TW555595B - Anion exchangers and processes for preparing them - Google Patents
Anion exchangers and processes for preparing them Download PDFInfo
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- TW555595B TW555595B TW91111012A TW91111012A TW555595B TW 555595 B TW555595 B TW 555595B TW 91111012 A TW91111012 A TW 91111012A TW 91111012 A TW91111012 A TW 91111012A TW 555595 B TW555595 B TW 555595B
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- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
Description
555595 五、發明說明(1) [發明領域] 本發明係有關能夠吸附 子交換劑及其製造方法。尤 子交換劑及其製造方法。 [先前技藝] 一般所知為離子交換劑 類成具有磺基等之強酸性陽 基等之強鹼性陰離子交換樹 離子交換樹脂群及具有三級 脂群。其中最廣泛被使用的 交換樹脂及強鹼性陰離子交 在製備這些離子交換樹 交聯之聚苯乙烯球珠形式之 之強酸性陽離子交換樹脂時 績酸將此基本樹脂予以磺化 而獲得強酸性陽離子交換樹 強驗性陰離子交換樹脂時, 基化’然後藉由與三級胺如 以得到強鹼性陰離子交換樹 強驗性陰離子交換樹脂 分裂容量,其低於強酸性陽 2· Omeq/mL)。當強鹼性陰離 鹽時由於其需要較大用量而 此’ i試著導入更多的陰離 空氣中或水中之離子成分的離 其’本發明係有關新穎之陰離 之球珠狀離子交換樹脂主要八 離子交換樹脂群,具有四級^ 脂群’具有羧基等之弱酸性陽 胺基等之弱鹼性陰離子交換樹 離子交換樹脂為強酸性陽離子 換樹脂。 脂時,通常使用與二乙烯基笨 基本樹脂。當欲製備具有楓基 ,例如,以磺化劑如硫酸或氣 以將楓基導入基本樹脂中,由 脂。當欲製備具有四級錢基之 例如,將此基本樹脂予以氣甲 三甲基胺之反應而予以四級化 脂。 通常具有1.2meq/mL之中性鹽 離子父換樹脂者(約 子交換樹脂使用於水處理的脫 此導致成本增加的問題。因 子交換基至基本樹脂中以降低555595 V. Description of the invention (1) [Field of the invention] The present invention relates to an adsorbent exchanger capable of being adsorbed and a method for producing the same. Youzi exchanger and its manufacturing method. [Prior art] It is generally known that ion exchangers are strongly basic anion exchange trees with strong acidic cations such as sulfo groups, ion exchange resin groups, and tertiary lipid groups. Among them, the most widely used exchange resins and strongly basic anions are used in the preparation of these acid-exchange tree-crosslinked polystyrene spheres. Strongly acidic cation-exchange resins. The basic resin is sulfonated to obtain strong acidity. When a cation-exchange tree is a strong anion-exchange resin, it is basicized and then used with a tertiary amine to obtain a strong basic anion-exchange tree. ). When a strong alkaline anion salt needs a larger amount, this 'i try to introduce more ion components in the air or water from the ionization.' The present invention relates to a novel anionized ion The exchange resin is mainly composed of eight ion exchange resin groups, and a weakly basic anion exchange tree ion exchange resin having a quaternary ^ lipid group having a weak acidic amine group such as a carboxyl group is a strongly acidic cation exchange resin. When using grease, it is usually used with divinyl base resin. When it is desired to prepare a maple group, for example, a sulfonating agent such as sulfuric acid or gas is used to introduce maple group into a basic resin, and the resin is made of a lipid. When it is desired to prepare a quaternary base, for example, this base resin is subjected to a reaction of monomethylamine to give a quaternary grease. Usually has 1.2 meq / mL of neutral salt ion exchange resin (about the exchange of resin used in the treatment of water treatment. This leads to the problem of increased cost. Because the exchange of the base into the base resin to reduce
555595 五、發明說明(2) ^本,由於導入大量四級銨基至基本樹脂中而招致三甲基 胺臭味增強的問題。此係歸因於所謂的霍夫曼(H〇fmann) 降解’其係指藉由加熱等而消除四級銨基,此乃由於四級 f基對熱之低化學安定性之故。此胺臭味的問題不僅是當 導入大量四級銨基至基本樹脂時的主要議題,而且亦是一 般具有四級銨基之強鹼性陰離子交換劑的主要議題。 [發明之揭露] 本發明係本案發明人細心研究以藉由導入大量的陰離 子交換基至基本樹脂中且沒有造成由於霍夫曼降解之胺臭 味的問題而獲得具有高中性鹽分裂容量之新穎強鹼性陰離 子交換劑的結果所達成。 為了解決上述問題,本發明係有關一種包括衍生自在 有機聚合物基料之主鏈上之苯環上具有齒烷基之苯乙烯化 合物之接枝聚合物侧鏈的陰離子交換劑,其特徵在於衍生 自具有一個二級胺基及一個或多個一級、二級或三級胺基 及/或四級銨基之多胺化合物的官能基已導入至該接枝聚 合物側鏈上。 [本發明之最佳具體實例] 以下詳細說明本發明之各方面。在下述說明中,”在 苯環上具有函烧基之笨乙烯化合物”簡稱為”函烷基取代之 苯乙烯”。 用以製備本發明陰離子交換劑之有機聚合物基料較佳 為聚烯經為主之有機聚合物基料。