TW494162B - Cationically charged coating on hydrophobic polymer fibers with poly(vinyl alcohol) assist and method of preparing the fibrous filter - Google Patents
Cationically charged coating on hydrophobic polymer fibers with poly(vinyl alcohol) assist and method of preparing the fibrous filter Download PDFInfo
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- TW494162B TW494162B TW088120644A TW88120644A TW494162B TW 494162 B TW494162 B TW 494162B TW 088120644 A TW088120644 A TW 088120644A TW 88120644 A TW88120644 A TW 88120644A TW 494162 B TW494162 B TW 494162B
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- polymer
- cationic
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- fiber
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Description
494162 A7 五、發明說明(1 ) 背景 本發明是關於纖維物質。更且;^ # "也說’本發明是關熱命 何改變的纖維。 疋闕於笔 在此技術中電荷改變的纖維是眾所皆知的。並、$口 微孔性薄膜組成或使用玻璃纖維及纖維素纖維的 纖維素纖維及矽粒子的混合物質。戽 口處或 * 构x確保包覆的持久,兩 何改變通常藉由以電荷改變作用劑 ^ 膜或至少㈣份的纖維來完成。離\鏈作用劑包覆薄 雖然微孔性薄膜通常能夠有效的過濾、,但通過薄膜的产 動速率通常比纖維過遽物慢。再者,在過_間,微孔性= 膜的反壓通常比纖維過㈣高。所以,需要―種適用於具電 荷粒子而具有效過濾能力的纖維質纖維。再者,亦需要二: 以玻璃纖維所組成的纖維質纖維,而不需纖維素纖維或石夕粒 子。 開孔薄膜,梭織物和非織造物質已被用作過濾薄片來去 除或分離液體中的纖維粒子。此類過濾薄片通常依賴某形式 的拉伸或物理作用。當欲過濾的粒子尺寸比過濾薄片的平均 孔徑小時,此類薄片的作用便有限。 已產生出具有修正表面電荷特性的改良過遽物,使得藉 過濾、物表面和水溶液中的粒子之間的電子交互作用來擄獲及 吸收顆粒。此類電荷改變的過濾物通常是以微孔性薄膜組成 或使用玻璃纖維及纖維素纖維的混合物質或纖維素纖維及石夕 粒子的混合物質。爲了確保包覆的持久,電荷改變通常藉由 以電荷改變作用劑和分離交鏈作用劑包覆薄膜或至少某部份 ㈣張尺細中嶋鮮(CNS)A4規格⑽1公髮) (請先閱讀背面之注意事項再填寫本頁) --------訂---------線· 經濟部智慧財產局員工消費合作社印製 YHW-PK-001.〇584 494162 A7 B7 五、發明說.明(2 的纖維來完成。 雖然微孔性薄膜通常能夠有效的過濾,但通過薄膜的流 動速率通¥比纖維過濾物慢。再者,在過濾期間,微孔性薄 膜的反壓通常比纖維過濾物高。 較期望利用合成聚合物所製備的纖維,因此類纖維較便 罝且可形成具有多孔性的非織造纖維而能夠過濾液體中的顆 粒。然而,此類合成聚合物通常具疏水性,此特性使得難以 用電荷改變的物質來持久地此類聚合物所製的纖維。所以, 便產生了利用根據疏水性聚合纖維之電荷改變的過濾物質的 機會。 換5之,期望能夠使用較便宜的物質來製造具有改變之 表面電荷特性的過濾物,使其能夠過濾水溶液中非常細緻的 粒子。例如,在製造開孔薄膜片,梭織物,和非織造物質中, 聚烯烴被廣泛地使用到。許多種類的聚烯烴薄片傾向疏水性 且較不具活性。亦即,聚婦烴(如聚丙埽)的低表面自由能和 其相對化學自然活性會產生在過濾薄片應用上並不適合的未 改變之聚烯烴,但改變的表面電荷使較被期望的,以去除水 溶液中的粒子。例如,許多化學電荷改變物(如陽離子樹脂, 聚電荷粒子等)黏著在傳統未改變的疏水性聚烯烴薄片的情 況都不佳。 在過去,化學包覆或内部添加劑(如蛋白質)可從溶液沉 澱至不同基質(如物質薄片)來改變基質的表面特性或當作化 學反應的作用表面。然而,許多經濟上所期望的基質(如聚烯 文工等I合物所形成的基質)其表面卻不適合生物官能物質快 (請先閱讀背面之注意事項再填寫本頁) -IAW--------tr---------線」 經濟部智慧財產局員工消費合作社印製
494162 經濟部智慧財產局員工消費合作社印製 A7 Β7 五、發明說.明(3 ) 速且低花費地沉澱,尤其當期望具有持久,密封包覆的附著 時。 即使便宜,持久,牢固的包覆可黏著在所欲隻較經濟的 基質上,但僅以生物官能物質(如蛋白質)所組成的包覆其作 用有限’尤其若此包覆缺乏所欲的化學特性,如改變的表面 電荷特性。 因此,需要一種實用且便宜的化學電荷改變的過濾物以 去除水溶液中微米至次微米尺寸的電荷顆粒。另需要一種由 未改變的,較不具活性的疏水性基質(如未改變之較不具活性 的聚埽煙基質)所形成的過滤物。亦需要一種利用實用及便宜 的化學電荷改變過濾、物(如未改變,較不具活性之聚婦烴基質 所形成的化學電荷改變過濾物)來去除水溶液中具電荷,微米 至次微米大小顆粒的方法。 除了上述所需外,另需要一種簡單,實用,且便宜的化 學電荷改變過濾物來去除水溶液中的水生病原體。