反應溶液藉由IR測定來追蹤水解反應。在水解為進行100%之時間點,將溶液濃縮並藉由再沈澱、洗淨、乾燥,而得到幾乎為定量的乙烯醇/四氟乙烯共聚物。交互率為62%。
將各成分以25℃混合,得到乙烯醇/四氟乙烯共聚物(乙烯醇/四氟乙烯=49/51(莫耳比)、交互率=62%、皂化度=100%)11.5質量%、偏二氟乙烯/四氟乙烯共聚物(偏二氟乙烯/四氟乙烯=80/20(莫耳%))9.0質量%、聚環氧乙烷(PEG600)1.5質量%、二甲基乙醯胺78.0質量%之聚合物溶液。將此聚合物溶液由雙層管式金屬口,伴隨著作為內部液體之離子交換水同時地吐出,並在離子交換水中進行固化。得到的中空纖維膜為外徑
0.84mm、內徑0.73mm。於25℃之純水透過係數為4.4×10-9〔m3/m2/Pa/s〕,50nm之聚苯乙烯微粒子之除去率為98%以上。中空纖維膜係認為具有50nm以下之孔徑。最大點破斷強度為4.3MPa,最大點伸度為270%。
將各成分以25℃混合,得到偏二氟乙烯/四氟乙烯共聚物(偏二氟乙烯/四氟乙烯=80/20(莫耳%))18.0質量%、聚環氧乙烷(PEG600)3.0質量%、二甲基乙醯胺79.0質量%之聚合物溶液。將此聚合物溶液由雙層管式金屬口,伴隨著作為內部液體之離子交換水同時地吐出,並在離子交換水中進行固化。得到的中空纖維膜為外徑0.91mm、內徑0.80mm。雖然已於25℃施加水壓0.1MPaG,但純水無法透過。最大點破斷強度為4.7MPa,最大點伸度為590%。
於3L不銹鋼製高壓釜中置入乙酸丁酯溶劑1200g及乙酸乙烯酯單體140g,並加入觸媒的Perbutyl PV 7.2g,關緊凸緣並將高壓釜取代成真空,封入四氟乙烯200g,以攪拌速度200rpm使槽內昇溫至60℃來開始反應。由聚合壓力之下降可確認到氣體單體之消耗,以6小時攪拌後停止,吹氣於殘留氣體而結束反應。
反應結束後,以大量的甲醇溶液使聚合物溶液再沈澱並進行聚合物之純化,得到乙酸乙烯酯/四氟乙烯共聚物。
藉由氟之元素分析而求得乙酸乙烯酯/四氟乙烯共聚物之組成為43/57(莫耳比)。
使乙酸乙烯酯/四氟乙烯共聚物(乙酸乙烯酯/四氟乙烯=43/57(莫耳比))20.0g溶解於四氫呋喃150ml中。於此溶液中加入26質量%NaOH溶液(水/甲醇=50/50(質量%))8g並予以攪拌。將反應溶液藉由IR測定來追蹤水解反應。在水解為進行100%之時間點,將溶液濃縮並藉由再沈澱、洗淨、乾燥,而得到幾乎為定量的乙烯醇/四氟乙烯共聚物。交互率為40%。
將各成分以25℃混合,得到乙烯醇/四氟乙烯共聚物(乙烯醇/四氟乙烯=43/57(莫耳比)、交互率=40%、皂化度=100%)11.5質量%、偏二氟乙烯/四氟乙烯共聚物(偏二氟乙烯/四氟乙烯=80/20(莫耳%))11.5質量%、二甲基乙醯胺78.0質量%之聚合物溶液。將此聚合物溶液由雙層管式金屬口,伴隨著作為內部液體之離子交換水同時地吐出,並在離子交換水中進行固化。得到的中空纖維膜為外徑0.73mm、內徑0.61mm。於25℃之純水透過係數為3.1×10-9〔m3/m2/Pa/s〕,50nm之聚苯乙烯微粒子之除去率為95%以上。中空纖維膜係認為具有50nm
以下之孔徑。最大點破斷強度為4.6MPa,最大點伸度為95%。
將各成分以25℃混合,得到偏二氟乙烯/四氟乙烯共聚物(偏二氟乙烯/四氟乙烯=80/20(莫耳%))18.0質量%、二甲基乙醯胺82.0質量%之聚合物溶液。將此聚合物溶液由雙層管式金屬口,伴隨著作為內部液體之離子交換水同時地吐出,並在離子交換水中進行固化。得到的中空纖維膜為外徑0.92mm、內徑0.84mm。雖然已於25℃施加水壓0.1MPaG,但純水無法透過。最大點破斷強度為8.0MPa,最大點伸度為740%。
將各成分以25℃混合,得到乙烯醇/四氟乙烯共聚物(實施例1中記載者)18.0質量%、二甲基乙醯胺82.0質量%之聚合物溶液。將此聚合物溶液使用塗抹器(203μm)塗布於聚酯不織布(Unitika(股)製、20557FLV)上,並直接浸漬於25℃之水凝固浴中5分鐘,再以浸漬於92℃之熱水中2分鐘而得到平膜的多孔質膜。於25℃之純水透過係數為4.9×10-6〔m3/m2/Pa/s〕。膜之接觸角(水)為88°。
於300ml不銹鋼製高壓釜中置入乙酸丁酯溶劑50g及硬脂酸乙烯酯單體10.0g,並加入觸媒的Perbutyl PV 0.4g,關緊凸緣並將高壓釜取代成真空,封入四氟乙烯3.0g,放入60℃的震盪式恆溫槽中來開始反應。由聚合壓力之下降可確認到氣體單體之消耗,以2小時震盪後停止,吹氣於殘留氣體而結束反應。
反應結束後,以大量的甲醇溶液使聚合物溶液再沈澱並進行聚合物之純化,得到硬脂酸乙烯酯/四氟乙烯共聚物。
藉由氟之元素分析而求得硬脂酸乙烯酯/四氟乙烯共聚物之組成為68/32(莫耳比)。
