TW202100581A - 具有氟化共聚物作為表面處理的多孔膜 - Google Patents
具有氟化共聚物作為表面處理的多孔膜 Download PDFInfo
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- TW202100581A TW202100581A TW109113346A TW109113346A TW202100581A TW 202100581 A TW202100581 A TW 202100581A TW 109113346 A TW109113346 A TW 109113346A TW 109113346 A TW109113346 A TW 109113346A TW 202100581 A TW202100581 A TW 202100581A
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Classifications
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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Abstract
本發明揭示多孔膜,其包括多孔載體及包含共聚物的塗層,該共聚物具有單體單元A及B以及視需要的單體單元C;其中A為四氟乙烯以外的鹵化乙烯基單體、鹵化烷基乙烯基醚或式Cn
H2n
的烯(其中n為1-6);B為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺酸基團或其鹽、一或多個磺醯氟基團、一或多個磺醯胺基團或一或多個磺酸酯基團,以及C為偏二氟乙烯。本發明也揭示製備此種多孔膜的方法以及藉由使用此等膜處理流體的方法。
Description
本發明關於包含多孔氟化聚合載體及包含第一共聚物的塗層的多孔膜、製備此種多孔膜的方法以及使用此種多孔膜處理或過濾流體的方法。
氟聚合物膜例如多孔PTFE膜之性質,包括其機械強度、耐化學性或化學惰性、非黏附性、極佳介電性質、高溫熱穩定性及低摩擦係數使其對各種應用極具吸引力。然而,對於某些應用,有益的是改質PTFE之表面而不影響其固有性質。已努力改質PTFE膜之表面及化學性質以改良該膜對於特定應用之適用性。舉例而言,努力包括表面塗佈、摻合、高能量表面改質(例如寬頻紫外照射或BBUV),其中膜曝露於波長250-450 nm之UV照射)、及電漿處理、自由基、及臭氧蝕刻、原子層沉積及經改質之類PTFE聚合物之合成。然而,當暴露於腐蝕性極強的流體諸如微電子遇到的如熱硫酸或氧化性流體,大部分這些努力並未導致令人滿意的膜性能。
前述內容顯示存在對耐腐蝕性或氧化性流體的多孔氟聚合物膜未獲滿足的需求。
本發明提供多孔膜,其包含多孔氟化聚合載體及包含第一共聚物的塗層,
第一共聚物包含聚合的單體單元A及B以及視需要的聚合單體單元C;
其中A為四氟乙烯以外的鹵化乙烯基單體、鹵化烷基乙烯基醚或式Cn
H2n
的烯(其中n為1-6);B為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺酸基團或其鹽、一或多個磺醯氟基團、一或多個磺醯胺基團或一或多個磺酸酯基團,以及C為偏二氟乙烯;
若存在C,則其存在量達A、B及C之和約30 mol%的範圍;
且第一共聚物具有每個磺酸基團或其鹽約1200至約3000的當量。
本發明另外提供製備包含多孔氟化聚合載體及包含第一共聚物的塗層的多孔膜的方法,
第一共聚物包含聚合的單體單元A及B以及視需要的聚合的單體單元 C;其中:A為四氟乙烯以外的鹵化乙烯基單體、鹵化烷基乙烯基醚、或式Cn
H2n
的烯(其中n為1-6);B為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺酸基團或其鹽、一或多個磺醯氟基團、一或多個磺醯胺基團,或一或多個磺酸酯基團,以及C為偏二氟乙烯;
若存在C,則其存在量達約30 mol%的範圍;
且第一共聚物具有每個磺酸基團約1200至約3000的當量;該方法包含:
提供多孔氟化聚合載體及用第一共聚物塗佈多孔氟化聚合載體;且當B為具有一或多個磺醯氟基團或磺酸酯基團的全氟(烷基乙烯基)醚時,用鹼水解一或多個磺醯氟基團或磺酸酯基團。
本發明另外提供藉由使用此等多孔膜處理或過濾流體的方法。
多孔膜的具體實例的優點在於,膜在150℃至200℃範圍的溫度下在熱濃硫酸中具有長期穩定性。
根據具體實例,本發明提供多孔膜,其包含多孔氟化聚合載體及包含第一共聚物的塗層,
