TW469168B - Charged mosaic membrane, its production, method for using the membrane, and device provided with the membrane - Google Patents
Charged mosaic membrane, its production, method for using the membrane, and device provided with the membrane Download PDFInfo
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- TW469168B TW469168B TW088102689A TW88102689A TW469168B TW 469168 B TW469168 B TW 469168B TW 088102689 A TW088102689 A TW 088102689A TW 88102689 A TW88102689 A TW 88102689A TW 469168 B TW469168 B TW 469168B
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- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
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- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
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- 125000004424 polypyridyl Polymers 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 125000004076 pyridyl group Chemical group 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/243—Dialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
Description
6
7 7 A B 明 '-a 明 發 域 領術技 的 Μ 所 明發 法 方 造。 製置 之裝 膜之 鑲膜 嵌鑲 荷嵌 電荷 、t-膜有 鑲附 嵌及 荷法 電方 0W ΓΠΤ 有使 係^/ 明膜 發鑲本嵌 荷 術 技 知 習 荷質的 域電解緩 晶的電遲 物通之常 合貫*非 聚並子度 性列分速 子排低析 離互對透 陰交可有 與呈,或 域上膜, 晶質薄析 物實的忠 合向知能 聚方公未 性度此質 十厚,解 離之的電 陽膜知非 * 對公對 來η)係而 向aiM,。 g鑲析能 (d嵌ii:功 (4先間婧汴而之_"·Λ:Ψ項洱4.'1,:-本-¾ 經济部中央標來局B工消费合作杜印製 至於上述電荷嵌鑲膜之製造方法,有使用嵌段共聚物 之方法、與以聚合物微粒子之形式使用陽離子性及陰離子 性之至少一成分的方法正被提出,相對於使用嵌段共聚物 之方法,該製造方法非常困難的方法,而以聚合物微粒子 之形式使用陽離子性及陰離子性之至少一成分的方法,則 有其製造上非常容易的優點。 發明欲解決的誤顳 於採用上述聚合物微粒子之方法,使用微小球體作為 聚合物微粒子以製造電荷嵌鑲膜時,則由微小球體所具的 積體性及等方性可比較容易的製造出電荷嵌鑲膜。然而, 在此方法由於膜之大部分的構成成分係離子性聚合物,所 形成的膜在製膜乾燥時會收縮,又容易形成脆弱的薄膜, 在大面積之膜的製造上即有問題存在。 本紙張尺度適用中®阎^CNS ) Λ4^ΤΙΪ〇χ Η _______137 _______137 46 9168 經濟部中央標準局貝工消费合作权印« A7 五、發明説明() 至於改良上述問題之方法,在日本特開平1〇_87855 號公報内揭示有使用可撓性聚合物成分作為電荷嵌鑲膜之 ί的ί法:由此方法’大面積之電荷嵌鑲 ,係變成谷易製造,使用時之耐久性,處理操作性可予 南,惟製膜上需要長期間,陽離子性聚合物成分及陰離子 性聚合物成分(以下兩成分稱作「電荷性聚合物成分」)與 基夤成77之合及分散安定性上稍有問題,欲再製造出呈 有均勻的膜厚之薄膜係有困難的。 因此,本發明之目的,係提供採用可容易製造,且具 有優越的可選擇透過性之電荷性聚合物粒子的電荷嵌鑲、 膜,及製膜時間短,電荷性聚合物成分與基質成分之混八 ^分散安定性優越,再者膜厚均勻且薄膜之電荷絲膜; 製造方法。 解決課題所採的丰段 為達成上述目的’本發明係於其中一個態樣,由陽離 ^性聚合物成分、陰離子性聚合物成分及基質成分而成, 則述陽離子性聚合物成分及前述陰離子性聚合物成分係任 了者均今已交聯的粒狀聚合物粒子,基質成分係由聚砸 ^、聚芳香酯系、聚醯胺系、聚醯亞胺系、聚醯胺醯亞胺 系、聚胺酯系、氟碳系及矽氧系樹脂選出的至少一種聚合 ,為特徵之電荷嵌鑲膜,與其他的態樣,在製造上述的電 荷嵌鑲膜之際,採用使前述陽離子性聚合物及前述陰離子 ,聚合物成分分散於基質成分之有機溶劑溶液内而成的組 成物予以製膜為特徵的電何嵌鑲膜之製造方法,再於另外 本紙张尺度適用巾國财㈣-{ CNS ) ( 210X297.^ (ΐ?先閱.讀艿而之ίί,Λ穸項再填,:>';本页)
