1342788 • 叫年6月多曰更正替換頁 九、發明說明： ---- 【發明所屬之技術領域】 本發明係關於一種高吸水性樹脂之製造方法，特別是一種於 狀、不溶於水、可吸收水液、尿液或血液且可溶物含量低的言吸 水性樹脂之製造方法。 【先前技術】 高吸水性樹脂具有強大的保水力，可吸收百倍甚至於千倍於 • 本身重量的水，且吸水後可膨潤具有保持不流動的狀態，即使施 加壓力也不會滲漏，且被吸收的水可緩緩地在大氣中釋出。由於 具有上述之特性，所以最早使用於農森林業的土壤保水劑，近年 因高吸水性樹脂的生產技術有相當大的進步，所以也廣泛地運用 於衛生用品如尿布、成人失禁用品及婦女衛生用品的吸水劑及保 存食物用的保鮮應用等。 φ 问吸水性樹脂的成分材料習知有遇水分解型的澱粉丙烯腈 (hydiOlyzed starch-acrylonitrile)接枝聚合物（日本專利公開公報昭 49(1974)43,395)，中和之澱粉丙烯酸接枝聚合物（日本專利公開 公報昭51 (1976)·125,468)’皂化乙烯醋酸丙烯酯共聚物（曰本專 利公開公報日召52(1977)-14,689)，水解丙烯腈共聚物或丙烯醯胺 共聚物（日本專利公報昭53 (1978)-15,959)，及部份中和聚丙烯 酸（日本專利公開公告昭55(1980)-84,304)等。其中以使用丙烯 酸及丙烯酸㈣行交聯聚合所得之高吸水性樹脂佔最大部份也最 7 . 明年6月3日更正替換頁 樹::右Ϊ原因為两烯酸可迅迷由市售取得’且^^^ 一吸水能力’及具有製造成本低廉且最具經濟效益， 成為最普遍化的高吸水性樹脂。 聚合丙烯酸及丙稀酸鹽形成高吸水性樹脂的方法已被多方 面7開發成功’且衫種已朗紅業界生產，其聚合方法有鱗 膜=合反應（日本專利公告昭和48(1973)_42,466)，於輸送帶上進 行聚合反應（日本專利公_和58(1983>49,714)，進行逆相懸 斤液聚合反應（日本專利公開昭和59(1984)_37，⑽3)，或將單體 噴濃或塗覆於纖縣質上進行聚合反應（日本專利公開昭和 62(1987>53,309)。 此外，吸水性樹脂為不溶解化之親水性聚合體，樹脂内部具 有均勻性㈣橋結構’-般為了改善品質如:提高吸收速率、提高 膠體強度、提高抗結塊性、液體滲透料，會在樹脂的表面再作 進一步架橋，此表面交聯處理即利用具有能與酸基反應之多官能 基交聯劑，在此之前已有許多專利提出；如：分散高吸水性樹脂 與交聯劑於有機溶劑中進行表面交聯處理（jp_a_56_1316〇8、 JP-A-57-44627、JP-A-58-42602、JP-A58-117222)使用無機粉末 直接將父聯劑與父聯劑溶液混入高吸水性樹脂處理 (JP-A60-163956、JP-A-60-255814) ’添加交聯劑後以蒸氣處理 (JP-A-1-113406)，使用有機溶劑、水及多元醇進行表面處理 (JP-A-63-270741、JP-A-64-50707、JP-A-1-292004)使用有機溶 中7年6月？曰更正替換頁 液、水、_ (etheO 化合物（JP_A_2_15細） 的方法雖能提高魏辭提高壓力下财倍率，但將造成保持力 下降過多的不良後果，降低實際應用之性能。 【發明内容】 鑒於以上的問題’本發明的主要目的在於提供—種粉狀、不 溶於水、可吸收水液、尿液或血液且可溶物含量低的高吸水性樹 脂之製造方法’藉以解決先前技術所揭露之聚合方法反應不易控 制，製程不穩定的缺點，也解決此難程製備出的高吸水性樹脂 可溶份較高的問題。 本發明所提述之雛、不溶於水、可吸收水液 '尿液或血液 且可溶物含量低的高吸水性樹脂之製造方法至少包括：添加交聯 劑於中和率5GmGle%(莫耳百分比)以上之含酸基單體水溶液中， 含酸基單體可選自丙烯酸、甲基丙烯酸、2_丙烯胺_2_甲基丙綱 酸或其混合物，騎賴水溶液中対“痛(重量百分比） 的水溶性高分子；之後’將麵基單體溶液絲合反應引發劑於 雙螺桿混合機中滞留3〜_秒，以進行自由基聚合反紐提供凝 膠體；再以溫度1〇〇。(：至25Gt熱風進行乾燥、粉碎、騎、表面 交聯劑塗覆處理、以溫度賊至23〇t進行加熱表面處理及添加 惰性無機鹽粉末。 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 50 501342788 • In June, the number of corrections is replaced by the invention. The invention relates to a method for producing a super absorbent resin, in particular, in a form, insoluble in water, A method for producing a water-absorbent resin which can absorb water, urine or blood and has a low soluble content. [Prior Art] The superabsorbent resin has a strong water retention capacity, can absorb 100 times or even thousands of times of its own weight of water, and can be swollen after being absorbed to maintain a non-flowing state, even if pressure is applied, it does not leak, and The absorbed water can be slowly released in the atmosphere. Due to the above characteristics, the soil water retaining agent which was first used in the agricultural forestry industry has been widely used in hygienic products such as diapers, adult incontinence products and women's health due to considerable progress in the production technology of superabsorbent resins in recent years. Water absorbing agent for products and fresh-keeping applications for preserving food. φ The component material of the water-absorbent resin is a water-decomposable starch acrylonitrile graft polymer (Japanese Patent Laid-Open Publication