第一共聚物包含聚合的單體A及B以及視需要的聚合的單體C;
其中A為四氟乙烯以外的鹵化乙烯基單體、鹵化烷基乙烯基醚,或式Cn
H2n
的烯(其中n為1-6);
B為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物,或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺酸基團或其鹽、一或多個磺醯氟基團、一或多個磺醯胺基團,或一或多個磺酸酯基團,以及C為偏二氟乙烯;
若存在C,則其存在量達A、B及C 之和約30 mol%的範圍;
且第一共聚物具有每個磺酸基團或其鹽約1200至約3000的當量。
本發明另外提供製備多孔膜的方法,多孔膜包含多孔氟化聚合載體及包含第一共聚物的塗層,
第一共聚物包含聚合的單體單元A及B以及視需要的聚合的單體單元C;其中:A為四氟乙烯以外的鹵化乙烯基單體、鹵化烷基乙烯基醚,或式Cn
H2n
的烯(其中n為1-6);B為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺酸基團或其鹽、一或多個磺醯氟基團、一或多個磺醯胺基團或一或多個磺酸酯基團,以及C為偏二氟乙烯;
若存在C,則其存在量達約30 mol%的範圍;
且第一共聚物具有每個磺酸基團約1200至約3000的當量;該方法包含:
提供多孔氟化聚合載體以及用第一共聚物塗佈多孔氟化聚合載體;且當B為具有一或多個磺醯氟基團或磺酸酯基團的全氟(烷基乙烯基)醚時,用鹼水解一或多個磺醯氟基團或磺酸酯基團。
根據具體實例,A為選自氯三氟乙烯、溴三氟乙烯、六氟丙烯、三氟乙烯、H2
C=CHCF3
、H2
C=CFCF3
、CHF=CHCF3
、H2
C=CFCl、H2
C=CFBr、CF2
=CFOCF3
、CF2
=CFOC3
F7
、CF2
=CFOC2
H4
C6
F13
、CH2
=CHOC2
H4
C6
F13
、CF2
=CFOC2
H4
Br、乙烯、丙烯以及其任組合。特別的具體實例中,A為氯三氟乙烯。
根據任何以上具體實例,B為選自CF2
=CFOCF2
CF(CF3
)OC2
F4
SO2
F、CF2
=CFOCF2
CF(CF3
)OC2
F4
SO3
H、CF2
=CFOC2
F4
SO2
F、CF2
=CFOC2
F4
SO3
H、CF2
=CFC2
F4
SO2
F、 CF2
=CFC2
F4
SO3
H、CF2
=CFOC4
F8
SO2
F、CF2
=CFOC4
F8
SO3
H及其任何組合。
特別具體實例中,B為CF2
=CFOCF2
CF(CF3
)OC2
F4
SO2
F。另一具體實例中,B為CF2
=CFOCF2
CF(CF3
)OC2
F4
SO3
H。
根據任何以上具體實例,若存在C,則其存在量可達A、B及C之和約30 mol%、達約20 mol%、達約10 mol%、約5至約30 mol%、約5至約20 mol%、約10至約30 mo%、約10至約20 mol%、約2至10 mol%、或約1至約5 mol%的範圍。根據本發明的具體實例,當C以本文所述低量存在時,多孔膜對熱鹼性氧化溶液更穩定,例如,當暴露於熱鹼性氧化溶液時,重量損失顯著減少。熱鹼性氧化溶液在本領域中是習知的;如參見US專利5,928,792的實施例13。
共聚物可為無規共聚物或嵌段共聚物。
根據任何以上具體實例,多孔膜包含任何適合的多孔氟聚合物載體,例如由PTFE(聚四氟乙烯)、PVDF(聚偏二氟乙烯)、PFA(全氟烷氧基乙烯基聚合物)、PMA(全氟烷氧基乙烯基聚合物)、PVF(聚乙烯基氟化物)、 PCTFE(聚氯三氟乙烯)、FEP(氟化乙烯-丙烯聚合物)、ETFE(聚乙烯四氟乙烯)、ECTFE(聚乙烯-氯三氟乙烯)、PFPE(全氟聚醚)、FKM(聚氯三氟乙烯-偏二氟乙烯)及全氟聚氧雜環丁烷製成的載體。多孔載體較佳為PTFE、FEP、PFA或PCTFE、且最佳為PTFE。多孔載體可具有任何適合的孔徑,例如約2 nm至約10微米。
共聚物可為任何適合的分子量,例如在具體實例中,數目或重量(Mn或Mw)平均分子量約10 kDa至約1000 kDa、20 kDa至約600 kDa、較佳約75 kDa至約500 kDa、且更佳約100 kDa至約500 kDa。
共聚物可藉任何適合的方法製備,例如,藉由自由基聚合反應。可使用任何適合的自由基起始劑。自由基起始劑的適合實例包括2,2′-偶氮雙(2-甲基丙腈) (AIBN)、4,4'-偶氮雙(4-氰基戊酸) (ACPA)、過氧化氫、三級丁基過氧化氫、過苯甲酸三級丁酯、過苯甲酸三級戊酯、過辛酸三級丁酯、過辛酸三級戊酯、過氧新戊酸三級丁酯、過氧化二三級丁基、過氧化二碳酸三級丁基環己酯、三級戊基過氧化氫、過氧化二苯甲醯、過硫酸銨、過硫酸鉀、過硫酸鈉、過氧化甲乙酮及全氟-3-乙基-2,4-二甲基-3-戊基持久自由基。
