TWI378942B - Blend of ionic (co)polymer resins and matrix (co)polymers - Google Patents

Blend of ionic (co)polymer resins and matrix (co)polymers Download PDF

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TWI378942B
TWI378942B TW095118370A TW95118370A TWI378942B TW I378942 B TWI378942 B TW I378942B TW 095118370 A TW095118370 A TW 095118370A TW 95118370 A TW95118370 A TW 95118370A TW I378942 B TWI378942 B TW I378942B
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polymer
polyelectrolyte
poly
film
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TW095118370A
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TW200704646A (en
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James T Goldbach
Scott Gaboury
Robert J Umpleby
Julien Parvole
David A Mountz
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Arkema Inc
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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1378942 九、發明說明： 【發明所屬之技術領域】 本發明係關於聚合物摻合物’其含有摻合至聚合物或共 聚物基質中之聚電解質樹脂。特定言之，該等聚電解質樹 脂為不具有可水解基團之(共)聚合物。該基質聚合物為堅 韋刃且高度耐化學性之(共)聚合物，較佳為含氟聚合物。該 聚合物樹脂掺合物適合用於形成膜，尤其形成適用於燃料 電池之MEA之膜。 【先前技術】 全氟化碳離子交換薄膜提供高陽離子傳輸，且已廣泛用 作離子父換薄膜。聚合物離子交換薄媒可稱為固態聚合物 電解質或聚合物交換薄膜（ΡΕΜ)β由於對燃料電池應用之 迫切需要’最常使用且可購得之薄膜係由全氟項酸化之 Nafion®、Flemion®及Aciple，聚合物製成。然而，報導及 文獻將此等薄膜描述為工作良好，但展示諸多阻礙開發進 一步商業化之技術的限制。另外，其同氣體燃料一起工作 比同液體燃料一起工作更佳，其主要原因為會使電池效能 降低之液體燃料穿透性。對燃料電池應用而言薄膜之耐 化學性及機械強度為重要特性。實際上，薄膜經常承受高 壓差、水合-脫水循環以及其他壓力條件。在薄膜很薄（諸 如小於50微米）時機械強度亦變得重要。此外，在用於燃 料電池或電池應用時，在氧化及/或還原環境中，由於有 金屬離子存在及有時有溶劑存在，薄膜在可達2〇〇。〇之溫 度下處於酸性極高之介質中。此環境要求薄膜具有耐化學 J11346.doc 1378942 性、耐電化學性以及熱穩定性。 當前，許多含氟薄膜有以下缺陷中之—或多個： 0穿過薄膜之高液體及氣體穿透量； ϋ)氟化聚合物與導致不良特性之其他聚合物之間的異質 摻合； ' iii) 在一些液體燃料存在下，耐化學性不足； iv) 不良耐電化學性； v) 續化基團分佈不均； vi) 不良機械特性；及/或不良熱穩定性。 US 2005077233中描述了具有小晶嘴大小之聚電解質聚 合物摻合物及用於生產該等摻合物之方法。聚電解質聚合 物為未全氟化之含離子團及/或可離子化基團且尤其為磺 酸根或膦酸根及含氟聚合物基質之聚合物樹脂。所揭示之 聚電解質之一問題為彼等含水解不穩定基團之聚合物（諸 如酯及丙烯醯胺）易於在嚴酷化學環境中水解，從而導致 可離子化官能基之損失。 WO 99/67304揭示新的具有經氟代醚取代之芳族環之不 飽和化合物類別，及由此等化合物形成之聚合物。該等聚 合物之一用途係作為電化學電池中之隔離物。 需要一種克服燃料電池應用中之用途限制的薄膜。 令人驚奇的是，已發現含有含氟聚合物之聚合物摻合物 及不具有可水解基團之聚電解質可用於形成具有高度耐化 學性及機械強度之用於電化學電池之薄膜。 【發明内容】 111346.doc 1378942 本發明之-目標為提供具有極佳f子傳導率及耐化學性 之聚電解質。 本發明之另一目標為提供其中聚電解質均句分佈在基質 聚合物（諸如含氟聚合物）中且其中晶嘴大小非常小的二膜 或膜。 本發明之另-目標為提供適當定義之水解穩定（不可水 解）之聚電解質，其包括相對低成本之起始材料且可用最 少次數之轉變形成。 本發明的該等目標可由含有含氟聚合物之聚合物摻合物 及不含可水解基團之聚電解質根據本發明較佳實施例之原 理達成。含氟聚合物基質中之乙烯樹脂之晶疇大小較佳為 500 nm或更小。 【實施方式】 本文中使用之術語聚合物及（共）聚合物係指由一或多種 單體形成之聚合物。其包括均聚物、共聚物、三聚物及由 四種或四種以上單體形成之聚合物。共聚物係指無規共聚 物及嵌段共聚物以及接枝共聚物。共聚物亦用於描述類似 由均聚物之側基t之一些基團之部分反應/取代形成之共 聚物，從而產生具有兩個或兩個以上不同部分作為側鏈之 聚合物骨架》 本發明係關於聚合物樹脂穆合物，其含有穆合至聚合物 或共聚物基質中之聚電解質樹脂。特定言之，該等聚電解 質樹脂為不具有可水解基團之（共）聚合物。該基質聚合物 為堅韌且高度耐化學性之（共）聚合物，較佳為含氟聚合 111346.doc 1378942 物。 該基質聚合物可為如US2005077233中之基質所述的聚 合物及共聚物中之任一者’該案以引用之方式併入本文 中。該聚合物基質較佳含有至少一種含氟聚合物。該含氟 聚合物可為均聚物或其他類型之聚合物，且可為含氟聚合 物之混合物或含氟聚合物與不含氟聚合物之混合物。較佳 6亥含氟聚合物為熱塑性含氟聚合物且可與包括所存在之其 他聚合物的調配物之其他組份形成聚合物摻合物。較佳該 含氟聚合物為聚（偏二氟乙烯）聚合物，諸如聚（偏二氟乙 稀）均聚物。含氟聚合物之其他實例包括（但不限於）含有至 少一個氟原子之聚（伸烷基），諸如聚六氟丙烯、聚四氟乙 烯、聚（氟乙烯）或其組合。更佳該含氟聚合物為聚合物組 合物，其含有約30重量。/。至約100重量％之偏二氟乙烯及〇 重量°/〇至約70重量％之含有至少一個氟原子之至少一種聚 (伸烧基），諸如六氟丙烯、四氟乙烯、三氟乙烯（VF3)、三 氟氣乙烯及/或氟乙稀。可包括均聚物、共聚物、=聚 物、寡聚物及其他類型之含氟聚合物的分子量較佳為約 80,000 MW至約 1，000,000 MW，且更佳為約 1〇〇 〇〇〇 Mw至 約500,000 MW。該等含氟聚合物可使用美國專利第 3,051，677 號、第 3，178,399 號、第 3,475,396 號、第 3,857,827號及第5，093,427號中描述之技術製備，該等專利 均以引用之方式全部併入本文中。 該基質聚合物與一或多種聚電解質（共）聚合物摻合。該 聚電解質共聚物含有離子性或可離子化基團以及能夠交聯 111346.doc 1378942 之基團。該等可離子化基圓較佳為續隸 根。離子性或可離子化基團在聚電解質中之含量應=酸 較佳為2㈣重量％，更佳為5〇至95重量％，且最佳為7〇 至95重；f %。該等離子性或可離子化基團可存在於用於形 成聚電解質之單體上，或可在聚合後反應中添加至該聚電1378942 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polymer blend comprising a polyelectrolyte resin blended into a polymer or copolymer matrix. Specifically, the polyelectrolyte resins are (co)polymers having no hydrolyzable groups. The matrix polymer is a strong (chemically) (co)polymer, preferably a fluoropolymer. The polymer resin blend is suitable for use in forming a film, particularly a film of MEA suitable for use in a fuel cell. [Prior Art] The perfluorocarbon ion exchange membrane provides high cation transport and has been widely used as an ion exchange film. Polymer ion exchange thin media can be referred to as solid polymer electrolytes or polymer exchange membranes (ΡΕΜ) β. Due to the urgent need for fuel cell applications, the most commonly used and commercially available film is Nafion®, which is acidified by perfluorination. Flemion® and Aciple, made of polymer. However, the reports and literature describe these films as working well, but show many limitations that hinder the development of further commercial technologies. In addition, it works better with gaseous fuels than with liquid fuels, primarily because of the liquid fuel penetration that results in reduced battery performance. The chemical resistance and mechanical strength of the film are important characteristics for fuel cell applications. In fact, membranes are often subjected to high pressure differentials, hydration-dehydration cycles, and other pressure conditions. Mechanical strength also becomes important when the film is very thin, such as less than 50 microns. In addition, when used in fuel cell or battery applications, in the oxidizing and/or reducing environment, the film is up to 2 Å due to the presence of metal ions and sometimes solvents. It is in an extremely acidic medium at the temperature of 〇. This environment requires the film to be chemically resistant, electrochemically resistant, and thermally stable. Currently, many fluorine-containing films have one or more of the following defects: 0 high liquid and gas penetration through the film; ϋ) heterogeneous blending of the fluorinated polymer with other polymers that cause undesirable properties; ' iii) Insufficient chemical resistance in the presence of some liquid fuels; iv) poor resistance to electrochemistry; v) uneven distribution of the renewal groups; vi) poor mechanical properties; and/or poor thermal stability. A polyelectrolyte polymer blend having a small nozzle size and a method for producing the blend are described in US 2005077233. The polyelectrolyte polymer is a polymer resin which is not perfluorinated and which contains ion groups and/or ionizable groups and is especially a sulfonate or phosphonate and a fluoropolymer matrix. One problem with the disclosed polyelectrolytes is that their polymers containing hydrolysis labile groups, such as esters and acrylamide, are susceptible to hydrolysis in harsh chemical environments, resulting in loss of ionizable functional groups. WO 99/67304 discloses novel classes of unsaturated compounds having an aromatic ring substituted with a fluoroether, and polymers formed therefrom. One of these polymers is used as a separator in electrochemical cells. There is a need for a film that overcomes the limitations of use in fuel cell applications. Surprisingly, it has been found that polymer blends containing fluoropolymers and polyelectrolytes without hydrolyzable groups can be used to form films for electrochemical cells having high chemical and mechanical strength. SUMMARY OF THE INVENTION 111346.doc 1378942 The object of the present invention is to provide a polyelectrolyte having excellent feron conductivity and chemical resistance. Another object of the present invention is to provide a two film or film in which a polyelectrolyte is uniformly distributed in a matrix polymer such as a fluoropolymer and in which the nozzle size is very small. Another object of the present invention is to provide a suitably defined hydrolytically stable (non-hydrolyzable) polyelectrolyte comprising a relatively low cost starting material and which can be formed with a minimum number of transitions. These objects of the present invention can be achieved by a polymer blend comprising a fluoropolymer and a polyelectrolyte containing no hydrolyzable groups in accordance with the principles of the preferred embodiment of the present invention. The domain size of the vinyl resin in the fluoropolymer matrix is preferably 500 nm or less. [Embodiment] The term polymer and (co)polymer as used herein refers to a polymer formed from one or more monomers. It includes homopolymers, copolymers, terpolymers, and polymers formed from four or more monomers. The copolymer means a random copolymer and a block copolymer as well as a graft copolymer. Copolymers are also used to describe copolymers formed by partial reaction/substitution of some groups from the side groups t of the homopolymer, thereby producing a polymer backbone having two or more different moieties as side chains. It relates to a polymer resin compound which contains a polyelectrolyte resin which is incorporated into a polymer or copolymer matrix. Specifically, the polyelectrolytic resins are (co)polymers having no hydrolyzable groups. The matrix polymer is a tough and highly chemically resistant (co)polymer, preferably a fluoropolymer 111346.doc 1378942. The matrix polymer can be any of the polymers and copolymers described in the matrix of US2005077233, which is incorporated herein by reference. The polymer matrix preferably contains at least one fluoropolymer. The fluoropolymer may be a homopolymer or other type of polymer and may be a mixture of fluoropolymers or a mixture of fluoropolymers and non-fluoropolymers. Preferably, the 6 fluoropolymer is a thermoplastic fluoropolymer and can form a polymer blend with other components of the formulation comprising other polymers present. Preferably, the fluoropolymer is a poly(vinylidene fluoride) polymer such as a poly(vinylidene fluoride) homopolymer. Other examples of fluoropolymers include, but are not limited to, poly(alkylene) groups containing at least one fluorine atom, such as polyhexafluoropropylene, polytetrafluoroethylene, poly(fluoroethylene), or combinations thereof. More preferably, the fluoropolymer is a polymer composition containing about 30% by weight. /. Up to about 100% by weight of vinylidene fluoride and hydrazine from 〇/〇 to about 70% by weight of at least one poly(alkylene group) containing at least one fluorine atom, such as hexafluoropropylene, tetrafluoroethylene, trifluoroethylene ( VF3), trifluoroethylene and/or fluoroethylene. The molecular weight which may include homopolymers, copolymers, =polymers, oligomers, and other types of fluoropolymers is preferably from about 80,000 MW to about 1,000,000 MW, and more preferably about 1 Torr. Mw to about 500,000 MW. The fluoropolymers can be prepared by the techniques described in U.S. Patent Nos. 3,051,677, 3, 178, 399, 3, 475, 396, 3, 857, 827, and 5, 093, 427, all of which are incorporated herein by reference. Incorporated herein. The matrix polymer is blended with one or more polyelectrolyte (co)polymers. The polyelectrolyte copolymer contains an ionic or ionizable group and a group capable of crosslinking 111346.doc 1378942. The ionizable base circles are preferably continuous roots. The content of the ionic or ionizable group in the polyelectrolyte should be such that the acid is preferably 2 (four)% by weight, more preferably 5 to 95% by weight, and most preferably 7 to 95% by weight; The ionic or ionizable group may be present on the monomer used to form the polyelectrolyte or may be added to the polyelectropolymer in the post-polymerization reaction.

以共聚物之重量計’交聯部分之含量為“75重量％，較 佳為1-50重量。’更佳為1〇_3〇重量％，且最佳為重量 %。交聯可經由習知之方法進行，該等方法包括(但不限 於)自縮合、添加第二交聯劑或輻射交聯。此等方法於文 獻：充分描述且在此項技術中熟知。能夠經受自縮合交聯 之單體的實例包括（但不限於）· . 个限於）·第一胺、第二胺及第三 胺’ 甲基丙烯醯胺；異丁氧基曱基丙烯醯胺；斗亞甲 基雙丙稀醯胺；稀丙基、苯乙稀基…基丙焊酸縮水甘 油醋。第二交聯劑之實例包括游離及對端異氰酸醋、三聚 氰胺、環氧樹脂、叛酸醋、α，ω.二齒代院、^_二酿、叛 酸、燒氧基石夕烧、聚石夕氧、氮丙咬及碳化二酿亞胺。可選 擇用於特定交聯化學方法之純劑且可包括有機錫、續酸 或胺。輕射交聯之實例包括電子束、紫外線及γ射線。 聚電解質可為非全氣化、部分全氣化或完全全氣化之 (-)聚合物4 1化程度可對所得（共）聚合物之離子傳導 陡、機械強度及滲透性具有顯著影響。 適用於本發明之聚電解皙矣彡由笙 ^ 買為彼等含有不可水解基團之聚 解質。已發現：諸如醋（例如丙烯酸醋及甲基丙稀酸醋） 111346.doc 1378942 及丙稀醯胺的具有易水解基團之單體將在嚴酷化學環境中 (諸如在電池之酸中）水解且失去易離子化之能力。 較佳聚電解質為彼等具有苯乙稀或乙稀基醚結構之聚電 解質。 該聚電解質可藉由乳液、懸浮液、反相乳液或溶液聚合 反應形成。其亦可藉由聚合後改質形成。 現將參考其特定貫施例（即乙稀基謎型聚電解質，及苯 乙烯型聚電解質）整體且詳細地說明本發明之聚電解質及 製造該等聚電解質之方法。亦將說明特定及一般實施例， 其展示包括兩種單獨的單體之常規共聚合作用，與基於均 聚物之部分反應以形成兩個或兩個以上單獨的官能單體單 元而形成共聚物。 乙烯基醚型结構 本發明之乙烯基醚型聚電解質結構之一般結構為：The content of the crosslinked portion is "75% by weight, preferably 1 to 50% by weight" based on the weight of the copolymer. More preferably, it is 1% to 3% by weight, and most preferably % by weight. Crosslinking can be carried out by Known methods include, but are not limited to, self-condensation, addition of a second crosslinking agent, or radiation crosslinking. These methods are well described and well known in the art. They are capable of undergoing self-condensation crosslinking. Examples of the monomer include, but are not limited to, · limited to · first amine, second amine, and third amine 'methacrylamide; isobutoxy decyl acrylamide; Dilute propylamine; propyl, styrene-based propylene-acrylic acid glycidyl vinegar. Examples of the second crosslinking agent include free and opposite isocyanuric acid, melamine, epoxy resin, acid vinegar, α, ω. 二齿代院, ^_二酿, 叛酸, activating oxygen smelting, poly-stone oxygen, nitrogen-acrylic biting and carbonized di-iminoimide. Can be used as a pure agent for specific cross-linking chemical methods and can be Including organotin, acid or amine. Examples of light-crosslinking include electron beam, ultraviolet light and gamma rays. Polyelectrolytes can be incomplete The degree of polymerization of the (-) polymer, partial gasification or complete gasification may have a significant effect on the ion conduction, mechanical strength and permeability of the resulting (co)polymer.买 买 买 买 买 买 买 买 买 买 买 买 买 买 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The monomers of the group will hydrolyze in a harsh chemical environment, such as in the acid of the battery, and lose the ability to be easily ionized. Preferred polyelectrolytes are those polyelectrolytes having a styrene or ethylene ether structure. The polyelectrolyte can be formed by emulsion, suspension, inverse emulsion or solution polymerization. It can also be formed by polymerization after polymerization. Reference will now be made to its specific examples (ie, ethylene-based polyelectrolytes, and benzene). The polyelectrolyte of the present invention is a comprehensive and detailed description of the polyelectrolyte of the present invention and a method of producing the polyelectrolyte. Specific and general examples will also be described which demonstrate the conventional copolymerization of two separate monomers, Homopolymers of partially reacted to form two or more separate functional monomer units to form copolymers of vinyl ether type structure of the general structure of the present invention the vinyl ether type polyelectrolyte structures of:

其中： L=未全氟化之烷基或伸烷基-醚伸烷基-醚鍵 L'=鍵或烷基或伸烷基-醚伸烷基-醚鍵 n=25-99莫耳％，較佳大於50%，最佳大於70% 111=1-75莫耳％，較佳小於50%，最佳小於30% A=磺酸根、膦酸根或羧酸根 111346.doc 丄 B =能夠交聯之基團 該等共聚物之一般合成途徑為： + X-(-Y~4s〇3· M+Wherein: L = non-perfluorinated alkyl or alkylene-ether alkyl-ether linkage L'= bond or alkyl or alkyl-ether alkyl-ether linkage n=25-99 mol% Preferably, greater than 50%, optimally greater than 70% 111 = 1 - 75 mole %, preferably less than 50%, optimally less than 30% A = sulfonate, phosphonate or carboxylate 111346.doc 丄 B = capable of The general synthetic route of these copolymers is: + X-(-Y~4s〇3· M+

OHOH

X=C1 ' Br或 IX=C1 ' Br or I

Y=cz至c]2或含有芳基之脂族（、cH M=鹼 土金屬（Li、Na、K、Rb、Cs) n : m=較佳為80:20或90: l〇莫耳/莫耳 該等共聚物之一替代一般合成途徑為： 〇N/oY = cz to c] 2 or an aliphatic group containing an aryl group (, cH M = alkaline earth metal (Li, Na, K, Rb, Cs) n : m = preferably 80: 20 or 90: l 〇 mol / One of the copolymers of Moer et al. replaces the general synthetic route: 〇N/o

II

Z S〇3* M+Z S〇3* M+

S03' Μ* )(例如：-CH2-Ph-CH2-) Z=cz至cs之脂族或全氟脂族，或芳族或全氟芳族 MH=金屬氫化物（例如NaH) n : m=較佳為80:20或90:1〇莫耳/莫耳 轉化之條件可改變。通常，將聚（乙烯醇）(pvA)溶解於 DMS0中，且添加諸如氫氧化鉀、氫氧化鈉、強鹼性胺或 金屬氫化物之鹼性反應物，接著緩慢加入磺化烷基齒或磺 内酯並稍微加熱（約30至50。〇。處理由在適當溶劑中沉澱 聚合物並隨後用溶劑洗滌組成。 乙烯基醚型聚電解質之替代合成法類似於上述方法，然 而’金屬烷基磺酸鹽係以四烷基銨之形式使用。其提高其 111346.doc -12- 1378942 在非DMSO之有機溶劑中之溶解度，且提供作為四烷基銨 鹽之最终聚合物，其利於進一步處理及與聚偏二氟乙烯 (PVDF)摻合。 + X-f-Y-}S03- N(Alk)+· i ίS03' Μ* ) (eg: -CH2-Ph-CH2-) Z=cz to cs aliphatic or perfluoroaliphatic, or aromatic or perfluoroaromatic MH=metal hydride (eg NaH) n : m = preferably 80:20 or 90:1 〇 Mohr / Moel conversion conditions can be changed. Typically, poly(vinyl alcohol) (pvA) is dissolved in DMSO and an alkaline reactant such as potassium hydroxide, sodium hydroxide, a strong basic amine or a metal hydride is added, followed by slow addition of the sulfonated alkyl or The sultone is heated slightly (about 30 to 50. 处理. The treatment consists of precipitating the polymer in a suitable solvent and then washing with a solvent. The alternative synthesis method of the vinyl ether type polyelectrolyte is similar to the above method, however, 'metal alkyl The sulfonate is used in the form of a tetraalkylammonium which increases the solubility of its 111346.doc -12- 1378942 in an organic solvent other than DMSO and provides a final polymer as a tetraalkylammonium salt which facilitates further processing. And blending with polyvinylidene fluoride (PVDF) + XfY-}S03- N(Alk)+· i ί

N(Alk)+ CN(Alk)+ C

X—{~Y-)"S〇3' M+ X-(-V-}"S〇3HX—{~Y-)"S〇3' M+ X-(-V-}"S〇3H

- I Y S〇3* N(Alk)+- I Y S〇3* N(Alk)+

用於烷基磺酸鹽轉化之條件為：用HC1或H2S04將起始 鈉鹽水溶液酸化至ρΗ<0，蒸發至乾燥，以最少的水再次溶 解，及用氫氧化四烷基銨中和至pH>10。 在一變體中，首先將PVA轉化成醇金屬形式。其可藉由 使用於無水溶劑（DMSO)中之適當金屬氫化物（例如，氫化 納、氫化經-銘）完成。形成之醇金屬具有超過先前實例中 之醇類的增強的反應性。接著可添加鹵代烷基磺酸鹽（M+ 或四烷基銨形式）或磺内酯以提供所要聚合物。The conditions for the conversion of the alkyl sulfonate are: acidifying the initial aqueous sodium salt solution to ρ Η < 0 with HCl or H 2 SO 4 , evaporating to dryness, re-dissolving with minimal water, and neutralizing with tetraalkylammonium hydroxide to pH > 10. In one variation, the PVA is first converted to the alcohol metal form. This can be accomplished by using a suitable metal hydride (e.g., sodium hydride, hydrogenation) in an anhydrous solvent (DMSO). The alcohol metal formed has enhanced reactivity over the alcohols of the previous examples. The haloalkyl sulfonate (M+ or tetraalkylammonium form) or sultone can then be added to provide the desired polymer.