此需要亦 發展出一種利用實用且便宜的化學電荷改變過濾物來去除水 溶液中之水生病原體的簡單方法。 觀祭某些具有改變表面電荷特性發現對於不同種類的 水生病原體’如不同種類的細菌,會有不同的過濾效果。亦 即某些具有改變表面電荷的過遽物可良好地去除某些種類 的水生病原體(如某些種類的細菌),但其他種類就不行。此 關係的自然性很難預測。既然水生病原體中即使很小的差異 對去除效率亦很重要,則發覺過濾物或過濾系統與水生病原 體之間所具有的無法預測之強引力皆無法預料且高度被期 ----------------------訂---------線- - - ? (請先閱讀背面之注意事項再填寫本頁) 1 - --------,示干、八4現格(21〇: 297公釐) ό YHW-PK-001-0584 A7 五、發明說.明(4 ) 望’尤其若此過濾物可用爽 ^ ^ 〗來屋生飲用水時。此需要非常重要, 因爲以實用且便宜的方,* +人 里戈 界上仍爲-大挑戰。,溶液中的水生病原體在世 MM&M. 本發明藉由提供—且古 一有陽離子電荷包覆的疏水性聚合 纖維來解決上述討論中 了-中的問碭和困難,*中此包覆包括已藉 由加熱而形成交鏈的陽離子官能基聚合物。舉例而言,陽離 子耳能基聚合物可爲一種α_環氧氣丙燒官能多胺。另一例 子’陽離子耳能基聚合物可爲心環氧氯丙烷官能多氨胺。 訂· 本發明亦提供一種包含具有陽離子電荷包覆之疏水性 聚合物纖維的纖維軸物。此包覆包含已藉由加熱而形成交 鏈的陽離子g旎基聚合物。如前所述,此陽離子官能基聚合 物爲α -%氧氯丙烷耳能多胺或α _環氧氣丙烷官能多氨胺。 '本發明本發明進一步提供一種製備纖維過遽物的方 法。此万法包括了提供一種以疏水性聚合物纖維所組成的纖 維過遽物;將纖維過遽物處以藉由加熱形成交鏈的陽離子官 能基聚合物的水溶液,其是在能充分地以陽離子官能基聚合 物包覆纖維的情況下形成,其中溶液包含了陽離子官能基聚 合物,聚乙烯醇,聚乙埽醇的極性溶劑,以及水;並在一溫 度下將產生之已包覆的纖維過濾物加熱而與疏水性聚合纖維 中的陽離子官能基聚合物形成交鏈。舉例來説,陽離子官能 基聚合物可爲α -環氧氯丙烷官能基多胺或α _環氧氯丙院^ 頁能多氨胺。不期望被理論所限制,本發明認爲聚乙埽醇可 將纖維正常的疏水性表面改變成能夠藉由纖維的陽離子官能 YHW-PK-001^0584 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公釐 7 494162
基聚合物包覆而促進疏水性程度。此外,聚乙料中的某些 I 氫氧根可與陽離子官能基(如環氧基)中的活性基團產生交# 丨 而在纖維上形成一持久的正電荷包覆。 一 ! 另外,本發明提供一種製備纖維過遽物的方法。此方》黃j ’ 包括k供-種以疏水性聚合纖維所組成的纖維過遽物;將藉 | I · 由力,:、、形成X鏈的陽離子官能基聚合物溶液通過纖維過濾| _ | 物’其是在能充分地以陽離子官能基聚合物包覆纖維的情況I i 下形成’其中溶液包含了陽離子官能基聚合物,聚乙料,| i 以及水,並在一溫度下將產生之已包覆的纖維過濾物加熱而 | ‘丨 與疏水性聚合纖維中的陽離子官能基聚合物形成交鏈。另 j 外,陽離子官能基聚合物可爲α _環氧氯丙烷官能基多胺或α ] -環氧氯丙烷·官能多氨胺。 較佳富施例5羊細描娜 j 於此使用之“疏水性聚合物”(hydrophobic p〇lymer)一 | 詞是指任何可抵抗潮濕或無法輕易因水而濕潤的聚合物,即 ] 與水之間缺乏引力。疏水性物質的表面自由能通常爲4〇 i dyneS/cm(10-5牛頓/cmilN/cm)或更少。疏水性聚合物的例 f 經濟部智慧財產局員工消費合作社印製 子包括(僅作爲例證)聚烯烴,如聚乙烯,異丁烯,異戊間二 | 烯聚4-甲烷-1戊歸,聚丙烯,乙烯-丙烯共聚物,及乙烯_ ! 丙烯-己二烯共聚物;乙烯-乙烯基醋酸共聚物,苯乙烯聚合 | 物,如聚苯乙烯,聚2-甲烷苯乙烯,丙烯腈的莫耳百分比少 ! 於20的苯乙烯-丙烯腈,及苯乙烯-2,2,3,3,-四氟丙基甲烷丙 j 烯酸鹽共聚物;鹵化烴聚合物,如聚氣三氟乙烯,氯化三氟 | 乙烯-四氟乙烯共聚物,聚六氟丙烯,聚四氟乙烯,四氟乙烯 |
本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 8 YHW-PK-001-0584 494162 A7 五、發明說.明(6 -乙烯共聚物,聚三氟乙烯,聚氟乙烯,及聚二氟乙烯;乙歸 基聚合物,如聚乙烯酪酸鹽,聚乙烯基十二酸鹽,聚乙婦基 十鹽’聚乙婦基己自艾鹽’聚乙稀基丙酸鹽,聚乙埽基辛 酉父鹽’聚七狀異丙乳基乙埽’ 1-七敦異丙氧基-甲貌乙埽-順 丁烯二酸共聚物,聚七氟異丙氧基丙歸,聚甲烷丙烯腈,聚 乙烯醇’聚乙埽丁縮酸,聚乙氧基乙烯,聚甲氧基乙埽,聚 乙烯基;丙烯聚合物,如聚η- 丁烷醋酸鹽,聚乙烷丙烯酸醋, 聚1·氯二氟甲烷-四氟乙烷丙烯酸酯,聚二(氣-甲氟)甲氣丙 烯酸酯,聚1,1-二氫七氟丁烷丙烯酸酯,聚丨,^二氫戊_款異 丙烷丙烯酸酯,聚1,1-二氫十五氟辛烷丙烯酸酯,聚七款異 丙烷丙烯酸酯,聚5-(七氟異丙氧基)-戊烷丙烯酸酯,聚丨丨·(七 氟異丙氧基)十一烷丙婦酸酯,聚2·(七氟丙氧基)乙烷丙烯酸 酉曰’及聚九氟兴丁燒丙烯酸醋;甲基丙歸聚合物,如聚苯甲 基丙烯酸酯,聚η-丁烷甲基丙烯酸酯,聚異丁烷甲基丙埽酸 酯’聚t-丁氨乙燒甲基丙烯酸酯,聚十二燒甲基丙埽酸酿, 聚乙垸甲基丙婦酸酯’聚2_乙燒己燒甲基丙埽酸酯,聚 己烷甲基丙烯酸酯,聚二甲氨乙烷甲基丙烯酸酯,聚甲基丙 烯酸乙醋,聚苯甲基丙烯酸乙酯,聚n_丙烷甲基丙烯酸醋, 聚十八燒甲基丙烯酸酯,聚1,1-二-十八氟辛烷甲基丙埽酸 醋’聚七氟異丙燒甲基丙烯酸酯,聚十七氟辛烷甲基丙埽酸 酉旨’聚1-氫化四氣乙燒甲基丙埽酸醋,聚1,1_二氫化四氣丙 烷甲基丙烯酸酯’聚1-氫化六氟異丙燒甲基丙烯酸酯,及聚 t·九氟丁烷甲基丙烯酸酯;聚酯,如聚三氯乙醛,聚氧化丁 烯二醇,聚氧化異丁烯二醇,聚氧化癸亞甲基,分子量少於 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 9 (請先閱讀背面之注意事項再填寫本頁) .--------訂---------. 一 經濟部智慧財產局員工消費合作社印製 YHW-PK-00UQS84 494162