469168 Λ7 B7 五、發明説明( 經濟部中央標準局只工消φ;合作权印^ 的態樣,該電荷嵌鑲膜之使用方法,及再於另一能揭 有該傲鑲膜之裝置。 ' 依本發明之電荷嵌鎮膜’係对藥品性、财溶劑性、 水性等物性優越’化學上亦穩定,亦具有對加水分解或氧 化分解之耐久性,具有優越的可選擇透過性。 又,依本發明之製造方法,形成晶域之兩電荷性聚合 f成分不論何者均以已交聯的粒狀聚合物之形式被使用 $,至於基,形成聚合物成分,可採用聚砸系、聚芳香酯 55醯胺系、聚醯亞胺系、聚醯胺醯亞胺系、聚胺酯系、 氟碳系及石夕氧系樹脂選出的至少一種聚合物。於製膜之 ,藉由使由使作為電荷性聚合物成分之已交聯的粒狀聚 t物分散於基質成分之有機溶劑溶液内而成的組成物,可 1造出製膜時間短、電荷性聚合物成分及基質成分之混 δ,分散安定性上優越,膜厚均勻且薄膜之電荷嵌鑲膜。 因此’本發明之電荷嵌鑲臈,係可使用於電解質之可 k擇透過,例如電解質之移動、分離、濃縮或吸附等方面。 1·^簡單說明 ^1圖為表示使用本發明之電荷嵌鑲膜的裝置之一例 的透析裝置之縱截面。 圖 第2圖為表示實施例2之電荷嵌鑲膜之透析分離性之 .(計先Μ,-.ΐ ""'''-^^^""J^n Γ 、-°‘. 線 卜紙張尺度朗中咖家枕率 (CNS ) Λ视怙( Λ 6 9 I 6 8 五、發明説明() 發明之竇施形態 本發明之電荷嵌鑲膜,係形成膜之晶域的陽離子性及 陰離子性聚合物成分(以下稱作電荷性聚合物成分)之任一 者均已交聯的粒狀聚合物’基質成分為由聚5風系、聚芳香 酉旨系、聚醯亞胺系、聚酿胺醯亞胺系、聚胺醋系、葡域糸 及矽氧系樹脂選出的至少一種聚合物所構成為特徵,’'
.3T 又’於此電荷嵌鑲膜之製造方法,係以使用令上述兩 電何性聚合物分散於由聚5風糸、聚芳香酿系、聚酿胺系、 聚醯亞胺系、聚酸胺醯亞胺系、聚胺酯、I碳系及石夕氧系 樹脂選出的至少一種聚合物作為基質成分之有機溶劑溶液 内而成的組成物予以製膜為特徵。且,於本發明,構成電 荷敗鑲膜之電荷性聚合物成分之較佳的平均粒子徑為〇. Q1 〜20/zm之範圍,宜為0· 02〜10#m之範圍。 % 本發明使用的電荷性聚合物成分,係可舉出具有第一 級〜第三級之胺基,第四級銨基,吡啶基等的陽'離子性 基及該等的鹽之基的聚合物作為陽離子性聚合物成分,可 舉出具有磺酸基、羧酸基、硫酸酯基、磷酸酯基等陰離子 性基及該等的鹽之基的聚合物作為陰離子性聚合物成分。 鯉濟部中央標羋局只T.消费合作a印取 於以離子性基為該鹽之基之際,對陽離子性基,可使 用例如鹽酸、硫酸、填酸、有機酸等酸類,對陰離子性基, 可使用驗金屬、氨、胺、醇胺等鹼類。 又,電荷性聚合物成分,係於製備非電荷性的粒狀聚 合物後’例如藉由胺化、第四級銨化、加水分解、砸化' 硫酸酯化等的化學修飾處理可予各別製備,惟利用化學處 本紙張尺度適用中國國家if:準(CNS ) ( ) S 9 1 6 8 —— _ 五、發明説明( A7 B7 經漪部中央標窣局B工消费合作社印裝 ϊ方物係經予陽離子性或陰離子性化的處 理方法時,亦可使用例示以外的化學修飾處理法。 至於為製備電荷性聚合物成分而使用的代表性單體, 丙、烯酸、苯乙稀確酸、(甲基)丙烯酿氧 ί f^^、、(甲基)丙稀酸石黃丙醋、(甲基)丙烯酸2-石黃乙 S曰、2-(甲基)丙烯醯基胺基_2-甲基-丨-丙烷磺酸、2_(曱 基)丙烯醯基胺基-2-丙婦項酸、乙烯基减酸尊及守茸豳 等的陰離子性單體;4-乙稀基办定、 四級化合物;(曱基)丙烯酸二甲基胺基乙酯、(甲基)丙稀 酸二乙基胺基乙酯、4-乙烯基苄基二甲基胺' 2—羥基_3_(〒 基)丙烯氧基丙基二曱基胺等及該等的第四級化合物或,玄 等之鹽等的陽離子性單體。 / 11 又,至於藉由化學改質處理,製備經予轉換成電荷性 聚合物成分之非電荷性聚合物而使用的代表性單體,可列 舉有:笨乙烯、α-甲基苯乙烯、氣甲基苯乙烯、羥基曱 基本乙稀專之本乙稀系化合物,(曱基)丙稀酸曱醋、(甲 基)丙烯酸乙酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸聚 乙一醇、(甲基)丙稀酸每两S旨、(甲基)丙稀酸聚丙二醇等 的(甲基)丙烯酸醋化合物;(曱基)丙烯醯胺、Ν-曱基(曱 基)丙稀酿胺、Ν-經甲基(曱基)丙稀醯胺、丁氧基曱基(甲 基)丙烯醯胺、Ν,Ν-二曱基丙烯醯胺等之(曱基)丙稀g【胺 化合物;丙稀腈;醋酸乙稀酯等可進行化學改質處理的單 體。 ' (d"間请.汴而之注念赘項^"{'^本开 " 本紙张又度適用中國囤家桴準(CNS )以况怙(210Χ2Μ々^ 五 1 68 、發明説明( A7 137 經濟部中央標準局只工消资合作社印製 上琉學改質處理的非電荷性聚合物,係利用聚人 丙稀可列舉有(甲基) 予制ίϊίίί荷性單體或可進行化學改魏理的單體而 田士 ί何性及非電荷性的粒狀聚合物,在製膜之F由 ίΐ】ί;ί劑,故有交聯的必要。