聚合反應可以在本體(bulk),亦即在無溶劑下進行,或較佳在溶劑中進行。進行聚合反應的適合溶劑實例包括水、碳酸二甲酯、乙腈、乙酸甲酯、芳香族烴例如苯、甲苯、及二甲苯、脂族烴例如正戊烷、己烷、及庚烷、脂環烴例如環己烷、以及鹵化溶劑例如二氯甲烷、二氯乙烷、二氯乙烯、四氯乙烷、氯苯、二氯苯、三氯苯、1,1,1,3,3-五氟丁烷、甲氧基九氟丁烷(Novec® 7100)、及FC75(全氟(丁基四氫呋喃))以及其混合物。
聚合反應可在任何適合的溫度下進行,例如-20至+100 ºC或更高、較佳10 ºC至80 ºC、特別為45 °C至80 °C。
聚合物可藉由適合的技術分離,例如用非溶劑沉澱或凝結(coagulation)。
「SPM」意指120 °C至180 °C溫度下的熱硫酸過氧化氫混合物(H2
SO4
(96%):H2
O2
(30%),體積比為70:30、75:25或80:20)。
根據本發明的具體實例,多孔膜具有直徑為1 nm與100 nm、100 nm與1000 nm之間的孔,或直徑為1 µm與10 µm之間的孔。
用異丙醇潤濕PTFE多孔載體片,然後用0.1 wt%-10 wt%磺酸或磺酸鹽形式的聚合物溶液塗佈載體,可製備多孔膜。塗佈時間範圍為1秒與1小時之間。浸漬載體後,在60o
C至160 °C乾燥。乾燥時間範圍為10分鐘與96小時之間。可替代的,用0.1 wt%-10 wt%磺醯氟形式的聚合物溶液塗佈PTFE多孔載體片,可製備多孔膜。塗佈時間範圍為1秒與1小時之間。浸漬載體後,在60o
C至160 °C乾燥。乾燥時間範圍為10分鐘與96小時之間。然後,經塗佈的多孔載體可浸漬於鹼性溶液,以將磺醯氟基團水解為磺酸鹽基團。磺酸鹽基團可視需要地隨後藉由浸漬於酸性溶液(例如5 % HCl)被轉化為磺酸基團。
可以藉由測量臨界潤濕表面張力(CWST)來量測表面改質方面的表面張力變化。方法視特定組成的一組溶液而定。每一溶液有特定表面張力。溶液的表面張力的範圍為25至92 dyne/cm,以小幅的非等效增量變化。為了量測膜的表面張力,將膜置於白光台頂端,將一滴具有特定表面張力的溶液滴於膜表面,記錄溶液滴滲透膜且變為亮白色而視為光穿過膜的時間。當溶液滴滲透膜的時間 ≤ 10秒,視為立即潤濕。若時間 > 10秒,溶液被視為部分潤濕膜。
根據本發明具體實例的多孔膜可用於各種應用,包括例如用於電子業的過濾流體(例如,微電子業中過濾光阻劑流體、熱硫酸及熱SPM)及用於處理含有離子材料的流體,例如作為離子交換膜。
根據本發明具體實例,多孔膜可具有多種構型,包括平面、平片、縐褶、管狀、螺旋及中空纖維。
根據本發明具體實例的多孔膜通常設置於殼體中,該殼體包含至少一個入口及至少一個出口,且在入口與出口之間界定至少一個流體流動路徑,其中至少一個本發明膜或包括至少一個本發明膜的過濾器橫越流體流動路徑,以提供過濾器裝置或過濾器模組。具體實例中,提供的過濾器裝置包含殼體,該殼體包含入口及第一出口,且在入口與第一出口之間界定第一流體流動路徑;以及至少一個本發明膜或包含至少一個本發明膜的過濾器,本發明膜或包含至少一個本發明膜的過濾器設置於橫越第一流體流動路徑的殼體中。
較佳地,對交錯流(crossflow)應用而言,至少一個本發明的多孔膜或包含至少一個本發明膜的過濾器設置於殼體中,該殼體包含至少一個入口及至少二個出口,且在入口與第一出口之間界定至少第一流體流動路徑,以及在入口與第二出口之間界定第二流體流動路徑,其中本發明膜或包含至少一個本發明膜的過濾器橫越第一流體流動路徑,以提供過濾器裝置或過濾器模組。例示性具體實例中,過濾器裝置包含交錯流過濾器模組,殼體包含入口、包含濃縮物出口的第一出口以及包含滲透物出口的第二出口,且在入口與第一出口之間界定第一流體流動路徑,以及在入口與第二出之間界定第二流體流動路徑,其中至少一個本發明膜或包含至少一個本發明膜的過濾器設置橫越第一流體流動路徑。
過濾器裝置或模組為可消毒。可以使用適合形狀且提供入口及一或多個出口的任何殼體。
殼體可以由任何合適的剛性不透水材料製成,包括與待處理的流體相容的任何不透水熱塑性材料。例如,殼體可以由金屬例如不鏽鋼製成,或者由聚合物例如透明或半透明的聚合物例如丙烯酸、聚丙烯、聚苯乙烯或聚碳酸酯樹脂製成。
本發明另外提供過濾或處理流體的方法,該方法包含使流體通過以上所述多孔膜。