+氫化物 OH+ hydride OH

X-f*Y-)s〇3 irf1" (_).勹 O 0或〆\ I γ S03' M* (Ν(ΛΙΙ〇Λ 在另一有用變體中，起始聚合物為聚（乙酸乙 酯）（PVA)，當然，其為聚（乙烯醇）之前驅聚合物。在此狀 況下，在原位將酯轉換成醇化物且鹵代烷基磺酸鹽上之取 代均在一個步驟中發生。由於PVAc比PVA更易溶解於有機 溶劑中，所以其具有更廣泛變化之條件之優點。若使用鹵 代烷基磺酸鹽之四烷基銨形式，則該反應通常可因該等四 111346.doc -13- 1378942 烷基銨鹽可溶解於常用溶劑中而均勾 +>° X~f"Y~^S03· M+ (N(Alk)4+)Xf*Y-)s〇3 irf1" (_).勹O 0 or 〆\ I γ S03' M* (Ν(ΛΙΙ〇Λ In another useful variant, the starting polymer is poly(ethyl acetate) (PVA), of course, it is a poly(vinyl alcohol) precursor polymer. Under this condition, the conversion of the ester to the alcoholate in situ and the substitution on the haloalkyl sulfonate occur in one step. PVAc is more soluble in organic solvents than PVA, so it has the advantage of more widely varying conditions. If a tetraalkylammonium form of a haloalkyl sulfonate is used, the reaction is usually due to the four 111346.doc -13- 1378942 Alkyl ammonium salt can be dissolved in common solvents and both hooks +> ° X~f"Y~^S03· M+ (N(Alk)4+)

S03· Μ* (N(Alk)4+) 乙酸乙烯醋)之共聚物。因為乙烯單元之併入例如可有助 於機械強度及耐錄，所以其為有利的。苯乙稀結構亦可 藉由用適當的經酯或〇Η官能彳μ夕取/ 13< 凡 目月"*化之聚（苯乙烯）起始由類似機 制形成。Copolymer of S03·Μ* (N(Alk)4+) vinyl acetate). It is advantageous because the incorporation of ethylene units can, for example, contribute to mechanical strength and resistance to recording. The styrene structure can also be formed by a similar mechanism starting with the appropriate ester or hydrazine functional / 夕 13 13 13 & & * * * * 。 。 。 。 。 。 。 。

户〇, n:m > 1:1(莫耳/莫耳） 苯乙烯型結構 本發明之本乙稀型聚電解質余士 Z —鍵或脂族或芳族連接 體 構之一般結構為：〇, n:m > 1:1 (mole/mole) Styrene-type structure The general structure of the present invention for the ethylidene polyelectrolyte, Z-bond or aliphatic or aromatic linker is:

111346.doc 1378942 W=鍵、Ο、NH、S、SO或 S02 之烷基、芳族或伸烷基-醚伸烷基-醚鍵[例如（- CH2-),.12] Z=鍵、（^至(：12之烷基、芳族或伸烷基-醚伸烷基-醚鍵 n= 1-99莫耳％，較佳大於50%，最佳大於70% m= 1-99莫耳％，較佳小於50%，最佳小於30% A=磺酸根、膦酸根或羧酸根 B =能夠交聯之基團 基於上述一般結構，吾人可想像形成此等類型共聚物之 多種途徑，包括（但不限於）（共）聚合預官能化之單體，及 聚合後改質適當官能化之聚苯乙烯類。形成此等共聚物之 最佳途徑中之一些將於下文概述。 可進行4-乙烯基苯甲基磺酸鈉（NaVBS)與乙烯基苯甲醇 之直接共聚合。此等特殊單體係如文獻中所述合成。 [NaVBS - US 2909508，VBA -Bamford，C. H·，及 Lindsay， Η·; Polymer，14, 3 30-332 (1973)。]此等單體之溶液聚合可 使用標準技術在適當溶劑（諸如DMSO、NMP、DMF、 DM Ac及其類似物）中進行。雖然溶液聚合較佳，但此等單 體之共聚物亦可以乳液或反相乳液型聚合合成。111346.doc 1378942 W=Alkyl, aromatic or alkyl-ether-alkyl-ether linkage of a bond, hydrazine, NH, S, SO or S02 [eg (-CH2-), .12] Z= bond, (^ to (: 12 alkyl, aromatic or alkyl-ether alkyl-ether linkage n = 1-99 mole%, preferably greater than 50%, optimally greater than 70% m = 1-99 Mo Ear %, preferably less than 50%, optimally less than 30% A = sulfonate, phosphonate or carboxylate B = groups capable of crosslinking based on the above general structure, one can imagine multiple ways of forming copolymers of these types, These include, but are not limited to, (co)polymerization of pre-functionalized monomers, and modification of suitably functionalized polystyrenes after polymerization. Some of the best ways to form such copolymers are outlined below. Direct copolymerization of sodium 4-vinylbenzylsulfonate (NaVBS) with vinylbenzyl alcohol. These special single systems were synthesized as described in the literature. [NaVBS - US 2909508, VBA -Bamford, C. H. , and Lindsay, Η·; Polymer, 14, 3 30-332 (1973).] Solution polymerization of these monomers can be carried out in a suitable solvent (such as DMSO, NMP, DMF, DM Ac and the like) using standard techniques. Line. Although the preferred solution polymerization, but also copolymers of these monomers may be emulsion or inverse emulsion polymerization synthesis.

以下展示一種用於合成含有單個醚鍵之磺化苯乙烯單體 111346.doc -15. 1378942 且適用於形成本發明之聚電解質之方法。VBC(來自 Dow(Specialty Monomers division)之商品）係作為 3-乙稀基 異構體及4-乙烯基異構體之混合物獲得。此分子可與各種 α-經基、α-胺基或α-硫化物、ω-續酸鹽分子反應以提供苯 甲基氯位置之親核取代，從而產生在苯乙烯基單元與磺酸 根之間具有可變間隔基之苯乙烯型單體。A method for synthesizing a sulfonated styrene monomer having a single ether bond 111346.doc -15. 1378942 and suitable for use in forming the polyelectrolyte of the present invention is shown below. VBC (commercial from Dow (Specialty Monomers division)) is obtained as a mixture of a 3-ethylene isomer and a 4-vinyl isomer. The molecule can be reacted with various alpha-trans, alpha-amine or alpha-sulfide, ω-thanoate molecules to provide nucleophilic substitution of the benzyl chloride position, resulting in a styrene unit and a sulfonate. A styrene monomer having a variable spacer therebetween.

S03' M+ (NCA^S03' M+ (NCA^

其中VBC=4-乙烯苯曱基氣，3-乙烯基異構體與4-乙烯基異 構體之混合物 W=OH、NH2或 SHWherein VBC = 4-vinyl benzoquinone gas, a mixture of 3-vinyl isomer and 4-vinyl isomer W = OH, NH2 or SH

YsC^-Cu之院基、芳族或伸烧基-喊、伸烧基醚鍵 M=鹼土金屬（Li、Na、K、Rb、Cs)或四烷基銨平衡離子 說明之結構係於W = OH且Y = -CH2-CH2-CH2-時獲得。 接著可將形成之磺化苯乙烯單體如先前所說明與經羥基官 能化之苯乙烯單體共聚合以提供所要共聚物結構。 111346.doc -16-YsC^-Cu's courtyard, aromatic or extended-burning-shouting, extended-burning ether linkage M=alkaline earth metal (Li, Na, K, Rb, Cs) or tetraalkylammonium equilibrium ion structure is described in W Obtained when OH and Y = -CH2-CH2-CH2-. The formed sulfonated styrene monomer can then be copolymerized with a hydroxyl functionalized styrene monomer as previously described to provide the desired copolymer structure. 111346.doc -16-

6如以上說明’該聚電解質上之羥基(或其他可交聯基團) :能基可自經基官能單體獲得。或者，可在⑷聚合期間 ‘用適當㈣官能化之單體，並續後將該酯去保護（轉 )為所要醇。其（與上述磺化單體（聚合物）合成法聯合）將 產生所要最終（共）聚合物結構，如下所示。6 As explained above, the hydroxyl group (or other crosslinkable group) on the polyelectrolyte: the energy group can be obtained from a transfunctional monomer. Alternatively, the monomer functionalized with the appropriate (d) may be '(4) during the polymerization and the ester deprotected (turned) to the desired alcohol. This (in combination with the above sulfonated monomer (polymer) synthesis) will produce the desired final (co)polymer structure as shown below.

Y-C]至c]2之烧基、芳族、院基-醚或伸烧基-醚鍵[例如（_ CH2-)1·丨 2] Z鍵’（^至匚！2之烧基、芳族或烧基醚或伸烧基_醚鍵 R=Cii Cu之烷基或芳族 n= 1-99莫耳％，較佳大於50%，最佳大於70% m=l-99莫耳％ ’較佳小於5〇%，最佳小於3〇0/〇 111346.doc 17 1378942 S錯共聚單體在性質上未必恰姑 σ ^ 隹負不6妤為苯乙烯性的。其僅需 可與磺化（或其他官能性）苯乙烯單體共聚合。YC] to c]2 of the alkyl, aromatic, fenyl-ether or extended alkyl-ether bond [eg (_ CH2-)1·丨2] Z bond' (^ to 匚! 2 of the base, Fang Group or alkylene ether or alkylene group-ether linkage R=Cii Cu alkyl or aromatic n=1-99 mole%, preferably greater than 50%, optimally greater than 70% m=l-99 mole% 'preferably less than 5〇%, optimally less than 3〇0/〇111346.doc 17 1378942 S-type comonomer is not necessarily styrene in nature. It is only styrene. Sulfonated (or other functional) styrene monomers are copolymerized.

〇 >=〇〇 >=〇

RR

S〇3' M+ S03- M+ ls〇i M+ 以類似方式，磺酸根官能基不必在聚合反應之前併入單S〇3' M+ S03- M+ ls〇i M+ In a similar manner, the sulfonate functional group does not have to be incorporated prior to polymerization.

體’且伤。適畲官能性單體之聚合及磺酸根單元之隨後取代 將產生最終結構。說明此等兩種途徑（磺酸根取代及酯去 保瘦）之實例如下：Body' and hurt. Polymerization of the appropriate functional monomer and subsequent substitution of the sulfonate unit will result in the final structure. Examples of these two pathways (sulfonate substitution and ester de-skinning) are as follows:

鍵，ci_Ci2之烧基、院基-芳族、院基_鍵或伸坑基-轉鍵 X=鹵素（Cl、Br、I) W —W ’其中兩者不必具有完全相同的結構 Y=鍵，〇、NH、S、SO、S02 R=C〗至C〗2之烷基或芳族 R=Cl至C>2之烷基或芳族，其不必但可與R相同 η 1 -99莫耳。/。，較佳大於5〇%，最佳大於7〇〇/0 111346.doc •18· 1378942 m = 1-99莫耳％，較佳小於50%，最佳小於30% 在一實施例中，若 W=CH2，W，=鍵，R=CH3，X = Cl，Y =Ο且R1 = CH2-CH2-CH2，貝1J聚電解質之合成可為：Key, ci_Ci2, base, aromatic, ortho-bond or keel-transfer X = halogen (Cl, Br, I) W - W ', two of which do not have to have the exact same structure Y = bond , 〇, NH, S, SO, S02 R = C to C 2 alkyl or aromatic R = Cl to C > 2 alkyl or aromatic, which is not necessarily but the same as R η 1 -99 Mo ear. /. Preferably, greater than 5〇%, optimally greater than 7〇〇/0 111346.doc •18·1378942 m = 1-99 mole%, preferably less than 50%, optimally less than 30%. In one embodiment, W=CH2, W, = bond, R=CH3, X = Cl, Y = Ο and R1 = CH2-CH2-CH2, the synthesis of the shell 1J polyelectrolyte can be:

在一較佳實施例中，本發明之共聚物聚電解質係自單個 均聚物藉由選擇性官能化合成以形成所要（共）聚合物。該 官能化步驟必須受到極為良好之控制以在最終共聚物中產 生所要n: m比率。例如：In a preferred embodiment, the copolymer polyelectrolytes of the present invention are synthesized from a single homopolymer by selective functionalization to form the desired (co)polymer. This functionalization step must be subjected to extremely good control to produce the desired n: m ratio in the final copolymer. E.g:

其中：among them:

WsCrC丨2之烷基、芳族、烷基-醚或伸烷基-醚Alkyl, aromatic, alkyl-ether or alkyl-ether of WsCrC丨2

WbC^-Cu之烷基、芳族、烷基醚或伸烷基醚，但不必與W 相同 X=鹵素（CU、Br、I) X'=鹵素（Cl、Br、I)，其不必與X相同 Y=烷基或芳族酯 111346.doc 19 1378942 M=鹼土金屬（U、Na、K、Rb、Cs)或四烷基銨陽離子 一特定實例如下：WbC^-Cu alkyl, aromatic, alkyl ether or alkyl ether, but not necessarily the same as W X = halogen (CU, Br, I) X' = halogen (Cl, Br, I), which does not have to X is the same Y = alkyl or aromatic ester 111346.doc 19 1378942 M = alkaline earth metal (U, Na, K, Rb, Cs) or tetraalkylammonium cation A specific example is as follows:

另外，該羥基化均聚物可藉由直接聚合類似羥基化單體 形成。其無需轉化自帶有齒化物之單體。羥基化均聚物接 著可如上所示用於形成所要共聚物結構。 鲁Alternatively, the hydroxylated homopolymer can be formed by direct polymerization of a similar hydroxylated monomer. It does not need to be converted from a monomer with a dentate. The hydroxylated homopolymer can then be used to form the desired copolymer structure as indicated above. Lu

其中：W=Cl-Cl2之烷基、芳族、烷基醚或伸烷基-醚。 適用於本發明中之其他笨乙稀型單體包括（但不限於）續 基甜菜驗，其意謂該單體含有糾根基_及其本身之平 衡離子（第四錢）。對於以下展示之類型之苯乙婦基確基甜 菜驗型單體而言，取代無需在2位上而可能在3位或4位或 多個位置上。敍平衡離子亦可能側接於環，且不必為此實 例中所示之侦㈣子。所示之㈣基官能化之單體_ 於此報導中先前描述之彼等單體。如其他系統及如此項技 111346.doc -20. 1378942 術中所熟知’上述共聚物可由在適當溶劑中之典型自由基 共聚合反應產生。Wherein: W=Cl-Cl2 alkyl, aromatic, alkyl ether or alkylene-ether. Other stupid ethylene monomers suitable for use in the present invention include, but are not limited to, a sulphur beet test, which means that the monomer contains a rectifying base _ and its own counter ion (fourth money). For the phenomethoxy-based sweet-scented monomer of the type shown below, the substitution does not need to be in the 2 position but may be in the 3 or 4 position or positions. The counterbalance ions may also be flanked by rings and do not have to be detected (four) as shown in this example. The (iv)-functionalized monomers are shown as their previously described monomers in this report. As described in other systems and such techniques, 111346.doc -20. 1378942, the above copolymers can be produced by typical free radical copolymerization in a suitable solvent.

磺基甜菜餡單體Sulfobe beet monomer

本發明之另一實施例為含有具有側接氟化磺酸根基團之 芳族單體之聚合物或共聚物的聚電解質。一實例為wo 99/673〇4中描述之單體，該案以引用方式併入。此類型之 單體具有如下一般結構： 0 了 （Z) O-CF 2-R卜CF2S〇2Y(SO 2Rf，)n 其中Rf為氟伸烧基或氟伸炫基_謎；γ為C、ο或n;且Rf，為 氟伸烷基或氟伸烷基-醚；及Another embodiment of the invention is a polyelectrolyte comprising a polymer or copolymer having an aromatic monomer pendant to a fluorinated sulfonate group. An example is the monomer described in WO 99/673〇4, which is incorporated by reference. Monomers of this type have the following general structure: 0 (Z) O-CF 2-R Bu CF2S〇2Y(SO 2Rf,)n wherein Rf is a fluorine-expanding group or a fluorine-extension group; γ is C, Or ο; and Rf, is a fluoroalkyl or fluoroalkyl-ether;

R)m (2) O-CF 2-RrCF 2SO 2Y(SO 2Rf% 其中（R)m為可聚合基團' Br或I ;且Rf、Rf，及γ如上所述。 具有側接氟化磺酸根基團之芳族單體可用於形成均聚物， 或其可與其他烯性不飽和單體共聚合形成本發明之聚電解 質。用於形成共聚物之一較佳單體為苯乙烯。接著將該 lH346.doc (I, 丄378942 (共）聚合物摻合至基質聚合物中。 將聚電解質穆合至聚合物或共聚物基質中以形成本發明 之聚合物#合物。該聚合物摻合物可為上述兩種或兩種以 上聚合物之混合物的任何類型，且在此申請案中，其中至 少一種係選自基質聚合物之類別且一種係選自聚電解質之 .類別。較佳地，該聚合物摻合物為所選聚合物之均勻摻合 物。基質聚合物之量可為5至95重量％，且聚電解質之量 可為95至5重量％。較佳地，基質聚合物以4〇重量％至⑽重 量％之量存在，且聚電解質以20重量％至6〇重量％存在。 在多種狀況下，存在於聚電解質相上之酸基團最初為中 和形式。陽離子可由任何選自IA族金屬（Na、K、Cs、Rb) 之離子組成，或者為有機陽離子，諸如鱗、咪唑鑌或苯甲 酿胺娃。為有效地繼續摻合本發明之聚電解質與基質（共） 聚=物之過程，聚電解質上之續酸基團必須首先與質子離 子乂換（質子化）。其可藉由使聚電解質溶液通過已載入適 當離子交換樹脂之管柱完成。該管柱之直徑及長度可視將 要處理之聚電解質之數量改變。典型管柱將具射至 36.0付、較佳為6_至18対之直徑。該管柱長度將具有 12.0付至144.〇叶、較佳為24 〇忖至72时之長度。該管柱 之底。P為錐形且裝配了一活栓或類似裝置以控 備之液體的流量。 〜為提供聚電解質之離子交換（質子化），向該管柱添加一 疋1的離子交換樹脂。D。職Ma讀。n (d〇w㈤露❿， nc·)離子交換樹脂為可使用之-類樹脂的—實例。詳言 111346.doc -22- 1378942R)m (2) O-CF 2-RrCF 2SO 2Y (SO 2Rf% wherein (R)m is a polymerizable group 'Br or I; and Rf, Rf, and γ are as described above. The aromatic monomer of the acid group can be used to form a homopolymer, or it can be copolymerized with other ethylenically unsaturated monomers to form the polyelectrolyte of the present invention. One preferred monomer for forming the copolymer is styrene. The lH346.doc (I, 丄378942 (co)polymer is then blended into the matrix polymer. The polyelectrolyte is incorporated into the polymer or copolymer matrix to form the polymer # conjugate of the present invention. The blend of materials may be of any type of a mixture of two or more of the above polymers, and in this application, at least one of which is selected from the group consisting of matrix polymers and one selected from the group consisting of polyelectrolytes. Preferably, the polymer blend is a homogeneous blend of selected polymers. The amount of matrix polymer may range from 5 to 95% by weight, and the amount of polyelectrolyte may range from 95 to 5% by weight. The matrix polymer is present in an amount of from 4% by weight to (10% by weight), and the polyelectrolyte is present in an amount of from 20% by weight to 6% by weight In various conditions, the acid groups present on the polyelectrolyte phase are initially in a neutralized form. The cations may be composed of any ion selected from Group IA metals (Na, K, Cs, Rb) or an organic cation such as Scale, imidazolium or benzotriamide. In order to effectively continue the process of blending the polyelectrolyte of the present invention with the matrix (co)polymer, the acid-reducing group on the polyelectrolyte must first be exchanged with the proton ion (proton This can be done by passing the polyelectrolyte solution through a column that has been loaded with a suitable ion exchange resin. The diameter and length of the column can vary depending on the amount of polyelectrolyte to be treated. A typical column will shoot at 36.0. Preferably, the diameter is from 6 to 18. The length of the column will have a length of from 12.0 to 144. 〇, preferably from 24 72 to 72. The bottom of the column. P is tapered and assembled A flow plug or similar device to control the flow rate of the liquid. ~ To provide ion exchange (protonation) of the polyelectrolyte, add a 疋1 ion exchange resin to the column. D. Job Ma read. n (d〇w (5) Lucy, nc·) ion exchange resin is available With the - resin - Examples In detail 111346.doc -22- 1378942