、發明說明(7 1 500的聚氧化乙烯_二甲醚聚合物,聚氧化己二醇,聚氧化 1烯一醇’聚氧化丙烯_二甲醚,及聚氧化四亞甲基;聚醚共 聚物,如聚氧化乙埽-聚氧化丙烯-聚氧化乙婦塊狀共聚物, 氧化丙晞之莫耳分率大於20%的氧化乙婦_氧化丙婦共聚 物4化乙埽-氧化丙埽塊狀共聚物被聚氧化二甲基石夕婦塊狀 物所刀開的塊狀聚合物;聚酿胺,如聚L氧化癸次甲基亞氨, 聚1-氧化癸次甲基亞氨或耐論12,l h氧化己次甲基亞氨或 耐論6,聚i.氧化四次甲基亞氨或耐給4,聚二壬二亞氨, f壬二醯亞氨癸次甲基亞氨,及聚辛二醯亞氨辛此甲基亞 氨:聚亞虱’如聚苯亞氨乙烯,聚丁酸亞氨乙烯,聚十二醯 、氨乙烯十一醯亞氨乙烯-乙炔亞氨三次甲基共聚物,聚 庚醯亞氨乙烯’聚己醯亞氨乙烯,聚3甲基丁酸亞氨乙婦, =十五氟十八酸亞氨乙埽,和聚戊酿亞氨乙埽;聚氨基甲酸 酉曰’如Μ次甲基二苯二異氰酸鹽&聚氧化四次甲基二醇丁二 醇己/人甲基一兴氰酸鹽和三乙婦甘醇,以及心甲基_1,3_次 =基-亂酸鹽及三丙埽甘醇所製備的物質,聚發氧燒,如聚 氧化二甲基矽埽和聚氧化甲苯矽烯;以及纖維素,如澱粉醣, 支鏈殿粉,纖維㈣酸_鹽,乙I纖維素,半纖維素,及 硝化纖維素。 於此使用之陽離子電荷”(加‘^办charged) 一詞 是指-種在疏水性聚合纖維上的包覆且“陽離子的” (cati〇nic)疋和包覆且具有許多正電荷基團的聚合物。因此, “陽離子電荷”和“正電荷”爲同義。此類正電荷基團通常 包含許多季銨化合物基囷’但不限制於此。 本紙張尺度適财關綠準(CNS)A4規格(g_ x 297公釐) 10 YHW-PK-001-0584 494162 、 A7
...kp. I, ; ei —---- 訂---------線· · (請先閱讀背面之注意事項再填寫本頁) YHW-PK-001-0584 五、發明說明(9 ) 子官能基聚合物。附帶舉例,陽離子官能基聚合物心環氧氣 =官能基多胺。而另一例子’陽離子官能基聚合物可爲心 環氧氯丙燒-官能多氨胺。 本發明亦提供一纖維過遽物,其包含具有陽離子電荷包 覆的疏水性聚合物纖維。此包覆包括已藉由加熱而交鏈的陽 ::官能基聚合物。如前述’此陽離子官能基聚合物爲心 椒乳氯丙烷官能基多胺或心環氧氣丙烷·官能多氨胺。 大致上,纖維過遽物包含至少50%重量的疏水性聚合纖 維’其根據過滤物中所有纖維的重量而定。在某些實施例中, 爲1_的疏水性聚合物纖維。然而,若具有其它纖維時, 其通常爲纖維素纖維,玻璃纖維或此之混合物。 纖維素纖維的來源包括(僅作爲例證)樹木,如軟木和硬 木;稻麥和牧草,如稻,針茅草,小麥,黑麥,及sabai;贫 狀纖維和茅草,如薦渣;竹;木質莖,如黄麻,亞麻,洋麻, 和大麻m維,如亞麻類和学麻;葉子,域麻及壤麻; 經濟部智慧財產局員工消費合作社印製 :及種子’如棉和棉毛。軟木和硬木被廣泛地當作纖維素纖 、的來源;此纖維可藉由任何常用的製漿程序來製造,如機 ^ ’化學機械’半化學,和化學程序。軟木的例子包括(僅作 =證)大王松,小王松,德達松,黑雲杉,白雲杉,傑克松, 鐵杉’紅杉’和紅柏。硬木的例子包括(僅 例證)白揚’樺樹,山毛櫸,橡木,槭樹和橡膠樹。 理想上’疏水性聚合纖維爲以熱塑性聚烯烴或其混合物 所製備的纖維。熱塑性聚烯烴的例子包括聚乙埽,聚丙烯, 聚(1-丁埽)’聚(2-丁埽),聚(1.戊埽),聚(2戊埽),聚(3甲
本紙張尺度適^ (210 X 297 公釐) 12 A7 五、發明說明(ίο) 基]-戊埽),聚(4-甲基小戊埽)等。此外,“聚稀煙,,—詞是 指含以兩或更多不同未飽和單體所製備之隨意及塊狀共聚物 和兩或更多聚烯烴的混合物。因其商業上的重要性,最理想 的聚烯烴爲聚乙烯和聚丙烯。 纖維過濾物(無論前處理或後處理)的基重可在6 gsm至 400 gSm之間。例如,纖維過遽物的基重可介於丨2 gsm至25〇 ㈣。理想上,纖維過滤物的基重介於17 _至ι〇2㈣。 然而,本發明之任何數量的纖維過濾物皆可與其它物質結合 在-起而形成基重介於6_至彻卿甚至更大(例如大於 400 gsm)的結合物質。 本發明進一步提供一種製備纖維過濾物的方法。此方法 包含提供一種以疏水性聚合合纖維所組成的纖維過濾物;將 纖:過濾物處以藉由加熱形成交鏈的陽離子官能基聚合物的 水/合液,其疋在能充分地以陽離子官能基聚合物包覆纖維的 情況下形成’其中溶液包含了陽離子官能基聚合物,聚乙婦 醇’聚乙稀醇的極性溶劑’以及水;並在—溫度下將產生之 已包覆的纖維過濾物加熱而與疏水性聚合纖維中的陽離子官 能基^合物形成交鏈。舉例來説,陽離子官能基聚合物可爲 α-%氧氣丙烷官能基多胺或〇(_環氧氯丙烷_官能多氨胺。 對於有效的物質來説,陽離子官能基聚合物的水溶液通 常包含ο·ι至2%重量的陽離子官能基聚合物,〇1-4%重量 的聚乙烯醇’ & 1 〇_5〇 %重量的極性溶劑,而溶液的剩下部 伤爲水。舉例來説,_子官能基聚合物的水溶液包含〇 %重量的陽離子官能基聚合物,〇1_2名重量的聚乙烯醇,及 本紙張尺度適时關家標準(CNS)A4規格(21g χ挪公愛« 丫HW-PK-001-0584 線 13 62 五、發明說明(π) 15-45 %重量的異丙醇,溶液的剩下部份爲水。 商業上,聚乙歸醇是藉由聚乙烯醋酸的水解來製造。聚 乙烯醇的物理性質主要爲水解程度和分子量的函數。對於本 發明中有用的聚乙埽醇主要是指熱水溶性聚乙埽醇。此類物 質爲水解程度至少爲95%的高水解物質。理想上,聚乙埽醇 的水解程度爲99%或更大。