No. Sho 49 (1974) No. 43,395), and neutralized starch acrylic acid graft polymerization. (Japanese Patent Publication No. Sho 51 (1976) 125, 468) 'Saponified ethylene propylene acetate copolymer (Japanese Patent Publication No. 52 (1977)-14, 689), hydrolyzed acrylonitrile copolymer or acrylamide copolymer ( Japanese Patent Publication No. Sho 53 (1978)-15,959), and partially neutralized polyacrylic acid (Japanese Patent Laid-Open Publication No. Sho 55 (1980)-84,304) and the like. Among them, the superabsorbent resin obtained by cross-linking polymerization of acrylic acid and acrylic acid (four) is the largest and the most. 7. Replace the page tree on June 3rd next year: The right-handed reason is that the two-acids can be obtained by the market. 'And ^^^ a water absorption capacity' and low cost of manufacture and most economical, become the most general superabsorbent resin. The method of polymerizing acrylic acid and acrylic acid salt to form a super absorbent resin has been successfully developed in various aspects. 'The shirt type has been produced in the industry, and the polymerization method has a scaly film = combined reaction (Japanese Patent Publication No. 48 (1973) _42 , 466), polymerization is carried out on a conveyor belt (Japanese Patent Publication No. 58 (1983); 49, 714, and a reverse phase suspension polymerization reaction (Japanese Patent Laid-Open No. 59 (1984) _37, (10) 3), or a monomer The polymerization is carried out by spraying or coating on the fiber material (Japanese Patent Publication No. Sho 62 (1987) 53. 309. Further, the water-absorbent resin is an insoluble hydrophilic polymer, and the resin has uniformity inside (four) bridge structure'- In order to improve the quality, such as: increasing the absorption rate, increasing the strength of the colloid, increasing the anti-caking property, and the liquid permeating material, further bridging is carried out on the surface of the resin, and the surface cross-linking treatment utilizes a polyfunctional group capable of reacting with an acid group. The base cross-linking agent has been proposed in many patents before; for example, the surface of the superabsorbent resin and the cross-linking agent are cross-linked in an organic solvent (jp_a_56_1316〇8, JP-A-57-44627, JP-A). -58-42602 JP-A58-117222) Directly mixing the parent-linked agent and the parent-linking agent solution into the superabsorbent resin using an inorganic powder (JP-A60-163956, JP-A-60-255814) 'Vapor treatment after adding a crosslinking agent (JP-A60-163956, JP-A-60-255814) JP-A-1-113406), surface treatment using organic solvent, water and polyol (JP-A-63-270741, JP-A-64-50707, JP-A-1-292004) using organic solvent 7 In June, the method of replacing the page liquid, water, and _ (etheO compound (JP_A_2_15 fine) can improve the financial margin under the pressure of Wei, but it will cause the adverse effect of excessive retention and reduce the performance of the actual application. SUMMARY OF THE INVENTION In view of the above