之’可使用 Dowex Marathon A、Marathon B 或 Marathon C 樹脂。載入管柱中之樹脂的量等於待離子交換之酸基團之 數目的至少丨至10倍（按製造商之說明）。較佳地，所用樹脂 之量為待離子交換之酸基團之數目的1至5倍。接著用去離 子水洗務管枉若干次，直至自管柱洗出之水不低於pH = 5.〇。接著將經中和之聚電解質溶解於適當溶劑中形成均 質溶液。溶劑應根據聚電解質中存在之特定化學官能基選 擇通㊉使用極性質子性溶劑或極性非質子性溶劑，將聚 電解質溶液添加至管柱頂部且使其流出以與交換樹脂接 觸。將額外溶劑以足以防止樹脂變乾之量添加至管柱之頂 部。繼續監視溶離溶液之pH ^在溶離溶液之pH降至5 〇以 下時，自管柱之底部收集質子化之聚電解質溶液。在？11恢 復至5.0以上時停止聚電解質溶液的收集。藉此獲得質子 化聚電解質溶液。藉由熟習此項技術者所熟知之分析技術 量化任何剩餘陽離子之含量。 在一較佳實施例中，摻合過程係首先使聚電解質上之帶 有酸性質子之可離子化基團與適當氫氧化四烧基敍 (TAAOH)反應形成四烧基錄鹽開始。較佳地，㈣鹽具有 至少186之分子量。適合銨鹽之實例包括：四甲基銨、四 乙基銨、四丙基銨 '四丁基銨、四戊基銨及四己基銨。 此經TAA中和之聚電解f溶液接著可與—溶劑進行溶劑 交換，該溶劑可適當溶解所選基f (共）聚合物。若用於離 子乂換柱中及用κΤΑΑ0Ή中和之溶劑亦溶解基質（此）聚人 物’則此步驟不為必需。—較佳實施例包括溶劑自離= 111346.doc -23- 1378942 換柱運作之容劑"交換"為完全溶解經TAA中和《聚電 及基質（共）聚合物兩者之另一溶劑。此過程較佳由將新溶 劑添加至經TAA中和之溶液中、接著利用加熱及施加真空 (真空蒸餘）將原始溶劑移除組成。用於提供此"溶劑交換二 之其他方法包括：沉殿經TAA中和之聚電解質並隨後過遽 聚合物並重溶解於新的溶劑中。所有原始溶劑一經移除，、 即添加適當量的先前已溶解於相同溶劑中之基質⑷聚八 物。如上所述，在摻合物溶液中，基質聚合物之量可為^ 至95重1 %且聚電解f之量可為似5重量。較佳地，在 摻口物浴液令，基質聚合物係以4〇%至8〇重量％之量存在 且聚電解質係以2〇%至60重量％存在。接著將此摻合溶液 鎮成薄膜或經進-步加工以產生有用物品，諸如離子交換 薄膜。 ' 該掺合溶液之铸造可藉由熟f此項技術者所熟知之多種 不同程序進行。詳言之’選擇熱溶液鑄造。將一定量之聚 合物掺合物置放在-適當基板上。接著使一鋒利金屬刀割 過基板，並且刀與基板之間有-間隙。此間隙之厚度及該 聚合物摻合物溶液之點性控制所形成膜之厚度。所形成膜 之厚度係視材料之最終用途而定且可在i 〇师至2 〇 _之 間變化。較佳地，所形成膜具有1〇〇_至5〇〇〇_且最佳 2〇.〇 μπ^ 250.0 μηι之厚度。接著將此"濕"獏於高溫下在* 氣循環供箱内乾燥。用於乾燥該膜之時間與溫度可廣泛變 化所用之溫度為20°C至250°C，較佳為丨⑻艺至之加它，且 最佳為1聊至2〇η；。該濕膜之乾燥時間亦可廣泛變化。 ϊ I I346.doc •24· 1378942 烘箱滯留時間應商孝上；商田廿1^ ^ ^ /、上適用並可伸鈿’其中其可為1〇秒 至24小時，較佳為1 〇公妒 .刀鐘至2.0小時，且最佳為1〇分鐘至 45.0分鐘》 最終乾燥膜之厚度視乾燥前之濕膜之原始厚度而定。此 厚度將視欲用於最终物品之應用而改變。厚度可為1〇叫 至2.0 mm，較佳為5〇 μιη至5〇〇〇叫，最佳為⑺』叫至 300.0 μτη。乾燥膜係藉由彼等熟習此項技術者所熟悉的典'Dowex Marathon A, Marathon B or Marathon C resin can be used. The amount of resin loaded into the column is equal to at least 10 times the number of acid groups to be ion exchanged (as per the manufacturer's instructions). Preferably, the amount of resin used is from 1 to 5 times the number of acid groups to be ion exchanged. The deionized water is then rinsed several times until the water eluted from the column is not below pH = 5. 〇. The neutralized polyelectrolyte is then dissolved in a suitable solvent to form a homogeneous solution. The solvent should be selected based on the specific chemical functional groups present in the polyelectrolyte to use a polar protic solvent or a polar aprotic solvent to add the polyelectrolyte solution to the top of the column and allow it to flow out to contact the exchange resin. Additional solvent is added to the top of the column in an amount sufficient to prevent the resin from drying out. Continue monitoring the pH of the dissolving solution. When the pH of the dissolving solution drops below 5 ,, the protonated polyelectrolyte solution is collected from the bottom of the column. in? 11 When the recovery to 5.0 or more, the collection of the polyelectrolyte solution was stopped. Thereby, a protonated polyelectrolyte solution was obtained. The amount of any remaining cations is quantified by analytical techniques well known to those skilled in the art. In a preferred embodiment, the blending process begins by reacting an ionizable group having an acidic proton on the polyelectrolyte with a suitable tetrahydrocarbyl hydride (TAAOH) to form a tetraalkylate salt. Preferably, the (iv) salt has a molecular weight of at least 186. Examples of suitable ammonium salts include: tetramethylammonium, tetraethylammonium, tetrapropylammonium 'tetrabutylammonium, tetraamylammonium, and tetrahexylammonium. This TAA-neutralized polyelectrolytic f solution can then be solvent exchanged with a solvent which will suitably dissolve the selected group f (co)polymer. This step is not necessary if the solvent used in the ion exchange column and neutralized with κΤΑΑ0Ή also dissolves the matrix (this). - preferred examples include solvent ionization = 111346.doc -23 - 1378942 Replacing column operation agent "exchange" for complete dissolution of TAA and "polyelectro and matrix (co)polymers Solvent. This process preferably consists of adding a new solvent to the TAA neutralized solution, followed by heating and applying a vacuum (vacuum evaporation) to remove the original solvent. Other methods for providing this "solvent exchange 2 include: sinking the polyelectrolyte neutralized by TAA and then passing the polymer and redissolving it in a new solvent. Once all of the original solvent has been removed, an appropriate amount of the matrix (4) poly-eight which has previously been dissolved in the same solvent is added. As described above, in the blend solution, the amount of the matrix polymer may be from 1 to 95% by weight and the amount of the polyelectrolyte f may be 5 parts by weight. Preferably, in the bath of the admixture, the matrix polymer is present in an amount of from 4% to 8% by weight and the polyelectrolyte is present in an amount of from 2% to 60% by weight. This blended solution is then stencilized or further processed to produce useful articles such as ion exchange membranes. The casting of the blending solution can be carried out by a variety of different procedures well known to those skilled in the art. In detail, 'select hot solution casting. A quantity of the polymer blend is placed on a suitable substrate. A sharp metal knife is then cut through the substrate with a gap between the knife and the substrate. The thickness of the gap and the point of the polymer blend solution control the thickness of the film formed. The thickness of the film formed depends on the end use of the material and can vary from i 〇 to 2 〇 _. Preferably, the film formed has a thickness of from 1 〇〇 to 5 〇〇〇 _ and preferably from 2 〇. 〇 μπ 2 250.0 μη. Then, the "wet" is dried at a high temperature in a * gas circulation tank. The temperature and temperature for drying the film can be varied widely from 20 ° C to 250 ° C, preferably from 丨 (8), and preferably from 1 to 2 ;; The drying time of the wet film can also vary widely. ϊ I I346.doc •24· 1378942 The residence time of the oven should be Shangxiao; Shangtian 廿1^ ^ ^ /, applicable and can be extended, which can be from 1 sec to 24 hours, preferably 1 〇刀. Knife clock to 2.0 hours, and preferably 1 minute to 45.0 minutes. The thickness of the final dried film depends on the original thickness of the wet film before drying. This thickness will vary depending on the application for the final item. The thickness may be from 1 2.0 to 2.0 mm, preferably from 5 〇 μιη to 5 〇〇〇, and optimally (7) 』 to 300.0 μτη. Dry film is a code familiar to those familiar with the art.

型方法自基板移除。通常，膜可直接或借助於-金屬刀自 基板機械剝離。或者，膜可水合或浸沒在水中或溶劑中以 幫助將膜自基板移除。 铸膜中之聚電解質晶嘴大小較佳應小於1〇卿，且更佳 在1 nm至500 nm之間。本文中論述之晶_大小係關於最大 晶脅大小及/或平均晶嘴大小。在一較佳實施例中，所述 晶疇大小為最大晶疇大小，但可為平均晶疇大小。 本發明之聚合物摻合物之質子傳導率大於2〇 Μ—，較The type method is removed from the substrate. Typically, the film can be mechanically peeled from the substrate either directly or by means of a metal knife. Alternatively, the membrane can be hydrated or immersed in water or solvent to aid in the removal of the membrane from the substrate. The size of the polyelectrolyte nozzle in the cast film should preferably be less than 1 〇, and more preferably between 1 nm and 500 nm. The crystal size discussed herein relates to the maximum crystal size and/or average nozzle size. In a preferred embodiment, the domain size is the largest domain size, but may be the average domain size. The polymer blend of the present invention has a proton conductivity greater than 2 〇 , -

佳大於50 mS/cm，且最佳大於1〇〇 mS/cm。另外該聚合 物摻合物具有高程度之機械強度、水合時的低膨脹率、水 解（化學）穩定性及熱水或熱酸環境下的低程度的硫損失（若 $黃化）。 由本發明之聚合物摻合物製造之物品（諸如薄膜）即可直 接供使用’或可經一酸性洗滌步驟進一步處理以移除四烷 基，並同時重新質子化存在於起始（共）聚合物組份上之可 離^化基® H可採用交聯以改良空間穩定性。交聯 可藉由外部因素對存在於聚電解f、基f (共）聚合物或其 111346.doc 1378942 組合上之侧接官能基起作 用而進仃。併入内部交聯基團Preferably greater than 50 mS/cm, and optimally greater than 1 〇〇 mS/cm. In addition, the polymer blend has a high degree of mechanical strength, low expansion at hydration, hydrolyzed (chemical) stability, and low levels of sulfur loss (if yellowed) in hot water or hot acid environments. Articles made from the polymer blends of the present invention, such as films, may be used directly or may be further treated by an acidic washing step to remove tetraalkyl groups while reprotonating is present in the initial (co)polymerization. Crosslinking can be used to improve the stability of the space. Crosslinking can be effected by external factors on the pendant functional groups present on the polyelectrolyte f, the base f (co)polymer or its combination of 111346.doc 1378942. Incorporation of internal crosslinking groups

(/、已侧接在聚電解質或《暂「林、I 貝及基質（共）聚合物上）亦為可行的， 聚電解質及基質（共）聚合物接莫M ^ 接著藉由施加外部刺激（熱或輻 射）而適當活化》 由於上述各種優點，本發 货應用可包括（但不限於 膜、薄膜、燃料電池、塗屉'施工、 变層離子父換樹脂、油回收、生 物膜、電池及其類似物。所锃私ι σ π ^ 所侍物品可用作電池或燃料電池 應用之穿透選擇性薄膜。另外， ^ Γ 所仔物品可應用於構造薄 膜電極組件之電極，可吸妆久接 J及收各種液體，或可引入至增強消 光或多孔織物上或中以增加機械完整性。 聚合物離子薄膜或聚電解質薄膜可由本發明之聚合物摻 合物製成。形成之膜或薄膜可用作一單層，或可為一多層 膜或薄膜之部分。聚合物離子薄膜可由習知薄膜製備方法 (諸如熔體擠出、溶劑澆鑄、乳膠澆鑄及其類似方法）製 備。薄膜電極組件可由本發明之薄膜製成，且可製備使用 此薄膜電極組件之燃料電池。在使用本發明之聚合物形成 薄膜時，該等聚合物可具有任何當量（每公克總聚合物中 知·丨生基團之公克數）且對於聚合物摻合物中存在之聚電解 質’其較佳具有約200至約8,〇〇〇之當量，較佳為約2〇〇至 1，500且甚至更佳為約2〇〇至約ι，4〇〇。 更詳細地，本發明之組合物尤其適用於燃料電池、電池 及其類似物。除在形成聚合物離子交換薄膜中使用本發明 之Μ合物外’燃料電池及電池中使用之設計及組份可與習 知燃料電池及電池中相同。因此，如美國專利第5,795,668 111346.doc . •26· 1378942 號、EP 1 202 365 A1、PCT公開案第 w〇 98/22989、WO 02/075835 及 WO 98/20573 號、Lin 等人之 journai 〇f Applied Polymer Science，第70卷，m-127 (1998)中描述之製造燃料電池 及電池之設計及方式可用於本發明中，具其係以全文引用 之方式併入本文中。薄膜可單獨使用或可與習知填充劑 (諸如矽石及其類似物;)一起使用。燃料電池可使用液體或 氣態燃料，諸如如曱醇之液態烴或如氫氣之氣體❶本發明 之燃料電池能夠在雇範圍之工作條件下工作。本發明之燃 料電池具有多孔支撐層及離子交換樹脂，其中該離子交換 樹脂係支撐於該多孔支撐層之至少一側上。本發明可適用 於氫氣、直接甲醇或其他燃料電池。較佳地，本發明之燃 料電池具有低燃料穿透性、高質子傳導率及/或高機械強 度。薄膜之厚度可為習知的，但較佳為約〇 5至約1〇密耳 (mil)且更佳為約0.5密耳至約5密耳。此外，薄臈較佳具 有約200至約2500之當量，更佳為約2〇〇至約14〇〇。該多孔 支撐層可由任何習知材料製成，諸如含氟聚合物或其他含 烴聚合物（諸如聚烯烴）。該多孔支撐層具有關於孔直徑、 孔隙率及厚度之習知參數。本發明之燃料電池較佳具有極 佳的質子傳導率、耐化學性及低氣體穿透性、相對較高的 電阻及高質子傳導率。 實例 磺酸基烷基化聚（乙烯醇）合成 實例1 :磺酸基丙基化PVA (40%磺化，方法i) 於9(TC將5.0 g聚（乙烯醇）（PVA)(99〇/〇水解， -27- 1 11346.doc(/, has been flanked by polyelectrolytes or "temporary", I shell and matrix (co)polymers are also feasible, polyelectrolytes and matrix (co)polymers are connected to M ^ followed by external stimulation Appropriate activation (heat or radiation) Due to the above various advantages, this shipping application may include (but is not limited to film, film, fuel cell, coating 'construction, variable layer ion replacement resin, oil recovery, biofilm, battery And its analogs. The items served by ι σ π ^ can be used as a penetrating selective film for battery or fuel cell applications. In addition, ^ Γ can be applied to the electrode of the membrane electrode assembly, which can be used for makeup. Long-term J and various liquids, or can be introduced onto or in the enhanced matting or porous fabric to increase mechanical integrity. The polymer ion film or polyelectrolyte film can be made from the polymer blend of the present invention. The film can be used as a single layer or can be part of a multilayer film or film. The polymer ion film can be made by conventional film preparation methods such as melt extrusion, solvent casting, latex casting, and the like. The thin film electrode assembly can be made from the film of the present invention, and a fuel cell using the film electrode assembly can be prepared. When the film of the present invention is used to form a film, the polymer can have any equivalent (per gram of total polymer) Preferably, the polyelectrolyte present in the polymer blend has a polyelectrolyte of from about 200 to about 8, the equivalent of hydrazine, preferably from about 2 to about 1, 500 and even more preferably from about 2 Torr to about ι, 4 〇〇. In more detail, the composition of the present invention is particularly suitable for use in fuel cells, batteries, and the like, except that it is used in forming a polymer ion exchange membrane. The design and components used in the fuel cell and battery of the invention may be the same as in the conventional fuel cell and battery. Thus, for example, U.S. Patent No. 5,795,668, 111, 346, doc., No. 26,378,942, EP 1 202 365 Manufacturing of fuel cells as described in A1, PCT Publication No. WO 98/22989, WO 02/075835 and WO 98/20573, Lin et al., Journai 〇f Applied Polymer Science, Vol. 70, m-127 (1998) And battery design and methods For use in the present invention, it is incorporated herein by reference in its entirety. The film may be used alone or in combination with conventional fillers such as vermiculite and the like; fuel cells may be liquid or gaseous. A fuel, such as a liquid hydrocarbon such as decyl alcohol or a gas such as hydrogen, can be operated under the operating conditions of the present invention. The fuel cell of the present invention has a porous support layer and an ion exchange resin, wherein the ion exchange resin is Supported on at least one side of the porous support layer. The invention is applicable to hydrogen, direct methanol or other fuel cells. Preferably, the fuel cell of the invention has low fuel penetration, high proton conductivity and/or high Mechanical strength. The thickness of the film can be conventional, but is preferably from about 5 to about 1 mil and more preferably from about 0.5 mil to about 5 mils. Further, the thin mash preferably has an equivalent weight of from about 200 to about 2,500, more preferably from about 2 Torr to about 14 Torr. The porous support layer can be made of any conventional material, such as a fluoropolymer or other hydrocarbon-containing polymer such as a polyolefin. The porous support layer has conventional parameters regarding pore diameter, porosity, and thickness. The fuel cell of the present invention preferably has excellent proton conductivity, chemical resistance and low gas permeability, relatively high electrical resistance and high proton conductivity. Example sulfonate alkylated poly(vinyl alcohol) synthesis Example 1: sulfonate-propylated PVA (40% sulfonation, method i) at 9 (TC will be 5.0 g poly(vinyl alcohol) (PVA) (99 〇 /〇 hydrolysis, -27- 1 11346.doc