以下實施例進一步說明本發明,而當然不應以任何方式被解讀為限制其範圍。
實施例1-16
此等實施例說明,根據本發明具體實例藉由自由基引發的共聚合反應製備共聚物的方法。
PFSVE與不同單體的自由基共聚反應是在配備破裂圓盤、Bourdon-壓力表及入口與出口閥的Hastelloy Parr高壓釜(50 mL、100 mL或300 mL)中進行。電子裝置控制及調節高壓釜的加熱及攪拌二者。封閉容器,用30巴壓力的氮氣吹掃三次,每次2分鐘,以及在10 x 10-3
毫巴的真空吹掃15分鐘。經由緊密地連接至入口閥的漏斗導入自由基起始劑、PFSVE及溶劑(若適用)。高壓釜在-90°C冷凍,藉二次稱重轉移氣體(例如,氯三氟乙烯、CTFE)。然後將高壓釜加熱至所需要的溫度。攪拌18小時後,將高壓釜冷卻至室溫。脫氣以移除未反應的單體後,打開高壓釜。將反應混合物置入80 °C的真空烘箱(10毫巴)中達48小時。以重量分析法測定反應的產率(獲得共聚物的質量/轉移至高壓釜的單體質量)。
表1及2列出進行的聚合反應中的試劑組成及獲得的產物,由元素分析或19
F NMR計算。
表1.共聚物1-12及1C-3C的聚合反應條件及組成。
表1(續)
表2.共聚物13-16及4C的聚合反應條件及組成
表2 (續)
實施例 | VDF, g | CTFE, g | PFSVE, g | 起始劑, g | 溶劑, g | 溫度,o C | P, 巴 |
1 | 3 | 20 | 21 | KPS 0.035 | H2 O | 70 | 16 |
2 | 50 | 150 | KPS 0.10 | H2 O 180 | 70 | 20 | |
3 | 2 | 12 | 25 | KPS 0.20 | H2 O 30 | 70 | 14 |
4 | 8 | 51 | 110 | KPS 0.89 | H2 O 180 | 70 | 20 |
5 | 8 | 52 | 111 | KPS 0.45 | H2 O 180 | 70 | 20 |
6 | 37 | 110 | KPS 1.51 | H2 O | 70 | 20 | |
7 | 37 | 110 | APS 0.51 | H2 O 180 | 80 | 14 | |
8 | 2.5 | 6.5 | 25 | KPS 0.020 | H2 O 30 | 70 | 14 |
9 | 2 | 10 | 25 | T121 0.40 | DMC 30 | 73 | 6 |
10 | 1.5 | 8 | 25 | KPS 0.020 | H2 O | 70 | 11 |
11 | 2 | 12 | 25 | KPS 0.026 | H2 O 30 | 70 | 12 |
12 | 2 | 40 | 30 | PPFR 2.10 | 無 | 83 | 18 |
1C | 37 | 110 | KPS 0.61 | H2 O 180 | 70 | 20 | |
2C | 33 | 104 | PPFR 2.4 | 無 | 83 | 13 | |
3C | 2 | 32 | 104 | PPFR 3.6 | 無 | 83 | 16 |
實施例 | 產率,% | S% | Cl % | VDF mol% | CTFE mol% | PFSVE mol% | Eq wt |
1 | 37 | 1.00 | 26.26 | 96 | 4.1 | 3173 | |
2 | 9 | 1.58 | 22.75 | 93 | 7.1 | 1960 | |
3 | 42 | 1.91 | 19.91 | 17 | 75 | 8 | 1675 |
4 | 29 | 1.58 | 19.01 | 29 | 65 | 6 | 2025 |
5 | 28 | 1.65 | 20.74 | 18 | 76 | 6.7 | 1939 |
6 | 18 | 2.23 | 19.28 | 89 | 11 | 1355 | |
7 | 21 | 2.00 | 20.74 | 90 | 9.7 | 1537 | |
8 | 31 | 2.45 | 14.67 | 36 | 54 | 10 | 1306 |
9 | 10 | 2.25 | 15.80 | 34 | 57 | 9 | 1422 |
10 | 30 | 2.54 | 14.76 | 34 | 56 | 11 | 1260 |
11 | 29 | 1.43 | 21.31 | 20 | 75 | 5.6 | 2238 |
12 | 67 | 2.07 | 18.88 | 19 | 72 | 8.7 | 1538 |
1C | 23 | 2.63 | 17.99 | 86 | 14 | 1165 | |