problems, the main object of the present invention is to provide a method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content. The invention solves the problems that the polymerization method disclosed in the prior art is difficult to control and the process is unstable, and also solves the problem that the high water-absorptive resin prepared by the difficult process has a high soluble fraction. The present invention is insoluble in water, Absorbable liquid 'urine or blood and soluble content The method for producing a super absorbent resin comprises at least: adding a crosslinking agent to an aqueous solution of an acid group-containing monomer having a neutralization ratio of 5 GmGle% or more, and the acid group-containing monomer may be selected from the group consisting of acrylic acid and methacrylic acid. 2_Acrylamine 2-methylpropanoic acid or a mixture thereof, a water-soluble polymer of "pain (% by weight) in an aqueous solution; then a mixture of initiators of a surface-based monomer solution in a twin-screw mixture The machine was retained for 3 to _ seconds to provide a free radical polymerization reaction to provide a gel; (: to 25Gt hot air for drying, pulverization, riding, surface crosslinking agent coating treatment, heating surface treatment at a temperature of thief to 23 〇t and addition of inert inorganic salt powder. According to the preferred embodiment of the invention, the powder Insoluble in water, absorbable water 50 50
液、尿液或血液且可溶物含量 _ 中八U取 民的阿吸水性樹脂之製造方法，其 組之 2 乙稀醇，粉或職生物或上述群 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 =尿液或血液且可溶物含量低的高吸水性樹脂之製造方法，其 ^聯劑為具有兩個或兩個以上可參與自由基反應之官能基的水 5谷性化合物。 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 液、尿液或血液且可溶物含量低的高吸水性樹脂之製造方法，其 中中和率5〇莫耳百分比以上之含酸基單體水，中和所用之中和劑 為氫氧脑、錢氧仙、錢氧切、或碳驗、祕酸鈉、 或碳酸鉀、或魏纽、或鑛油、或碳魏喊上述群組之 混合物。 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 液、尿液或血液且可溶物含量低的高吸水性樹脂之製造方法，其 中聚合反應引發劑為熱分解型引發劑或氧化還原型引發劑。 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 液、尿液或血液且可溶物含量低的高吸水性樹脂之製造方法，其 中雙螺桿混合機包含下列元件：含交聯劑之反應單體入料管、聚 合引發劑入料管、兩支並列的螺桿及反應物料排出口。 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 半'(年6月)日更正替換頁 液、尿液或血液且可溶物含量低的高吸水性樹— 中滞留時間包括20-30秒，更包括5_2〇秒，其中滯留時間在5秒 以下則反應物舰合不料，後段自由絲合反應溫度不穩定， 有局部溫度較局的現象，且高吸水性樹脂的可溶份會較高。 依照本發明較佳實施綱述之粉狀、不溶於水、可吸收水 液、尿液或血液且可溶物含量低的高吸水性樹脂之製造方法，其 中凝膠體轉後粒徑分佈麵在⑽5至丨毫米(_)之間。 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 液、尿液或血液且可溶物含量低的高吸水性樹脂之製造方法，其 中表面乂聯劑為多元醇、或聚乙二醇二縮水甘細、或碳酸亞煙 酉曰或上述群組之混合物。而表面交聯劑添加範圍在重量百分比 0.005 至 5.0。 依照本發明較佳實施例所述之粉狀、不溶於水、可吸收水 液、尿液或錢且可溶物含量_高财_社製造方法，其 中惰性無機餘末為顧！g、或氧她、或氧傾、或氧化約、 或高嶺土、或二氧化石夕、或碳、或碳酸鎮等或上述群组之混 合物。而惰性無機鹽粉末添加制在重量百分_.Q1至4 〇。 …本發明所提供之高吸水性樹脂的製造方法，其聚合反應較為 均勻’反應熱也不致於過高，本發明方法的些特性除了能夠提 高製程穩定性與改善操作環境之外，本發明所製備出的高吸水性 樹脂更具備低可溶份的特性。 有關本發與實作，統合圖雜最錄施例詳細說 1342788 « • YI年6月多曰更正替換頁 ' 明如下。 ---—— 【實施方式】 以下舉出具體實施例以詳細說明本發明之内容，並以圖示作 為輔助說明。說明中提及之符號係參照圖式符號。 本發明提供一種粉狀、不溶於水、可吸收水液、尿液或血液 且可溶物含量低的高吸水性樹脂之製造方法，至少包括： 鲁 1)添加交聯劑於中和率50mole%以上之含酸基單體水溶液 中，含酸基單體可選自丙烯酸、曱基丙烯酸、2_丙稀胺_2· 甲基丙炫•磺酸或上述群組之混合物，而含酸基單體水溶液 中含有0〜5wt%的水溶性高分子； 2) 將含酸基單體溶液與聚合反應引發劑於雙螺桿混合機中滯 留3〜600秒時間，以進行自由基聚合反應後提供凝膠體； 以及 3) 將凝膠體以溫度i〇〇°c至250°C熱風進行乾燥、粉碎、薛 選、塗覆表面交聯劑、以溫度80°C至230°C加熱表面處理 及添加惰性無機鹽粉末。 