粒狀聚合 際,可糟由使交聯性單體其聚合而予進行。 寻 (甲笑體’可舉出有:二乙稀基笨、亞甲基雙 Άί:ίί:巧性單體、三(甲基)丙烯酸三羥甲基丙 ί。曰單體、或四官能性(〒基)丙稀醆_ ί ί;之錳使用°,1〜3°重量分,更宜為使用。μ 分之ίϋ/ίΐ單體及交聯性單體,製備粒狀聚合物成 :it⑵可舉出有水系或非水系之自由基聚 浮聚合、'Γ舉出有乳液聚合、無皂聚合、懸 形態並非特聚合等聚合方法’惟聚合之 發劑習用公知的自由基聚合所使用的引 種句T使用,可列舉有:2, 2,-偶氮異丁腈、 本紙乐尺度璉扣中國國家棉4Μ CNS) (对先吼掮背而之"-"f項再填〈巧本页) ,π 乂2们公炸 469168 Λ7 B7 五 、發明説明( 偶氮雙(甲基異丁酯)、2, 2’-偶氮雙(2, 4-2曱基戊 月η)、1,Γ-偶氮雙(環已烷+碳船、2, 2’_偶i雙(米 对先阽讀背而之/'ΐ.&ΐί-項再试,%本頁) 2 2, 2’ 一偶氮雙(2—脒基丙烷)二醋酸酯、 氮雙i,Ν —二亞甲基異丁耽)二氣化氫鹽等偶氮系 化合物;過軋化氫異丙苯、過氧化二異丙苯、過氧化苯甲 ί二過氧化月桂基等之有機過氧化物;過硫酸銨、過硫酸 鉀等之過硫酸鹽等的聚合引發劑。 π 本?明’構成電荷嵌鑲膜之基質成分,係由聚®系、 聚芳香酯系、聚醯胺系、聚醯亞胺系、聚醯胺醯亞胺系、 丁 、=» 聚,酯系、氟碳系及矽氧系樹脂選出的至少一種聚合物。 十等樹脂在形成電荷嵌鑲膜之際,具有藉由加熱乾燥等可 形成被膜之性質’所形成的樹脂基質在耐藥品性、耐溶劑 性、对水性等物理方面係優越的,在化學上亦係安定的, 對加水十解或氧化分解之耐久性優越,上述之經予選擇的 聚合物係最適合本發明之目的之基質成分。 經满部中央橾嗥局Λ工消f合作杜印製 聚石風系樹脂,係分子内具有磁基«〇2_基)之縮聚物, 具體而言,可舉計有:下述式(1)之聚5風樹脂、下述式(2) 之聚趟®樹脂、下述式(3)之聚伸苯基碰樹脂等的聚獵系 樹脂及該等之石風化物等。 聚芳香酿系樹脂,係分子内具有酯基之縮聚物,具體 而言,可舉出有下述式(4)〜(6)等。 聚酿胺系樹脂,係分子内具有醯胺基之縮聚物,具體 而言,可舉出有下述式(7)等。 46 9 ί 6 8 Α7 137 五、發明説明( 亞胺② 直亞’係分子内具有醯亞_之縮聚物, 出有τ述式⑽及⑴)等。又,亦可舉出 而言聚?i.f?述酿基之聚合物’具體 酷尿素樹脂。式(12)及⑽等。又,亦可舉出》 言’可舉述及怒J而成的聚合物’具體而 ㈣化物。具體以义^式㈤出氣破樹 聚合 之 計1閱"背而之注泠-^^斤填巧本苋 ^, 、ys 線 經漪部中央標泽局員工消坨合作社印裝 本紙張尺度適汛中國國家^^fTcNs' )八4規格(21ϋΧ2Μ.ϋ_ 五、發明説明() 經"部中央標苹局Μ H_消费合作社印製
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ο CHz)厂〇1—N (10) (U) 02) (13) 0 s 〆 N f V -CHi-CIV -(14) — -CHs-CH- η L F J (15) 計先吼M背而之注疗贪項^"r':i本打) 經濟部中决標準局只工消費合作杜印裂
-<CF*CF,)h—<Cr.CF^- icF^CFCF, icF*CF*S〇sH ^ CH,、 -ii-O- (17) (1G) CHa 11 本紙張尺度適州屮阐阄家1‘?:準((:NS ) AWH ( 2mx2W公綷 4 6 9 i 6 8 A7 經濟部中央標準局Β Τ.消贽合忭社印聚 五、發明説明( 上述式中之m及η係各自的樹脂之分子量成為約looo 〜50萬之值。 $上的各樹脂,可單獨亦可混合使用,再者為對所得 的電荷嵌鎮膜賦與可撓性,於該膜之形成用組成物内亦可 添加丁二烯系或乙烯一醋酸乙烯酯系樹脂等。 本發明之電荷嵌鑲膜之製造方法,係以電荷性聚合物 成分之任一者均已交聯的粒狀聚合物,使用以此粒狀聚合 ,为散於由作為基質成分之聚石風系、聚芳香酯系、聚驢胺 系、聚醯亞胺系、聚醯胺醯亞胺系、聚胺酯系、氟碳系及 石夕氧系樹脂選出的至少一種聚合物之有機溶劑溶液内而成 的組成物狀而製膜為特徵。 、3 ^先丨使電荷性聚合物成分及基質成分之有機溶劑溶 刀散,以製備塗布液。該時際,電荷性聚合物成 气散於有機溶劑之狀態而予使用為宜。使電荷性聚 i物、分散於基質成分之有機溶劑溶液内的方 ΐ仆ΐ未限制’惟例如利用超音波處理、溶解器、 均化态、攪拌器可予實施。 ^ 八及荷嵌鑲膜之晶域的電荷性聚合物成 全部齡之合計,基質成分 。 叙議為宜,以10〜仙重量%之範圍為 溶劑至ΐ忠機溶劑,為溶解基質成分之有機 ^川舉6十有卜甲基I卩比咯_、N-乙基-2♦各院