聚烯烴為主之有機聚合 物基料適合於藉由輻射引發之接枝聚合反應而導入接枝側555595 V. Description of the invention (2) The problem of enhanced trimethylamine odor caused by the introduction of a large amount of quaternary ammonium groups into the basic resin. This is due to the so-called Hofmann degradation ', which refers to the elimination of the quaternary ammonium group by heating or the like, which is due to the low chemical stability of the quaternary f group to heat. This problem of amine odor is not only the main issue when introducing a large amount of quaternary ammonium groups to the basic resin, but also the main issue of strong basic anion exchangers generally having quaternary ammonium groups. [Disclosure of the invention] The present invention is a careful study by the inventors of the present case to obtain a novel novel high-neutral salt splitting capacity by introducing a large amount of anion exchange groups into the basic resin without causing the problem of amine odor due to Huffman degradation The results of the strongly basic anion exchanger were achieved. In order to solve the above problems, the present invention relates to an anion exchanger comprising a graft polymer side chain derived from a styrene compound having a dentyl alkyl group on a benzene ring on the main chain of an organic polymer base material. Functional groups from a polyamine compound having one secondary amine group and one or more primary, secondary or tertiary amine groups and / or quaternary ammonium groups have been introduced into the graft polymer side chain. [Best Specific Examples of the Invention] Hereinafter, aspects of the invention will be described in detail. In the following description, "a stupid ethylene compound having a halo group on a benzene ring" is simply referred to as "haloalkyl-substituted styrene". The organic polymer binder used to prepare the anion exchanger of the present invention is preferably a polyene-based organic polymer binder. Polyolefin-based organic polymer binders are suitable for introduction into the graft side by radiation-induced graft polymerization
313717.ptd 第10頁 555595 五、發明說明(3) 鏈之目的,此乃由於其不因輻射而降解之故。十分適合於 使用作為製備本發明陰離子交換劑之有機聚合物基料之聚 烯烴為主之聚合物材料的特定實例包含,但不限於,聚烯 烴如聚乙烯及聚丙浠,·鹵化聚烯烴如pTFE及聚氣乙稀;以 及稀煙-齒化烯烴共聚物如乙烯—四氟化乙烯共聚物及乙烯 -乙烯醇共聚物(EVA)。 這些有機聚合物基料較佳 材、多孔膜等所組成之聚合物 物的形式。在經施加經常重現 狀離子交換樹脂中,重要的是 容量及再生效率,此乃由於希 理液體的量且較少之再生劑的 子交換劑係設計於單向用途, 用如吸附氣體中之微量氣體成 化作用中之微量金屬離子及顆 明陰離子交換劑之聚合物基料 膜材、多孔膜等之形式,此乃 且與習知樹脂相較下可輕易煅 合物具有足以增加金屬離子 為由其組件、網狀物、膜 基本纖維或織物或非織造織 處理-再生循環之習知球珠 在於每充填管柱之離子交換 望其儘可能增加每循環之處 量之故。然而,本發明之離 因其特別欲在先前以外之應 分,消除或轉移液體,或催 粒上有效。由此觀點,本發 較佳為纖維材料、網狀物、 由於其在處理期間容易控制 燒之故。又,這些形式之聚 555595 五、發明說明" — ^ ^1以過濾器形式使用之本發明之有機聚合物材料,因 L ^合使用作為輻射引發之接枝聚合反應之基料且質輕 又易於形成過濾器之故。 人物ί發明之陰離子交換劑的特徵在於如上述般在有機聚 二人二料的主鍵上形成衍生自鹵烧基取代之苯乙烯之接枝 承口側鏈且將陰離子交換基導入至此侧鏈上。 本發明中’將接枝聚合物側鏈導入至有機聚合物基料 鍵上的較佳手段為輻射引發之接枝聚合反應。輻射引 考之^枝聚合反應為藉由照射基料以產生自由基再使其與 接枝單體反應而將所要之接枝聚合物側鏈導入至有機聚合 物基料中之方法’對本發明之目的而言,此方法係最佳 者此乃由於接枝鏈的數目或長度相對上可自由控制且可 將聚合物側鏈導入各種形狀之現存聚合物材料中之故。 可使用於十分適合本發明目的之輻射引發之接枝聚合 反應的輻射包含α-射線、y5 -射線、射線、電子射 線、UV射線等,其中,本發明以使用r —射線及電子射線 較佳。輻射引發之接枝聚合反應包含涵蓋預先照射接枝基 料’然後使其與反應之可聚合單體(接枝單體)接觸之預照 射接枝聚合反應,及涵蓋同時照射基料及單體之同時照射 接枝聚合反應,且此任一方法均可使用於本發明。輻射引 發之接枝聚合反應包含單體與基料間之各種接觸方式,如 以浸潰在單體溶液中之基料進行之液相接枝聚合反應,以 使基料與單體蒸氣接觸進行之氣相接枝聚合反應,或將基 料浸潰在單體溶液中,然後以氣相自反應之單體溶液將其313717.ptd Page 10 555595 V. Description of the invention (3) The purpose of the chain is because it is not degraded by radiation. Specific examples of polyolefin-based polymer materials that are very suitable for use as the organic polymer binder for preparing the anion exchanger of the present invention include, but are not limited to, polyolefins such as polyethylene and polypropylene, and halogenated polyolefins such as pTFE And polygas ethylene; and dilute smoke-dentified olefin