本發明所提供之粉狀、不溶於水、可吸收水液、尿液或血液 且可溶物含量低的高吸水性樹脂之製造方法在於利用一雙螺桿混 合機於自由基聚合反應前先使反應物料均勻混合，再進一步排出 到反應器完成自由基聚合反應。 第1圖為本發明實施例粉狀、不溶於水、可吸收水液、尿液 12 1342788 • 训年（月）日更正替換頁 或血液且可溶物含量低的高吸水性樹脂之製造— 機設備簡圖。如第1圖所示’含交聯劑之反應單體在混合機機座 6上方由含交聯劑之反應單體入料管丨進入混合機機體中，而聚 合反應引發劑則由聚合反應引發劑入料管2進入機體，隨後反應 單體與聚合反應引發劑經由雙螺桿3之作用，均勻、單向地向前 推進，最後由反應物料排出口 4排出，進入皮帶反應器或批次反 應器中完成聚合反應。 鲁 上述之特徵係在聚合反應前將含交聯劑之單體溶液與聚合 引發劑滯留於一並列之雙螺桿混合機後，再連續加入到循環運行 的傳送帶或批次反應器中，進一步聚合成凝膠狀固體。如此一來， 除了能夠使單體溶液與觸媒充分混合而提高反應均勻性外，更可 藉著調整滯留時間來使單體溶液與觸媒達到如同預聚合反應之效 果。此外，使用並列之雙螺桿作為混合機可以確保物料單向向前 運動而不出現回流的現象，從而避免了聚合反應物料在混合機中 • 停留時間過長而形成凝膠狀固體，造成製程操作上的不便。 滯留時間的長短會影響反應單體與觸媒混合的均勻性，進而 影響反應情形與成品的可溶份含量。一般來說，滯留時間長，反 應單體與觸媒有充分時間混合，反應會較為均勻且穩定，可溶份 相對較低’但滯留時間也不可過長，以避免反應物料在混合機中 形成過度黏稠的預聚物或凝膠狀固體。至於滯留時間的長短則可 藉由螺桿的長度與轉速加以控制。 13 1342788 明.年6月彡曰更正替換頁 雙螺桿混合機將反應物料均勻、單向地排放至輸送帶式反應器 上或裝有攪拌葉之橫式反應器中進一步完成聚合反應，製備出之 向吸水性凝膠體先利用絞碎機切成直徑2〇_以下凝膠體，更可 以切成直徑l〇mm以下凝膠體’再進行烘乾。 本發明所製造之高吸水性樹脂所需的含酸基單體除了丙烯酸 外，尚可使用其它具有不飽合雙鍵的水溶性單體，如：曱基丙烯 春 酸、或馬林酸、或富馬酸、或2-丙烯胺-2-甲基丙烷磺酸等。單體 選用不特定限制只可使用一種，亦可合併多種單體一齊使用，亦 可視情況需要添加具有不飽和雙鍵其他親水性的單體，如:丙烯醯 胺、甲基丙烯醯胺、丙烯酸2-烴基乙酯、曱基丙烯酸2_烴基乙酯、 丙烯S文甲S曰、丙稀酸乙酯、二曱胺丙稀丙稀醯胺、氣化丙烯丙烯 醯胺基三伙’但添加量以不破壞高吸水輯脂之雛為原則。 在進行自由基聚合反應前’含酸基單體水溶液濃度宜控制在重 • 量百分比20至55間，適當濃度為重量百分比30至45之間，漢 度在重量百分比20以下時，聚合後水合凝膠體太軟且有黏性不利 機械加工，添加濃度在重量百分比55以上，接近飽和濃度，不易 調配且反應太快反應熱不易控制。 含酸基單體之羧酸基應部份中和以控制成品之pH值，使呈 中性或微酸性，中和劑為氫氧化裡、氫氧化鈉、氣氧化卸、碳醆 裡、竣酸納、碳酸卸、碳酸氫鐘、碳酸氫鈉、碳酸氫鉀及氨。含 14 1342788 « 00 训年έ月J日更正替換頁 次基早體之紐基將部份巾和成_或蝴細一 以上混合鹽類，中和濃度莫耳百分比為45 i 85，適當=為二 =分比5〇至75，中和濃度莫耳百分比為Μ以下時成品又之阳 值會偏低’中和濃度莫耳百分比為85以上時成品之pH值會偏 成品pH值若非呈中性或微性時，不慎與人體接觸時均不 太適合也車父不安全。 錢行自&絲合反縣含酸基單财溶射，亦可添加水 鲁溶性高分子以降低成本，此等水溶性高分子如：部份急化或完全 息化的聚乙烯醇、聚乙二醇、聚丙稀酸、聚丙_胺、殺粉S 粉衍生物如甲基纖維素，丙烯酸曱基纖維素’乙基纖維素等聚合 物；此等水溶性高分子的分子量並不特別限定，其中較佳的水溶 性高分子為澱粉、部份m完全皂化㈣乙_等單獨或混合 使用。咼吸水性樹脂含此等添加水溶性高分子的適當重量百分比 為0至20,更可以為重量百分比〇至1〇，尤能為重量百分比〇至 9 5，添加超過重量百分比20時會影響物性，使物性變差。 在進行自由基聚合反應前應先添加自由基聚合反應交聯劑 於未反應單體溶液中，此自由基聚合反應交聯劑可選用具有兩個 或兩個以上不飽和雙鍵的化合物，如:N，N-雙(2-丙烯基)胺、n，N‘-次甲基雙丙烯醯胺、N,N‘-次曱基雙曱基丙烯醯胺、丙烯酸丙稀 酉曰、乙一醇一丙浠酸·醋、聚乙二醇二丙埼酸醋、乙二醇二曱基丙 稀酸醋、聚乙二醇二曱基丙烯酸酯、甘油三丙烯酸酯、甘油三曱 15 1342788 /年6月 > 曰更正替換頁 基丙烯酸醋、甘油附加環氧乙烷之三丙烯酸醋^三曱基丙烤酸一~ 酯、三甲醇丙烷附加環氧乙烷之三丙烯酸酯或三曱基丙烯酸酯、 三甲醇丙烷三甲基丙烯酸酯、三曱醇丙烷三丙烯酸酯、N，N，N_三 (2-丙烯基)胺、二丙烯酸乙二醇酯、二丙烯三甘醇酯等，亦可選用 具有兩個或兩個以上環氧基的化合物，如山梨醇聚縮水甘油醚、 聚丙二醇^^細水甘油鱗、乙二醇二縮水甘油趟、二乙二醇二縮水 甘油醚、聚乙二醇二縮水甘油醚、雙丙三醇聚縮水甘油醚等。在 進行自由基反應後就可使高吸水性樹脂具有適當交聯度，而使高 吸水性樹脂膠體有適當的加工性。自由基聚合反應交聯劑可單獨 使用或兩種以上混合使用。自由基聚合反應交聯劑適當的添加劑 量在重量百分比0.001至5之間(以反應物總固形份為基準）’更適 當的用量重量百分比在〇.〇1至3之間，添加劑量在重量百分比 0.001以下聚合後水合體太軟且有黏性不利機械加工，添加劑量在 重量百分比5以上吸水性太低，降低樹脂性能。 聚合反應由自由基聚合反應起始劑的分解產生自由基開 始。自由基起始劑可選用熱分解型起始劑，適合的熱分解型起始 劑有過氧化物’如：過氧化氫、二_第三丁基過氧化物、過氧化酸 胺或過硫酸鹽(銨鹽、鹼金屬鹽)等，及偶氮化合物如·· 2,2，_偶氮基 雙(2-脒基丙烷)二鹽酸鹽、2,2，-偶氮基雙(ν,ν—二伸甲基異丁脒)二 鹽酸鹽；亦可使用還原劑，使成為氡化還原型起始劑，如：酸性 亞硫酸鹽、硫代硫酸鹽、抗壞域或亞鐵鹽；或將氧化還原型起 1342788 .· 年6月彡曰更正替換頁 . 始劑和熱分解型起始劑合併使用，首先氧化還^起始劑先 應產生自由基，當自由基轉移至單體上即引發聚合反應的進行， 由於聚合反應進行時會釋放出大量的熱量而使溫度升高，當溫度 到達熱分解型起始劑的分解溫度時，又會引發第二段熱分解型起 始劑的分解，而使整個聚合反應更臻於完全。一般自由基聚合反 應起始劑適當用量為重量百分比為0001至10(以中和丙烯酸鹽重 量為基準）’更適當用量則在重量百分比0.1至5之間，使用重量 • 百分比0.0〇ι以下時，反應太慢不利經濟效益，使用重量百分比 10以上時’反應太快反應熱不易控制。 烘乾溫度可於100C至25(TC下進行乾燥，乾燥溫度則以12〇 °〇至180°Cit行烘乾為宜，當烘乾溫度12叱以下則洪乾時間太久 不具經濟效益，純溫度⑽。