私紙張尺度適用中國围家榡準(C、NS 12 . 訂- 線, (Μ先吼分乃而之>x.A..'it項洱^!(η本订) A7 469168 五、發明説明() 酮、N-乙烯基-2- □比嘻烧酮、N,N-二曱基甲醯胺、N,N-一乙基甲醯胺' N,N-二甲基乙醢胺、N, N-二乙基乙醯胺等 含氮系溶劑;二啤烷、四氫呋喃等醚系溶劑;曱乙基酮、 甲基,丁基酮等鲷系溶劑;二曱基亞楓、丙二醇單甲醚、 異丙醇、丙二醇單曱醚乙酯、二曱笨、二氣乙烯、氯仿、 環已烷等。 於該種有機溶劑之中,混合電荷性聚合物成分及基質 成分之際、,電荷性聚合物成分以已分散於有機溶劑之狀態 予以使用為宜’以電荷性聚合物成分之分散性及分散安定 性優越的含氮系溶劑較佳。又,限於不使分散系不安定的 情形,亦可合併使用其他的有機溶劑或水系。 訂 其次,於基材上不採用塗布裝置保持原狀的,或採用 公知的塗布方法塗布或流展上述而得的塗布液,或於支持 體上塗布、浸潰或流展上述而得的塗布液,其後利用乾燥 已塗布的塗布液,去除溶劑而製得電荷嵌鑲膜,乾燥後所 形成的膜,視需要時施以加熱熔著處理、加熱加壓模壓處 理、第四級化處理等的處理,而得本發明之電荷嵌鑲膜。 紐濟部中央榡卑局只工消贽合作社印5Ϊ 子於本發明所使用的基材,可列舉有:玻璃板、鋁板 或鐵I氟龍(Teflon ’商標名)、聚丙稀、聚乙稀等塑膠製薄 片、薄膜或成形板、矽氧樹脂或聚丙烯樹脂被覆脫模紙等。 又,至於本發明所使用的支持體,可列舉有:織物、 非織物:網孔狀物、紙、濾紙狀物、中空絲、多孔質體等。 至於此等支持材之材料,可列舉有:不銹鋼、鋁、陶瓷、 本紙張尺度適用令國围家栉準(CNS ) 2ΙΟχ"2ντ'.ί> A*. 7 68 五、 發明説明( Λ7 H7 聚酯、耐綸、聚醯胺、聚碳酸酯、聚丙烯、聚乙烯、纖維 素、幾丁質、鐵氟龍、聚胺酯、聚5風等。 至於將塗布液塗布於上述基材及支持體之方法,有滾 ,法、刮塗法、擠塗法、氣刀塗布法、凹版塗布法、桿塗 法、噴塗法'浸潰、内灌等習用公知的塗布方法^ 巧上述方法所塗布的塗布液,例如可以鼓式乾燥、送 ,乾燥、紅外線燈乾燥等予以乾燥,而形成本發明之電荷 =鑲膜。相關的膜之較宜的厚度為〇. 1〜1〇〇〇ym之範圍, 更宜為0· 5〜200/zm之範圍。 成惟 作, 可狀 係形 ’等 膜狀 搬絲 鑲空 荷中 免、 之狀 明摺 發折。 本、者 的狀制 造筒限 製圓別 般、特 述狀受 上旋非 如螺並 ,、狀 且狀形 骐之 平膜 晶上解功 分質電的 成實之緩 物呈*遲 合*子f^ 聚向分非 性方低度 十度有速 秦厚具過 陽之,透 有臈造或 具對構過 係域之透 ,晶勝可 膜分著不 鑲成穿質 嵌物貫解 荷合上電 電聚體非 之性整而 明子,, 發離列過 本陰排透 與互可。 域交質能 經濟部中央標準局只工消t合作杜印取 ,本發明之電荷嵌鑲膜,係可使用於電解質之可 拥算又S亡氣化鈉、氣化卸、硫酸納、鱗酸鋼、氣化 亡I子1之電解質之脫鹽用,再者用作鹽酸、醋酸 2離子用等係有用的’至於具體例,在飲料用 介、純水、超純水等的製造而用之水處理的脫 π字工業、金屬工業等工業廢水之脫鹽、色素製造工 本紙張尺度賴巾關幻碑(t:NS) .14 (21()x2y·!公分 >
产 -V 1 Λ 1 6 8 ΑΊ 一-:-------Β7 五、發明説明() 業的染料及顏料之脫鹽、發酵工業及食品工業等生化學相 -製品之脫鹽、醫藥品之脫鹽、記錄媒體用染料之吸附等 係有用的。 尤其本發明之電荷嵌鑲膜,係在蛋白質、DNA等之脫 鹽、染料、顏料、界面活性劑等的脫鹽等向來由於發熱而 使目的物質變質’致使離子之吸附引起膜污染等電氣透析 未能適用的領域上係有用的。 又’本發明之電荷嵌鑲膜’由於具有上述般的膜構造, 在利用膜之導電性、離子之通過性等性質之電氣透析、擴 散透析、電氣分解、電池反應等隔膜方面亦係有用的。
、1T 其次’舉合成例及實施例’更具體的說明本發明,且, 文中之分及%若未予特別規定時,係指重量基準。 合成例1 (聚合物A :陽離子性交聯粒狀聚合物) 4 -乙烯基u比咬 20. 0分 二乙烯基苯 2.0分 2, 2’-偶氮雙(2-脒基丙烷)二氯化氫 〇.4分 1000 分 經漪部中灰標準局只工消费合作社印製 將上述成分饋入燒瓶内’在氮氣氣流下,於8〇°c聚合 8小時。將聚合生成物凍結乾燥,而得内部已交聯的粒狀 聚合物。該粒狀聚合物之平均粒子徑在以掃瞄型電子顯微 鏡測定時約350nm。 ____________15 一 本紙張尺度適用中國®家枕卑(CNS ) Λ4队格(2!Ox2y7^y·) t 4 6 9:68 A? 經漪部中央櫺苹局只.T.ii'lf合作社印裝 五、發明説明() 合成例2 (聚合物B :陽離子性交聯粒狀聚合物) 使聚合物A之聚4-乙烯基□比咬粒子分散於曱醇内,於 該分散液内添加碘化甲基並攪拌12小時,再以鹽酸進行' 鹽交換,充分水洗後而得聚4-乙烯基□比啶之第四級化物。 由凍結乾燥而得之交聯的粒狀聚合物之平均粒子徑為約 360nm ° 合成例3 (聚合物C :陽離子性交聯粒狀聚合物) 氣甲基苯乙烯 200. 0 分 二乙稀基苯 10.0 分 過硫酸鉀 4.0分 硫代硫酸鈉 4.0分 月桂基硫酸鈉 40. 0 分 水 1000 分 將上述成分饋入燒瓶内,在氮氣氣流下,於50°C聚合 12小時。以溫水及甲醇充分清洗已分離的交聯粒狀聚合 物,去除交聯粒狀聚合物表面之界面活性劑。其次,令交 聯粒狀聚合物分散於水、製備分散液,於其中添加三乙胺、 攪拌12小時,其後凍結乾燥,而得交聯粒狀聚合物之第 四級銨鹽,其平均粒子徑為約150nm。 ^ _____—16______ 本紙悵尺度過用中國_家枕準(CNS > Λ4规枯(2丨〇Χ297ϋ ) 訂------線 {誚先Μιιίιϊ-而之注項再填ϊΐ:本) Λ7 Η 7 469168 五、發明説明( 合成例4(聚合物D :陰離子性交聯粒狀聚合物) 苯乙烯 41. 6分 丙烯腈 7.1分 曱基丙烯酸羥乙酯 8.1分 二乙烯基苯 8. 7分 過硫酸鉀 〇. 5分 水 1000分 將上述成分饋入燒瓶内,在氣氣氣流下,於80°C聚合 8小時,所得的交聯粒狀聚合物之平均粒子徑為約i80nm。 利用過濾方式分離出上述交聯粒狀聚合物,乾燥後粉碎 其後’將已粉碎的粒狀聚合物1〇〇分徐徐添加入650分之 98%濃硫酸内,在5〇°C攪拌24小時,其次在8(TC攪拌3 ^時。其後’冷卻’將反應混合液投入大量的冰水内。以 碳酸鈉中和後,經過濾,分離出如此處理的粒狀聚合物, 充分以水清洗。 所得的交聯粒狀聚合物’係利用紅外線吸收光譜及離 子層析儀等的分析,可確認出芳香環上導入有約略丨個之 磺酸基。此交聯粒狀聚合物之平均粒子徑為約24〇nm。 尤 間- 讀 If 而 冬 t K 再 f 訂 經淡-部中央標卑局:=:Η消费合作社印f 本紙張尺度適川中國囡家撑卑(CNS) Λϋ( 2u>xW;t.n 46 9 1 6 8 A7 五、發明説明() 合成例5(聚合物E :陰離子性交聯粒狀聚合物) 苯乙烯磺酸鈉 25. 0 分 笨乙烯 10. 0 分 丙烯酸丁酯 5.0分 丙烯酿胺 2. 8分 二乙烯基苯 1.8分 2, 2’-偶氮雙(2-脒基丙烷)二氣化氫 1.0分 水 1000 分 經濟部中央梂準局只工消费合作社印裝 將上述成分饋入燒瓶内,在氮氣氣流下,於75°C聚合 10小時。以丙酮一水之再沈澱粉精製所得的交聯粒狀聚合 物。此交聯粒狀聚合物之平均粒子徑為約lOOnm。 實施例1 令前述聚合物A3· 6分分散於曱基-2-ift咯烷酮8. 5 分。將此分散液與聚®(Amoco化學公司製分子量30, 000) 之20%N-甲基-2-吡咯烷酮60分混合1小時,再混合由此 分散液與聚合物D8. 4分及N-曱基-2-吡咯烷酮19. 5分而 成的分散液,並製備塗布液。 以刮塗器塗布上述塗布液於聚丙烯樹脂塗布脫模紙上 及熱風乾燥。於職化甲基氣圍中在室溫下靜置所得的膜 小時後’水洗、風乾後’而得本發明之電荷嵌鑲膜。 以上述方法製膜的電荷嵌鑲膜,係具有約3〇 之均 勻膜厚。 線 (CNS ) 怙(2ΙΟχ297Ήί~7
^ ^:
修正本 2001/1/18 發明説明( 經濟部智慧財產局負工消費合作钍印製 膜之評估 萄糖Ϊ氣化卸水溶液與以葡 ϊίίϊϊί貝葡萄糖水溶液】_放乂第ί ί介ΐϊί 子u邊予授拌容11 α、β之内ί物 ^足行透_,如第2騎示般,顯 實施例2 s? η ^5巧合物A 2,0分分散於\一曱基—2 —妣°各烧酮 & 〇 〃刀内’將此分散液與聚芳香酯(Unichika公司製U—丨⑽, 商品名)之10%N—甲基—2—吡咯烷酮溶液66 7分混合1 小時,再將此分散液與聚合物D4. 7分及N—甲基一2—吡咯 烷酮18. 7分而成的分散液混合而製備塗布液。用到塗器塗 布此塗布液於聚丙烯樹脂被覆脫臈紙上,進行熱風乾燥。 再者,將所得的膜置放於碘化甲基氣圍中在室溫靜置12小 時後’水洗、風乾而得本發明之電荷嵌鑲膜。以此方法製 膜的電荷嵌鑲膜’係具有約50/zm之均勻膜厚。 此外,與實施例1同法評估電解質之透析分離性能, 惟與實施例約略同等的結果。 將述聚合物B 3· 6分混合於聚醯胺樹脂之10% N —甲 基一2-吡咯烷酮溶液90.9分2小時,並使分散。於此分散 19 本紙張尺度適用中國囤家標隼(CNS〉/U叱樁(210Χ 297公廣〉
A7 H7 …1 6 8 五、發明説明( 布液。用刮塗器塗布此塗布液於聚丙烯樹脂被覆脫模紙 上,進行熱風乾燥。再者,將所得的膜置放於碘化甲基氣 ΐ Ϊ在ί溫靜置12小時後,水洗、風乾而得本發明之電 荷嵌鑲膜。如此製得的電荷嵌鑲膜,係具有約3〇Am之均 勻膜厚,再者與實施例1之電荷嵌鑲膜相較,具有可撓性。 圖式之簡單說.明 第1圖為表示使用本發明之電荷嵌鑲膜的裝置之一例 的透析裝置之縱戴面。 圖 第2圓為表示實施例1之電荷嵌鑲膜之透析分離性之 圖號之簡單說明 授拌子(將經予切短的鐵線封入玻璃管内而予製作 而得) 電荷嵌鑲膜(可視作合成樹脂製) 線 經漪部中央if-嗥局貝τ.ίί'ί*:合作社印裝 一度 尺一 3 -# in
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Claims (1)