2C | 9 | 3.37 | 15.70 | 81 | 19 | 936 | |
3C | 56 | 4.07 | 12.10 | 11 | 65 | 24 | 786 |
實施例 | VDF, g | HFP, g | TrFE, g | PMVE, g | CTFE, g | PFSVE, g | 起始劑, g | 溶劑, g | 溫度,o C |
13 | 5 | 24 | 10 | KPS 0.034 | H2 O 30 | 70 | |||
14 | 5 | 15 | 23 | KPS 0.030 | H2 O 30 | 70 | |||
15 | 8 | 11 | KPS 0.017 | H2 O 30 | 70 | ||||
16 | 2 | 40 | 30 | P16S 1.80 | 無 | 60 | |||
4C | 5 | 8.7 | KPS 0.013 | H2 O 30 | 70 |
實施例 | P, 巴 | 產率, % | VDF mol% | HFP mol% | TrFE mol% | PMVE mol% | CTFE mol% | PFSVE mol% | Eq wt |
13 | 25 | 24 | 51 | 42 | 7 | 1908 | |||
14 | 24 | 12 | 67 | 26 | 7 | 1616 | |||
15 | 23 | 41 | 94 | 6.0 | 1731 | ||||
16 | 12 | 70 | 8 | 84 | 8 | 1733 | |||
4C | 25 | 40 | 87 | 13 | 874 |
以上所用縮寫如下所述:
VDF:偏二氟乙烯
CTFE:氯三氟乙烯
HFP:六氟丙烯
TrFE:三氟乙烯
PMVE:全氟甲基乙烯基醚
PFSVE:全氟(4-甲基-3,6-二氧雜-7-辛烯)磺醯氟
PPFR:全氟-3-乙基-2,4-二甲基-3-戊基持久自由基
APS:過硫酸銨
KPS:過硫酸鉀
DMC:碳酸二甲酯
T121:過氧化-2-乙基己酸三級戊酯
P16S:過氧化二碳酸三級丁基環己酯。
實施例17-30
此等實施例說明當暴露於熱濃硫酸時根據本發明具體實例表面處理的膜的穩定性。
將Pall公司製造的孔徑 <10 nm的PTFE膜片浸入實施例1-10、12-14、1C,或2C的聚合物溶液中60秒,然後從溶液中取出。樣品在60 °C乾燥15分鐘。然後將樣品浸入氫氧化鉀於50/50 IPA/水中的0.1M溶液中1小時。然後將樣品浸入60/40的IPA/水中15分鐘,然後浸漬於水中1小時三次。樣品在60 °C乾燥20分鐘。藉滴加已知表面張力的溶液及記錄完全潤濕樣品的最高表面張力以量測CWST。將新鮮樣品浸入異丙醇5分鐘,然後浸入水中10分鐘,再浸入水中1小時。將樣品浸入水中隔夜。將樣品浸入150 °C的濃硫酸中2小時。從酸中取出樣品,浸入水中數次,每次至少1小時。樣品在60 °C乾燥20分鐘。藉滴加已知表面張力的溶液及記錄完全潤濕樣品的最高表面張力以量測CWST。
以下表3列示的結果顯示經塗佈膜具有高於未經處理膜的CWST值,且經塗佈膜在熱濃硫酸中為穩定的。
表3.暴露於熱濃硫酸的表面處理的穩定性
實施例32-40
實施例 | 聚合物實施例 | 起始CWST dyne/cm | 經H2 SO4 處理的CWST dyne/cm |
17 | 1 | 32 | N/A |
18 | 2 | 33 | 33 |
19 | 3 | 33 | 34 |
20 | 4 | 32 | N/A |
21 | 5 | 33 | 33 |
22 | 6 | 33 | 33 |
23 | 7 | 34 | 36 |
24 | 8 | 34 | 34 |
25 | 9 | 39 | 39 |
26 | 10 | 36 | 36 |
27 | 12 | 34 | 36 |
28 | 13 | 32 | 32 |
29 | 14 | 33 | 36 |
30 | 16 | 33 | 34 |
31 | 4C | 36 | 32 |
無 | <31 | <31 |
此等實施例說明另一種製備本發明膜的方法以及在熱濃硫酸中表面處理的穩定性。
將四甲基氫氧化銨於1:1的水:IPA中的12%溶液加入實施例2、6、7及2C的聚合物於6:1 Novec® 72DE:Novec® 7100中的1%溶液。加入10當量的鹼,並在偶而搖動下攪拌溶液約8小時。加入水(〜0.5-1體積),並經由過濾收集產物,用水洗滌並乾燥。