聚乙埽醇的分子量至少爲 _00,其與至少的聚合度相對應。理想上,聚乙婦醇的 分子量爲15000至20000,其對應的聚合度介於25〇 435之 間。 大致上,極性溶劑可爲任何有機溶劑,其中聚乙埽醇可 部份或完全溶解。極性溶劑的例子包括(僅作爲例證)低醇 類’如甲醇,乙醇,i-丙醇,異丙醇,Ν丁醇,異丁醇,和 卜丁醇;酮類’如丙酮’丁綱,二乙銅;二鳴燒;及⑽二 甲基甲醯胺。理想上,極性溶劑爲異丙醇。 最後’本發明額外地提供—種製備纖維過遽物的方法, 此方法包括提供以疏水性聚合纖維所組成的纖維㈣物;將 藉由加Μ成交鏈㈣離子官能基聚合物溶液通過纖維過滤 物’其是在能充分地以陽離子官能基聚合物包覆纖維的情況 下形成’其中溶液包含了陽離子官能基聚合物,聚乙婦醇, 以及水;並在-溫度下將產生之已包覆的纖維過遽物加執而 與疏水性聚合纖維中的陽離子官能基聚合物形成交鏈。另 外,陽離子官能基聚合物可爲α_環氧氣丙燒官能基多胺或〇 -琢氣氯丙貌-官能多氨胺。 根據陽離子官能基聚合物,可能理想上或需要調整含聚 本紙張尺度賴+關家鮮(CNS)A4雜⑵ 1广屋 YHW-PK-001-0584 (請先閱讀背面之注意事項再填寫本頁) ·------.--訂---------線· 494162 經濟部智慧財產局員工消費合作社印製 A7 五、發明說.明(彳2) 合物水溶液的pH値。例如, s & α·%虱氣丙烷-官能多胺或α_ 環氧氣丙烷-官能多氨胺的水溶潘
,谷履具有鹼性或微酸性的pH
値。例如,此類溶液的pH値备认^ Ί A P値,1於6-10。pH値可輕易地利用 精於此項技術者所知的方法來調整。例如可利用添加無機酸 (如鹽酸或硫酸)之稀釋溶液至聚合溶液中來調整,或㈣ 酸’如氫氧化納,氫氧化鉀,或氫氧化胺。 可利用任何此項技術中已知的方法來將陽離子官能基 聚合物的溶液通過纖維過i慮物。例如,溶液可藉由在卿 已施加壓力之側的反侧減少壓力而使溶液吸引而通過過滤 物。或者,可利用壓力而強迫溶液通過過濾物。 一旦纖維過濾物被陽離子官能基聚合物包覆,則聚合物 藉由在一溫度下充分地加熱一段時間而與聚合物中的官能基 團產生交鏈。此溫度通常可在別艺-丨⑽它之間變化。加熱時 間通常爲溫度以及陽離子聚合物中之官能基團種類的函數。 例如,加熱時皆可在1-60分鐘内變化或更久。 本發明將藉由以下的範例而做進一步的説明。然而,這 些範例並不限制本發明的範圍和精神。所有的比例和百分比 皆以重量爲準。 範例1 在85下將0·5份的聚乙烯醇(Milwaukee,Wisconsin的
Aledch Chemical Company,目錄編號 No. 18,934-0,88% 水 解且重量平均粉子量爲96000)在99·5份的水中加熱至聚合 物溶解來製備聚乙烯醇溶液。將產生的溶液冷卻至室溫(2〇 C -2 5 °〇 ),將足夠量的α •環氧氯丙烷-官能多氨胺 木紙張尺度適用中國國家標準(CNS)A4規格(21〇 χ 297公釐) 15 丫HW-PK-001-0584 11 ---·--------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 494162 Α7 Β7 五、發明說明(I3) (Wilmington Delaware 的 Hercules Inc.之 Kymene® 450,20
% 固體)和異丙醇(得自 Aldrich Chemical Company,以 HPLC 測里;展度爲99.5%)加入溶液中而形成最後含有035%聚乙 烯醇,0.35% Kymene® 450,和29%異丙醇的最終水溶液。 將7英叶X30英吋(18 cm X 76cm)且基重爲每平方碼1盎司或 1 osy(每平方公尺34克或34 gsm)的熔喷織物浸入此最終的 聚乙烯醇溶液中直到完全濕潤(1_2分鐘)。把飽和的織物從溶 液中取出並以空氣乾燥。然後將織物放在85亡的爐子中1小 時使織物中之纖維表面上的α _環氧氯丙烷-官能多氨胺形成 交鏈。 . 將六層已處理的織物裁成直徑1英吋(2.5 cm)的圓形並 放在不銹剛注射容器(Clifton,New Jersey的Whatman Inc., 目錄編號No· 1980-002,直徑25 mm )中且以在每亳升水中有 108 個表面活化劑(得自 Fishers,Indiana 的 Bangs Laboratory,
Inc.)粒子懸浮之直徑〇·5微米的聚苯乙埽乳膠微粒子(其具有 叛酸官能基團,表面滴定値爲7.〇 aeg/g)來促進活性。利用 注射容器使粒子懸浮液通過此層狀過濾物。99·9 %以上的粒 子藉由此六層織物而被除去。99.9 %以上的粒子藉由使溶液 通過結合基重爲6 osy (203 gsm)的織物層過濾、而除去。 範例2 在85°C下將1份的聚乙烯醇(Wilmington Deware的 Dupont Chemical的Evanol® 7006)在99份的水中加熱至聚合 物溶解來製備聚乙烯醇溶液。產生的溶液冷卻至室溫(2〇〇c _25。0後,將5〇 ml的溶液與2 ml的α-環氧氯丙烷_官能多 (請先閱讀背面之注意事項再填寫本頁) -1 --------^---------線· 經濟部智慧財產局員工消費合作社印製
YHW-PK-001-0584 162