- π Α8 Β8 C8 D8 修正本 2001/1/18 夂' 申請專利範圍經济部智.¾)时 i C? Π 工消f作Ti:!J· 【申請專利範圍】 1、一種電荷嵌鑲膜,係指由陽離子性聚合物成分、陰 離子聚合物成分及基質成分而成的電荷嵌鑲膜,其特 徵在於前述陽離子性聚合物成分及前述陰離子性聚合 物成分係任一者均係已交聯的粒狀聚合物,基質成分 係由聚碾系、聚芳香酯系、聚醯胺系、聚醯亞胺系、 聚醯胺醯亞胺系、聚胺酯系、氟碳系及矽氧系樹脂選 出的至少一種聚合物;前述陽離子性聚合物成分及前 述陰離子性聚合物成分之平均粒子徑各為0.01〜20μm 之範圍,又陽雖子性聚合物成分為具有第一級至第三 級之胺基,第四級銨基或吡啶鐡基或該等之鹽之基的 聚合物,而陰離子性聚合物成分為具有確酸、叛酸、 硫酸酯或磷酸酯基或該等之鹽之基的聚合物;其中構 成電荷嵌鑲膜之晶域之前述陽離子性聚合物成分及前 述陰離子性聚合物成分對基質成分之使用比率,基質 成分對兩成分之合計係在2〜95重量%之範圍。 2、如申清專利抱圍苐1項之電荷破镶膜,其中厚度係 在0.1〜1000//m之範圍。 ---------罠------訂-------味 (請先閱讀背面之注意事項再填寫本頁) ::9 A8 B8 C8 D8 修正本 .2001/1/18 4 申請專利範圍 、一種電荷嵌鑲膜之製造方法’其特徵在於製造申請 專利範圍第1項之電荷嵌鑲膜之際’採用令前述陽離 子性聚合物成分及前述陰離子性聚合物成分之兩者分 散於前述基質成分之有機溶劑溶液而成的組成物予以 製膜。 、一種供透過電解質用之電荷嵌鑲膜之使用方法,係 將申請專利範圍第i項之電荷歲鑲膜使用於透過 質而成。 畔 、厂種附錢敬_之裝£,係具有”專利 第1項之電荷嵌鑲膜而成。 ----------茛-------訂-------乘 , » (請先閱讀背面之注意事項再填寫本頁〕 經濟部智总时是^:只工4#合作社:·:;,^ 23 :二 K) ·、. ;:97公聲
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW088102689A TW469168B (en) | 1998-02-25 | 1999-04-02 | Charged mosaic membrane, its production, method for using the membrane, and device provided with the membrane |
Country Status (7)
Country | Link |
---|---|
US (1) | US6663775B2 (zh) |
EP (1) | EP0941760B1 (zh) |
JP (1) | JP3453067B2 (zh) |
KR (1) | KR100406743B1 (zh) |
CN (1) | CN1257007C (zh) |
AU (1) | AU752751B2 (zh) |
TW (1) | TW469168B (zh) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2278555T3 (es) * | 1999-02-22 | 2007-08-16 | DAINICHISEIKA COLOR & CHEMICALS MFG. CO. LTD. | Membranas selectivas de iones, su procedimiento de produccion, empleo de las membranas selectivas de iones y aparatos suministrados con las membranas selectivas de iones. |
DE10034098C2 (de) * | 2000-07-13 | 2002-11-21 | Fresenius Medical Care De Gmbh | Hydrophobe mikroporöse Hohlfasermembran und Verfahren zur Herstellung dieser Membran sowie deren Verwendung in der Membranoxygenierung |
KR100376379B1 (ko) * | 2000-07-18 | 2003-03-15 | 한국화학연구원 | 유기 혼합물 분리용 상호 침투 다가 이온 착물 복합막과이의 제조방법 |
JP4679773B2 (ja) * | 2001-09-28 | 2011-04-27 | ピジョン株式会社 | 繊維芽細胞活性深層水の製造方法 |
US7402283B2 (en) * | 2002-09-11 | 2008-07-22 | Dionex Corporation | Electrolytic eluent generator and method of use |
WO2004071966A1 (ja) * | 2003-02-14 | 2004-08-26 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | 脱塩方法 |
US7425266B2 (en) | 2004-03-04 | 2008-09-16 | Freeman Mark C | Water-filtering media and filters |
PL382303A1 (pl) * | 2004-03-04 | 2007-08-06 | Jon J. Freeman | Środki filtrujące wodę i filtry |
JP4730942B2 (ja) * | 2005-04-25 | 2011-07-20 | 株式会社タクマ | モザイク荷電膜及びその製造方法 |