將四甲基氫氧化銨於1:1的水:IPA中的12%溶液加入實施例1、3-5及8的聚合物於6:1 Novec® 72DE:Novec® 7100中的1%溶液,加入1.9當量的鹼。並在偶而搖動下攪拌溶液約8小時。在旋轉蒸發器中移除約2/3溶劑。用約3倍體積的水萃取樣品,藉由在旋轉蒸發器移除溶劑以回收所得產物。
將Pall公司製造的孔徑 <10 nm的PTFE膜片浸入經水解聚合物溶液中60秒,然後從溶液中取出。樣品在60 °C乾燥15分鐘,經稱重。藉滴加已知表面張力的溶液及記錄完全潤濕樣品的最高表面張力以量測CWST。將新鮮樣品浸入異丙醇5分鐘,然後浸入水中10分鐘,再浸入水中1小時。將樣品浸入水中隔夜。將樣品浸入150 °C的濃硫酸中2小時。從酸中取出樣品,浸入水中數次,每次至少1小時。樣品在60 °C乾燥20分鐘。藉滴加已知表面張力的溶液及記錄完全潤濕樣品的最高表面張力以量測CWST。表4列示的結果顯示經塗佈膜具有高於未經處理膜的CWST值,且經塗佈膜在熱濃硫酸中為穩定的。
表 4. 經表面處理膜的CWST值
C,例如本文的2C,指的是比較實施例。
實施例41-47
實施例 | 前驅物聚合物實施例 | 起始CWST dyne/cm | 經H2 SO4 處理的CWST dyne/cm |
32 | 1 | 33 | 33 |
33 | 8 | 33 | 31 |
34 | 2 | 36 | 33 |
35 | 3 | 36 | 39 |
36 | 4 | 34 | 37 |
37 | 5 | 33 | 34 |
38 | 1C | 36 | 39 |
39 | 6 | 33 | 33 |
40 | 7 | 34 | 36 |
無 | <31 | <31 |
此等實施例說明,當共聚物的分子量較高時,PTFE膜對共聚物的吸收較高。
將PTFE微濾膜片浸入2重量/體積%的實施例3-7或2C的聚合物溶液中60秒,從溶液中取出。樣品在60 °C乾燥15分鐘。然後將樣品浸入氫氧化鉀於50/50 IPA/水中的0.1M溶液中1小時。然後將樣品浸入60/40的IPA/水中15分鐘,然後浸漬於水中1小時三次。樣品在60 °C乾燥20分鐘。然後將樣品置入75 °C的IPA浴中隔夜。樣品在60°C乾燥20分鐘並稱重。結果列於表5中,顯示具有較高分子量的樣品的聚合物吸收較高。
表5.經表面處理的膜的CWST值
C指的是比較實施例。
實施例48-57
實施例 | 聚合物實施例 | Mn, kDa | 重量增加,% |
41 | 4 | 38 | 8.1 |
42 | 3 | 35 | 6.6 |
43 | 3 | 35 | 5.1 |
44 | 5 | 28 | 5.9 |
45 | 1C | 19 | 3.6 |
46 | 6 | 15 | 3.6 |
47 | 7 | 15 | 2.9 |
此等實施例說明,當塗佈本發明具體實例的共聚物的PTFE膜在熱異丙醇中洗滌時,具有更高當量的共聚物以更大量被保留。
將PTFE微濾膜片浸入2重量/體積%的實施例1-5、8、2C-4C的聚合物或Nafion® D521的溶液中60秒,從溶液中取出。樣品在60 °C乾燥15分鐘。然後將樣品浸入氫氧化鉀於50/50 IPA/水中的0.1M溶液中1小時。然後將樣品浸入60/40的IPA/水中15分鐘,然後浸漬於水中1小時三次。將樣品短暫浸入70/30 IPA/H2O,用水沖洗,然後浸入5% HCl達2小時。用水充分沖洗後,樣品在60 °C乾燥20分鐘並稱重。塗佈Nafion®的樣品未經HCl處理。然後將樣品置入75 °C的IPA浴中隔夜。樣品在60°C乾燥20分鐘並稱重。顯示的大部分數據為二或更多實驗的平均值。表6列出的結果顯示,當量為1300或更高的共聚物的保留率(例如保留分率)高於當量較低的樣品的保留率。
表6.沖洗後載體的保留率
C指的是比較實施例
實施例58-71
實施例 | 聚合物實施例 | 當量 | 保留分率 |
48 | 1 | 3130 | 0.97 |
49 | 4 | 2040 | 0.98 |
50 | 2 | 1960 | 1.01 |
51 | 5 | 1920 | 0.92 |
52 | 3 | 1670 | 1.02 |
53 | 8 | 1300 | 0.98 |
54 | 1C | 1220 | 0.77 |
55 | Nafion D521 | 1090 | 0.86 |
56 | 2C | 940 | 0.68 |
57 | 3C | 790 | 0.82 |
此等實施例說明,當塗佈本發明具體實例的共聚物的PTFE膜在鹼性氧化溶液中沖洗,具有較低偏二氟乙烯(VDF)含量的共聚物被大量保留。