Aldrich)溶解於200 mL無水DMSO中，接著冷卻至室溫。 在氮氣下，單獨將28.80 g (1.13當量，相對於〇H)3_溴丙烧 磺酸鈉（NaBPS)溶解於1〇〇 mL無水DMSO中。在氮氣下， 將3.0 g (1.1當量，相對於〇H)氫化鈉（NaH)溶解於150 mL· 無水DMSO中以形成漿料。在氮氣下，將該NaH漿料快速 添加至一已配備250 mL加料漏斗、機械搜拌器及隔膜之2 l 圓底燒瓶中。接者將該P VA溶液倒入該加料漏斗中且緩慢 添加至該NaH漿料中並快速攪拌。將此混合物攪拌1小 時’直至氣體析出停止。接著快速添加該NaBPS溶液，且 於室溫下將反應混合物檀拌18小時。加入1. 〇 mL 5.0重量 %之鹽酸水溶液’接著將該反應溶液傾入2 L快速授拌之丙 酮中。過濾出灰白色沉澱物，將其用500 mL丙酮洗務並在 真空中乾燥》(8.50 g，40%)NMR (D2〇): δ 4.40-δ 3.80 (寬峰，4.79Η，骨架 CH-O，丙基-0-CH2)，δ 3.35-δ 3.15 (寬峰，2Η，丙基 CH2-S03)，δ 2.40-δ 2·20 (寬峰，2Η，丙 基 C-CH2-C)，δ 2.20·δ 1·70 (寬峰，4.82Η，骨架 CH2)。 實例2 :磺酸基丙基化PVA (60%磺化，方法1) 除使用溶解於200 mL無水DMSO中之43.33 g NaBPS (1.7 當量’相對於OH)外，此部分之程序同實例1中概述之程序 相同。（12.65 g，59%)NMR (D20): δ 4.40-3.80 (寬峰， 骨架 CH-0，丙基0-CH2)，δ 3.35 - δ 3.15 (寬峰，2Η，丙基 CH2-S03)，δ 2.40-δ 2.20 (寬峰，2Η，丙基 C-CH2-C)，δ 2·20-δ 1.70 (寬峰，3·23Η，骨架 CH2)。 實例3 :磺酸基丙基化PVA (10%磺化，方法1) 111346.doc -28· 1378942 除使用溶解於300 mL無水DMSO中之20.0 g pvA、溶解 於200 mL無水DMSO中之15.46 g NaBPS (〇.15當量，相對 於OH)及100 mL無水DMSO中之1·66 g (0.15當量，相對於 OH) NaH外，此部分之程序同實例1中概述之程序相同。 (26.5 g，75%) 4 NMR (D20): δ 4.40-3.80 (寬峰，μη，骨 架CH-O，丙基0-CH2)，δ 3.35-δ 3.15 (寬峰，2Η，丙基 CH2-S03)，δ 2.40-δ 2.20 (寬峰 ’ 2.17Η ’ 丙基C-CH2-C), δ 2·20-δ 1.70 (寬峰，23.5Η，骨架 CH2)。 實例4 :磺酸基丙基化PVA (100%磺化，方法2) 於90°C將5.0 g聚（乙烯醇）（PVA)(99%水解，Mw〜144k， Aldrich)溶解於200 mL無水DMSO中，接著冷卻至室溫。 在氮氣下，單獨將13.90 g (1.00當量’相對於〇H)丙烷續 内酯溶解於50 mL無水DMSO中。在氮氣下，將3.0 g (1.1 當量，相對於OH)氫化鈉（NaH)溶解於150 mL無水DMSO中 以形成漿料。在氮氣下，將該NaH漿料快速添加至一已配 備250 mL加料漏斗、機械攪拌器及隔膜之2 l圓底燒瓶 中。接著將該PVA溶液倒入該加料漏斗中且緩慢添加至該 NaH漿料中並快速攪拌。將此混合物攪拌1小時，直至氣 體析出停止。接著經15分鐘添加該丙烷續内酯溶液，且於 室溫下將反應混合物攪拌1 8小時。加入1 ·〇 mL 5·0重量％ 之鹽酸水溶液，接著將該反應溶液傾入2 L快速攪拌之丙 酮中。過渡出灰白色沉澱物，將其用5〇〇 mL丙酮洗滌並在 真空中乾燥。（20.2 g，95%)NMR (D20): δ 4.40-3.80 (寬 峰，2.66Η ’ 骨架CH_〇，丙基〇_CH2)，δ 3 35_δ 3 15 (寬 m346.doc -29- 1378942 峰，2H，丙基CH2-S03)，δ 2.40-δ 2.20 (寬峰，2H，丙基C· CH2-C)，δ 2.20-δ 1.70 (寬蜂，1.98H，骨架 CH2)。 實例5 :磺酸基丙基化PVA (70%磺化，方法2)Aldrich) was dissolved in 200 mL of anhydrous DMSO and then cooled to room temperature. Under nitrogen, 28.80 g (1.13 equivalents, relative to 〇H) of sodium bromopropane sulfonate (NaBPS) was dissolved in 1 mL of anhydrous DMSO. 3.0 g (1.1 equivalents, relative to 〇H) of sodium hydride (NaH) was dissolved in 150 mL of anhydrous DMSO under nitrogen to form a slurry. The NaH slurry was quickly added under nitrogen to a 2 l round bottom flask equipped with a 250 mL addition funnel, mechanical stirrer and septum. The PVA solution was poured into the addition funnel and slowly added to the NaH slurry and stirred rapidly. The mixture was stirred for 1 hour until gas evolution ceased. The NaBPS solution was then quickly added and the reaction mixture was sanded for 18 hours at room temperature. 1. 〇 mL 5.0% by weight aqueous hydrochloric acid was added. Then, the reaction solution was poured into 2 L of rapidly-mixed acetone. The off-white precipitate was filtered off, washed with 500 mL of acetone and dried in vacuo. (8.50 g, 40%) NMR (D2 〇): δ 4.40-δ 3.80 (wide peak, 4.79 Η, skeleton CH-O, Propyl-0-CH2), δ 3.35-δ 3.15 (wide peak, 2 Η, propyl CH2-S03), δ 2.40-δ 2·20 (wide peak, 2 Η, propyl C-CH2-C), δ 2.20 · δ 1·70 (wide peak, 4.82 Η, skeleton CH2). Example 2: Sulfopropylpropylated PVA (60% sulfonation, Method 1) The procedure for this section is the same as in Example 1 except that 43.33 g of NaBPS (1.7 equivalents vs. OH) dissolved in 200 mL of anhydrous DMSO was used. The procedures outlined are the same. (12.65 g, 59%) NMR (D20): δ 4.40-3.80 (broad peak, skeletal CH-0, propyl 0-CH2), δ 3.35 - δ 3.15 (broad peak, 2 Η, propyl CH2-S03), δ 2.40-δ 2.20 (wide peak, 2 Η, propyl C-CH2-C), δ 2·20-δ 1.70 (wide peak, 3.23 Η, skeleton CH2). Example 3: sulfonate-propylated PVA (10% sulfonation, Method 1) 111346.doc -28· 1378942 Except for the use of 20.0 g of pvA dissolved in 300 mL of anhydrous DMSO, 15.46 g dissolved in 200 mL of anhydrous DMSO The procedure for this part was the same as that outlined in Example 1 except for NaBPS (〇15 equivalent, relative to OH) and 1.66 g (0.15 equivalents vs. OH) NaH in 100 mL anhydrous DMSO. (26.5 g, 75%) 4 NMR (D20): δ 4.40-3.80 (broad peak, μη, backbone CH-O, propyl 0-CH2), δ 3.35-δ 3.15 (broad peak, 2 Η, propyl CH2- S03), δ 2.40-δ 2.20 (wide peak ' 2.17 Η 'propyl C-CH2-C), δ 2·20-δ 1.70 (wide peak, 23.5 Å, skeleton CH2). Example 4: Sulfopropylated PVA (100% sulfonation, Method 2) 5.0 g of poly(vinyl alcohol) (PVA) (99% hydrolyzed, Mw~144k, Aldrich) was dissolved in 200 mL of anhydrous at 90 °C. In DMSO, it was then cooled to room temperature. 13.90 g (1.00 equivalents vs. 〇H) propane lactone was dissolved in 50 mL of anhydrous DMSO alone under nitrogen. 3.0 g (1.1 equivalents, relative to OH) of sodium hydride (NaH) was dissolved in 150 mL of anhydrous DMSO under nitrogen to form a slurry. The NaH slurry was quickly added under nitrogen to a 2 l round bottom flask equipped with a 250 mL addition funnel, mechanical stirrer and septum. The PVA solution was then poured into the addition funnel and slowly added to the NaH slurry and stirred rapidly. The mixture was stirred for 1 hour until the gas evolution stopped. The propane lactone solution was then added over 15 minutes and the reaction mixture was stirred at room temperature for 18 hours. 1 · 〇 mL of a 5.0% by weight aqueous hydrochloric acid solution was added, and then the reaction solution was poured into 2 L of rapidly stirred acetone. The off-white precipitate was transferred, washed with 5 mL of acetone and dried in vacuo. (20.2 g, 95%) NMR (D20): δ 4.40-3.80 (broad peak, 2.66 Η 'backbone CH_〇, propyl hydrazine_CH2), δ 3 35_δ 3 15 (width m346.doc -29- 1378942 peak , 2H, propyl CH2-S03), δ 2.40-δ 2.20 (wide peak, 2H, propyl C. CH2-C), δ 2.20-δ 1.70 (broad bee, 1.98H, backbone CH2). Example 5: Sulfopropylpropylated PVA (70% sulfonation, Method 2)

除使用溶解於450 mL無水DMSO中之25.0 g PVA、溶解 於100 mL無水DMSO中之51.0 g丙烷磺内酯及450 mL無水 DMSO中之10.91 g (0.80當量，相對於OH) NaH外，此部分 之程序同實例4中概述之程序相同。（106.8 g，128% (DMSO 雜質））4 NMR (D20): δ 4.40-3.80 (寬峰，3.17H，骨架 CH-0，丙基0-CH2)，δ 3.35-δ 3.15 (寬峰，2H，丙基（：112-S03)，δ 2·40-δ 2.20 (寬峰，2Η，丙基C-CH2-C), δ 2.20-δ 1·7〇 (寬峰，2.65Η，骨架 CH2)。 實例6 :磺酸基丙基化PVA (50%磺化，方法2)This section was used except that 25.0 g of PVA dissolved in 450 mL of anhydrous DMSO, 51.0 g of propane sultone dissolved in 100 mL of anhydrous DMSO, and 10.91 g (0.80 equivalents, relative to OH) of NaH in 450 mL of anhydrous DMSO were used. The procedure is the same as that outlined in Example 4. (106.8 g, 128% (DMSO impurity)) 4 NMR (D20): δ 4.40-3.80 (broad peak, 3.17H, backbone CH-0, propyl 0-CH2), δ 3.35-δ 3.15 (wide peak, 2H , propyl (: 112-S03), δ 2·40-δ 2.20 (wide peak, 2 Η, propyl C-CH2-C), δ 2.20-δ 1·7〇 (wide peak, 2.65 Η, skeleton CH2) Example 6: Sulfopropylpropylated PVA (50% sulfonation, Method 2)

除使用溶解於200 mL無水DMSO中之20.0 g PVA、溶解 於100 mL無水DMSO中之28.10 g丙烷磺内酯（0.50當量，相 對於OH)及150 mL無水DMSO中之5.46 g (0.50當量，相對 於OH) NaH外，此部分之程序同實例4中概述之程序相 同。（52.5 g，99%) 4 NMR (D20): δ 4.40-3.80 (寬峰， 3.83Η，骨架 CH-0，丙基0-CH2)，δ 3·35-δ 3.15 (寬峰， 2Η，丙基CH2-S03)，δ 2.40-δ 2.20 (寬峰，2Η，丙基0(：112-C)，δ 2.20-δ 1.70 (寬峰，3.87Η，骨架 CH2)。In addition to using 20.0 g PVA dissolved in 200 mL anhydrous DMSO, 28.10 g propane sultone (0.50 equivalents vs. OH) dissolved in 100 mL anhydrous DMSO and 5.46 g (0.50 equivalents in 150 mL anhydrous DMSO, relative The procedure for this part is the same as the procedure outlined in Example 4 except for OH) NaH. (52.5 g, 99%) 4 NMR (D20): δ 4.40-3.80 (broad peak, 3.83 Η, skeleton CH-0, propyl 0-CH2), δ 3·35-δ 3.15 (wide peak, 2 Η, C Base CH2-S03), δ 2.40-δ 2.20 (wide peak, 2 Η, propyl 0 (: 112-C), δ 2.20-δ 1.70 (wide peak, 3.87 Η, backbone CH2).

實例7 :磺酸基丁基化PVA 除使用溶解於350 mL無水DMSO中之34.0 g PVA、85.0 g (63.6 mL)丁烷磺内酯（0.80當量，相對於OH)及250 mL無水 DMSO中之19.47 g (1_05當量，相對於OH) NaH外，此部分 111346.doc -30- 1378942 之程序同實例4中概述之程序相同。（128.7 g，103% (殘留 DMSO)) NMR (D20): δ 6.05-5.81 (寬峰m，0.29H，烯丙 基 CH)，δ 5.25-δ 5.05 (寬峰 m，0.58H，婶丙基CH2)，δ 4.16-δ 3.40 (寬峰，2.45H，骨架CH-0，丁基-0-CH2)，δ 3.10-δ 2·85 (寬峰m，2Η，丁基-CH2-S03)，δ 2.60-δ 2.40 (寬峰m， 0.59Η烯丙基〇C-CH2-)，δ 2·10-δ 0.50.(寬峰，5.42Η，丁 基-CH2-CH2-，骨架-CH2-)。 磺酸基烷基化聚苯乙烯共聚物合成 單體合成 實例8 :乙烯基苯曱基磺酸鈉（NaVBS)，程序a 將亞硫酸鈉（872.1 g，6.919 mol, Aldrich)及氯化四丁基 錢（37.0 g，〇·ΐ33 mol，Fluka)於去離子水（6000.0 g，6.00 L) 中之溶液倒入一 22 L圓底燒瓶中並加熱至45。(：並機械攪 拌。將乙烯基苯曱基氯（1000.0 g，6.29 mol，Dow，96% 純’ 57%間位，43%對位）添加至碘化鈉（1037 g，6.919 mol， Aldrich)於丙酮（4740 g，6·00 L)中之溶液中，將其添加至 一 12 L圓底燒瓶中並於40°c下攪拌0 25小時。藉由過濾移 除沉澱物（NaCl)並用200 mL丙酮洗滌。立即將經過濾之丙 酮溶液添加至鹽水溶液中。於40°C下將兩相混合物攪拌8〇 分鐘。在真空中蒸發丙闕。過遽剩餘的含水混合物以得到 白色糊狀的濕乙烯基苯甲基磺酸鈉（NaVBS)。在真空中乾 燥該糊狀物。（694 g，50.1%) NMR (D2〇): δ 7.30-7.55 (m，4Η ’ 芳族），S 6.80 (dd，1Η，乙烯基），δ 5.87 (dd，1Η， 乙烯基），δ 5.33 (dd，1H’ 乙烯基），δ 4·16 (s，2H，苯曱 111346.doc -31 · 1378942 基）。Example 7: Sulfonicated Butylated PVA Except using 34.0 g PVA, 85.0 g (63.6 mL) butane sultone (0.80 equivalents vs. OH) dissolved in 350 mL anhydrous DMSO and 250 mL anhydrous DMSO 19.47 g (1_05 eq., relative to OH) The procedure for this section 111346.doc -30- 1378942 is the same as that outlined in Example 4. (128.7 g, 103% (residual DMSO)) NMR (D20): δ 6.05-5.81 (broad peak m, 0.29H, allyl CH), δ 5.25-δ 5.05 (broad peak m, 0.58H, fluorenylpropyl) CH2), δ 4.16-δ 3.40 (wide peak, 2.45H, backbone CH-0, butyl-0-CH2), δ 3.10-δ 2·85 (wide peak m, 2Η, butyl-CH2-S03), δ 2.60-δ 2.40 (wide peak m, 0.59 decyl propyl C-CH2-), δ 2·10-δ 0.50. (wide peak, 5.42 Η, butyl-CH2-CH2-, skeleton-CH2-) . Sulfonic acid alkylated polystyrene copolymer synthesis monomer synthesis Example 8: sodium vinyl benzoyl sulfonate (NaVBS), procedure a sodium sulfite (872.1 g, 6.919 mol, Aldrich) and tetrabutyl chlorinated A solution of (37.0 g, 〇·ΐ33 mol, Fluka) in deionized water (6000.0 g, 6.00 L) was poured into a 22 L round bottom flask and heated to 45. (: mechanically stirred. Vinyl phenylhydrazine chloride (1000.0 g, 6.29 mol, Dow, 96% pure '57% meta, 43% para) was added to sodium iodide (1037 g, 6.919 mol, Aldrich) In a solution of acetone (4740 g, 6·00 L), it was added to a 12 L round bottom flask and stirred at 40 ° C for 0 25 hours. The precipitate was removed by filtration (NaCl) and used with 200 Wash with mL of acetone. Immediately add the filtered acetone solution to the brine solution. Stir the two-phase mixture for 8 minutes at 40 ° C. Evaporate the propionate in vacuo. The remaining aqueous mixture was passed over to give a white paste. Wet sodium vinyl sulfonate (NaVBS). The paste was dried in vacuo (694 g, 50.1%) NMR (D2 〇): δ 7.30-7.55 (m, 4 Η 'aromatics), S 6.80 (dd, 1 Η, vinyl), δ 5.87 (dd, 1 Η, vinyl), δ 5.33 (dd, 1H' vinyl), δ 4·16 (s, 2H, benzophenone 111346.doc -31 · 1378942 ).

實例9:乙烯基苯甲基磺酸鈉（NaVBS)，程序B 於室溫下給100加侖之玻璃襯裏之反應器裝入46.5加余 水及20.0加舍丙酮。向該混合物中添加18.0公斤亞硫酸 鈉、1.0公斤碘化鈉及20.0公斤乙烯基苯曱基氯（D〇w Specialty Monomers，55%間位、45%對位異構體）。以說氣 充氣此混合物30分鐘，接著將其加熱至50°C並維持此溫度 24小時。接著’藉由真空蒸餾移除丙酮及大約2〇加侖水。 將剩餘漿料冷卻至10°C並過濾，回收淺黃色固體。將據液 送回至反應器，且藉由真空蒸餾移除額外的15加侖水。合 併該等固體並於40°C下在真空中乾燥。回收之產量為丨^ 公斤（45%)。4 NMR (D20):Example 9: Sodium vinylbenzylsulfonate (NaVBS), Procedure B A 100 gallon glass lined reactor was charged with 46.5 plus water and 20.0 plus acetone at room temperature. To the mixture were added 18.0 kg of sodium sulfite, 1.0 kg of sodium iodide and 20.0 kg of vinyl benzoyl chloride (D〇w Specialty Monomers, 55% meta, 45% para isomer). This mixture was aerated for 30 minutes, then heated to 50 ° C and maintained at this temperature for 24 hours. Next, acetone was removed by vacuum distillation and approximately 2 gallons of water was removed. The remaining slurry was cooled to 10 ° C and filtered to recover a pale yellow solid. The liquid was returned to the reactor and an additional 15 gallons of water was removed by vacuum distillation. The solids were combined and dried in vacuo at 40 °C. The recovered output is 丨^ kg (45%). 4 NMR (D20):

實例10 :乙烯基苯甲醇（VBA)，程序A 將乙烯基笨甲基氣（VBC，90%，間位及對位異構體之混 合物，穩定，4.3 g，25 mmol)添加至乙酸鉀（KOAc)(3.2 g， 3 3 mmol)於DMSO (11 .〇 g)中之混合物中。將該混合物於 4〇°C下攪拌2小時。取出5 mL反應混合物樣本且將其添加 至10 mL水中。將此溶液用2〇 mL乙酸乙酯萃取兩次。將乙 酸乙醋蒸發得到黃色油。iH NMR (DMSO-d6): δ 7,35 (m， 4H ’ 芳族），δ 6·70 (m，1H，乙烯基），δ 5.75 (d，1H，乙烯 基），δ 5.25 (d，1H，乙烯基）δ 5 07 (s，2H，笨甲基）52.07 (s，3H，曱酯）。Example 10: Vinylbenzyl alcohol (VBA), Procedure A A vinyl stupid methyl gas (VBC, 90%, a mixture of meta and para isomers, stable, 4.3 g, 25 mmol) was added to potassium acetate ( KOAc) (3.2 g, 3 3 mmol) in a mixture of DMSO (11. g). The mixture was stirred at 4 ° C for 2 hours. A 5 mL sample of the reaction mixture was taken and added to 10 mL of water. This solution was extracted twice with 2 mL of ethyl acetate. Ethyl acetate was evaporated to give a yellow oil. iH NMR (DMSO-d6): δ 7,35 (m, 4H 'aromatic), δ 6·70 (m, 1H, vinyl), δ 5.75 (d, 1H, vinyl), δ 5.25 (d, 1H, vinyl) δ 5 07 (s, 2H, methyl) 52.07 (s, 3H, decyl ester).

將乙醇（7 mL)、去離子水（36 mL)及NaOH (1.19 g，30 mmol) 添加至剩餘的反應混合物中，並回流1小時。用40 mL 111346.doc -32- (¾) 1378942Ethanol (7 mL), deionized water (36 mL) and NaOH (1.19 g, 30 mmol) were added to the remaining mixture and refluxed for one hour. With 40 mL 111346.doc -32- (3⁄4) 1378942

EtOAc萃取、繼而經Mg2S04乾燥並將溶劑蒸發得到黃色油 (3·18 g，99%產率）。4 NMR (DMS0-d6): δ 7.35 (m，4H， 芳族），δ 6.70 (m，1H，乙烯基），δ 5.75 (d，1H，乙烯基），δ 5_25 (d，1H，乙烯基），§ 4.65 (d，2H，苯曱基）。Extracted with EtOAc, dried over EtOAc (EtOAc)EtOAc. 4 NMR (DMS0-d6): δ 7.35 (m, 4H, aromatic), δ 6.70 (m, 1H, vinyl), δ 5.75 (d, 1H, vinyl), δ 5_25 (d, 1H, vinyl ), § 4.65 (d, 2H, benzoinyl).

實例11:乙烯基苯甲醇（VBA)，程序B 為一 12 L三頸圓底燒瓶配備機械攪拌器、冷凝器及熱電 偶。向此燒瓶中添加2.3 L冰乙酸' 663.0 g乙酸鉀及613.7 g 乙烯基苯甲基氯。將此混合物於n 0〇c下攪拌丨8小時。使 用薄層層析法確定反應之程度。用2 L EtOAc (乙酸乙酯） 萃取產物兩次。合併有機萃取物並用NaHC03 (碳酸氫納） 之水溶液洗滌’直至呈中性（ph〜7)，且接著再次用2 L水洗 務。於減壓下移除EtOAc以產生703 g淺褐色油。（99%產 率）。H NMR (DMSO-d6): δ 7.35 (m，4H，芳族），δ 6.70 (m，1Η，乙烯基），δ 5.75 (d，1Η，乙烯基），δ 5.25 (d，1Η， 乙烯基），δ 5.07 (s，2H，苯甲基），6 2.07 (s，3H，甲酯）。 給已配備機械授拌器、冷凝器及熱電偶之第二12 l燒瓶 裝入761.0 g (13.56 mol) K0H (氫氧化鉀）、3.5 L (86.6 mol)Example 11: Vinylbenzyl alcohol (VBA), Procedure B A 12 L three-necked round bottom flask was equipped with a mechanical stirrer, condenser and thermocouple. To the flask was added 2.3 L of glacial acetic acid '663.0 g of potassium acetate and 613.7 g of vinylbenzyl chloride. The mixture was stirred at 0 ° C for 8 hours. The extent of the reaction was determined using thin layer chromatography. The product was extracted twice with 2 L EtOAc (EtOAc). The organic extracts were combined and washed with an aqueous solution of NaHC03 (NaHCO3) until neutral (pH~7), and then washed again with 2 L of water. The EtOAc was removed under reduced pressure to give EtOAc. (99% yield). H NMR (DMSO-d6): δ 7.35 (m, 4H, aromatic), δ 6.70 (m, 1 Η, vinyl), δ 5.75 (d, 1 Η, vinyl), δ 5.25 (d, 1 Η, vinyl ), δ 5.07 (s, 2H, benzyl), 6 2.07 (s, 3H, methyl ester). A second 12 l flask equipped with a mechanical stirrer, condenser and thermocouple was charged with 761.0 g (13.56 mol) K0H (potassium hydroxide) and 3.5 L (86.6 mol).