JP4944536B2 (ja) * | 2006-08-08 | 2012-06-06 | 公立大学法人高知工科大学 | 電解質の分離装置および電解質の分離方法 |
JP2008284521A (ja) * | 2007-05-21 | 2008-11-27 | Takuma Co Ltd | 中空糸状両性荷電膜及びその製造方法 |
JP2010115592A (ja) * | 2008-11-13 | 2010-05-27 | Takuma Co Ltd | 同符号イオン選択性単層両性荷電膜及びその製造方法 |
WO2010110437A1 (ja) * | 2009-03-27 | 2010-09-30 | 国立大学法人山口大学 | モザイク荷電膜及びその製造方法 |
EP2418013A4 (en) * | 2009-04-09 | 2013-10-23 | Univ Yamaguchi | CHARGE MOSAIC MEMBRANE |
CN102458618B (zh) * | 2009-04-13 | 2016-07-13 | 国立大学法人山口大学 | 离子交换膜及其制造方法 |
US8857629B2 (en) | 2010-07-15 | 2014-10-14 | International Business Machines Corporation | Composite membrane with multi-layered active layer |
US9022227B2 (en) * | 2011-03-21 | 2015-05-05 | International Business Machines Corporation | Composite membranes and methods of preparation thereof |
US9561474B2 (en) | 2012-06-07 | 2017-02-07 | International Business Machines Corporation | Composite membrane with multi-layered active layer |
TWI568491B (zh) * | 2015-12-31 | 2017-02-01 | 財團法人工業技術研究院 | 過濾材料 |
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DE1498903B2 (de) * | 1963-07-22 | 1970-12-23 | Metrirapex Magyar Müszeripari Külkeres-Kedelmi Vallalat, Budapest | Ionenselektive Membran und Verfahren zu ihrer Herstellung |
US3541030A (en) * | 1966-12-08 | 1970-11-17 | Nasa | Method of making inorganic ion exchange membranes |
NL6809170A (zh) * | 1968-06-28 | 1969-12-30 | ||
FR2283167A1 (fr) | 1974-06-04 | 1976-03-26 | Rhone Poulenc Ind | Utilisation en dialyse selective de membranes a base de polymeres echangeurs d'ions et d'un liant |
US4191811A (en) * | 1977-03-01 | 1980-03-04 | Ionics, Incorported | Ion exchange membranes based upon polyphenylene sulfide and fluorocarbon polymeric binder |
US5127925A (en) * | 1982-12-13 | 1992-07-07 | Allied-Signal Inc. | Separation of gases by means of mixed matrix membranes |
US4615786A (en) * | 1985-04-18 | 1986-10-07 | Dorr-Oliver Incorporated | Non ion selective membrane in an EAVF system |
US5017420A (en) * | 1986-10-23 | 1991-05-21 | Hoechst Celanese Corp. | Process for preparing electrically conductive shaped articles from polybenzimidazoles |