將Pall公司製造的孔徑 <10 nm的PTFE膜片浸入實施例2、3、5-13、1C、3C或4C聚合物的溶液中60秒,然後從溶液中取出。樣品在60 °C乾燥15分鐘。然後將樣品浸入氫氧化鉀於50/50 IPA/水中的0.1M溶液中1小時。然後將樣品浸入60/40的IPA/水中15分鐘,然後浸漬於水中1小時三次。樣品在60°C乾燥20分鐘並稱重。將新鮮樣品浸入異丙醇5分鐘,然後浸入水中10分鐘,再浸入水中1小時。將樣品浸入水中隔夜。將樣品浸入熱鹼性氧化溶液中。從溶液取出樣品,然後將樣品浸入水中數次,至少每次小時。樣品在60°C乾燥20分鐘並再稱重。表7列出的結果顯示,具有較少VDF含量的共聚物相較於具有較大VDF含量的樣品更穩定且重量損失較少。
表7. VDF含量對損失率的效應
C指是比較實施例。
實施例 | 聚合物實施例 | VDF mol% | 損失率 |
58 | 4C | 87 | 0.69 |
59 | 12 | 53 | 0.61 |
60 | 13 | 51 | 0.80 |
61 | 8 | 36 | 0.59 |
62 | 9 | 34 | 0.90 |
63 | 10 | 34 | 0.35 |
64 | 11 | 20 | 0.55 |
65 | 3 | 17 | 0.41 |
66 | 5 | 18 | 0.47 |
67 | 3C | 11 | 0.42 |
68 | 2 | 0 | 0.03 |
69 | 6 | 0 | 0.00 |
70 | 7 | 0 | 0.19 |
71 | 2C | 0 | 0.05 |
本文中所引用之所有參考文獻,包括公開案、專利申請案及專利均以引用之方式併入本文中,其引用程度就如同個別及特定地指示各參考文獻以引用之方式併入且全文闡述於本文中一般。
除非本文中另外指示或與上下文明顯矛盾,否則在描述本發明之上下文中(尤其在以下申請專利範圍之上下文中),應將術語「一(a/an)」及「該(the)」及「至少一個(至少一個)」及類似涉及對象之使用解釋為涵蓋單數與複數兩者。除非本文另外指示或與上下文明顯矛盾,否則使用術語「至少一個」後接一或多個項目之清單(例如「A及B中之至少一者」)應解釋為意謂選自所列舉項目之一個項目(A或B)或所列舉項目之兩個或超過兩個之任何組合(A及B)。除非另外指出,否則術語「包含(comprising)」、「具有(having)」、「包括(including)」及「含有(containing)」應解釋為開放式術語(亦即,意謂「包括但不限於(including, but not limited to,)」)。除非本文另外指示,否則本文中數值範圍之敍述僅意欲充當個別提及屬於該範圍內之各獨立值之速記方法,且各獨立值併入本說明書中,如同在本文中個別敍述一般。除非本文另外指示或另外與上下文明顯矛盾,否則本文所述之所有方法可以任何合適順序進行。除非另外主張,否則使用本文所提供之任何及所有實例或例示性語言(例如「諸如」)僅意欲更好地闡明本發明而非對本發明之範疇造成限制。本說明書中之語言不應理解為指示實施本發明所必需之任何未主張要素。
本文描述本發明之較佳具體實例,其包括本發明者已知用於進行本發明之最佳模式。在閱讀前文描述之後,彼等較佳具體實例之變化對於一般技術者而言可變得顯而易見。本發明人期望熟習此項技術者適當時採用此類變化,且本發明人意欲以不同於本文中特定描述之其他方式來實施本發明。因此,在適用法律允許下,本發明包括隨附於本文之申請專利範圍中所敍述之主題的所有修改及同等物。此外,除非本文另外指示或另外與上下文明顯矛盾,否則本發明涵蓋上述要素呈其所有可能變化形式之任何組合。
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Claims (10)
- 一種多孔膜,其包含多孔氟化聚合載體及包含第一共聚物的塗層, 該第一共聚物包含聚合的單體單元A及B以及視需要的聚合的單體單元C;其中: A為四氟乙烯以外的鹵化乙烯基單體、鹵化烷基乙烯基醚或式Cn H2n 的烯(其中n為1-6); B為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺酸基團或其鹽、一或多個磺醯氟基團、一或多個磺醯胺基團或一或多個磺酸酯基團;以及 C為偏二氟乙烯;且若存在C,則其存在量達A、B及C之和約30 mol%的範圍;且 該第一共聚物具有每個磺酸基團或其鹽、磺醯氟基團、磺醯胺基團或磺酸酯基團約1200至約3000的當量。