MeOH (曱醇）、l.i l (58.38 mol)水，及來自先前步驟的 703 g乙酸乙烯基苯曱酯，從而生成暗紅色溶液。加熱該 反應至回流並繼而TLC，其指示反應於丨小時後完成。將 反應混合物冷卻至室溫並用4 L二***萃取兩次。將醚層 用4 L氯化鈉水溶液洗滌三次，接著用4 L水洗滌兩次。用 MgS〇4 (硫酸鎂）乾燥醚層並過濾。於減壓下將醚自濾液移 除以產生褐色油（487.0 §，91%產率）（總體為94%)。4!^]^11 111346.doc •33- 1378942 (DMS0-d6): δ 7.35 (m，4H，芳族），δ 6.70 (m，1H，乙烯 基），δ 5.75 (d，1H，乙烯基），δ 5.25 (d，1H，乙烯基），δ 4·65 (d，2Η，苯甲基）。 - 實例12 :氯化4-(乙烯基苯基）鎂（vP-MgCl) • 給一 250如雙頸圓底燒瓶裝上2.5 g鎂（Mg)屑（〇·ΐ4 m〇i)、 一攪拌棒、一加料漏斗及一冷凝器。在氮氣下，用力攪拌 鎮屑隔夜。經由注射器將1〇〇 二溴乙烷於1〇⑹無 φ 水四氫呋喃（THF)中之溶液添加至Mg卡。將此混合物在室 下攪拌’直至其變成淺褐色。經由加料漏斗經1小時添 加於30 ml無水THF中之13.85 g 4-氯苯乙烯（(M mol)，同 時將反應溫度維持在1(rc以下。在加入所有4·氯苯乙烯 後，將混合物升溫至室溫並另外攪拌3〇分鐘。接著升高溫 度並回流2小時以上。將反應冷卻至〇。〇並立即用於隨後之 反應。 實例13: 1-(4-乙烯基苯基）乙醇（lvpE) • 向如此部分之實例12中製備之VP-MgC】溶液中加入4. S4 g 乙酿（0.11福）於50 ml THFt之溶液。經由加料漏斗將該 溶液逐滴加入，同時將反應溫度維持在〇t。接著將反應 於0C下另外授拌1小時。經由加料漏斗加入6〇 2 M鹽酸 (HC1)水溶液’同時將溫度維持在耽以下。過遽反應且 用100 mL二***萃取兩次。合併有機相，經乞燥並 過瀘、。於室溫下藉由真空蒸發移除二乙驗。（ΐ3·6 g淺黃色 油 ’ 9K6%)。丨η NMR _s〇_d6): s 74〇 ⑼，4h，芳族） δ6.72〇η，1Η，乙烤基），55.82(d lH，乙稀基），δ 5 23 ^ 111346.doc -34· 1378942 1H ’ 乙稀基），δ 4.73 (q，1H，CH-O)，δ 1.35 (d，3H，CH3)。 實例14 : 2-(4-乙烯基苯基）乙醇（2-VPE) 向如此部分之實例12中製備之VP-MgCl溶液中添加4 84 g 環氧乙烷（0.11 mol)K50 ml THF中之溶液。經由加料漏斗 經1小時添加該溶液，同時將反應混合物維持在。在添 加完成後於(TC下攪拌1小時以上》接著於〇艺下將該反應 另外攪拌1小時。經由加料漏斗加入6〇 ml 2 M鹽酸（HC1)水 溶液’同時將溫度維持在2〇〇c以下。過濾反應且用1〇〇 二***萃取兩次。合併有機相、經MgS〇4乾燥並過濾。於 室溫下藉由真空蒸發移除二***。（11.2 g白色蠟狀固體， 75.7%)。NMR (DMSO-d6): δ 7.20-δ 7.40 (m，4H，芳 族）’ δ 6.72 (m，1H，乙烯基），δ 5.75 (d，1H，乙烯基），§ 5.23 (d，1Η’ 乙烯基），δ 4.70 (t，1Η，0Η)，δ 3 65 (t，2Η， CH2-0)，δ 2.72 (t，2Η, CH2-C)。 (共）聚合物合成（聚合作用） 實例 14 :聚（NaVBS) 將乙烯基笨曱基磺酸鈉（2〇 00 g，0 073则1，80%純）於去 離子水（266 g)中之溶液加熱至4(TC同時攪拌，且接著以氮 氣充氣10分鐘。在充氣時期最後加入Vazo 56 WSP (74 mg, 0·27 mmol, DuPont)。將反應混合物加熱至85°C並授拌24 小時。將聚合物沉澱於丙酮（2.25 L)中，並將液體傾析。 在真空中將其乾燥得到聚（乙烯基笨曱基磺酸鈉）（半透明 片，14.55 g，91%)。（GPC: Mw=91 k，PDI=2.2相對於聚丙 烯酸嚴格標準），〗H NMR (D20): δ 7.22 (寬峰，2H，芳 111346.doc -35- 1378942 族），δ 6.67 (寬峰，2H，芳族），δ 4.15 (寬峰，2H，苯曱基 CH2)，δ 0.30-2.55 (寬译，3H，骨架 CH，CH2)。 實例15 :聚（VBA) 將10.0 g乙烯基苯曱醇（VBA)(74.6 mol)、29.0 mL去離子 水、3.82 mL20.0重量％之十二烷基磺酸鈉（SDDS)(2.48 mol) 水溶液、1.83 mL 5.0重量％之碳酸氫鈉（NaHCO3)(0.86 mol) 水溶液及1.83 mL 5.0重量％之過硫酸鉀水溶液（0.5莫耳％， 相對於VBA)添加至一 1 00 mL圓底燒瓶中。將此混合物冷 卻至〇°C歷時1小時，此後加入1.30 mL 5.0重量％之焦亞硫 酸鈉（0.5莫耳％，相對於VBA)水溶液。以氮氣充氣該溶液 1 5分鐘。用一橡膠隔膜封閉該燒瓶且將其置於30°C油浴中 2.5小時。在此之後，將聚合物沉澱於300 mL曱醇中，過 濾並在真空中乾燥。（9.80 g, 98%)，（GPC: Mw=80 k， PDI=4.0相對於聚丙烯酸嚴格標準），NMR (DMSO-d6): δ 7·30-δ 6.10 (寬峰，4Η，芳族），δ 4.65-δ 4.25 (寬峰，2Η， 苯曱基CH2)，δ 2.20-δ 0.90 (寬峰，3Η，骨架CH，CH2)。 實例16 :聚（VBC)MeOH (nonanol), l.i l (58.38 mol) of water, and 703 g of vinyl benzoyl acetate from the previous step gave a dark red solution. The reaction was heated to reflux and then TLC, which indicated that the reaction was completed after EtOAc. The reaction mixture was cooled to room temperature and extracted twice with 4 L diethyl ether. The ether layer was washed three times with a 4 L aqueous sodium chloride solution and then twice with 4 L water. The ether layer was dried over MgS 4 (MgSO.sub.4) and filtered. The ether was removed from the filtrate under reduced pressure to give a brown oil (487.0 s, 91% yield) (94% overall). 4!^]^11 111346.doc •33- 1378942 (DMS0-d6): δ 7.35 (m, 4H, aromatic), δ 6.70 (m, 1H, vinyl), δ 5.75 (d, 1H, vinyl ), δ 5.25 (d, 1H, vinyl), δ 4·65 (d, 2 Η, benzyl). - Example 12: 4-(vinylphenyl)magnesium chloride (vP-MgCl) • A 250 ml double-necked round bottom flask was charged with 2.5 g of magnesium (Mg) crumb (〇·ΐ4 m〇i), stirred A rod, an addition funnel and a condenser. Stir the chips overnight under nitrogen. A solution of 1 Torr of dibromoethane in 1 Torr (6) of φ water in tetrahydrofuran (THF) was added via syringe to a Mg card. This mixture was stirred under the chamber until it turned light brown. 13.85 g of 4-chlorostyrene ((M mol) in 30 ml of anhydrous THF was added via an addition funnel over 1 hour while maintaining the reaction temperature below 1 (rc below. After all 4 chlorostyrene was added, the mixture was The temperature was raised to room temperature and stirred for an additional 3 minutes. The temperature was then raised and refluxed for more than 2 hours. The reaction was cooled to hydrazine and immediately used in the subsequent reaction. Example 13: 1-(4-vinylphenyl)ethanol (lvpE) • To a solution of such a portion of the VP-MgC prepared in Example 12, a solution of 4. S4 g (0.11 liter) in 50 ml of THFt was added. The solution was added dropwise via an addition funnel while the reaction was The temperature was maintained at 〇t. The reaction was then stirred for another hour at 0 C. The aqueous solution of 6〇2 M hydrochloric acid (HC1) was added via an addition funnel while maintaining the temperature below 耽. The reaction was over-extracted and extracted with 100 mL of diethyl ether. The organic phase was combined, dried and dried, and the residue was removed by vacuum evaporation at room temperature (ΐ3·6 g pale yellow oil '9K6%). 丨η NMR _s〇_d6) : s 74〇(9), 4h, aromatic) δ6.72〇η,1Η, B-bake base), 55.82(d lH, B Dilute), δ 5 23 ^ 111346.doc -34· 1378942 1H 'Ethyl), δ 4.73 (q, 1H, CH-O), δ 1.35 (d, 3H, CH3). Example 14: 2-(4-Vinylphenyl)ethanol (2-VPE) To a portion of the VP-MgCl solution prepared in Example 12 was added 4 84 g of ethylene oxide (0.11 mol) in K50 ml THF. Solution. The solution was added via an addition funnel over 1 hour while maintaining the reaction mixture. After the completion of the addition, the mixture was stirred at (TC for 1 hour or more) and the reaction was further stirred for 1 hour under a succinct process. 6 liters of a 2 M aqueous solution of hydrochloric acid (HC1) was added via an addition funnel while maintaining the temperature at 2 〇〇c. The reaction was filtered and extracted twice with 1 mL of EtOAc. EtOAc (EtOAc m. NMR (DMSO-d6): δ 7.20-δ 7.40 (m, 4H, aromatic)' δ 6.72 (m, 1H, vinyl), δ 5.75 (d, 1H, vinyl), § 5.23 (d, 1Η' vinyl), δ 4.70 (t,1Η,0Η), δ 3 65 (t,2Η, CH2-0), δ 2.72 (t,2Η, CH2-C). (co)polymer synthesis (polymerization) Example 14: Poly(NaVBS) A solution of sodium vinyl alkane sulfonate (2 〇 00 g, 0 073, 1, 80% pure) in deionized water (266 g) was heated to 4 (TC while stirring) And then aerated with nitrogen for 10 minutes. At the end of the aeration period, Vazo 56 WSP (74 mg, 0·27 mmol, DuPont) was added. The reaction mixture was heated to 85 ° C and allowed to mix for 24 hours. In acetone (2.25 L), the liquid was decanted. It was dried in vacuo to give poly(vinyl succinylsulfonate) (translucent sheet, 14.55 g, 91%). (GPC: Mw=91 k, PDI=2.2 vs. polyacrylic acid strict standard), H NMR (D20): δ 7.22 (wide peak, 2H, aromatic 111346.doc -35- 1378942), δ 6.67 (wide peak, 2H, aromatic) , δ 4.15 (wide peak, 2H, phenylhydrazine CH2), δ 0.30-2.55 (translation, 3H, backbone CH, CH2). Example 15: Poly(VBA) 10.0 g of vinyl benzofuranol (VBA) ( 74.6 mol), 29.0 mL deionized water, 3.82 mL 20.0% by weight sodium dodecyl sulfate (SDDS) (2.48 mol) aqueous solution, 1.83 mL 5.0% by weight sodium bicarbonate (NaHCO3) (0.86 mol) aqueous solution And 1.83 mL of a 5.0% by weight aqueous potassium persulfate solution (0.5 mol% vs. VBA) was added to a 100 mL round bottom flask. The mixture was cooled to 〇 ° C for 1 hour, after which 1.30 mL 5.0 weight was added. % aqueous solution of sodium metabisulfite (0.5 mol% vs. VBA). The solution was aerated with nitrogen for 15 minutes. The flask was closed with a rubber septum and placed in a 30 ° C oil bath. 2.5 hours. After this, the polymer was precipitated in 300 mL of methanol, filtered and dried in vacuo. (9.80 g, 98%), (GPC: Mw=80 k, PDI=4.0 vs. polyacrylic acid strict standard), NMR (DMSO-d6): δ 7·30-δ 6.10 (wide peak, 4 Η, aromatic) , δ 4.65-δ 4.25 (wide peak, 2 Η, phenylhydrazine CH 2 ), δ 2.20-δ 0.90 (wide peak, 3 Η, skeleton CH, CH 2 ). Example 16: Poly(VBC)

將50.0 g乙稀基苯甲基氣（VBC)(Dow Specialty Monomers，55%的3位異構體及45%的4位異構體）、145.0 mL 去離子水、16.65 mL 20.0重量％之十二烷基硫酸鈉（SDDS) 水溶液（12.40 mmol)、8.0 mL 5_0重量％之碳酸氫鈉 (NaHC03)水溶液（3.75 mmol)及8.0 mL 5.0重量％之過硫酸 鉀水溶液（〇.5莫耳％，相對於VBC)添加至一 500 mL圓底燒 瓶中。將此混合物冷卻至〇°C歷時1小時，此後加入5.65 mL 111346.doc -36- 1378942 5.0重量％之焦亞硫酸鈉 以氮氣充氣該溶液1 5分 其置於30°C油浴中3小 1500 ^甲醇中’過遽並在真空中乾燥。（47.5 g，95%)， (GPC: Mw=733 k，PDI=6.3相對於聚丙烯酸嚴格標準），咕 匪!1 _SO-d6): δ 7.30_δ 6.2〇 (寬峰，4H，芳族）s 4 π δ 4.30 ,2H, ^CH2)j δ 24〇§ 〇9〇(t^550.0 g of ethylene benzyl gas (VBC) (Dow Specialty Monomers, 55% of the 3 isomer and 45% of the 4 isomer), 145.0 mL of deionized water, 16.65 mL of 20.0% by weight of ten Sodium dialkyl sulfate (SDDS) aqueous solution (12.40 mmol), 8.0 mL of 5_0% by weight aqueous sodium hydrogencarbonate (NaHC03) solution (3.75 mmol) and 8.0 mL of 5.0% by weight aqueous potassium persulfate solution (〇.5 mol%, Add to a 500 mL round bottom flask relative to VBC). The mixture was cooled to 〇 ° C for 1 hour, after which 5.65 mL of 111346.doc -36 - 1378942 5.0% by weight of sodium metabisulfite was aerated with nitrogen and the solution was placed in a 30 ° C oil bath for 3 small 1500 ^ 'Turning in methanol' and drying in vacuum. (47.5 g, 95%), (GPC: Mw=733 k, PDI=6.3 vs. polyacrylic acid strict standard), 咕匪!1 _SO-d6): δ 7.30_δ 6.2〇 (wide peak, 4H, aromatic) s 4 π δ 4.30 , 2H, ^CH2)j δ 24〇§ 〇9〇(t^5

實例17 :聚（t-BuOS)程序AExample 17: Poly(t-BuOS) Procedure A

水溶液（0‘5莫耳％，相對於VBC)。 鐘。用—橡膠隔膜封閉該燒瓶且將 時在此之後，將聚合物沉殿於 3Η，骨架 CH，CH2)。 將8.79 g第三丁氧基苯乙烯（t_Bu〇s)(46 3醒〇1)、23 3 mL 去離子水、3.82 mL 20.0重量％之十二燒基硫酸鋼（sdds) 水溶液（2.48 mmol)、h83 mL 5 〇重量％之碳酸氫鈉 (NaHC〇3)水溶液（0.86 mmol)及1.29 mL 5〇重量％之過硫酸 鉀水溶液（0.5莫耳％，相對於t_Bu〇s)添加至一1〇〇 mL圓底 燒瓶中。將此混合物冷卻至or歷時丨小時，此後加入〇92 mL 5.0重量％之焦亞硫酸鈉水溶液（〇 5莫耳％，相對於卜 BuOS)。以氮氣充氣該溶液15分鐘。用一橡膠隔膜封閉該 燒瓶且將其置於3 0 C油浴中3小時。在此之後，將聚合物 沉澱於300 mL甲醇中，過濾並在真空中乾燥。（6 15 g， 70%)，（GPC: Mw=12〇〇 k，PDI=10.0相對於聚苯乙烯嚴格標 準），NMR (DMSO-d6): δ 6·75·δ 6.20 (寬峰，4H，芳 族），δ 2_13-δ 0.80 (寬峰 ’ 12Η，骨架 CH，CH2，第三 丁基-Aqueous solution (0 '5 mol%, relative to VBC). bell. The flask was closed with a rubber septum and, after that, the polymer was allowed to settle at 3 Å, skeleton CH, CH2). 8.79 g of tert-butoxystyrene (t_Bu〇s) (46 3 awake 1), 23 3 mL of deionized water, 3.82 mL of 20.0% by weight aqueous solution of 12% sodium sulphate (sdds) (2.48 mmol) , h83 mL 5 〇% by weight aqueous solution of sodium bicarbonate (NaHC〇3) (0.86 mmol) and 1.29 mL of 5 〇% by weight aqueous potassium persulfate solution (0.5 mol%, relative to t_Bu〇s) was added to 1 〇 〇mL round bottom flask. The mixture was cooled to or for an hour, after which time 92 mL of a 5.0% by weight aqueous solution of sodium metabisulfite (〇 5 mol% vs. BuOS) was added. The solution was aerated with nitrogen for 15 minutes. The flask was closed with a rubber septum and placed in a 30 C oil bath for 3 hours. After this time, the polymer was precipitated in 300 mL of methanol, filtered and dried in vacuo. (6 15 g, 70%), (GPC: Mw = 12〇〇k, PDI = 10.0 vs. polystyrene), NMR (DMSO-d6): δ 6·75·δ 6.20 (wide peak, 4H) , aromatic), δ 2_13-δ 0.80 (wide peak '12Η, skeleton CH, CH2, tert-butyl-

CH3)。 實例18 :聚（t-BuOS)程序B lU346.doc -37- (δ) 1378942 除使用1.0莫耳％之引發劑（相對於t-BuOS)(即，2 58 5〇重量％之過硫酸鉀水溶液，1.84 mL 5.0重量。之焦亞硫 酸鈉水溶液）外，聚合係以與為”程序A"描述之相同方式進 行。（GPC: Mw=700 k，PDI=5.0相對於聚苯乙稀嚴格標 準），4 NMR (DMS0-d6): δ 6.75-δ 6.20 (寬峰，4H，芳 族），δ 2.13-δ 0.80 (寬峰，12H，骨架CH，CH2，第三丁基 CH3) »CH3). Example 18: Poly(t-BuOS) procedure B lU346.doc -37- (δ) 1378942 In addition to using 1.0 mol% of initiator (relative to t-BuOS) (ie, 2 58 5 wt% potassium persulfate) The aqueous solution, except 1.84 mL of 5.0 wt. aqueous sodium metabisulfite solution, was polymerized in the same manner as described for "Program A" (GPC: Mw = 700 k, PDI = 5.0 vs. polystyrene). 4 NMR (DMS0-d6): δ 6.75-δ 6.20 (wide peak, 4H, aromatic), δ 2.13-δ 0.80 (wide peak, 12H, backbone CH, CH2, tert-butyl CH3) »