五、發明說明(14) 胺溶液(Wilmington Dela醫e 的 Hercules Inc 之 Kyme⑽ 2064,20% 固體),3〇 ml 的異丙醇(得自 Aldrich Chemicai Company,以HPLC測量濃度爲99.5%)和18 ml的去離子水 充分混合。將7英吋X52英吋(18 cmx 132cm)的均句聚丙烯 溶噴織物浸泡在100 ml的聚乙烯醇/陽離子官能基溶液中直 到其完全濕潤。把飽和的織物從溶液中取出並使其通過實驗 室攪扭機來去除殘留的溶液。然後將織物以空氣乾燥並放在 85¾的爐子中1小時使織物中之纖維表面上的〇-環氧氯丙 烷-官能多胺形成交鏈。 從已處理的織物裁出直徑爲1.875英吋(4.8 cm)的圓形 樣本。將六層此圓形樣本所組成的過濾物放在直徑2英吋(5 ·丄 cm)的Nalgene再使用過濾容器(得自Naperville,Illinois之 Nalge Nunc Internationa卜稱號 Nalgene # 300-4000 , 250 ml) 中。在過濾容器中以5公升的水來清洗過濾物。然後以範例 1中的直徑0.5微米聚苯乙烯乳膠微粒子100 ml來測試過濾 物的獲取效率。利用重力使粒子懸浮液通過過濾物。90 %以 上的粒子藉由使溶液通過結合基重爲6 osy(203 gsm)的織物 層過濾而除去。 範例3 在85°C下將〇·2份的聚乙烯醇(Wilmington Deware的 Dupont Chemical 的 Evanol® 7006)在 99.8 份的水中力口 熱至聚 合物溶解來製備聚乙烯醇溶液。產生的溶液冷卻至室溫(2〇 t:-25°C)後,將68 ml的溶液與2 ml的α-環氧氯丙烷-官能 多胺溶液(Wilmington Delaware 的 Hercules Inc.之 Kymene® 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) 17
訂 經濟部智慧財產局員工消費合作社印製 YHW-PK-001-0584 494162 A7 經濟部智慧財產局員工消費合作社印製 --— B7_____ 五、發明說.明(ϊ 5) 2064’ 20%固體)充分混合。將產生的溶液以氫氧化鈉水溶液 調整pH値至10,然後加入3〇⑹的異丙醇(得自施心 Chemical Company,以HPLC測量濃度爲99 5 %)。將7英吋 X52英吋(18 cmX132cm)的均句聚丙埽熔喷織物浸泡在ι〇〇 ml的聚乙婦醇/陽離子官能基溶液中直到其完全濕潤。把飽 和的織物從浴液中取出並使其通過實驗室攪扭機來去除殘留 的溶液。然後將織物以空氣乾燥並放在85。〇的爐子中丨小時 使織物中之纖維表面上的α -環氧氯丙烷_官能多胺形成交 鍵。 從已處理的織物裁出直徑爲L875英吋(48 cm)的圓形 樣本。將六層此圓形樣本所組成的過濾物放在直徑2英吋(5.1 cm)的Nalgene再使用過濾容器(得自Naperville,Illinois之 Nalge Nunc Internationa卜稱號 Nalgene # 300-4000,250 ml) 中。在過遽谷器中以4公升的水來清洗過遽物。然後以範例 1中的直徑0.5微米聚苯乙烯乳膠微粒子100 ml來測試過濾 物的獲取效率。利用重力使粒子懸浮液通過過濾物。99 %以 上的粒子藉由使溶液通過結合基重爲6 OSy(203 gsm)的織物 層過遽而除去。範例4 在85¾下將0.2份的聚乙烯醇(Wilmington Deware的 Dupont Chemical的Evanol® 7006)在97份的水中加熱至聚合 物溶解來製備聚乙烯醇溶液。產生的溶液冷卻至室溫(2〇。〇 _25°C)後,將溶液與範例3中3 ml的α-環氧氯丙烷-官能多 胺溶液(Wilmington Delaware 的 Hercules Inc·之 Kymene® (請先閱讀背面之注意事項再填寫本頁) » ------—---------^ ^ 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) 18 YHW-PK-001-0584 494162
五、發明說明(I6) 2 064,20 %固體)充分混合。製備六層均勻熔喷織物所組成的 過濾物,其中每一層皆爲直徑1875英吋(4·8 cm)的圓形。將 此過濾物放在直控2英吋(5·1 cm)的Naigene再使用過濾容器 (ί于自 Naperville, Illinois 之 Nalge Nunc International,稱號
Nalgene # 300-4000,250 ml)中。藉由減少過濾容器下側的 壓力來吸引上述所製備的α _環氧氣丙烷官能多胺溶液使其 通過過濾物10秒。發現到此步驟會使織物濕潤。然後將過濾 物在85。〇的爐子中加熱1小時使織物中之纖維表面上的α-環氧氣丙烷-官能多胺形成交鏈。 加熱後,以4公升的去離子水來清洗過濾物然後再以1〇〇 ml的0.1 %重量之氣化鈉水溶液清洗。過濾物的獲取效率測 試如範例3所述。99.9 %以上的粒子藉由使溶液通過結合基 重爲6 osy(203 gsm)的織物層過濾而除去。 在以下的範例中,本發明的熔噴物質測試是要測試包覆 持久性,不同流速中的粒子獲取效率,和病源體獲取效率。 範例5 將基重爲1 osy(34 gsm)的聚丙烯熔喷織物以前述範例 中所述的方法處理。將400克的聚乙烯醇(Wilmington Deware 的 Dupont Chemical 的 Evanol® 7006),600 ml 的 α -環氧氣 丙燒-έ 能多胺溶液(Wilmington Delaware 的 Hercules Inc.之 Kymene® 2064,20 %固體),和水混合而形成總體積爲22公 升的溶液。此溶液的pH値爲7.5-8。將過濾物在85eC的爐子 中加熱1小時使織物中之纖維表面上的α-環氧氯丙烷-官能 多胺形成交鏈。 本紙張_ ¥鮮(CNS)A4規格⑽ X 297 公ϋ 19 (請先閱讀背面之注意事項再填寫本頁) 訂---------線| 經濟部智慧財產局員工消費合作社印製 YHW-PK-001-0584 494162 A7 B7 五、發明說.明(17) 不因流速下的粒子擭1效率 (請先閱讀背面之注意事項再填寫本頁) 從已處理的織物裁出直徑爲1875英吋(4·8 cm)的圓形 樣本。將六層此圓形樣本所組成的過濾物放在直徑2英吋(5.1 cm)的 Nalgene 再使用過濾容器(得自 Naperville,Illinoisi