copolymers such as ethylene-tetrafluoroethylene copolymers and ethylene-vinyl alcohol copolymers (EVA). These organic polymer binders are preferably in the form of a polymer composed of a material, a porous membrane, and the like. In the existing ion exchange resins, the capacity and regeneration efficiency are important. This is because the sub-exchanger of the regenerant with a small amount of Greek liquid is designed for one-way use. In the form of trace metal ions and polymer anion exchangers in the form of polymer base materials, porous membranes, etc., this can be easily calcined when compared with conventional resins. The conventional bead from its components, nets, membrane basic fibers or fabrics or non-woven weaving-recycling cycles is because the ion exchange per packed column is expected to increase the amount per cycle as much as possible. However, the reason for the present invention is that it is specifically intended to be effective in applications other than previously, eliminating or transferring liquid, or catalysis. From this point of view, the present invention is preferably a fibrous material, a mesh, because it is easy to control burning during processing. In addition, these forms of polymer 555595 V. Description of the invention-^ ^ 1 The organic polymer material of the present invention used in the form of a filter is used as a base material for the radiation-induced graft polymerization reaction and is lightweight because of its combination. It is easy to form a filter. The anion exchanger invented by the person is characterized in that, as described above, a graft socket side chain derived from a halogenated styrene substituted on the main bond of the organic polydione and the anion exchange group is introduced onto the side chain. . In the present invention, a preferred means for introducing the side chain of the graft polymer to the bond of the organic polymer base is radiation-induced graft polymerization. Radiation-induced graft polymerization is a method of introducing a desired graft polymer side chain into an organic polymer base by irradiating the base material to generate free radicals and reacting it with the graft monomer. For the purposes of this method, this method is the best because the number or length of the graft chains is relatively freely controllable and the polymer side chains can be introduced into existing polymer materials of various shapes. The radiation that can be used for the radiation-induced graft polymerization reaction that is very suitable for the purpose of the present invention includes α-rays, y5-rays, rays, electron rays, UV rays, and the like. Among them, it is preferred to use r-rays and electron rays in the invention. . Radiation-initiated graft polymerization reactions include pre-irradiation graft polymerization that covers pre-irradiation of the graft base material and then bringing it into contact with the reacted polymerizable monomer (graft monomer), and coverage of simultaneous irradiation of the base material and monomers. Simultaneous irradiation of the graft polymerization reaction, and any of these methods can be used in the present invention. Radiation-initiated graft polymerization includes various contact methods between the monomer and the base material, such as liquid phase graft polymerization with the base material immersed in the monomer solution, so that the base material and the monomer vapor contact Gas-phase graft polymerization, or immerse the base material in the monomer solution, and then
313717.ptd 第12頁 555595313717.ptd Page 12 555595
移除之浸潰氣相 發明。Removal of the immersion gas phase Invention.