使硬脂酸乙烯酯/四氟乙烯共聚物(硬脂酸乙烯酯/四氟乙烯=68/32(莫耳比))4.3g溶解於四氫呋喃50ml中。於此溶液中加入26質量%NaOH溶液(水/甲醇=50/50(質量%))5g並予以攪拌。將反應溶液藉由IR測定來追蹤水解反應。在水解為進行100%之時間點,將溶液濃縮並藉由過濾、再沈澱、洗淨、乾燥,而得到幾乎為定量的乙烯醇/四氟乙烯共聚物。交互率為25%。
將各成分以25℃混合,得到乙烯醇/四氟乙烯共聚物(乙烯醇/四氟乙烯=68/32(莫耳比)、交互率=25%、皂化度=100%)18.0質量%、二甲基乙醯胺82.0質量%
之聚合物溶液。將此聚合物溶液使用塗抹器(203μm)塗布於聚酯不織布(Unitika(股)製、20557FLV)上,並直接浸漬於25℃之水凝固浴中5分鐘,再以浸漬於92℃之熱水中2分鐘時,聚合物成分流出於凝固浴中,無法得到均勻的多孔質膜。
將各成分以25℃混合,得到乙烯醇/四氟乙烯共聚物(實施例1中記載者)9.0質量%、偏二氟乙烯/四氟乙烯共聚物(偏二氟乙烯/四氟乙烯=80/20(莫耳%))9.0質量%、二甲基乙醯胺82.0質量%之聚合物溶液。將此聚合物溶液使用塗抹器(203μm)塗布於聚酯不織布(Unitika(股)製、20557FLV)上,並直接浸漬於25℃之水凝固浴中5分鐘,再以浸漬於92℃之熱水中2分鐘而得到平膜的多孔質膜。於25℃之純水透過係數為2.3×10-8〔m3/m2/Pa/s〕。膜之接觸角(水)為77°,水滴為於10分鐘以內滲入至膜內中。
將各成分以25℃混合,得到偏二氟乙烯/四氟乙烯共聚物(偏二氟乙烯/四氟乙烯=80/20(莫耳%))18.0質量%、二甲基乙醯胺82.0質量%之聚合物溶液。將此聚合物溶液使用塗抹器(203μm)塗布於聚酯不織布(Unitika(股)製、20557FLV)上,並直接浸漬於25℃之
水凝固浴中5分鐘,再以浸漬於92℃之熱水中2分鐘而得到平膜的多孔質膜。於25℃之純水透過係數為4.6×10-10〔m3/m2/Pa/s〕。又,以相同之方法於另外的玻璃板上製作多孔質膜,該接觸角(水)為89°。
將各成分以25℃混合,得到乙烯醇/四氟乙烯共聚物(實施例1中記載者)9.0質量%、聚偏二氟乙烯(大金工業(股)製)9.0質量%、二甲基乙醯胺82.0質量%之聚合物溶液。將此聚合物溶液使用塗抹器(203μm)塗布於聚酯不織布(Unitika(股)製、20557FLV)上,並直接浸漬於25℃之水凝固浴中5分鐘,再以浸漬於92℃之熱水中2分鐘而得到平膜的多孔質膜。於25℃之純水透過係數為7.3×10-9〔m3/m2/Pa/s〕。膜之接觸角(水)為78°,水滴為於10分鐘以內滲入至膜內中。
將各成分以25℃混合,得到聚偏二氟乙烯(大金工業(股)製)18.0質量%、二甲基乙醯胺82.0質量%之聚合物溶液。將此聚合物溶液使用塗抹器(203μm)塗布於聚酯不織布(Unitika(股)製、20557FLV)上,並直接浸漬於25℃之水凝固浴中5分鐘,再以浸漬於92℃之熱水中2分鐘而得到平膜的多孔質膜。於25℃之純水透過係數為5.9×10-10〔m3/m2/Pa/s〕。又,以相同之方法
於另外的玻璃板上製作多孔質膜,該接觸角(水)為112°。
本發明之高分子多孔質膜可使用於各種用途,特別適合使用於水處理用途。
Claims (6)
- 一種高分子多孔質膜,其特徵係由共聚物(A)所構成,共聚物(A)具有乙烯醇單位及四氟乙烯單位,且乙烯醇單位與四氟乙烯單位之交互率為30%以上。
- 如請求項1之高分子多孔質膜,其中,共聚物(A)之乙烯醇單位及四氟乙烯單位之莫耳比(乙烯醇單位/四氟乙烯單位)為25~75/75~25。
- 如請求項1或2之高分子多孔質膜,其係由共聚物(A)進而與偏二氟乙烯系樹脂所構成。
- 如請求項1、2或3之高分子多孔質膜,其係藉由非溶劑誘發相分離法、熱誘發相分離法、或此等雙方之組合而製作者。
- 如請求項1、2、3或4之高分子多孔質膜,其係中空纖維膜。
- 如請求項1、2、3、4或5之高分子多孔質膜,其係水處理用。
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Publication number | Priority date | Publication date | Assignee | Title |
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TWI668046B (zh) * | 2018-07-18 | 2019-08-11 | 國立臺北科技大學 | 過濾材的製造方法、過濾材的製造裝置及使用該方法所得之過濾材 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2014084356A1 (ja) * | 2012-11-30 | 2014-06-05 | 旭硝子株式会社 | 含フッ素共重合体からなる分離膜 |
JP6075452B2 (ja) * | 2013-06-26 | 2017-02-08 | ダイキン工業株式会社 | 組成物、高分子多孔質膜及び親水化剤 |