- 如請求項1的多孔膜,其中A為選自氯三氟乙烯、溴三氟乙烯、六氟丙烯、三氟乙烯、H2 C=CHCF3 、H2 C=CFCF3 、CHF=CHCF3 、H2 C=CFCl、H2 C=CFBr、CF2 =CFOCF3 、CF2 =CFOC3 F7 、CF2 =CFOC2 H4 C6 F13 、CH2 =CHOC2 H4 C6 F13 、CF2 =CFOC2 H4 Br、乙烯、丙烯及其任何組合。
- 如請求項1或2的多孔膜,其中B為選自CF2 =CFOCF2 CF(CF3 )OC2 F4 SO2 F、CF2 =CFOCF2 CF(CF3 )OC2 F4 SO3 H、CF2 =CFOC2 F4 SO2 F、CF2 =CFOC2 F4 SO3 H、CF2 =CFC2 F4 SO2 F、CF2 =CFC2 F4 SO3 H、CF2 =CFOC4 F8 SO2 F、CF2 =CFOC4 F8 SO3 H及其任何組合。
- 如請求項1的多孔膜,其中該第一共聚物從包含聚合的單體單元A及B’以及視需要的聚合的單體單元C的第二共聚物製備, 其中B’為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物,或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺醯氟基團或磺酸酯基團, 以及用鹼性溶液水解該第二共聚物的一或多個磺醯氟基團或磺酸酯基團。
- 如請求項1或2的多孔膜,其中該氟化聚合載體為選自聚四氟乙烯、氟化乙烯-丙烯共聚物(FEP)、全氟烷氧基乙烯基聚合物(PFA)、聚氯三氟乙烯(PCTFE)及其任何組合。
- 如請求項1或2的多孔膜,其中A在該第一共聚物的存在量為約50至約95 mol%的範圍,且B在該第一共聚物的存在量為約5至約20 mol%的範圍。
- 一種製備包含多孔氟化聚合載體及包含第一共聚物的塗層的多孔膜的方法, 該第一共聚物包含聚合的單體單元A及B以及視需要的聚合的單體單元 C;其中: A為四氟乙烯以外的鹵化乙烯基單體、鹵化烷基乙烯基醚、或式Cn H2n 的烯(其中n為1-6); B為全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每一化合物具有一或多個磺酸基團或其鹽、一或多個磺醯氟基團、一或多個磺醯胺基團,或一或多個磺酸酯基團,以及C為偏二氟乙烯; 若存在C,則其存在量達約30 mol%的範圍; 且 該第一共聚物具有每個磺酸基團約1200至約3000的當量;該方法包含: 提供多孔氟化聚合載體及 用該第一共聚物塗佈該多孔氟化聚合載體;且當B為具有一或多個磺醯氟基團的全氟(烷基乙烯基)醚時,用鹼水解一或多個磺醯氟基團。
- 如請求項7的方法,其中A在該第一共聚物的存在量為約50至約95 mol%的範圍,且B在該第一共聚物的存在量為約5至約20 mol%的範圍。
- 一種過濾腐蝕性流體的方法,其包含使該腐蝕性流體通過如請求項1或2的多孔膜。
- 一種從流體移除離子材料的方法,其包含使該流體通過如請求項1或2的多孔膜。
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US4754009A (en) * | 1981-08-20 | 1988-06-28 | E. I. Du Pont De Nemours And Company | Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole |
JPS5892415A (ja) | 1981-11-30 | 1983-06-01 | Asahi Glass Co Ltd | 液体混合物の分離方法 |
US5976380A (en) | 1997-05-01 | 1999-11-02 | Millipore Corporation | Article of manufacture including a surface modified membrane and process |
US6354443B1 (en) | 1997-05-01 | 2002-03-12 | Millipore Corporation | Surface modified porous membrane and process |
US5928792A (en) | 1997-05-01 | 1999-07-27 | Millipore Corporation | Process for making surface modified porous membrane with perfluorocarbon copolymer |
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