玎使用於本 接枝聚合反應,且任一方法均 纖維組件所組成之纖維及織物/非織造鐵物係使用 ^ ”,、’傷本發明陰離子交換劑之有機聚合物基料的最佳材 料且特別適合使用於浸潰氣相接枝聚合反應,此乃由於 其易=保持單體溶液之故。 ^ 導入本發明陰離子交換劑中之有機聚合物基料之聚合 物主鏈上之接枝聚合物側鏈係衍生自齒烷基取代之苯乙 烯。此聚合物側鏈係藉由接枝聚合齒炫基取代之苯乙烯至 有機聚合物基料之主鏈上而導入。較佳使用於本發明之齒 烷基取代之苯乙烯的實例為下式所示之n—鹵烷基取代之苯 乙烯:最佳 It is used in the graft polymerization reaction, and the fiber and fabric / non-woven iron system composed of fiber components are used in any method ^ ", the best material for the organic polymer base that hurts the anion exchanger of the present invention It is particularly suitable for use in immersion gas phase graft polymerization because it is easy to maintain a monomer solution. ^ Grafting on the polymer backbone of the organic polymer base introduced into the anion exchanger of the present invention The polymer side chain is derived from dentyl-substituted styrene. This polymer side chain is introduced by graft polymerizing dentyl-substituted styrene onto the main chain of the organic polymer base. It is preferably used in An example of the alkyl-substituted styrene of the present invention is n-haloalkyl-substituted styrene represented by the following formula:
X=CIP Brp I; π=1-7〇 特佳為下式所示之氯甲基苯乙烯:X = CIP Brp I; π = 1-7〇 Particularly preferred is chloromethylstyrene represented by the following formula:
其中’特佳為氯甲基苯 且具有高化學耐久性之故。 在對位上具有乙烯基及氣甲 因其可使用於形成具有優異 劑之故。 導入有機聚合物基料中 基取代之苯乙烯與另一可聚 如’氣甲基苯乙烯與親水性 共聚合至有機聚合物基料上 增加聚合度。 本發明之陰離子交換齊】 及一個或多個一級、二級或 胺化合物的官能基已藉由使 般導入具有接枝聚合物側鏈 至接枝聚合物側鍵上。可用 鏈或支鏈多胺如二乙撐三胺 狀多胺如下式所示之三乙撐 乙烯,此乃因其可增加聚合度 就本發明之目的而言,最佳為 基之對-氣甲基苯乙烯,此乃 之離子移除性能之陰離子交換 之接枝聚合物側鏈亦可為鹵烷 合單體之接枝共聚物側鏈。例 可聚合單體如丙烯醯胺可接枝 以在基料上賦與另外的功能或 中’衍生自具有一個三級胺基 二級胺基及/或四級銨基之多 該種多胺化合物與具有如上述 之有機聚合物基料反應而導入 於本發明之多胺化合物包含直 及二乙撐三胺;及環狀或多環 二胺:Among them, chloromethylbenzene is particularly preferred because of its high chemical durability. It has vinyl and aerosol in the para position because it can be used to form an excellent agent. The polymer-substituted styrene introduced into the organic polymer base and another polymerizable polymer such as 'aeromethylstyrene' and hydrophilic are copolymerized onto the organic polymer base to increase the degree of polymerization. The anion exchange of the present invention] and one or more functional groups of the primary, secondary, or amine compound have been generally introduced with a graft polymer side chain to the graft polymer side bond. Usable chain or branched chain polyamines such as diethylene triamine-like polyamines are triethylene ethylene as shown in the following formula, because it can increase the degree of polymerization. Methylstyrene, which is an anion-exchange graft polymer side chain with ion-removing properties, may also be a graft copolymer side chain of a haloalkane monomer. For example, a polymerizable monomer such as acrylamide can be grafted to impart additional functionality to the base material or derived from as many polyamines as having one tertiary amino secondary amine group and / or quaternary ammonium group. The polyamine compound introduced into the present invention by reacting the compound with an organic polymer binder as described above includes straight and diethylenetriamine; and cyclic or polycyclic diamine:
下式所示之1, 一般名稱稱為"二氮雜雙環十一碳稀One of the following formulas, the general name is " diazabicyclic eleven carbon dilute
313717.ptd 第14頁 555595 五、發明說明(7)313717.ptd Page 14 555595 V. Description of Invention (7)
及以下式所示之六亞甲基四胺:And hexamethylenetetramine shown by the following formula:
尤其,以上述化學式所示例之多胺化合物具有稱為橋頭之 孤對,使得其具有高度反應性。因此,其可輕易地四級化 以大大地有助於增加離子交換容量同時具有未使用於鍵結 至接枝聚合物側鏈之高反應性的胺基。 當具有至少一個三級胺基及一個或多個一級、二級或 三級胺基及/或四級銨基之多胺化合物反應至衍生自鹵烷 基苯乙烯之接枝聚合物側鏈時,將三級胺基予以四級化以 在該部位造成鏈結。然而,含於多胺化合物中之其他胺基 或銨基保持不反應。亦即,每一個鹵烷基分子導入兩個或 更多個胺基或銨基,結果與習知離子交換樹脂相較下導入 兩倍或更多倍之陰離子交換基。 多胺化合物亦可導入習知球珠狀之離子交換樹脂中, 但聚合度或離子交換容量的增加皆顯然比本發明之陰離子 交換劑低。此可能是因為球珠狀之離子交換樹脂之基料的 交聯結構阻礙多胺化合物進入樹脂中或造成多胺化合物本 身交聯。