EP3061512B1 (en) * | 2013-10-23 | 2020-12-09 | Daikin Industries, Ltd. | Embossed filter medium for air filter, filter pack, air filter unit, and production method for embossed filter medium for air filter |
US10040033B2 (en) | 2013-12-13 | 2018-08-07 | Toray Industries, Inc. | Multilayer separation membrane |
JP6447623B2 (ja) * | 2014-03-03 | 2019-01-09 | Jnc株式会社 | 複合微多孔質膜及びこれを用いたフィルター |
KR101738732B1 (ko) | 2014-07-04 | 2017-05-24 | 연세대학교 산학협력단 | 안티파울링 특성이 강화된 고분자막의 제조 방법 |
CN104377377B (zh) * | 2014-09-18 | 2016-07-06 | 苏州经贸职业技术学院 | 一种燃料电池复合聚合物膜及其制备方法 |
JP6810386B2 (ja) * | 2014-12-26 | 2021-01-06 | 国立大学法人 奈良先端科学技術大学院大学 | 低タンパク質吸着性材料、低タンパク質吸着性物品、低細胞付着性材料および低細胞付着性物品 |
US20180022846A1 (en) * | 2015-02-20 | 2018-01-25 | Daikin Industries, Ltd. | Hydrophilizing agent, composition containing hydrophilizing agent, and porous polymer film |
CN105988627B (zh) * | 2015-02-25 | 2020-06-30 | 宸鸿科技(厦门)有限公司 | 触控显示装置及其制造方法 |
JP6592306B2 (ja) * | 2015-08-21 | 2019-10-16 | 学校法人 中央大学 | リン吸着用多孔質膜およびその製造方法 |
CN107793515A (zh) * | 2017-10-12 | 2018-03-13 | 江门建滔电子发展有限公司 | 四氟乙烯‑乙烯醇共聚物及采用其制备的半固化片和覆铜板 |
JP7177016B2 (ja) * | 2019-07-24 | 2022-11-22 | 富士フイルム株式会社 | 多孔質膜およびフィルターカートリッジ |
US11617989B1 (en) * | 2020-09-04 | 2023-04-04 | King Saud University | Extraction of benzene from benzene/cyclohexane mixture |
CN114277509B (zh) * | 2021-12-24 | 2023-01-03 | 江南大学 | 一种静电纺聚酰亚胺均匀小孔径纳米纤维膜及其制备方法与应用 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52156789A (en) * | 1976-06-23 | 1977-12-27 | Asahi Chem Ind Co Ltd | Ion exchange membrane contg. halogen element and production thereof |
DE3129744A1 (de) * | 1981-07-28 | 1983-03-10 | Hoechst Ag, 6000 Frankfurt | Fuer fluessigkeiten sowie gase selektiv-durchlaessige formkoerper aus fluorgruppen enthaltendem copolymerisat, die zugleich oleophob und oleophil sind |
JPS5892447A (ja) * | 1981-11-27 | 1983-06-01 | Asahi Glass Co Ltd | 気体選択透過素子 |
JPH02502832A (ja) * | 1987-11-20 | 1990-09-06 | アライド‐シグナル・インコーポレーテッド | フッ素化共重合体、そのフィルム及び該共重合体の製造法 |
JPH05261256A (ja) | 1992-03-19 | 1993-10-12 | Japan Gore Tex Inc | 含フッ素共重合体膜及び分離膜 |