⑶上縣使交·提早進行交聯Liquid, urine or blood and soluble content _ a method for producing a water-absorbent resin of the group, wherein the group of 2 ethylene glycol, powder or occupational organism or the above group is according to a preferred embodiment of the present invention a method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water = urine or blood, and has a low soluble content, and has a function of having two or more functional groups capable of participating in a radical reaction Base water 5 gluten compound. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content according to a preferred embodiment of the present invention, wherein the neutralization rate is 5 〇 mol% The above-mentioned acid-containing monomer water, neutralizing agent used for the neutralization is oxyhydrogen brain, oxonol, chitoche, or carbon test, sodium silicate, or potassium carbonate, or Wei New, or mineral oil, or Carbon Wei shouted a mixture of the above groups. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content according to a preferred embodiment of the present invention, wherein the polymerization initiator is thermally decomposed Initiator or redox initiator. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs aqueous liquid, urine or blood and has a low soluble content according to a preferred embodiment of the present invention, wherein the twin-screw mixer comprises the following components: A reaction monomer feed pipe containing a crosslinking agent, a polymerization initiator feed pipe, two parallel screws, and a reaction material discharge port. A superabsorbent tree having a powdery, water-insoluble, and absorbable water half-year (June 6) correction for replacing page liquid, urine or blood and having a low soluble content in accordance with a preferred embodiment of the present invention - The residence time includes 20-30 seconds, including 5_2 〇 seconds, wherein the residence time is less than 5 seconds, the reaction ship is unsatisfactory, the temperature of the free silk reaction in the latter stage is unstable, there is a local temperature, and the super absorbent resin The soluble fraction will be higher. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content according to a preferred embodiment of the present invention, wherein the particle size distribution surface after the gel is transferred Between (10) 5 and 丨 mm (_). A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content according to a preferred embodiment of the present invention, wherein the surface crosslinking agent is a polyol, Or polyethylene glycol diglycidate, or methylene iodide or a mixture of the above groups. The surface crosslinker is added in the range of 0.005 to 5.0 by weight. According to a preferred embodiment of the present invention, the powdery, water-insoluble, absorbable liquid, urine or money and soluble matter content is high in the production method, wherein the inert inorganic residue is taken care of! g, or oxygen, or oxygen, or oxidized about, or kaolin, or sulphur