然而,本發明之陰離子交換劑中,多胺化合物已In particular, the polyamine compounds exemplified by the above-mentioned chemical formula have lone pairs called bridgeheads, making them highly reactive. Therefore, it can be easily quaternized to greatly contribute to increase the ion exchange capacity while having a highly reactive amine group which is not used for bonding to the side chain of the graft polymer. When a polyamine compound having at least one tertiary amine group and one or more primary, secondary or tertiary amine groups and / or quaternary ammonium groups is reacted to the side chain of a graft polymer derived from a haloalkylstyrene The tertiary amine group is quaternized to cause a link at this site. However, other amine or ammonium groups contained in the polyamine compound remain unreacted. That is, two or more amine or ammonium groups are introduced per haloalkyl molecule, and as a result, two or more times of anion exchange groups are introduced as compared with conventional ion exchange resins. Polyamine compounds can also be introduced into conventional spherical bead-shaped ion exchange resins, but the increase in polymerization degree or ion exchange capacity is obviously lower than that of the anion exchanger of the present invention. This may be because the crosslinked structure of the base material of the bead-shaped ion exchange resin prevents the polyamine compound from entering the resin or causes the polyamine compound itself to crosslink. However, in the anion exchanger of the present invention, the polyamine compound has been
313717.ptd 第15頁 555595 五、發明說明(8) 導入有機聚合物基料之接枝聚合物側鏈中,使得該已導入 多胺化合物之部位具有較高的電荷而彼此相斥以擴大接枝 聚合物側鏈間的距離,由而多胺化合物可輕易地進入。此 不僅具有增加聚合度的效果而且亦具有抑制交聯的效果, 結果可獲得具有非常高離子交換容量的離子交換劑。與聚 合物主鏈彼此交聯以補償由於導入離子交換基之基體之物 理強度劣化之習知球珠狀之離子交換樹脂相反,本發明之 陰離子交換劑可藉由在基料的聚合物主鏈上提供含有陰離 子交換基之聚合物鏈形式之側鏈而在有機聚合物基料上賦 予高陰離子交換容量同時保持聚合物主鏈的物理強度。在 本發明之陰離子交換劑中,主鏈扮演保持物理強度或保持 形狀的角色。 ' [本發明的優點] 本發明之陰離子交換劑中,藉由將多胺化合物導入有 機聚合物基料之接枝聚合物側鏈中而得到高度胺化以解決 習知方法在導入較多胺時無可避免降低強度的問題。本^ 明亦解決習知方法胺臭味隨著胺化度增加的問題。此可食1 係因為本發明所使用之在一個分子中具有兩個或更多個胺 基之化合物具有隨著官能基數目上升的彿點以降低蒸氣 壓,因此抑制胺臭味的發出。此外,本發明之陰離子交換 劑可藉由煅燒或其他手段予以輕易地清理而且與習知離子 交換樹脂相較下較輕又較不昂貴。 本發明之陰離子交換劑可使用作為消除水中的金屬離 子或吸附空氣中的微量氣體成分等之材料。313717.ptd Page 15 555595 V. Description of the invention (8) Introduce the side chain of the graft polymer of the organic polymer base material, so that the site where the polyamine compound has been introduced has a higher charge and repel each other to expand the connection. The distance between the side chains of the branch polymer allows the polyamine compound to easily enter. This has not only an effect of increasing the degree of polymerization but also an effect of suppressing cross-linking, and as a result, an ion exchanger having a very high ion exchange capacity can be obtained. In contrast to the conventional spherical bead-shaped ion exchange resins in which the polymer main chains are crosslinked with each other to compensate for the deterioration of the physical strength of the matrix introduced with the ion exchange group, the anion exchanger of the present invention can be provided on the polymer main chain of the base material. Contains side chains in the form of polymer chains of anion exchange groups to impart high anion exchange capacity on the organic polymer binder while maintaining the physical strength of the polymer backbone. In the anion exchanger of the present invention, the main chain plays a role of maintaining physical strength or maintaining shape. '[Advantages of the present invention] In the anion exchanger of the present invention, a high degree of amination is achieved by introducing a polyamine compound into the graft polymer side chain of an organic polymer base to solve the conventional method of introducing more amines Inevitably, the problem of lowering strength is inevitable. The present invention also solves the problem that the amine odor of the conventional method increases with the degree of amination. This edible 1 is because a compound having two or more amine groups in one molecule used in the present invention has a Buddha point which increases with the number of functional groups to reduce the vapor pressure, thereby suppressing the emission of amine odor. In addition, the anion exchanger of the present invention can be easily cleaned by calcination or other means and is lighter and less expensive than conventional ion exchange resins. The anion exchanger of the present invention can be used as a material for removing metal ions in water or adsorbing trace gas components in the air.