JP3286696B2 (ja) * | 1992-06-22 | 2002-05-27 | ジャパンゴアテックス株式会社 | 親水性多孔質フッ素樹脂材料の製造方法 |
CN1785490A (zh) * | 2005-09-20 | 2006-06-14 | 丽水学院 | 聚四氟乙烯亲水性微滤膜的制备方法 |
CA2625523C (en) * | 2005-10-13 | 2012-07-17 | Asahi Kasei Chemicals Corporation | Porous multilayered hollow-fiber membrane and process for producing the same |
JP5318385B2 (ja) * | 2006-08-10 | 2013-10-16 | 株式会社クラレ | フッ化ビニリデン系樹脂よりなる多孔膜及びその製造方法 |
WO2011126056A1 (ja) * | 2010-04-08 | 2011-10-13 | 旭硝子株式会社 | 含フッ素オレフィン/ビニルアルコール共重合体、およびその製造方法 |
JP2011225659A (ja) * | 2010-04-16 | 2011-11-10 | Asahi Glass Co Ltd | 親水化されたエチレン/テトラフルオロエチレン共重合体多孔体の製造方法およびエチレン/テトラフルオロエチレン共重合体多孔体 |
WO2012165503A1 (ja) * | 2011-06-03 | 2012-12-06 | 旭硝子株式会社 | 親水化処理剤組成物、親水化方法、親水化樹脂多孔体およびその製造方法 |
CN103842389B (zh) * | 2011-10-05 | 2016-05-18 | 旭硝子株式会社 | 含氟烯烃/乙烯基醇共聚物的制造方法及由包含该共聚物的组合物成形而成的膜 |
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2012
- 2012-12-26 KR KR20147020679A patent/KR20140116146A/ko not_active Application Discontinuation
- 2012-12-26 EP EP12862678.5A patent/EP2784108A4/en not_active Withdrawn
- 2012-12-26 US US14/363,139 patent/US20150021261A1/en not_active Abandoned
- 2012-12-26 JP JP2012282453A patent/JP2013151671A/ja active Pending
- 2012-12-26 IN IN1268KON2014 patent/IN2014KN01268A/en unknown
- 2012-12-26 WO PCT/JP2012/083690 patent/WO2013099966A1/ja active Application Filing
- 2012-12-26 CN CN201280059751.XA patent/CN103975005A/zh active Pending
- 2012-12-27 TW TW101150530A patent/TW201341046A/zh unknown
-
2014
- 2014-04-07 JP JP2014078827A patent/JP5861734B2/ja active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI668046B (zh) * | 2018-07-18 | 2019-08-11 | 國立臺北科技大學 | 過濾材的製造方法、過濾材的製造裝置及使用該方法所得之過濾材 |
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JP2013151671A (ja) | 2013-08-08 |
JP2014166632A (ja) | 2014-09-11 |
IN2014KN01268A (zh) | 2015-10-16 |
EP2784108A1 (en) | 2014-10-01 |
WO2013099966A1 (ja) | 2013-07-04 |
US20150021261A1 (en) | 2015-01-22 |
EP2784108A4 (en) | 2015-08-12 |
CN103975005A (zh) | 2014-08-06 |
JP5861734B2 (ja) | 2016-02-16 |
KR20140116146A (ko) | 2014-10-01 |
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