Nalge Nunc Internationa卜稱號 Nalgene # 300-4000,250 ml) 中。在過濾容器中以100 ml的〇·! %氣化鈉水溶液來清洗過 濾物。以範例1中的直徑〇·5微米聚苯乙埽乳膠微粒子i〇〇 ml 來測試過濾物的獲取效率。利用減少壓力來吸引粒子懸浮液 通過過濾物。99%以上的粒子藉由使溶液通過結合基重爲6 〇sy(203 gsm)的織物層過濾而除去,其懸浮液的流動速率介 於 3.8-470 ml min·1 in·2 之間。 處以大量之自来太後的包覆持夂Hi生 經濟部智慧財產局員工消費合作社印製 在有孔金屬中心的四周包裹六層已處理的熔噴織物來 產生一過濾物。每層的基重爲1 osy(34 gsm)且面積爲18.2 in2。將產生的結構物固定在能允許液體流至外部表面而完全 通過六層且進入金屬中心的不銹鋼容器。使200加侖(757公 升)的活栓壓力自來水通過過遽物。將結構物從容器中取出且 小心地將各層從金屬中心取下。將每熔喷包裹物裁出3個直 徑1.875英吋(4.8 cm)的圓形且如前面範例所述在重力流動 下測試其粒子獲取效率;然而,在此情況中,微粒子懸浮液 含有每毫升2.94X108個微粒子。此粒子獲取效率列於表一。 在此表中,薄片1爲最外層的薄片,而薄片6爲最内層的薄 片,亦即第一層包裹在金屬中心四周的薄片。 表一 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公叙) 20 YHW-PK-001-0584 494162 A7 B7 ---丨一本 經濟部智慧財產局員工消費合作社印製 五、發明說明(18) 3fe孑獲取敢率的概要情沉 Γ L 薄片 __ 獲取百分比 ―- 1 74.1+2.3 2 77·0±1·8 3 78·6±3·2 4 72·8±5·0 5 74·1±2·3 6 75.0±0.9 控制纟^__ 76·6±1·4 L __ 1 — ^.......... 從表一中可看出平均粒子獲取效率在73 % -79 %之間。若計 算標準差,則範圍會稍微變大,如從65 %至82 %。控制織物, 即已處以陽離子官能基聚合物但未以自來水沖洗的織物,其 平均粒子獲取效率爲77%。表中的數據顯示出電荷改變的包 覆是持久的,因此數據是以200加侖自來水清洗過濾物之後 所得的數據。 病A體擭取鈇爭 在此將病原體獲取效果定義爲殘留在過濾水中的細胞 數目對病原體懸浮液中本來之細胞數目的比例。其藉由將原 始懸浮液和過濾水的樣本植在tryptic soy agar (tsa)生長培 養皿(得自 Maryland,Cockeyville,Beet〇n_Dickins〇n 的祖⑧ TSA培養皿)上且在37。〇培養過夜後計算看見的菌落數目。 一個菌落成型單位(CFU)表示—個單獨存活的細胞。雖然如 此L起來很簡單,但此類測試有時也會有複雜的因子。可溶 的陽離子,如應料本_中的陽離子官能基聚合物,是很 強的抗菌物。若將包覆過滹或法垃奋 、“戎/先掉會殺死過濾水中的任何細 。告此情形發生’由於溶液中妹夕 成T ^夕的細胞死掉,過濾水會 紙張尺度適鮮(CNS)A4規彳^ YHW-PK-001-0584 ΙΊ ·------------------:--^---------^ I A_w------------------------ (請先閱讀背面之注意事項再填寫本頁) 21 A7
五、發明說明(13 表二 所選擇聚合味離子的最小抑制濃度a 經濟部智慧財產局員工消費合作社印製 ·◊、丁出極明顯的人爲細胞減少。所以,經由兩部份的程序(稱 爲包覆持久性測試和過濾、效果檢驗)來決定過遽效果。 知數層已處理的聚丙烯熔喷織物放在過濾容器設備 (Rochester,NY 的 Nalgene Inc 的 Nalgene Fih以 H〇ider);層 的平均厚度爲3 mm。&完成包覆持久性測試,们00 ml的 〇· 1 %要菌食鹽水藉由重力流動或降低壓力使其通過過濾 物。然後將細菌加入流出的食鹽水而形成105-10ό細胞/ml的 洛液且培養30分鐘。細胞濃度根據上述在37。〇培養過夜後 決疋。任何從測試織物過濾陽離子官能基聚合物所造成的細 胞叱ττ將藉由與含菌的控制溶液(即未通過過濾物的含菌溶 液)比較而更加清楚。 過遽檢驗或包覆持久性測試僅能夠決定可查覺得過濾 量,其與微生物對陽離子官能基聚合物的敏感度有關。細菌 敏感度已由最小抑制濃度研究(MIC)或觀察得的無生長之濃 度來決定。表二列出各種微生物的數個MIC研究結果。 (請先閱讀背面之注意事項再填寫本頁) ϋ n ϋ ϋ ϋ ον _ ΜΗ ΜΙ· ΜΜΒ ΜΜΙ Μ·· ΜΜ 置 1 I -ϋ βϋ n II ·.1 ·ϋ »ϋ ml· ϋ n ϋ n V. cholerae Reten® 201b <250 ppm Kymene® 450c <33 ppm Kymene® 2064d <16 ppm E. coli — <33 ppm <16 ppm S. cholerasuis --- <16 ppm — K. terrigena --- — <16 ppm S. aureus ~ - < 16 ppm -±- <8 ppm 如微生物年市釋(試管)生長方法(Microdilution Broth Met: Vol· 13, No· 25, Dec 1993)中所诚 _(NCCLS, 一種含有季銨基團的陽離子聚合物(Hercules Inc. Wilmington,Delaware) 。一種 α-環氧氯丙燒官能多氨胺(Hercules Inc· Wilmington,Delaware) d— 種 α-環氧氯丙虎官能多胺(Hercules Inc. Wilmington,Delaware) —" — —『…1 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 22 YHW-PK-001-0584 494162 A7 五、發明說明(2(¾ 過遽效果藉由將過遽物處以⑽ml的G i%含菌食趟水 來決定。