會例19 :聚（t-BuOS)程序C 除使用1.5莫耳％之引發劑（相對於t_BuOS)(即，3.87 mL 5.0重直％之過硫酸狎水溶液，2.76 mL 5.0重量％之焦亞硫 酸鈉水溶液）外，聚合係以與為"程序A"描述之相同方式進 行。（GPC: Mw=185 k，PDI=4.0相對於聚苯乙稀嚴格標 準）’丨H NMR (DMS0-d6): δ 6.75-δ 6.20 (寬峰，4H，芳 族），δ 2·13-δ 0.80 (寬峰，12H，骨架 CH，CH2，第三丁基 CH3)。 實例20 :聚（乙醯氧基苯乙烯） 將 10.0 g 乙醯氧基苯乙烯（AcS)(AIdrich，96%)、29〇 mL 去離子水、3.33 mL 20.0重量％之十二烷基硫酸鈉（SDDS) 水溶液（2.48 mmol) ' h6 mL 5_〇重量％之碳酸氫鈉 (NaHC〇3)水溶液（〇.75 mmol)及！ 6 mL 5 〇重量％之過硫酸 鉀水溶液（0.5莫耳％，相對於AcS)添加至一1〇〇 mL圓底燒 瓶中。將此昆合物冷卻至(TC歷時丄小時，此後加入i i3乱 5.0重量％之焦亞硫酸鈉水溶液（〇.5莫耳％，相對於vba)。 以氮氣充氣該溶液15分鐘。用一橡膠隔膜封閉該燒瓶且將 111346.doc -38, 1378942 其置於30°C油浴中3小時。在此之後，將聚合物沉澱於3〇〇 mL甲醇中，過滤並在真空中乾燥。（9.5〇 g，95%)，（GPC: Mw=554 k，PDI=4_0相對於聚丙烯酸嚴格標準），iH nmR (DMSO-d6): δ 7·00-δ 6.25 (寬峰，4H，芳族），δ 2.38-δ 2.00 (寬峰，3Η，乙醯基CH3), δ 2.05-δ 1.00 (寬峰，3Η， 骨架 CH，CH2)。 實例 21 :聚（NaVBS-共-VBA) 於35°C下，將乙烯基苯甲醇（207 g，1.39 mol)添加至乙烯 基苯甲基續酸鈉（NaVBS，1058 g，2.49 mol, 5 1.9%的單體， 35.1%的水，13%的填化物雜質）於去離子水（8766 g)中之溶 液中。以氣氣1充氣§玄混合物〇. 5小時。在充氣時期的最後 加入 Vazo 56WSP (2.71 g，1〇.〇 min〇l，DuPont)。在氮氣 下’將反應混合物加熱至8(TC並攪拌3.5小時。在3.5小時 的反應時間後，第二次裝入Vazo 56WSP (1.35 g, 5.00 mmol), 且使聚合另外繼續進行2小時。在聚合之後，將溶液維持 在80 C並用氮氣淨化以將體積減小約5〇〇/0。自丙酮沉澱出 聚合物。重量分析並分光光度分析評估NaVBS至聚合物之 轉化百分比（95%轉化）。咕NMR (D2〇): δ 7.16 (寬峰， 2Η，芳族），δ 6.63 (寬峰，2Η，芳族），δ 4·43 (寬峰，〇 4 Η，笨甲醇CH2)，δ 4.08 (寬岭，1.6Η，苯曱基項酸根CH2)， δ -0.75-2.75 (寬峰 ’ 3H ’ 骨架 CH，CH2)。 實例 22:聚（NaVBS-共-HEMA) 於40°C下，在一 250 mL圓底燒瓶中，將9.30 g (42.2 mmol)Example 19: Poly(t-BuOS) Procedure C In addition to using 1.5 mol% of initiator (relative to t_BuOS) (ie, 3.87 mL of 5.0% by weight aqueous solution of barium persulfate, 2.76 mL of 5.0% by weight aqueous solution of sodium metabisulfite) In addition, the aggregation is performed in the same manner as described for "Program A". (GPC: Mw=185 k, PDI=4.0 vs. polystyrene strict standard) '丨H NMR (DMS0-d6): δ 6.75-δ 6.20 (wide peak, 4H, aromatic), δ 2·13- δ 0.80 (wide peak, 12H, backbone CH, CH2, third butyl CH3). Example 20: Poly(ethoxylated styrene) 10.0 g of ethoxylated styrene (AcS) (AIdrich, 96%), 29 〇mL of deionized water, 3.33 mL of 20.0% by weight of sodium lauryl sulfate (SDDS) Aqueous solution (2.48 mmol) 'h6 mL 5_〇% by weight of sodium bicarbonate (NaHC〇3) in water (〇.75 mmol) and! 6 mL of a 5 wt% potassium persulfate aqueous solution (0.5 mol% vs. AcS) was added to a 1 〇〇 mL round bottom flask. The solution was cooled to (TC for a few hours, after which time i i3 was added with 5.0% by weight aqueous sodium metabisulfite solution (〇.5 mol%, relative to Vba). The solution was aerated with nitrogen for 15 minutes. The flask was closed and 111346.doc - 38, 1378942 was placed in a 30 ° C oil bath for 3 hours. After this time, the polymer was precipitated in 3 mL of methanol, filtered and dried in vacuo. g, 95%), (GPC: Mw = 554 k, PDI = 4_0 vs. polyacrylic acid strict standard), iH nmR (DMSO-d6): δ 7·00-δ 6.25 (wide peak, 4H, aromatic), δ 2.38-δ 2.00 (wide peak, 3 Η, acetonitrile CH3), δ 2.05-δ 1.00 (wide peak, 3 Η, skeleton CH, CH2). Example 21: poly(NaVBS-co-VBA) at 35 ° C Vinylbenzyl alcohol (207 g, 1.39 mol) was added to sodium vinylbenzyl sodium (NaVBS, 1058 g, 2.49 mol, 5 1.9% monomer, 35.1% water, 13% filler impurities) ) in a solution of deionized water (8766 g). Inflate with a gas 1 § 玄 mixture 〇. 5 hours. At the end of the aeration period, add Vazo 56WSP (2.71 g, 1 〇.〇min〇l, DuPont). In nitrogen Next, the reaction mixture was heated to 8 (TC and stirred for 3.5 hours. After 3.5 hours of reaction time, Vazo 56WSP (1.35 g, 5.00 mmol) was charged a second time, and the polymerization was further continued for 2 hours. The solution was maintained at 80 C and purged with nitrogen to reduce the volume by about 5 〇〇 / 0. The polymer was precipitated from acetone. Gravimetric analysis and spectrophotometric analysis of NaVBS to polymer conversion percentage (95% conversion). NMR (D2〇): δ 7.16 (wide peak, 2 Η, aromatic), δ 6.63 (wide peak, 2 Η, aromatic), δ 4·43 (wide peak, 〇4 Η, stupid methanol CH2), δ 4.08 ( Kuanling, 1.6 Η, phenylhydrazine base acid CH2), δ -0.75-2.75 (wide peak '3H ' skeleton CH, CH2). Example 22: Poly(NaVBS-co-HEMA) at 40 ° C, in one In a 250 mL round bottom flask, 9.30 g (42.2 mmol)

NaVBS溶解於水中。將此溶液用氮氣淨化丨5分鐘。將丨22名 I11346.doc -39- (S) 1378942 (9.39 mmol)曱基丙烤酸2-經乙醋（HEMA)及34.11 mg (0.125 8 mmol) VAZO 56WSP添加至該溶液中。將混合物於 85°C下加熱24小時。聚合物沉澱於875 mL丙酮中並在真空 中乾燥。（產率9.22 g，92%)凝膠滲透層析指示高分子量 (280k，相對於聚苯乙烯磺酸鹽嚴格標準）。4 NMR (D20): δ 7.50-δ 6.25 (寬峰，4H，芳族），δ 4.25-δ 3.75 (寬 峰，2Η，苯甲基），δ 3·60-δ 2.80 (寬峰，1.08 Η，乙基 CH2), δ 2.50-δ 1.00 (寬峰，骨架CH，CH2)，δ 1·0-δ 0.20 (寬 峰，0.84 Η，CH3)。自1Η NMR數據計算出併入了 22%的 HEMA。 實例 23:聚（NaVBS-共-1-VPE) 向一 250 mL圓底燒瓶裝以 6.60 g NaVBS (30.0 mmol)、 2.96 g 1-VPE (20.0 mmol) ' 27.0 mg Vazo 56WSP (0.10 mmol) ' 66.0 ml水及一攪拌棒。將混合物用氮氣起泡15分鐘，用橡 膠隔膜封閉該燒瓶並將其放在80°C油浴中並用力攪拌24小 時。接著伴以用力攪拌將反應混合物缓慢沉澱於300 mL丙 酮中。過濾白色沉澱物並用丙酮洗滌其且在真空中乾燥。 (7.90 g，83 %，Mw=45 k，PDI = 2.25相對於磺化聚苯乙烯嚴 格標準）。NMR (D20): δ 8.25-δ 5·50 (寬峰，4H，芳族）， δ 4.50-δ 3.50 (寬峰，1.44Η，苯曱基ic)，δ 2·75-δ 0.25 (寬 峰，骨架 CH CH2, C-CH3)。 實例 24:聚(NaVBS-共-2-VPE) 向一 250 mL 圓底燒瓶裝以 13.20 g NaVBS (60·0 mmol)、 4.44 g 2-VPE (30.0 mmol) ' 54.0 mg Vazo 56WSP (0.2 mmol) ' 111346.doc -40- 1378942 1 3 3 mL水及一攪拌棒β以氮氣充氣該混合物丨5分鐘，接著 用橡勝隔膜封閉燒瓶並將其放在8〇。〇油浴中並用力攪拌24 小時。接著伴以用力攪拌將反應混合物緩慢沉澱於5〇〇 mL 丙嗣中。過瀘白色沉澱物，用丙酮洗滌，並在真空中乾 燥。（16.0 g，91 %，Mw=47.6 k，PDI=2.1相對於磺化聚苯乙 烯嚴格標準）。1η NMR (D20): δ 8·25-δ 5.50 (寬峰，4H， 芳族），δ 4.60-δ 3.20 (寬峰，2H，苯曱基及 CH2-0)，δ 3.20-δ 2.30 (寬峰，笨甲基_CIi2_c)，δ 2.30-d 0.25 (寬峰，骨架 CH2及 CH)。 實例 25 :聚（NaSS-共-VBA)NaVBS is dissolved in water. This solution was purged with nitrogen for 5 minutes. Twenty-two I11346.doc-39-(S) 1378942 (9.39 mmol) mercaptopropanoid acid 2-ethyl acetate (HEMA) and 34.11 mg (0.125 8 mmol) VAZO 56WSP were added to the solution. The mixture was heated at 85 ° C for 24 hours. The polymer was precipitated in 875 mL of acetone and dried in vacuo. (Yield 9.22 g, 92%) Gel permeation chromatography indicated high molecular weight (280 k, relative to the polystyrene sulfonate stringent standard). 4 NMR (D20): δ 7.50-δ 6.25 (wide peak, 4H, aromatic), δ 4.25-δ 3.75 (wide peak, 2 Η, benzyl), δ 3·60-δ 2.80 (wide peak, 1.08 Η , ethyl CH2), δ 2.50-δ 1.00 (wide peak, skeleton CH, CH2), δ 1·0-δ 0.20 (wide peak, 0.84 Η, CH3). The incorporation of 22% HEMA was calculated from 1 NMR data. Example 23: Poly(NaVBS-co--1-VPE) A 250 mL round bottom flask was charged with 6.60 g NaVBS (30.0 mmol), 2.96 g 1-VPE (20.0 mmol) ' 27.0 mg Vazo 56WSP (0.10 mmol) ' 66.0 Ml water and a stir bar. The mixture was bubbled with nitrogen for 15 minutes, the flask was closed with a rubber septum and placed in an 80 ° C oil bath and stirred vigorously for 24 hours. The reaction mixture was then slowly precipitated in 300 mL of acetone with vigorous stirring. The white precipitate was filtered and washed with acetone and dried in vacuo. (7.90 g, 83%, Mw = 45 k, PDI = 2.25 vs. sulfonated polystyrene stringency standard). NMR (D20): δ 8.25-δ 5·50 (wide peak, 4H, aromatic), δ 4.50-δ 3.50 (wide peak, 1.44 Η, phenyl fluorenyl ic), δ 2·75-δ 0.25 (wide peak , skeleton CH CH2, C-CH3). Example 24: Poly(NaVBS-co-2-VPE) A 250 mL round bottom flask was charged with 13.20 g NaVBS (60·0 mmol), 4.44 g 2-VPE (30.0 mmol) ' 54.0 mg Vazo 56WSP (0.2 mmol) '111346.doc -40- 1378942 1 3 3 mL of water and a stir bar β were aerated with nitrogen for 5 minutes, then the flask was closed with a rubber septum and placed at 8 Torr. Stir in the oil bath for 24 hours. The reaction mixture was then slowly precipitated in 5 mL of acetonitrile with vigorous stirring. The white precipitate was passed over, washed with acetone and dried in vacuo. (16.0 g, 91%, Mw = 47.6 k, PDI = 2.1 vs. sulfonated polystyrene). 1η NMR (D20): δ 8·25-δ 5.50 (wide peak, 4H, aromatic), δ 4.60-δ 3.20 (wide peak, 2H, phenylhydrazine and CH2-0), δ 3.20-δ 2.30 (width Peak, stupid methyl _CIi2_c), δ 2.30-d 0.25 (wide peak, backbone CH2 and CH). Example 25: Poly (NaSS-co-VBA)

向一 500 ml圓底燒瓶裝以 27.9 g NaSS (135.3 mmol)、8.1 g VBA (60.2 mmol)、109 mg Vazo 56WSP (0.4 mmol)、396 mL 水及一攪拌棒。以氮氣充氣該混合物15分鐘，接著用橡膠 隔膜封閉燒瓶並將其於80。(：下加熱並用力攪拌24小時。接 著伴以用力攪拌將反應混合物缓慢沉澱於500 mL丙酮中。 過濾白色沉澱物，用丙酮洗滌，並在真空中乾燥。（22 g， 64莫耳％之磺化單體，Mw=237 k，ΡΟΙ=2·6相對於磺化聚苯 乙烯嚴格標準）。1h NMR (D20): δ 7·84-δ 5.85 (寬峰，芳 族），δ 4.60-δ 4.06 (寬峰，2Η，苯曱基-CH2-〇)，δ 2.50-δ 0.50(寬峰，骨架CH2及CH)。 實例 26:聚（NaSS-共-HEMA)A 500 ml round bottom flask was charged with 27.9 g NaSS (135.3 mmol), 8.1 g VBA (60.2 mmol), 109 mg Vazo 56WSP (0.4 mmol), 396 mL water and a stir bar. The mixture was aerated with nitrogen for 15 minutes, and then the flask was closed with a rubber septum and placed at 80. (: Heat and stir vigorously for 24 hours. Then slowly react the reaction mixture in 500 mL of acetone with vigorous stirring. Filter the white precipitate, wash with acetone, and dry in vacuo. (22 g, 64 mol% Sulfonated monomer, Mw = 237 k, ΡΟΙ = 2. 6 vs. sulfonated polystyrene.) 1h NMR (D20): δ 7·84-δ 5.85 (wide peak, aromatic), δ 4.60- δ 4.06 (wide peak, 2 Η, phenylhydrazine-CH2-〇), δ 2.50-δ 0.50 (wide peak, backbone CH2 and CH). Example 26: Poly(NaSS-co-HEMA)

向一 500 ml 圓底燒瓶裝以 27.9 g NaSS (135.3 mmol)、8.1 g HEMA (60.2 mmol)、109 mg Vazo 56WSP (0·4 mmol)、396 mL 水及一攪拌棒。以氮氣充氣該混合物15分鐘，接著用橡膠 111346.doc -41 · 1378942 隔膜封閉燒瓶並將其於80°C下加熱並用力攪拌24小時。接 著伴以用力攪拌將反應混合物緩慢沉澱於500 mL丙酮中。 過濾白色沉澱物，用丙酮洗滌，並在真空中乾燥。（39.4 g， 磺化單體％為64莫耳％，Mw=457 k，PDI=3.7相對於磺化聚 苯乙烯嚴格標準）。4 NMR (D20): δ 7·90-δ 5.95 (寬峰， 芳族），δ 3·72-δ 2.86 (寬峰，4Η，0-CH2-CH2-0H)，δ 2.13-δ 0.05 (寬峰，骨架 CH3，CH2 及 CH)。 實例27 :聚（NaSS)A 500 ml round bottom flask was charged with 27.9 g NaSS (135.3 mmol), 8.1 g HEMA (60.2 mmol), 109 mg Vazo 56WSP (0.4 mmol), 396 mL water and a stir bar. The mixture was aerated with nitrogen for 15 minutes, then the flask was closed with a rubber 111346.doc -41 · 1378942 septum and heated at 80 ° C and stirred vigorously for 24 hours. The reaction mixture was then slowly precipitated in 500 mL of acetone with vigorous stirring. The white precipitate was filtered, washed with acetone and dried in vacuo. (39.4 g, sulfonated monomer% 64 mol%, Mw = 457 k, PDI = 3.7 vs. sulfonated polystyrene). 4 NMR (D20): δ 7·90-δ 5.95 (wide peak, aromatic), δ 3·72-δ 2.86 (wide peak, 4 Η, 0-CH2-CH2-0H), δ 2.13-δ 0.05 (width Peak, skeleton CH3, CH2 and CH). Example 27: Poly(NaSS)

向一 500 ml圓底燒瓶裝以 13.8 g NaSS (66.9 mmol)、109 mg Vazo 56WSP (0.4 mmol)、196 mL水及一搅拌棒。以氮氣充 氣該混合物15分鐘，接著用橡膠隔膜封閉燒瓶並將其於 80°C下加熱並用力攪拌24小時。接著伴以用力攪拌將反應 混合物缓慢沉澱於500 mL丙嗣中。過滤白色沉澱物，用丙 酮洗務，並在真空中乾燥。（10 g，Mw=490 k，PDI=3.6相對 於磺化聚苯乙烯嚴格標準）。4 NMR (D20): δ 7·94-δ 5.94 (寬峰，芳族），δ 2.10-δ 0.22 (寬峰，骨架CH2及CH)。 實例28 :聚（2-丙烯胺基-2-甲基丙烷磺酸）(p(AMPS)) 為一 1000 ml圓柱形反應器配備回流冷凝器、機械攪拌 器且裝以50.0 mL去離子水並加熱至75°C。將151.6 g AMPS、545.2 mL水一同在一單獨器皿中攪拌，直至AMPS 完全溶解。以氮氣充氣該反應器及AMPS溶液15分鐘。將 446 mg Vazo 56WSP單獨溶解於9.47g水中。經1小時的時 間，將AMPS及Vazo 5 6WSP溶液缓慢饋入至該反應器中， 同時將反應溫度維持在75°C並用力攪拌。在75°C下攪拌反 111346.doc •42- 1378942 應物另外攪拌2小時。將最終反應混合物冷卻至室溫。觀 察到混合物極其黏稠，起說明存在高分子量聚合物。 (共）聚合物合成（聚合後改質） 、 實例29 :磺酸基乙基化p(VBC) 在氮氣下，在一已配備一加料漏斗之250 mL圓底燒瓶 中，將1.0 g聚（乙烯基苯甲基氯溶解於99 0 g無 水二甲亞礙（DMSO)中並磁力攪拌。在氮氣下，單獨將 籲 丨.068 g (1.1當量’相對於C1)經乙基磺酸鈉（NaISA)溶解於 19.0 g DMSO中〇在一第三器皿中，在氮氣下，將〇 165 g (1.05當量，相對於Cl)氫化鈉（NaH)添加至3.1 g DMSO中並 搜拌以形成漿料。接著’在氮氣淨化並磁力攪拌下，將該 NaH漿料添加至一250 mL圓底燒瓶中。接著緩慢加入該 NalSA溶液並快速攪拌。於室溫下將NaH/NaISA混合物（羥 乙基磺酸二鈉）攪拌30分鐘，直至氣體析出停止。接著將 此混合物快速轉移至P(VBC)反應器之加料漏斗。接著將該 • 羥乙基磺酸二鈉溶液伴以快速攪摔緩慢添加至p (V B C )溶液 中》於室溫下將此混合物另外攪拌18小時。在此之後加 入1.0 mL 5.0 Wv%鹽酸水溶液。接著將此溶液伴以快速攪 拌缓慢傾入1 。過濾該沉 L四氫呋喃中，形成白色沉澱物 澱物，將其再溶解於丨00mL去離子水令並緩慢傾入8〇〇mL 四氫呋喃中《藉由過濾收集白色聚合物粉末並在真空中乾 燥。1Η ------- 4.60-δA 500 ml round bottom flask was charged with 13.8 g NaSS (66.9 mmol), 109 mg Vazo 56WSP (0.4 mmol), 196 mL water and a stir bar. The mixture was purged with nitrogen for 15 minutes, then the flask was closed with a rubber septum and heated at 80 ° C and stirred vigorously for 24 hours. The reaction mixture was then slowly precipitated in 500 mL of hydrazine with vigorous stirring. The white precipitate was filtered, washed with acetone and dried in vacuo. (10 g, Mw = 490 k, PDI = 3.6 vs. sulfonated polystyrene). 4 NMR (D20): δ 7·94-δ 5.94 (wide peak, aromatic), δ 2.10-δ 0.22 (wide peak, skeleton CH2 and CH). Example 28: Poly(2-propenylamino-2-methylpropanesulfonic acid) (p(AMPS)) A 1000 ml cylindrical reactor equipped with a reflux condenser, mechanical stirrer and loaded with 50.0 mL of deionized water. Heat to 75 °C. 151.6 g of AMPS and 545.2 mL of water were stirred together in a separate vessel until the AMPS was completely dissolved. The reactor and AMPS solution were aerated with nitrogen for 15 minutes. 446 mg Vazo 56WSP was dissolved separately in 9.47 g of water. The AMPS and Vazo 5 6 WSP solutions were slowly fed into the reactor over a period of 1 hour while maintaining the reaction temperature at 75 ° C and stirring vigorously. Stir at 75 ° C. Reverse 111346.doc • 42-1378942 The mixture was stirred for an additional 2 hours. The final reaction mixture was cooled to room temperature. It was observed that the mixture was extremely viscous, indicating the presence of a high molecular weight polymer. (co)polymer synthesis (upgraded after polymerization), Example 29: sulfonate ethylation p(VBC) 1.0 g of poly(in a 250 mL round bottom flask equipped with an addition funnel under nitrogen) Vinylbenzyl chloride was dissolved in 99 0 g of anhydrous dimethoprim (DMSO) and stirred magnetically. Under nitrogen, 068 g (1.1 equivalents vs. C1) was sodium sulfonate alone. NaISA) was dissolved in 19.0 g DMSO in a third vessel, and 〇165 g (1.05 eq., relative to Cl) of sodium hydride (NaH) was added to 3.1 g of DMSO under nitrogen to mix and form a slurry. Then, the NaH slurry was added to a 250 mL round bottom flask under nitrogen purge and magnetic stirring. Then the NalSA solution was slowly added and stirred rapidly. NaH/NaISA mixture (hydroxyethyl sulfonate) at room temperature. Stirring the acid) for 30 minutes until the gas evolution ceases. The mixture is then quickly transferred to the addition funnel of the P(VBC) reactor. The disodium hydroxyethyl sulfonate solution is then slowly added to the solution. This mixture was stirred for an additional 18 hours at room temperature in p (VBC) solution. Add 1.0 mL of 5.0 Wv% aqueous hydrochloric acid solution, then pour the solution slowly into the mixture with rapid stirring. Filter the precipitate in tetrahydrofuran to form a white precipitate, re-dissolve in 00 mL of deionized water and slowly pour. Into 8 〇〇mL tetrahydrofuran "Collect the white polymer powder by filtration and dry in vacuum. 1 Η ------- 4.60-δ

乙基-CH2-S03)，δ 3.25-δ 2.80 (寬峰，2Η 乙基-o-ch2-c)， ΙΑ 1 ΤΤ χτχ ,τχ 一、 _ (冤峰，2Η， 111346.doc -43 - 1378942 δ 2.25-δ 0.75 (寬峰，3H，骨架 CH2，CH)。 實例30 :磺睃基丙基化p(VBC) 在氮氣下，在一已配備一加料漏斗之250 mL圓底燒瓶 中，將1.0 g聚（乙烯基苯甲基氯）(p(VBC))溶解於99.0 g無 水二甲亞礪（DMSO)中並磁力攪拌。在氮氣下，單獨將 2.13 g (2.0當量，相對於Cl)3-羥基丙烷磺酸鈉（NaHPS)溶 解於42.5 g無水DMSO*。在一第三器皿中’在氮氣下，Ethyl-CH2-S03), δ 3.25-δ 2.80 (wide peak, 2 Η ethyl-o-ch2-c), ΙΑ 1 ΤΤ χτχ , τχ I, _ (冤峰, 2Η, 111346.doc -43 - 1378942 δ 2.25-δ 0.75 (wide peak, 3H, backbone CH2, CH). Example 30: sulfonylpropylated p(VBC) under nitrogen in a 250 mL round bottom flask equipped with an addition funnel 1.0 g of poly(vinylbenzyl chloride) (p(VBC)) was dissolved in 99.0 g of anhydrous dimethyl hydrazine (DMSO) and stirred magnetically. Under nitrogen, 2.13 g (2.0 eq. relative to Cl) was added separately. Sodium 3-hydroxypropane sulfonate (NaHPS) was dissolved in 42.5 g of anhydrous DMSO* in a third vessel 'under nitrogen,