dioxide, or carbon, or carbonated or the like or a mixture of the above groups. The inert inorganic salt powder is added in a weight percentage of _.Q1 to 4 〇. The method for producing a super absorbent resin provided by the present invention has a relatively uniform polymerization reaction, and the heat of reaction is not too high. In addition to improving the process stability and improving the operating environment, the present invention has the following features. The prepared superabsorbent resin is further characterized by low solubility. Regarding this issue and implementation, the most detailed examples of the integration plan are 1342788 « • YI year June more correction correction page ' is as follows. [Embodiment] Hereinafter, specific embodiments will be described in detail to explain the present invention, and are illustrated by the accompanying drawings. The symbols mentioned in the description refer to the schema symbols. The invention provides a method for manufacturing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content, and at least comprises: Lu 1) adding a crosslinking agent at a neutralization rate of 50 mole In the aqueous solution containing more than 100% of the acid group-containing monomer, the acid group-containing monomer may be selected from the group consisting of acrylic acid, methacrylic acid, 2-propyleneamine-2·methylpropanesulfonic acid or a mixture of the above groups, and containing an acid. The base monomer aqueous solution contains 0 to 5 wt% of the water-soluble polymer; 2) the acid group-containing monomer solution and the polymerization initiator are retained in the twin-screw mixer for 3 to 600 seconds for the radical polymerization reaction. Providing a gel; and 3) drying, pulverizing, smashing, selecting a surface crosslinking agent, and heating the surface at a temperature of 80 ° C to 230 ° C at a temperature of from 〇〇 ° c to 250 ° C Treat and add inert inorganic salt powder. The method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content provided by the present invention consists in using a twin-screw mixer before radical polymerization. The reaction materials are uniformly mixed and further discharged to the reactor to complete the radical polymerization. Fig. 1 is a view showing the manufacture of a superabsorbent resin which is powdery, insoluble in water, absorbable liquid, and urine 12 1342788 in the embodiment of the present invention. • The replacement of the page or blood and the low soluble content of the superabsorbent resin in the training year (month) Machine equipment diagram. As shown in Fig. 1, the reaction monomer containing a crosslinking agent enters the mixer body through the reaction monomer inlet pipe containing the crosslinking agent above the mixer base 6, and the polymerization initiator is polymerized. The initiator feed pipe 2 enters the body, and then the reaction monomer and the polymerization initiator are uniformly and unidirectionally advanced by the action of the twin screw 3, and finally