將含菌溶液控制在1GMG6細胞/ml。藉重力流動或 減壓的影響下使液體經過過遽物。如同包覆持久性測試,將 流出的食鹽水培養3〇分鐘。在抑培養過夜後如上所述判 足細胞濃度。將結果與原始懸浮液的培養皿菌落數比較且記 錄値以對數(log reduetiGn)表示。研究的變數包括微生物種 類,經過過濾物的流動速率,和懸浮液的PH値。結果列於 表三至五。 表三 不同微生物的過濾效果 微生物 對數值 ~~ 濾出物 K. terrigena(ATCC 33257)a 3.51±0.3b ----——-- 無 E. coli(ATCC 13706) _ _ 明· 3.36 土 0.3 __無 |aEPA測試微生物 |b此表示懸浮液中的微生物因過濾而完全地減少(或除去) 表四 -1------------------Γ I ^ 111111. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 E· coli在不同流速的過濾效^ 流速 對數值 濾出物 5 ml min'1 in*2 ^3.5 無 10 ml min'1 in"2 ^3.5 無 1 5 ml min'1 in-2 ^3.5 無 20 ml min'1 in'2 ^3.5 無 I 50 ml min'1 in'2 ^3.5 Γ·. _ " """ 無 YHW-PK-001-0584 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 23 494162 Α7 Β7 五、發明說.明(2 b 表五
表三至五中的數據顯示出下列意義: 經濟部智慧財產局員工消費合作社印製 ♦ 不同的微生物在在已知的過遽物中會略有不同的過濾、 效果(然而,必須承認這些不同可能藉由運用一過濾物質來過 濾一特定的微生物而消除); ♦ 在此研究的範圍内’過滤效果不視流經過滤物的速度而 定;以及 ♦ 對微生物研究而言,過濾效果是根據過濾液體的pH値 而定;此影響是因爲微生物的淨電荷與pH値有關。 雖然本説明書已詳細地説明了相關的具體實施例,其將 被精於此項技術者所重視而一旦瞭解了前述内容後,可輕易 地思索出這些實施例的替換物,改變及同等物。所以,本發 明的範圍應視附加的申請專利範圍和任何由此之同等物而 定0 (請先閱讀背面之注咅?事項再填寫本頁) 馨! it!——線,·!!----------------- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 24 YHW-尸 Κ-00Ν05δ4
Claims (1)
- 經濟部智慧財產局員工消費合作社印製 '申請專利範圍 1 · 一種疏水性聚合纖維,其上具有陽離子電荷包覆, 此包覆包含: -種陽離子官能基聚合物,#已藉由加熱而形成交鍵。 2·如申請專利範圍第1項所述的疏水性聚合纖維,並 中此陽離子官能基聚合物爲CX-環氧氯丙燒官能基多胺。’、 3.如申請專利範園第丨項所述的疏水性聚合纖維,其 中陽離子T能基聚合物爲心環氧氣丙虎官能基多氛胺。 4· 一種纖維過濾物,其包含具有陽離子電荷包覆的疏 水性聚合纖維,此包覆包含: 種陽離子官能基聚合物,其已藉由加熱而形成交鏈。 5.如申請專利範園第4項所述的纖維過濾物,其中陽 離子耳能基聚合物爲α_環氧氯丙烷官能基多胺。 6·如申請專利範圍第4項所述的纖維過濾物,其中陽 離子耳能基聚合物爲α_環氧氯丙烷官能基多氨胺。 7. 一種製備纖維過濾物的方法,此方法包含: 提供一種以疏水性聚合纖維所組成的纖維過濾物; 知、减、、隹過;慮物處以藉由加熱形成交鏈的陽離子官能夷 聚合物的水溶液,其是在能充分地以陽離子官能基聚合物包 覆纖維的情況下形成,Α中溶液包含了陽離子官能基聚合 物,聚乙烯醇,聚乙烯醇的極性溶劑,和水; 並在一溫度下將產生之已包覆的纖維過濾物充分地加 熱一段時間而與疏水性聚合纖維中的陽離子官能基聚合物 形成交鏈。 8·如申請專利範圍第7項所述的方法,其中陽離子官 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 25 YHW-PK-001-0584 ——--------—----訂---------^ I ^__w— (請先閱讀背面之注意事項再填寫本頁)經濟部智慧財產局員工消費合作社印製 YHW-PK-001-0584 494162 六、申凊專利範圍 此基聚合物爲α _環氧氣丙烷官能基多胺。 9 ·如申請專利範圍第7項所述的方珐,其中陽離子官 能基聚合物爲α-環氧氣丙烷官能基多氨胺。 10·如申請專利範圍第7項所述的方珐,其中陽離子官 能基聚合物的水溶液包含: 陽離子έ能基聚合物,其重量含量在〇·ι%至2%之間; 聚乙烯醇,其重量含量在0.1%至4%之間;以及 極性》谷劑’其重量含量在10幺至5 0 %之間; 而溶液的剩餘部份爲水。 U·如申請專利範園第10項所述的方法,其中極性溶 劑爲異丙醇。 12. 如申請專利範圍第η項所述的方法,其中陽離子 官能基聚合物的水溶液包含: 陽離子官能基聚合物,其重量含量在〇·2%至之間; t乙烯醇,其重量含量在0.1%至2%之間;以及 極性溶劑,其重量含量在15 %至45 %之間; 而溶液的剩餘部份爲水。 13. —種製備纖維過濾物的方法,此方法包含: 提供一種以疏水性聚合纖維所組成的纖維過濾物; 將藉由加熱形成交鏈的陽離子官能基聚合物溶液通過 纖維過濾物,其是在能充分地以陽離子官能基聚合物包覆纖 維的情況下形成,其中溶液包含了陽離子官能基聚合物,聚 乙烯醇,以及水; 並在一溫度下將產生之已包覆的纖維過濾物充分地加 本紙張尺渡適用中國國家標準(CNS)A4規格(210 X 297公爱) 26 (請先閱讀背面之注意事項再填寫本頁) 泰 n ϋ n n 一5、· ϋ I i ϋ n ml I n ϋ ϋ n ·ϋ I I ϋ ϋ I ϋ I ϋ ϋ ϋ ϋ ϋ ϋ ϋ ^ynioz申請專利範圍 “、、叙時間而與疏水性聚合纖維中的陽離子官能基聚人 形成交鏈。 