555595 五、發明說明(9) 下述實施例說明本發明之各種具體實例,然而,本發 明並不侷限於此。 [實施例]555595 V. Description of the invention (9) The following examples illustrate various specific examples of the invention, however, the invention is not limited thereto. [Example]
實施JLL 使用直彼約1 7 # m由聚乙烯(殼)/聚丙稀(芯)複合纖維 所製成之具有55g/m2之密度及〇_ 35mm之厚度的熱熔化非織 造織物作為有機聚合物基料。在氮氣氛中以於150kGy之電 子射線照射此非織造基料。使氣甲基苯乙烯(Se i m iImplementation of JLL The use of hot-melt nonwoven fabrics with a density of 55 g / m2 and a thickness of 0-35 mm made of polyethylene (shell) / polypropylene (core) composite fibers with about 7 # m straight as the organic polymer Binder. This nonwoven substrate was irradiated with electron rays of 150 kGy in a nitrogen atmosphere. Gas-methylstyrene
Chemical出品,商品名CMS-AM)通過活化氧化鋁的填充床 以移除聚合抑制劑,然後再以氮氣吹氣予以去氧化。使經 照射之非織造基料浸潰於此氯甲基苯乙稀溶液令再於5 t 反應6小時。自此溶液移除此非織造織物再於甲苯中浸清3 小時以移除均聚物。由乾燥後得到之重量所計算的接枝度 為 1 6 10/〇。 使此接枝之非織造織物浸潰於1 〇%三乙撐二胺水溶液 中再於8 0 °C反應3小時。反應後,以水沖洗此非織造基 料’然後再藉由於5%氫氧化鈉水溶液中浸潰1小時而予以 再生。以純水徹底地沖洗再於5 0 °C真空乾燥器中乾燥3小 時。 、 獲得具有l_67meq/g之中性鹽分裂容量及3.43meq/g之 〜父換谷1的強驗性陰離子交換非織造織物。亦即,其含 有能夠於I67med/g分裂中性鹽及於l_76meq/g未反應之三 級胺基的四級銨基,其相對應於總交換容量與中性鹽分裂 容量間的差異。因此,四級銨基與三級胺基的量大約相Chemical (trade name: CMS-AM) was passed through a packed bed of activated alumina to remove the polymerization inhibitor, and then deoxidized by blowing nitrogen gas. The irradiated nonwoven substrate was immersed in this chloromethyl styrene solution and allowed to react for another 6 hours at 5 t. The non-woven fabric was removed from this solution and immersed in toluene for 3 hours to remove the homopolymer. The degree of grafting calculated from the weight obtained after drying was 16 10/0. The grafted non-woven fabric was immersed in a 10% aqueous solution of triethylenediamine and reacted at 80 ° C for 3 hours. After the reaction, the nonwoven substrate 'was washed with water and then regenerated by immersion in a 5% sodium hydroxide aqueous solution for 1 hour. Rinse thoroughly with pure water and dry in a vacuum dryer at 50 ° C for 3 hours. 1. Obtain a strong anion-exchange nonwoven fabric with a neutral salt splitting capacity of l_67meq / g and a density of 3.43meq / g to 1. That is, it contains a quaternary ammonium group capable of splitting a neutral salt at I67 med / g and an unreacted tertiary amine group at 1 to 76 meq / g, which corresponds to the difference between the total exchange capacity and the neutral salt splitting capacity. Therefore, the amount of quaternary ammonium and tertiary amine groups is approximately the same.