將0.3464 g (2.2當量，相對於C1)氫化鈉（NaH)添加至5.0 g DMSO中並攪拌以形成漿料。接著，在氮氣淨化及磁力攪 拌下，將該NaH漿料添加至一 250 mL圓底燒瓶中。接著伴0.3464 g (2.2 equivalents, relative to C1) of sodium hydride (NaH) was added to 5.0 g of DMSO and stirred to form a slurry. Next, the NaH slurry was added to a 250 mL round bottom flask under nitrogen purge and magnetic stirring. Followed by

以快速授拌緩慢加入該NaHPS溶液。於室溫下將 NaH/NaHPS混合物（羥基丙烷續酸二鈉）攪拌3〇分鐘’直至 氣體析出停止。接著將此混合物快速轉移至p(VBC)反應器 之加料漏斗。接著伴以快速攪拌將羥基丙烷磺酸二鈉溶液 緩慢添加至p(VBC)溶液中。於室溫下將此混合物另外攪拌 1 8小時。在此之後，加入1 〇 mL 5 〇 v/v。/。鹽酸水溶液。接 著將伴以快速攪拌該溶液緩慢傾入丨L丙酮中形成白色沉 澱物。過濾該沉澱物，將其再溶解於1〇〇 mL去離子水中並 緩慢傾入800 mL丙酮中。藉由過濾收集白色聚合物粉末並 在真空中乾燥。H NMR (D2〇): δ 7.40-δ 5.75 (寬峰，4H， 方族），δ 4.60-δ 4·2〇 (寬峰，2Η，苯甲基），δ 4 2〇δ 3 5〇 (寬峰，2Η ’ 丙基-〇-CH2-)，δ 3·1〇_δ 2 6〇 (寬峰，2Η，丙 基-CH2-S03)，δ 2.25-δ 1·75 (寬峰，2Η，丙基-C-CH2-C)，δ ΜΟ-δ 0.50 (寬峰 ’ 3Η，骨架ch_CH2) β 111346.doc -44 1378942 實例31: p(tBuOS)轉化為聚（乙烯基苯酚） 在一 250 mL圓底燒瓶中，將 2.0 g p(NBu〇s)(Mw〜12〇〇k， PDI=10.0)溶解於62.0 g !，4·二噁烷中。向此溶液添加179 • 辰鹽酸（於水中’ 37.0重量°/。）。在氮氣下，於80°C下將該 ： 混合物攪拌4小時。接著將反應溶液傾入400 mL水中。藉The NaHPS solution was slowly added with rapid mixing. The NaH/NaHPS mixture (disodium hydroxypropane acid) was stirred at room temperature for 3 minutes until gas evolution ceased. This mixture was then quickly transferred to the addition funnel of the p(VBC) reactor. The disodium hydroxypropane sulfonate solution was then slowly added to the p(VBC) solution with rapid stirring. The mixture was stirred for an additional 18 hours at room temperature. After that, add 1 〇 mL 5 〇 v/v. /. Aqueous hydrochloric acid solution. This solution was then slowly poured into 丨L acetone to form a white precipitate. The precipitate was filtered, redissolved in 1 mL of deionized water and poured slowly into 800 mL of acetone. The white polymer powder was collected by filtration and dried in vacuo. H NMR (D2〇): δ 7.40-δ 5.75 (wide peak, 4H, clan), δ 4.60-δ 4·2〇 (wide peak, 2Η, benzyl), δ 4 2〇δ 3 5〇 ( Broad peak, 2Η 'propyl-〇-CH2-), δ 3·1〇_δ 2 6〇 (wide peak, 2Η, propyl-CH2-S03), δ 2.25-δ 1·75 (wide peak, 2Η , propyl-C-CH2-C), δ ΜΟ-δ 0.50 (wide peak '3Η, skeleton ch_CH2) β 111346.doc -44 1378942 Example 31: conversion of p(tBuOS) to poly(vinylphenol) at 250 In a mL round bottom flask, 2.0 gp (NBu〇s) (Mw~12〇〇k, PDI=10.0) was dissolved in 62.0 g of ?,4. dioxane. To this solution was added 179 HCl (in water > 37.0 wt. /.). This was stirred at 80 ° C under nitrogen for 4 hours. The reaction solution was then poured into 400 mL of water. borrow

由添加5.0重量0/。之氫氧化鈉水溶液將此漿料中和至 pH=7。過濾並在真空中乾燥聚合物粉末。（丨3〇 g，95%， . Mw=600 k，PDI=8.0相對於聚（丙烯酸）嚴格標準）NMR (DMSO-d6): δ 9·10-δ 8.80 (寬峰，1Η，〇Η), δ 6.75-δ 6.20 (寬峰，4Η，芳族），δ 2.20-δ 0.90 (寬峰，骨架CH，Ch2)。 實例32 : p(乙醯氧基苯乙烯）轉化為聚（乙烯基苯酚） 於室溫下將1.0 g聚（乙醯氧基苯乙烯）（6 16 minol乙醯氧 基）溶解於37.7 mL 1，4-二噁烷中。向此快速攪拌之溶液中 添加2.47 g氫氧化鈉（61.7 mmol)於19.3 mL去離子水中之溶 液。接著將反應混合物加熱至40°C歷時4小時。將所得混 . 合物冷卻至室溫並用過量的5·〇 ν/ν%鹽酸水溶液酸化。將 沉澱出的聚合物用去離子水洗滌若干次並在真空中乾燥。 (0.73 g，98 %，Mw=630 k，PDI=5.0相對於聚（丙烯酸）嚴格 標準）。NMR (DMSO-d6): δ 9.10-δ 8.80 (寬峰，1H， 〇Η)，δ 6.75-δ 6.20 (寬峰，4Η，芳族），δ 2.20-δ 0.90 (寬 峰，骨架CH，CH2)。 實例33:聚（乙烯基苯酚）(pVPh)之磺酸基丙基化 在氮氣下，在一已配備一加料漏斗之1 〇〇 mL圓底燒瓶 中’將 1.0 g pVPh (Mw〜600k，PDI〜4.0)溶解於 19.0 g無水 111346.doc • 45· 1378942 二甲亞硬_犯）中。在氮氣下，單獨將i88g(i〇當量， 相對於0H)3-溴丙烷磺酸鈉（NaBps)溶解於5 64 g無水 DMSOf。在-第二器皿中，在氮氣下，將。當 量相對於0H)氫化鈉（NaH)添加至5 0 g DMS〇中並攪拌 以形成水料。接著在氮氣淨化及磁力搜掉下，將該Να装 料添加至25G mL圓底燒瓶中。接著伴以快速授拌緩慢加 入pVPh溶液。於室溫下將NaH/pVph混合物（聚（乙烯基苯 酚鈉))攪拌30分鐘’直至氣體析出停止。接著快速添加 NaBPS溶液並於室溫下授拌18小時。接著伴以快速授摔將 該溶液緩慢傾人500 mL丙酮中形成白色❹物。藉由過渡 收集白色聚合物粉末並在真空中乾燥。（2 〇 g，91 %)，】h nmr (d2〇): δ 7.10_δ 5 90 (寬峰，4H，芳族），δ 4 叫 3.80 (寬峰，2Η，丙基_〇_Ch2_), δ 2 9〇δ 2 5〇 (寬峰， 2Η，丙基-Ch2-S〇3)，δ 2·2〇_δ ! 8〇 (寬峰，2Η，丙基心 CH2-C)’ δ 2.00-δ 0.50 (寬♦，3Η ’ 骨架 CH-CH2)。 鹽形式（共）聚合物離子交換為質子化（共）聚合物 多種類型之可溶於水之鹽形式酸性聚合物之通用程序 實例34 :小規模離子交換 向破螭苢柱（直徑為7.5 cm，長24 cm)添加Dowex® Marathon C離子交換樹脂（約3〇〇 g)。用去離子水徹底沖洗 此管柱，接著裝入聚（乙烯基苯甲基磺酸鈉-共·乙烯基苯甲 醇）（4人49 g)於去離子水（191 2 g)中之1〇重量。/❶溶液。收集 溶離份中之溶離劑，將其用pH試片測試以確定質子化聚合 物之存在。合併含有聚合物之溶離份以藉由元素分析及用 M1346.doc • 46 - 1378942By adding 5.0 weight 0 /. The aqueous sodium hydroxide solution neutralized the slurry to pH = 7. Filter and dry the polymer powder in vacuo. (丨3〇g, 95%, . Mw=600 k, PDI=8.0 vs. poly(acrylic acid) strict standard) NMR (DMSO-d6): δ 9·10-δ 8.80 (wide peak, 1 Η, 〇Η) , δ 6.75-δ 6.20 (wide peak, 4 Η, aromatic), δ 2.20-δ 0.90 (wide peak, skeleton CH, Ch2). Example 32: Conversion of p(acetoxystyrene) to poly(vinylphenol) 1.0 g of poly(ethoxylated styrene) (6 16 minol ethoxylated) was dissolved in 37.7 mL at room temperature 1 , 4-dioxane. To this rapidly stirred solution was added a solution of 2.47 g of sodium hydroxide (61.7 mmol) in 19.3 mL of deionized water. The reaction mixture was then heated to 40 °C for 4 hours. The resulting mixture was cooled to room temperature and acidified with an excess of a 5·〇ν/ν% aqueous hydrochloric acid. The precipitated polymer was washed several times with deionized water and dried in vacuo. (0.73 g, 98%, Mw = 630 k, PDI = 5.0 vs. poly(acrylic acid) strict standard). NMR (DMSO-d6): δ 9.10-δ 8.80 (wide peak, 1H, 〇Η), δ 6.75-δ 6.20 (wide peak, 4 Η, aromatic), δ 2.20-δ 0.90 (wide peak, skeleton CH, CH2 ). Example 33: Sulfopropylation of poly(vinylphenol) (pVPh) Under nitrogen, in a 1 〇〇mL round bottom flask equipped with an addition funnel, '1.0 g pVPh (Mw~600k, PDI) ~4.0) Dissolved in 19.0 g of anhydrous 111346.doc • 45·1378942 dimethyl sub-hard _ in the). I88g (i〇 equivalent, relative to 0H) of sodium 3-bromopropane sulfonate (NaBps) was dissolved in 5 64 g of anhydrous DMSOf under nitrogen. In a - second vessel, under nitrogen, will. The amount was added to 50 g of DMS crucible relative to 0 H) of sodium hydride (NaH) and stirred to form a water. The Να charge was then added to a 25 G mL round bottom flask under nitrogen purge and magnetic search. The pVPh solution was then slowly added with rapid mixing. The NaH/pVph mixture (poly(vinyl phenylphenolate)) was stirred at room temperature for 30 minutes' until gas evolution ceased. The NaBPS solution was then quickly added and allowed to mix for 18 hours at room temperature. The solution was then slowly poured into 500 mL of acetone to form a white mash. The white polymer powder was collected by transition and dried in vacuo. (2 〇g, 91 %),] h nmr (d2〇): δ 7.10_δ 5 90 (wide peak, 4H, aromatic), δ 4 is 3.80 (wide peak, 2Η, propyl_〇_Ch2_), δ 2 9〇δ 2 5〇 (wide peak, 2Η, propyl-Ch2-S〇3), δ 2·2〇_δ ! 8〇 (wide peak, 2Η, propyl heart CH2-C)' δ 2.00 - δ 0.50 (width ♦, 3 Η ' skeleton CH-CH2). Salt-form (co)polymer ion exchange for protonated (co)polymers Various types of water-soluble salt forms of acidic polymers General procedure Example 34: Small-scale ion exchange to a broken column (diameter 7.5 cm) , 24 cm long) Add Dowex® Marathon C ion exchange resin (approx. 3 〇〇g). The column was thoroughly rinsed with deionized water and then charged with sodium poly(vinylbenzylsulfonate-co-vinylbenzyl alcohol) (49 g for 4 persons) in deionized water (191 2 g). weight. /❶ solution. The eluent in the dissolved fraction was collected and tested on a pH test strip to determine the presence of the protonated polymer. Combine the dissolved fractions containing the polymer for analysis by elemental analysis and use M1346.doc • 46 - 1378942

NaOH酸鹼滴定至酚酞終點得到3%的聚（乙烯基苯甲基磺 酸-共-乙烯基苯甲醇）(38.6 g，90。/。）溶液，99+%的交換效率 (H+交換 Na+)。 實例35 :大規模離子交換 為一玻璃管柱（直徑為30.5 cm、長度為122 cm)配備一壓 縮氮氣管線（最大壓力為25 psi)及去離子水入口，接著加 入Dowex® Marathon C離子交換樹脂（21 74 L，濕）。用去 離子水徹底沖洗此管柱，接著裝入聚（乙烯基苯甲基磺酸 鈉-共-乙烯基苯f醇）（3970 g)於去離子水（14 〇公斤）中之2〇 重量％溶液》利用氮氣過壓（高達17 psig)迫使該溶液以每 小時0.4床體積之速率流過管柱且收集溶離份中之溶離 劑。用pH測試試片連續測試溶離劑之pH以確定質子化聚 合物之存在。合併含有最高濃度聚合物之溶離份以藉由元 素分析及用NaOH酸鹼滴定至酚酞終點得到17·5重量％之聚 (乙烯基苯曱基磺酸-共-乙烯基苯曱醇）(254〇笆，69〇/〇)溶 液，99.8%交換效率（H+交換Na+)。 質子化聚電解質溶液之TAAOH中和 實例36. I(本乙稀續酸）之氫氧化四丁基錄中和 將15.〇〇 g 30重量％之聚（苯乙烯磺酸）（構自ρ〇ι__ MW=70 kg/mol)水溶液與9.22 g 55重量％之氣氧化四丁基 銨（TBAOH)水溶液組合且於室溫下攪掉6〇分鐘。接著將 15.03 g NMP添加至該經中和之聚電解質溶液中。接著將 經中和之聚電解質溶液在真空中加熱至㈣以移除水。其 產生38重量％之經TBA0H中和之聚（苯乙婦續酸鹽）於驗 H1346.doc -47- 1378942 中之溶液，並且殘餘水含量不超過0.2重量％。 實例37:聚（苯乙烯磺酸鹽-共-乙烯基苯甲醇）之氫氧化四 丁基錢中和 將153.94 g 2.6重量％之聚（苯乙烯磺酸·共-乙稀基苯甲 醇）(MW=237 kg/mol，70重量％之笨乙烯磺酸）水溶液與6 79 g 55重量％之ΤΓΒΑΟΗ水溶液組合並於室溫下攪拌至少6〇分 鐘。接著將30_0 g NMP添加至該經中和之聚電解質溶液。 接著在真空中將該經中和之聚電解質溶液加熱至6〇t以移 除水。其產生20重量％之經BA〇h中和之聚（苯乙烯磺酸鹽_ 共·乙稀基苯甲醇）於NMP中之溶液，並且殘餘水量含不超 過0·7重量％。 實例38:聚（乙烯基苯曱基磺酸_共_羥乙基甲基丙烯酸酯）之 氫氧化四丁基銨中和 將7.03 g 12.2重量％之聚（乙烯基苯甲基磺酸·共_羥乙基 甲基丙稀酸醋）(MW=190 kg/mol，79重量〇/〇之VBS)水溶液與 1.56 g 55重量％2ΤΒΑΟΗ水溶液組合並於室溫下授拌至少 60刀鐘》接著將6·91 g NMP添加至該經中和之聚電解質溶 液中。接著在真空中將該經中和之聚電解質溶液加熱至 6〇°C以移除水。其產生27重量％之經tbaoh中和之聚 (VBS-共-經乙基甲基丙烯酸酯）κΝΜρ中之溶液。 實例39·聚（乙烯基苯甲基磺酸_共_乙烯基苯曱醇）之 TPAOH中和 將24.02 g 16.8重量％之聚（VBS_*_乙烯基苯曱醇）(mw= 60 kg/m〇l，86重量％之VBS)水溶液與8 3丨g 4〇 9重量％之氫 I11346.doc • 48· 1378942 氧化四丙基銨（TPAOH)水溶液組合並於室溫下攪拌至少60 分鐘。接著將29.74 g ΝΜΡ添加至該經中和之聚電解質溶 液。接著在真空中將該經中和之聚電解質溶液加熱至60°C 以移除水。其產生20重量％之經TPAOH中和之聚（VBS-共-乙烯基苯甲醇）於NMP中之溶液。 實例40:聚（乙烯基苯曱基磺酸-共-乙烯基苯曱醇）之 TBAOH中和 將72.31 g 13.9重量％之聚（乙稀基苯曱基磺酸-共-乙烯基 苯甲醇）(MW=260 kg/mol，85 重量0/〇 VBS)水溶液與 19.26 g 55重量％之TBAOH水溶液組合，並於室溫下攪拌至少60分 鐘。接著將79.36 g NMP及143.86 g乙腈添加至該經中和之 聚電解質溶液中。槔著在真空中將該經中和之聚電解質溶 液加熱至60°C以藉由共沸蒸餾移除水。其產生20重量％之 經TBAOH中和之聚（乙烯基苯甲基磺酸鹽-共-乙烯基苯曱 醇）於NMP中之溶液，並且殘餘水含量不超過0.09重量°/〇。 實例41 :聚（2-丙烯胺基-2-曱基丙烷磺酸鹽）之TBAOH中和 將17.25 g 20.1重量％之聚（2-丙烯胺基-2-甲基丙烷磺酸 鹽）水溶液（MW=120 kg/mol)與 6.35 g 55% 之 TBAOH 水溶液 組合，並於室溫下攪拌至少60分鐘。接著將15.35 g NMP 添加至該經中和之聚電解質溶液中。接著在真空中將該經 中和之聚電解質溶液加熱至60 °C以移除水。其產生35重量 %之經TBAOH中和之聚（2-丙烯胺基-2-曱基丙烷磺酸鹽）於 NMP中之溶液。 實例42:聚（丙烯酸）之TBAOH中和 111346.doc •49· (S) 藉由將4.98§聚（丙烯酸）(1^评=450 1<^/111〇1)溶解於81.40§ NMP中製備聚（丙烯酸）酸溶液。聚（丙烯酸）係自Sigma-Aldrich購得，作為標準品使用。將7.58 g聚（丙烯酸）溶液 與0.649 g 55重量％之TBAOH水溶液組合，並於室溫下攪 拌至少60分鐘。 實例43 : spPVA之TBAOH中和 將15.7 g 10.9重量％之磺酸基丙基化PVA (MW=144 kg/mol，56莫耳％磺化）水溶液與3.84 g 55%之TBAOH水溶 液在一小瓶中組合，並於室溫下攪拌至少60分鐘。接著將 8.04 g NMP添加至該經中和之聚電解質溶液中。接著在真 空中將該經中和之聚電解質溶液加熱至60°C以移除水。其 產生3 1重量％之經TBAOH中和之磺酸基丙基化聚（乙烯醇） 於NMP中之溶液，並且殘餘水含量不超過0.2重量％。 將經中和之聚電解質溶液與基質共聚物摻合 實例44 :經TBAOH中和之聚（苯乙烯磺酸鹽）與Kynar®NaOH acid-base titration to the phenolphthalein end point to obtain 3% poly(vinylbenzylsulfonic acid-co-vinylbenzyl alcohol) (38.6 g, 90%) solution, 99+% exchange efficiency (H+ exchange Na+) . Example 35: Large-scale ion exchange for a glass column (diameter 30.5 cm, length 122 cm) equipped with a compressed nitrogen line (maximum pressure 25 psi) and deionized water inlet followed by Dowex® Marathon C ion exchange resin (21 74 L, wet). Rinse the column thoroughly with deionized water, followed by 2 g of poly(vinyl benzene sulfonate-co-vinyl benzene f-ol) (3970 g) in deionized water (14 〇 kg) The % solution used a nitrogen overpressure (up to 17 psig) to force the solution to flow through the column at a rate of 0.4 bed volumes per hour and collect the leaching agent in the dissolved fraction. The pH of the eluent was continuously tested using a pH test coupon to determine the presence of the protonated polymer. The fractions containing the highest concentration of the polymer were combined to obtain 17.5% by weight of poly(vinylphenylsulfonic acid-co-vinylbenzofuran) by elemental analysis and titration with NaOH acid to the phenolphthalein end point (254 〇笆, 69〇/〇) solution, 99.8% exchange efficiency (H+ exchange Na+). TAAOH neutralization of the protonated polyelectrolyte solution. Example 36. I (this ethyl ether acid) tetrabutyl hydroxide recorded and 15. g g 30% by weight of poly(styrenesulfonic acid) (constructed from ρ An aqueous solution of 〇ι__ MW = 70 kg/mol) was combined with 9.22 g of a 55 wt% aqueous solution of tetrabutylammonium oxide (TBAOH) and stirred at room temperature for 6 minutes. Next, 15.03 g of NMP was added to the neutralized polyelectrolyte solution. The neutralized polyelectrolyte solution is then heated to (iv) in a vacuum to remove water. It produced 38% by weight of a TBA0H-neutralized poly(p-phenanthrate) solution in H1346.doc -47-1378942, and the residual water content did not exceed 0.2% by weight. Example 37: Neutralization of poly(styrenesulfonate-co-vinylbenzyl alcohol) tetrabutylammonium hydroxide 153.94 g of 2.6% by weight of poly(styrenesulfonic acid·co-ethylenebenzyl alcohol) An aqueous solution of MW = 237 kg/mol, 70% by weight of stupid vinyl sulfonic acid) was combined with 6 79 g of a 55 wt% aqueous solution of hydrazine and stirred at room temperature for at least 6 minutes. Next, 30_0 g of NMP was added to the neutralized polyelectrolyte solution. The neutralized polyelectrolyte solution was then heated to 6 Torr in vacuo to remove water. It produces 20% by weight of a solution of BA(h)-neutralized poly(styrenesulfonate-co-ethenylbenzyl alcohol) in NMP, and the residual water content does not exceed 0.7% by weight. Example 38: Neutralization of tetrabutylammonium hydroxide with poly(vinylphenylsulfonylsulfonyl-co-hydroxyethyl methacrylate) 7.03 g of 12.2 wt% of poly(vinylbenzylsulfonic acid) _Hydroxyethyl methacrylate vinegar (MW = 190 kg / mol, 79 wt 〇 / 〇 VBS) aqueous solution combined with 1.56 g 55 wt% 2 ΤΒΑΟΗ aqueous solution and at least 60 knives at room temperature. 6.91 g of NMP was added to the neutralized polyelectrolyte solution. The neutralized polyelectrolyte solution was then heated to 6 ° C in vacuo to remove water. It produced 27% by weight of a solution of tbaoh neutralized poly(VBS-co-ethyl methacrylate) κΝΜρ. Example 39. Poly(vinylbenzylsulfonic acid_co-vinylbenzophenone) TPAOH neutralization 24.02 g 16.8 wt% poly(VBS_*_vinylbenzophenone) (mw = 60 kg/m) 〇1, 86% by weight of VBS) aqueous solution was combined with 8 3 丨g 4 9% by weight of hydrogen I11346.doc • 48· 1378942 tetrapropylammonium oxide (TPAOH) aqueous solution and stirred at room temperature for at least 60 minutes. Next, 29.74 g of hydrazine was added to the neutralized polyelectrolyte solution. The neutralized polyelectrolyte solution was then heated to 60 ° C in vacuo to remove water. It produced 20% by weight of a solution of TPAOH neutralized poly(VBS-co-vinylbenzyl alcohol) in NMP. Example 40: TBAOH neutralization of poly(vinylphenylsulfonylsulfonic acid-co-vinylbenzophenone) 72.31 g of 13.9% by weight of poly(ethylene benzoylsulfonic acid-co-vinylbenzyl alcohol) (MW = 260 kg/mol, 85 wt. 0 / 〇 VBS) aqueous solution was combined with 19.26 g of a 55 wt% aqueous solution of TBAOH and stirred at room temperature for at least 60 minutes. Next, 79.36 g of NMP and 143.86 g of acetonitrile were added to the neutralized polyelectrolyte solution. The neutralized polyelectrolyte solution was heated to 60 ° C in a vacuum to remove water by azeotropic distillation. It produced a solution of 20% by weight of TBAOH-neutralized poly(vinylbenzylsulfonate-co-vinylbenzoquinone) in NMP, and the residual water content did not exceed 0.09 wt. Example 41: TBAOH neutralization of poly(2-propenylamino-2-mercaptopropane sulfonate) 17.25 g of 20.1% by weight aqueous solution of poly(2-propenylamino-2-methylpropane sulfonate) ( MW = 120 kg/mol) was combined with 6.35 g of 55% aqueous TBAOH solution and stirred at room temperature for at least 60 minutes. Next, 15.35 g of NMP was added to the neutralized polyelectrolyte solution. The neutralized polyelectrolyte solution was then heated to 60 ° C in vacuo to remove water. It produced 35% by weight of a solution of poly(2-propenylamino-2-mercaptopropane sulfonate) neutralized with TBAOH in NMP. Example 42: Neutralization of TBAOH of poly(acrylic acid) 111346.doc •49· (S) Prepared by dissolving 4.98 § poly(acrylic acid) (1^ rating = 450 1 <^/111〇1) in 81.40 § NMP Poly(acrylic acid) acid solution. Poly(acrylic acid) was purchased from Sigma-Aldrich and used as a standard. A solution of 7.58 g of poly(acrylic acid) was combined with 0.649 g of a 55 wt% aqueous solution of TBAOH and stirred at room temperature for at least 60 minutes. Example 43: TBAOH neutralization of spPVA A solution of 15.7 g of 10.9 wt% sulfonated propylated PVA (MW = 144 kg/mol, 56 mol% sulfonated) and 3.84 g of 55% aqueous TBAOH in a vial Combine and stir at room temperature for at least 60 minutes. Next, 8.04 g of NMP was added to the neutralized polyelectrolyte solution. The neutralized polyelectrolyte solution was then heated to 60 ° C in the air to remove water. It produced 31% by weight of a solution of TBAOH-neutralized sulfonated propylated poly(vinyl alcohol) in NMP, and the residual water content did not exceed 0.2% by weight. Blending the neutralized polyelectrolyte solution with the matrix copolymer Example 44: Poly(styrene sulfonate) neutralized with TBAOH and Kynar®