discharged from the reaction material discharge port 4, into the belt reactor or batch. The polymerization is completed in the reactor. The above characteristics are characterized in that the monomer solution containing the crosslinking agent and the polymerization initiator are retained in a juxtaposed twin-screw mixer before the polymerization, and then continuously added to the circulating conveyor belt or the batch reactor to further polymerize. A gelatinous solid. In this way, in addition to being able to sufficiently mix the monomer solution with the catalyst to improve the reaction uniformity, the residence time can be adjusted to achieve the effect of the prepolymerization reaction between the monomer solution and the catalyst. In addition, the use of a parallel twin-screw as a mixer ensures that the material moves forward in one direction without reflow, thereby avoiding the polymerization of the material in the mixer. • The residence time is too long to form a gel-like solid, causing process operation. Inconvenience. The length of residence time affects the uniformity of the mixing of the reactive monomer with the catalyst, which in turn affects the reaction situation and the soluble fraction of the finished product. In general, the residence time is long, the reaction monomer and the catalyst have sufficient time to mix, the reaction will be more uniform and stable, and the soluble fraction is relatively low', but the residence time should not be too long to avoid the formation of the reaction material in the mixer. Overly viscous prepolymer or gelatinous solid. As for the length of the residence time, it can be controlled by the length and rotation speed of the screw. 13 1342788 Ming. June 彡曰 Correction Replacement Page Twin-screw Mixer Discharges the reaction material uniformly and unidirectionally onto a conveyor belt reactor or a horizontal reactor equipped with a stirring blade to further complete the polymerization. The water-absorbent gel is first cut into a gel having a diameter of 2 〇 _ or less by a mincer, and can be cut into a gel having a diameter of l 〇 mm or less and then dried. The acid group-containing monomer required for the super absorbent resin produced by the present invention may use other water-soluble monomers having unsaturated double bonds, such as mercaptopropionic acid or malic acid, in addition to acrylic acid. Or fumaric acid, or 2-propenylamine-2-methylpropane sulfonic acid, and the like. The monomers may be used in a single type, and may be used in combination with a plurality of monomers. Optionally, other hydrophilic monomers having unsaturated double bonds may be added, such as acrylamide, methacrylamide, and acrylic acid. 2-hydrocarbylethyl ester, 2-mercaptoethyl methacrylate, propylene S-formin, ethyl acrylate, diammonium acrylamide, gasified propylene propylene amide, but not added The quantity is based on the principle of not destroying the high water absorption album. Before the radical polymerization, the concentration