土 > 口物 14·如申請專利範圍第13項所述的方法 耳能基聚合物爲α-環氧氣丙烷官能基多胺。 15.如申請專利範圍第14項所述的方法 耳能基聚合物爲α-環氧氣丙烷官能基多氨胺, 16.如申請專利範㈣13項所述的方法,其中陽離子 基聚合物的水溶液包含: ^ 陽離子官能基聚合物,其重量含量在01%至4%之間; 聚乙烯醇,其重量含量在0.1%至2%之間;以及 而溶液的剩餘部份爲水。 17·如申請專利範園第16項所述的方珐,其中極性溶 劑爲異丙醇。 < 18·如申請專利範圍第16項所述的方法,其中陽離子 官能基聚合物的水溶液包含: 陽離子官能基聚合物,其重量含量在〇 2%至2%之間·, 聚乙烯醇,其重量含量在〇1%至1%之間;以及 而溶液的剩餘部份爲水。 其中陽離子 其中陽離子 (請先閱讀背面之注意事項再填寫本頁} Λ 「r -----丨丨訂--------·線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公爱) 27 YHW-PK-001-0584
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-
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- 1999-12-14 AR ARP990106377A patent/AR021674A1/es not_active Application Discontinuation
- 1999-12-16 BR BRPI9916295-4A patent/BR9916295B1/pt not_active IP Right Cessation
- 1999-12-16 AT AT99967382T patent/ATE323794T1/de not_active IP Right Cessation
- 1999-12-16 PE PE1999001275A patent/PE20001525A1/es not_active Application Discontinuation
- 1999-12-16 WO PCT/US1999/030092 patent/WO2000036207A1/en active IP Right Grant
- 1999-12-16 MY MYPI99005528A patent/MY130849A/en unknown
- 1999-12-16 DE DE69930965T patent/DE69930965T2/de not_active Expired - Lifetime
- 1999-12-16 CN CNB998162582A patent/CN1211527C/zh not_active Expired - Fee Related
- 1999-12-16 AU AU23670/00A patent/AU761743B2/en not_active Ceased
- 1999-12-16 EP EP99967382A patent/EP1149198B1/en not_active Expired - Lifetime
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2002
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113301977A (zh) * | 2019-01-16 | 2021-08-24 | 恩铂锘有限公司 | 水处理过滤器及其制造方法 |
CN113301977B (zh) * | 2019-01-16 | 2022-12-16 | 恩铂锘有限公司 | 水处理过滤器及其制造方法 |
Also Published As
Publication number | Publication date |
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BR9916295A (pt) | 2001-12-26 |
AU761743B2 (en) | 2003-06-12 |
DE69930965D1 (de) | 2006-05-24 |
EP1149198A1 (en) | 2001-10-31 |
BR9916295B1 (pt) | 2009-01-13 |
US6537614B1 (en) | 2003-03-25 |
MY130849A (en) | 2007-07-31 |
ATE323794T1 (de) | 2006-05-15 |
EP1149198B1 (en) | 2006-04-19 |
CN1211527C (zh) | 2005-07-20 |
AR021674A1 (es) | 2002-07-31 |
CN1348521A (zh) | 2002-05-08 |
DE69930965T2 (de) | 2006-08-31 |
US6673447B2 (en) | 2004-01-06 |
AU2367000A (en) | 2000-07-03 |
WO2000036207A1 (en) | 2000-06-22 |
US20020122939A1 (en) | 2002-09-05 |
PE20001525A1 (es) | 2001-01-04 |
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