PVDF 將 24.36 g含 Kynar® PVDF 2801 及 NMP (15 重量 ％ PVDF) 之溶液與10.08 g得自實例36之38重量％之經TBAOH中和之 聚（苯乙烯磺酸鹽）組合，並在薄膜鑄造前於室溫下攪拌4小 時。PVDF combines 24.36 g of a solution containing Kynar® PVDF 2801 and NMP (15% by weight PVDF) with 10.08 g of 38% by weight of TBAOH-neutralized poly(styrene sulfonate) from Example 36 and cast in film. Stir at room temperature for 4 hours.

II

實例45 ··經TBAOH中和之聚（苯乙烯磺酸鹽）與Kynar® PVDF 將 18.99 g含 Kynar® PVDF 2801 及 NMP (15 重量 ％ PVDF) 之溶液與14.17 g得自實例37之20重量％之經TBAOH中和之 111346.doc -50- 1378942 聚（苯乙烯磧酸鹽-共-乙烯基苯曱醇）組合，並於室溫下攪 拌4小時。向此溶液中添加0.9973 g Desmodur N 3300A交 聯劑（Bayer之脂族聚異氰酸酯），並在薄膜鑄造前於室溫下 攪拌2小時。Example 45··TBAOH-neutralized poly(styrene sulfonate) and Kynar® PVDF 18.99 g of a solution containing Kynar® PVDF 2801 and NMP (15% by weight PVDF) with 14.17 g of 20% by weight from Example 37 It was combined with TBAOH neutralized 111346.doc -50 - 1378942 poly(styrene citrate-co-vinyl benzofuran) and stirred at room temperature for 4 hours. To this solution, 0.9973 g of Desmodur N 3300A crosslinking agent (Bayer's aliphatic polyisocyanate) was added, and stirred at room temperature for 2 hours before film casting.

實例46 :經TBAOH中和之聚（VBS-共-曱基丙烯酸羥乙基 酯）與 Kynar® PVDF 將 10.73 g含 Kynar® PVDF 2801 及 NMP (15 重量 ％ PVDF) 之溶液與6.16 g得自實例38之27重量％之經TBAOH中和之 聚（苯乙烯磺酸鹽-共-乙烯基苯甲醇）組合，並於室溫下攪 拌4小時。向此溶液中添加0.7135 g Desmodur BL 3 175A交 聯劑（Bayer之嵌段脂族聚異氰酸酯）及0.030g Fascat 4202 (Arkema Inc.之二丁基錫二月桂酸鹽）。在薄膜鎮造前將該 溶液於室溫下攪拌2小時。Example 46: Poly(VBS-co-mercaptohydroxyethyl acrylate) and Kynar® PVDF neutralized by TBAOH 10.73 g of a solution containing Kynar® PVDF 2801 and NMP (15% by weight PVDF) and 6.16 g were obtained from the examples. 27% by weight of TBAOH-neutralized poly(styrenesulfonate-co-vinylbenzyl alcohol) was combined and stirred at room temperature for 4 hours. To this solution was added 0.7135 g of a Desmodur BL 3 175A crosslinking agent (Bayer's block aliphatic polyisocyanate) and 0.030 g of Fascat 4202 (dibutyltin dilaurate of Arkema Inc.). The solution was stirred at room temperature for 2 hours before film formation.

實例47 :經TPAOH中和之聚（VBS-共-VBA) 及Kynar® PVDF 將 13.69 g含 Kynar® PVDF 2801 及NMP (15 重量 ％ PVDF) 之溶液與8.03 g得自實例39之20重量％之經TPAOH中和之 聚（苯乙烯磺酸鹽-共-乙烯基苯曱醇）組合，並於室溫下攪 拌4小時。向此溶液中添加0.85 g的Desmodur BL 3 175 A交 聯劑及0.026 g的Fascat 4202。接著在薄膜鑄造前將該溶液 於室溫下攪拌2小時。Example 47: Poly(VBS-co-VBA) and Kynar® PVDF via TPAOH Neutralization 13.69 g of a solution containing Kynar® PVDF 2801 and NMP (15% by weight PVDF) and 8.03 g of 20% by weight of Example 39 The poly(styrene sulfonate-co-vinyl benzofuran) neutralized with TPAOH was combined and stirred at room temperature for 4 hours. To this solution was added 0.85 g of Desmodur BL 3 175 A cross-linking agent and 0.026 g of Fascat 4202. The solution was then stirred at room temperature for 2 hours before film casting.

實例48 :經TBAOH中和之聚（VBS-共-VBA)與Kynar® PVDF 將 12.96 g含 Kynar® PVDF 2801 及 NMP (15 重量 ％ PVDF) liI346.doc 51 1378942 之溶液與11.12 g得自實例40之20重量％之經TBAOH中和之 聚（苯乙烯磺酸鹽-共-乙烯基苯曱醇）組合，並於室溫下攪 拌4小時。向此溶液中添加0.3420 g的Desmodur N 3 300A交 聯劑。在薄膜鑄造前將該溶液於室溫下攪拌2小時。Example 48: TBAOH-neutralized poly(VBS-co-VBA) with Kynar® PVDF 12.96 g of a solution containing Kynar® PVDF 2801 and NMP (15 wt% PVDF) liI346.doc 51 1378942 with 11.12 g from Example 40 20% by weight of the TBAOH-neutralized poly(styrenesulfonate-co-vinylbenzophenone) was combined and stirred at room temperature for 4 hours. To this solution was added 0.3420 g of Desmodur N 3 300A crosslinking agent. The solution was stirred at room temperature for 2 hours before film casting.

實例49 :經TBAOH中和之聚（2-丙烯胺基-2-曱基丙烷磺酸 鹽）與 Kynar® PVDF 將 43.06 g含 Kynar® PVDF 2801 及 NMP (15 重量 ％ PVDF) 之溶液與19.3 g得自實例41之35重量％之經TBAOH中和之 聚（2-丙烯胺基-2-甲基丙烷磺酸鹽）組合，並在薄膜鑄造前 於室溫下攪拌4小時。Example 49: Poly(2-propenylamino-2-mercaptopropane sulfonate) neutralized with TBAOH and Kynar® PVDF 43.06 g of a solution containing Kynar® PVDF 2801 and NMP (15% by weight PVDF) with 19.3 g A 35 wt% TBAOH neutralized poly(2-propenylamino-2-methylpropane sulfonate) combination from Example 41 was obtained and stirred at room temperature for 4 hours prior to film casting.

實例50 :經TPAOH中和之聚（丙烯酸）及Kynar® PVDF 接著將5.30 g含Kynar® 2801及NMP (15重量％聚合物）之 溶液與8.23 g得自實例42之經中和之聚（丙烯酸）溶液摻 合，並在薄膜鑄造前於室溫下攪拌4小時。Example 50: Poly(acrylic acid) and Kynar® PVDF neutralized with TPAOH Next 5.30 g of a solution containing Kynar® 2801 and NMP (15% by weight polymer) and 8.23 g of neutralized poly(Acrylic Acid) from Example 42 The solution was blended and stirred at room temperature for 4 hours before film casting.

實例 51 :經 TBAOH 中和之 spPVA與 Kynar®PVD 將 4.72 g 含 Kynar® PVDF 2801及 NMP (15重量 ％ PVDF)之 溶液與5.5 g得自實例43之31重量％之經TBAOH中和之磺酸 基丙基化聚乙烯醇組合，並於室溫下攪拌4小時。在薄膜 鑄造前將該溶液於室溫下攪拌2小時。 聚合物摻合物溶液之乾燥 實例52 :實例44-5 1中描述之聚合物摻合物溶液鑄造為薄 膜係使用一Mathis LTE實驗室乾燥器進行。將近似尺寸為 1 5 X 1 2平方吋之鋁箔用作鑄造基板。將大約15 g聚合物溶 液分散在該箔上且用一刮刀將其向下拉至厚度為約300 μηι 111346.doc -52- 1378942 之濕膜。接著，將所得薄膜M177°c下以18〇〇 23〇〇 RpM之 氣流加熱7分鐘。接著將該等乾燥薄膜自烘箱移除並冷卻 至室溫》全部聚合物摻合物溶液組合物產生乾燥膜厚度在 25至50 μηι之間的薄膜。 聚電解質/基質（共）聚合物摻合物膜之洗滌及酸化Example 51: spPVA and Kynar® PVD neutralized with TBAOH 4.72 g of a solution containing Kynar® PVDF 2801 and NMP (15% by weight PVDF) and 5.5 g of 31% by weight of TBAOH neutralized sulfonic acid from Example 43 The propylated polyvinyl alcohol was combined and stirred at room temperature for 4 hours. The solution was stirred at room temperature for 2 hours before film casting. Drying of the polymer blend solution Example 52: The polymer blend solution described in Example 44-5 1 was cast as a film system using a Mathis LTE laboratory dryer. An aluminum foil having an approximate size of 1 5 X 1 2 square feet was used as the cast substrate. Approximately 15 g of the polymer solution was dispersed on the foil and pulled down with a spatula to a wet film having a thickness of about 300 μη 111346.doc -52 - 1378942. Next, the obtained film was heated at a flow rate of 18 〇〇 23 〇〇 RpM for 7 minutes at M177 °C. The dried film is then removed from the oven and cooled to room temperature. The total polymer blend solution composition produces a film having a dry film thickness between 25 and 50 μηι. Washing and acidification of polyelectrolyte/matrix (co)polymer blend membrane

實例53 :將實例52尹在鋁箔上鑄造之該等薄膜浸沒在18 ΜΩ 去離子水中以將自該基板釋放該等薄膜。接著，將該等無 支撐薄膜浸沒在60-65。(：之1 Μ鹽酸水溶液浴中12〇分鐘。 隨後，將該等薄膜用去離子水洗滌並浸沒在6〇65。〇之1 μ 硫酸溶液中120分鐘。接著將該等薄膜自硫酸浴移除並用 18 ΜΩ去離子水洗滌以移除殘餘酸。接著將該等酸性薄膜 用空氣乾燥並於室溫下儲存以備將來使用。 製備薄膜電極組件 用於自由上述方法製造之多種類型之聚電解質/基質（共） 聚合物摻合物膜製備薄膜電極組件（ΕΜΑ)之通用程序 實例54 :將可購得之電極及塾片切割成適當大小/形狀以 適合測試單元。電極與墊片之間應無縫隙及/或重疊。分 別將㈤電極及塾片置放在—不錄鋼熱慶板/插件上。接 著用去離子水則電極之表面。接著將—片濕薄膜置放在 該電極表面上並將其弄平。接著將下面的去離子水層塗覆 至上。Ρ薄膜表面且將第二電極置放在此層上。將該等電極 對準並將多制水輕輕㈣1第二墊片置放在腦之頂 部上’繼而插人並頂塵板。接著於m時間及溫度下， 將整個組件置放在—預熱壓力機内。接著在低氣⑧.2版) 111346.doc -53- 1378942 下將其移除並冷卻至室溫。將MEA自不銹鋼壓板小心移除 (薄膜可稍黏附於插件）並將多餘的薄膜/墊片材料裁減掉。 將完成的MEAi放在測試單元巾轉螺栓以適當的預定之 【圖式簡單說明】Example 53: The films cast on Example 52 on aluminum foil were immersed in 18 ΜΩ deionized water to release the films from the substrate. Next, the unsupported films are immersed at 60-65. (1: 1 Μ hydrochloric acid in a bath for 12 。 minutes. Subsequently, the films were washed with deionized water and immersed in a 6 〇 65 〇 1 μ sulfuric acid solution for 120 minutes. Then the films were removed from the sulphuric acid bath. The residual acid was removed by washing with 18 ΜΩ deionized water. The acidic film was then air dried and stored at room temperature for future use. The film electrode assembly was prepared for free of various types of polyelectrolytes produced by the above method. /Matrix (co) Polymer Blend Membrane General Procedure for Preparing Thin Film Electrode Assembly (Example) 54: Commercially available electrodes and cymbals are cut to size/shape to fit the test unit. Between the electrode and the spacer There should be no gaps and/or overlaps. Place the (5) electrode and the cymbal on the non-recorded steel plate/plug, then use deionized water to the surface of the electrode. Then place the wet film on the electrode. Surface and flatten it. Then apply the lower layer of deionized water to the top. Ρ film surface and place the second electrode on this layer. Align the electrodes and light the water (four) 1 Two spacers placed On the top, 'then insert and dust the board. Then place the whole assembly in the preheating press at m time and temperature. Then in the low gas version 8.2) 111346.doc -53- 1378942 It was removed and cooled to room temperature. Carefully remove the MEA from the stainless steel platen (the film can be slightly adhered to the insert) and cut off the excess film/gasket material. Place the finished MEAi on the test unit towel transfer bolt to the appropriate order. [Simplified illustration]

1描繪如實例54中 所述的典型薄膜.電極纽件。1 depicts a typical film.electrode blank as described in Example 54.

111346.doc111346.doc

Claims (1)

、申請專利範圍： 種不具有可水解基團之聚合物摻合物，其包含： a)具有下列通式之一的聚電解質共聚物：Patent Application Range: A polymer blend having no hydrolyzable groups, comprising: a) a polyelectrolyte copolymer having one of the following formulas: w=鍵、ο、NH ' s、so或 so2 Y (^至匚〗2之烧基鰱、芳族醚或伸烧基醚鍵聯 Z鍵’（^至匚!2之烧基醚、芳族峻或伸烧基醚鍵聯 n=大於50% m=小於50% L=未全氟化之炫基醚或伸烷基醚鍵聯 L'=鍵或烷基醚或伸烷基醚鍵聯 A=磺酸根、膦酸根或羧酸根 B =能夠交聯之基團 及 b)基質聚合物， 其中a)與b)不同，且其中a)具有小於5〇〇 nm之晶疇大 〇 2_如請求項1芩聚合物摻合物，其中n大於70%且111小於 111346.doc 1378942 3 0% 〇 3. 如請求項1之聚合物摻合物，其中該基質聚合物包含含 免聚合物。 4. 如請求項丨之聚合物摻合物，其中該等晶疇大小為丨 至 100 nm。 5. 如請求項1之聚合物摻合物’其中該能夠交聯之基團（B) 為羥基。 Aw=key, ο, NH ' s, so or so2 Y (^ to 匚 2 2 of the base 芳, aromatic ether or extended alkyl ether linkage Z bond ' (^ to 匚! 2 of the alkyl ether, Fang Agglomerate or extended alkyl ether linkage n=greater than 50% m=less than 50% L=non-perfluorinated daether ether or alkyl ether linkage L'= bond or alkyl ether or alkyl ether bond A = sulfonate, phosphonate or carboxylate B = a group capable of crosslinking and b) a matrix polymer, wherein a) is different from b), and wherein a) has a domain larger than 5 〇〇 nm 〇 2 The polymer blend of claim 1 wherein n is greater than 70% and 111 is less than 111346.doc 1378942 3 0% 〇 3. The polymer blend of claim 1 wherein the matrix polymer comprises a polymerization-free polymer Things. 4. A polymer blend as claimed in claim 1, wherein the domains have a size from 丨 to 100 nm. 5. The polymer blend of claim 1 wherein the group (B) capable of crosslinking is a hydroxyl group. A 6. 如請求項丨之聚合物摻合物，其中該基團（A)為磺酸根基 團。 7. 如請求項1之聚合物掺合物，其中該聚電解質共聚物⑷ 為四烷基銨鹽。 8. 一種包含一或多個層之物品，其中至少一層包含如請求 項1之聚電解質。 9·如請求項8之物品，其包含燃料電池薄膜、離子交換薄 膜、塗層、燃油回收薄膜、生物薄膜、MEA或電池。6. A polymer blend as claimed in claim 1, wherein the group (A) is a sulfonate group. 7. The polymer blend of claim 1 wherein the polyelectrolyte copolymer (4) is a tetraalkylammonium salt. 8. An article comprising one or more layers, at least one of which comprises a polyelectrolyte as claimed in claim 1. 9. The article of claim 8 which comprises a fuel cell membrane, an ion exchange membrane, a coating, a fuel recovery membrane, a biofilm, an MEA or a battery. 10. —種用於形成如請求項丨之聚電解質溶液之方法其包 含： a) b) c)d) e) 使用適當的離子交換柱及樹脂將該聚電解質之初始 鹽形式離子交換成質子形式（質子化）； 用氫氧化四貌基銨中和該聚電解質勾； 替換該聚電解質存在於其中之溶劑； 將該經中和之聚合物與基質聚合物之溶液摻合； 自該摻合溶液形成膜或薄膜。 Ui346.doc10. A method for forming a polyelectrolyte solution as claimed in claim 1, comprising: a) b) c) d) e) ion-exchange of the initial salt form of the polyelectrolyte into protons using a suitable ion exchange column and resin Forming (protonation); neutralizing the polyelectrolyte hook with tetraammonium hydroxide; replacing the solvent in which the polyelectrolyte is present; blending the neutralized polymer with a solution of the matrix polymer; The solution forms a film or film. Ui346.doc
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