3l37l7.ptd 第17頁 555595 五、發明說明(ίο) 等,顯示導入三乙撐二胺而沒有被交聯。由重量改變所計 算之接枝聚合之氯甲基苯乙烯的聚合度高至如94%。 於氫氧化鈉溶液中使此非織造織物再生再予以乾燥, 然後貯存於拉上拉鍊之塑膠袋中。當在一個月後打開塑膠 袋時,並無注意到胺臭味。 比較例1 藉由於5 0 °C之1 0 %三甲基胺溶液中浸潰3小時而將實施 例1中之氣甲基苯乙烯-接枝之非織造織物予以四級化。以 與實施例1相同之方式進行再生處理。獲得具有2· 2meq/g 之中性鹽分裂容量之強鹼性陰離子交換非織造織物。每單 位重量之中性鹽分裂容量高且由重量改變所計算之每接枝 聚合之氣甲基苯乙烯的聚合度為96%,其足以與實施例1之 值相比。 於氫氧化鈉溶液中使此非織造織物再生再予以乾燥, 然後貯存於拉上拉鍊之塑膠袋中。當在一個月後打開塑膠 袋時,注意到重的胺臭味。以水沖洗再以相同方式貯存於 塑膠袋中,然後將其打開,注意到相同的胺臭味。 基於實施例1與比較例1之強鹼性陰離子交換非織造織 物具有幾乎相同之長度及寬度的事實,比較實施例1與比 較例1之強鹼性陰離子交換非織造織物之每單位面積的離 子交換容量,顯示中性鹽分裂容量幾乎可相比而總交換容 量大約高兩倍。其亦推測實施例1之強鹼性陰離子交換非 織造織物不僅可再生,沒有胺臭味並易於處理而且亦有空 氣中低氣體發出的特徵。3l37l7.ptd Page 17 555595 V. Description of the Invention (ίο) etc. shows that triethylenediamine was introduced without being crosslinked. The degree of polymerization of the graft-polymerized chloromethylstyrene calculated from the weight change was as high as 94%. The non-woven fabric was regenerated in a sodium hydroxide solution, dried, and then stored in a zippered plastic bag. When the plastic bag was opened after one month, no amine odor was noticed. Comparative Example 1 The gas methylstyrene-grafted nonwoven fabric in Example 1 was quaternized by immersion in a 10% trimethylamine solution at 50 ° C for 3 hours. The regeneration process was performed in the same manner as in Example 1. A strongly basic anion exchange nonwoven fabric having a neutral salt splitting capacity of 2.2 meq / g was obtained. The neutral salt has a high splitting capacity per unit weight and the degree of polymerization of methylstyrene per graft polymerized gas calculated from the weight change is 96%, which is sufficiently compared with the value of Example 1. The non-woven fabric was regenerated in a sodium hydroxide solution, dried, and then stored in a zippered plastic bag. When the plastic bag was opened after one month, heavy amine odor was noticed. Rinse with water and store in a plastic bag in the same way, then open it and notice the same amine odor. Based on the fact that the strongly basic anion exchange nonwoven fabrics of Example 1 and Comparative Example 1 have almost the same length and width, the ions per unit area of the strongly alkaline anion exchange nonwoven fabrics of Example 1 and Comparative Example 1 are compared. The exchange capacity shows that the neutral salt splitting capacity is almost comparable and the total exchange capacity is approximately twice as high. It is also speculated that the strongly basic anion-exchange nonwoven fabric of Example 1 is not only recyclable, has no amine odor, is easy to handle, but also has characteristics of low gas emission in air.
313717.ptd 第18頁 555595 五、發明說明(11) 實施例2 將實施例1所獲得之強鹼性陰離子交換非織造織物(可 再生)試樣裝配在直徑為5cm之聚氣乙晞管柱中,再於第1 圖所示之氣體移除性能試驗裝置中進行氣化氫氣體移除試 驗。第1圖中的參考數字係表示下述元件: 1 :管柱,2 :非織造織物試樣,3 :測量入口濃度之取樣 口,4 :測量出口濃度之取樣口,5 :泵,6 :滲透器,7 : 過濾器支撐物。控制滲透器以調整於管柱入口的氣化氫氣 體濃度至lppm,並使管柱於15L/min之空氣流動下通風。 起初,於出口沒有偵測到氣化氫,而在通風3 4 · 5小時後於 出口的氯化氫氣體濃度保持低於〇. lppm。 比較例2 以與實施例2相同之方式對比較例1所獲得之強鹼性陰 離子交換非織造織物進行氣化氫氣體移除試驗。起初,於 出口沒有偵測到氣化氫,而在通風1 8 · 1小時後於出口的氣 化鼠氣體》辰度保持低於Q . 1 p p m。 當比較實施例2與比較例2時,本發明之陰離子交換劑 具有比比,例之陰離子交換劑長約兩倍之以服務壽命所表 示之離子^氣體移除性能。在兩情形下,初始移除性能皆為 9 9 %或更南。313717.ptd Page 18 555595 V. Description of the invention (11) Example 2 The strong alkaline anion-exchange nonwoven fabric (renewable) sample obtained in Example 1 was assembled on a 5 cm diameter polyacetic acid fluorene column In the gas removal performance test apparatus shown in Fig. 1, a hydrogenated gas removal test was performed. The reference numerals in Figure 1 indicate the following components: 1: a pipe string, 2: a nonwoven fabric sample, 3: a sampling port for measuring the inlet concentration, 4: a sampling port for measuring the outlet concentration, 5: a pump, 6: Permeator, 7: Filter support. The permeator was controlled to adjust the gaseous hydrogen gas concentration at the inlet of the column to 1 ppm, and the column was ventilated under an air flow of 15 L / min. At the beginning, no hydrogen gas was detected at the outlet, and the hydrogen chloride gas concentration at the outlet remained below 0.1 ppm after 3,4 · 5 hours of ventilation. Comparative Example 2 The strongly alkaline anion-exchange nonwoven fabric obtained in Comparative Example 1 was subjected to a hydrogenated gas gas removal test in the same manner as in Example 2. Initially, no hydrogen gas was detected at the outlet, but the gasification of rat gas at the outlet after 18 · 1 hour of ventilation remained below Q. 1 p p m. When Example 2 and Comparative Example 2 are compared, the anion exchanger of the present invention has a specific ratio, the anion exchanger of the example is approximately twice as long as the ion removal gas performance represented by the service life. In both cases, the initial removal performance was 99% or less.