FR2618440B1 (fr) * | 1987-07-20 | 1990-06-22 | Acome Soc Coop Travailleurs | Materiau polymere insoluble a sites reactifs condenses, notamment du type groupe anhydride ou ester actif, procede de preparation de ce materiau polymere et application de ce materiau |
US4976860A (en) * | 1987-08-04 | 1990-12-11 | Kao Corporation | Conjugated polymer-cation exchanger composite membrane |
GB2250469B (en) * | 1990-12-03 | 1995-03-22 | Aligena Ag | Charged asymmetric mosaic membranes |
US5346924B1 (en) * | 1992-09-23 | 2000-04-25 | Ionpure Techn Corp | Heterogenous ion exchange materials comprising polyethylene of linear low density or high density high molecular weight |
EP0589133B1 (en) * | 1992-09-25 | 2001-10-17 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Processes for the production of charge mosaic membranes |
IL109240A (en) * | 1994-04-07 | 1998-02-22 | Yeda Res & Dev | Ion exchange membranes |
MY113226A (en) * | 1995-01-19 | 2001-12-31 | Asahi Glass Co Ltd | Porous ion exchanger and method for producing deionized water |
AU676971B1 (en) * | 1995-08-24 | 1997-03-27 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Production process of connected microgel particles and articles treated with connected microgel particles |
-
1998
- 1998-08-24 JP JP23770898A patent/JP3453067B2/ja not_active Expired - Fee Related
-
1999
- 1999-02-22 US US09/255,017 patent/US6663775B2/en not_active Expired - Lifetime
- 1999-02-24 AU AU18408/99A patent/AU752751B2/en not_active Expired
- 1999-02-24 EP EP99103594.0A patent/EP0941760B1/en not_active Expired - Lifetime
- 1999-02-25 KR KR10-1999-0006283A patent/KR100406743B1/ko not_active IP Right Cessation
- 1999-02-25 CN CNB991061055A patent/CN1257007C/zh not_active Expired - Lifetime
- 1999-04-02 TW TW088102689A patent/TW469168B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
CN1235061A (zh) | 1999-11-17 |
JP3453067B2 (ja) | 2003-10-06 |
JP2000070687A (ja) | 2000-03-07 |
KR19990072935A (ko) | 1999-09-27 |
EP0941760B1 (en) | 2014-05-14 |
EP0941760A1 (en) | 1999-09-15 |
KR100406743B1 (ko) | 2003-11-20 |
US6663775B2 (en) | 2003-12-16 |
US20030192828A1 (en) | 2003-10-16 |
AU752751B2 (en) | 2002-09-26 |
CN1257007C (zh) | 2006-05-24 |
AU1840899A (en) | 1999-09-09 |
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