tJkMA 於氮乱氛中在乾冰冷卻下於1〇〇kGy以r —射線照射實 施例1所4用之熱可熔化非織造織物。然後,以與實施例工 相同之方式接枝聚合氣甲基苯乙烯以得到具有138%接枝度tJkMA was irradiated with r-rays at a temperature of 100 kGy under dry ice in a nitrogen atmosphere, and the heat-fusible nonwoven fabric used in Example 4 was irradiated. Then, polymer gas methylstyrene was grafted in the same manner as in the example to obtain a degree of grafting of 138%.
第19頁 555595Page 19 555595
之氯甲基苯乙烯接枝之非織造織物。使此接枝之非織造織 物浸潰於在80 °C於二曱基曱醯胺中之二氮雜雙環十一碳稀 之20%’谷液中再反應6小時。以氫氧化納使此非織造織物再 生,然後測量離子交換容量。於1· 41 meq/g之中性鹽分裂 容量及2· 65meq/g之總交換容量得到同時具有強鹼性陰離 子交換基及弱鹼性陰離子交換基料之陰離子交換非織造織 物。亦即’其含有能夠於14imeq/g分裂中性鹽及於 1 · 2 4 m e q / g未反應之三級胺基的四級銨基,其相對應於總 交換容量與中性鹽分裂容量間的差異。因此,四級銨基"與 二級胺基的量大約相等,顯示導入二氮雜雙環十一碳烯而 沒有被交聯。 /於氫氧化鈉溶液中使此非織造織物再生再予以乾燥, 然後貯存於拉上拉鍊之塑膠袋中。當在一個月後打開塑 袋時,並無注意到胺臭味。 ^ 實施例左 一藉由與實施例2相同之程序對實施例3所獲得之陰離子 ,換非織造織物進行氣化氫氣體移除試驗。起初,於出口 次有偵測到氯化氫,而在通風3丨小時後於出口的氣化氫濃 度保持低於〇·1ΡΡιη,顯示使用多胺化合物的效果。 敗Non-woven fabrics grafted with chloromethylstyrene. This grafted nonwoven fabric was immersed in a 20% 'dilute solution of diazabicycloundecunde in diamidoxamine at 80 ° C for another 6 hours. This nonwoven fabric was regenerated with sodium hydroxide, and the ion exchange capacity was measured. An anion-exchange nonwoven fabric having both a strongly basic anion exchange group and a weakly basic anion exchange base was obtained at a neutral salt splitting capacity of 1. 41 meq / g and a total exchange capacity of 2. 65 meq / g. That is, it contains a quaternary ammonium group capable of splitting a neutral salt at 14imeq / g and an unreacted tertiary amine group at 1.24 meq / g, which corresponds to the total exchange capacity and the neutral salt splitting capacity. The difference. Therefore, the amount of the quaternary ammonium group is about the same as that of the secondary amine group, indicating that diazabicycloundecene was introduced without being crosslinked. / The non-woven fabric was regenerated in a sodium hydroxide solution and dried, and then stored in a zippered plastic bag. When the plastic bag was opened after one month, no amine odor was noticed. ^ Example Left The same procedure as in Example 2 was used for the anion obtained in Example 3, and the nonwoven fabric was replaced with a hydrogenated hydrogen gas removal test. Initially, hydrogen chloride was detected at the outlet, but the concentration of hydrogen gas at the outlet remained below 0 · 1ppm after 3 hours of ventilation, showing the effect of using polyamine compounds. defeat
555595 圖式簡單說明 [圖式之簡單說明] 第1圖為顯示使用於本發明實施例中之氣體移除性能 試驗裝置的示意圖。 [元件符號說明] 1 管柱 2 非織造織物試樣 3 測量入口濃度之取樣口 4 測量出口濃度之取樣口 5 泵 6 滲透器 7 過濾器支撐物555595 Brief description of drawings [Simplified description of drawings] Fig. 1 is a schematic diagram showing a gas removal performance test device used in the embodiment of the present invention. [Explanation of component symbols] 1 String 2 Non-woven fabric sample 3 Sampling port for measuring inlet concentration 4 Sampling port for measuring outlet concentration 5 Pump 6 Permeator 7 Filter support
313717.ptd 第21頁313717.ptd Page 21
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CN105073878A (en) * | 2013-10-01 | 2015-11-18 | 日东电工株式会社 | Ionomer solution in which anion exchange resin is dissolved in solvent |
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JP2002346400A (en) | 2002-12-03 |
WO2002096560A1 (en) | 2002-12-05 |
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