of the aqueous solution containing the acid-based monomer should be controlled between 20 and 55 weight percent, the appropriate concentration is between 30 and 45, and the hydration after polymerization is less than 20% by weight. The gel is too soft and sticky. It is unfavorable for mechanical processing. The added concentration is above 55% by weight, close to the saturation concentration. It is difficult to formulate and the reaction is too fast. The reaction heat is not easy to control. The carboxylic acid group of the acid group-containing monomer should be partially neutralized to control the pH value of the finished product to make it neutral or slightly acidic. The neutralizing agent is hydrogen hydroxide, sodium hydroxide, gas oxidizing, carbon ruthenium, ruthenium. Sodium, carbonic acid, hydrogen carbonate, sodium bicarbonate, potassium bicarbonate and ammonia. Contains 14 1342788 « 00 Training Year of the Month J. Correction of the replacement page of the base of the New Zealand base will be part of the towel and into a _ or a fine combination of more than one salt, the concentration of molar concentration of 45 i 85, appropriate = For the second=fraction ratio of 5〇 to 75, when the percentage of neutralization concentration is below Μ, the positive value of the finished product will be lower. 'The neutralization concentration of the molar percentage is 85 or more. The pH value of the finished product will be partial to the finished product. When it is neutral or micro, it is not suitable for inadvertent contact with the human body and the car father is not safe. Qian Xing from & Silken anti-county acid-containing single-acid spray, can also add water-soluble polymer to reduce costs, such water-soluble polymers such as: partially accelerated or fully-interested polyvinyl alcohol, poly A polymer such as ethylene glycol, polyacrylic acid, polyacrylamide, powdered S powder derivative such as methyl cellulose, decyl cellulose acrylate, or ethyl cellulose; the molecular weight of such water-soluble polymers is not particularly limited Among them, a preferred water-soluble polymer is starch, a part of m is completely saponified (tetra), and the like is used singly or in combination. The water-absorbent resin may have a suitable weight percentage of the water-soluble polymer to be added in an amount of from 0 to 20, more preferably from 〇 to 1 〇, especially from 〇 to 95, and the addition of more than 20% by weight may affect physical properties. To make the physical properties worse. Before the radical polymerization reaction, a radical polymerization crosslinking agent should be added to the unreacted monomer solution, and the radical polymerization crosslinking agent may be selected from a compound having two or more unsaturated double bonds, such as :N,N-bis(2-propenyl)amine, n,N'-methine bis acrylamide, N,N'-nonyl bis-decyl acrylamide, acrylonitrile acrylate, ethyl alcohol Propionate, vinegar, polyethylene glycol dipropylene vinegar, ethylene glycol dimercapto acrylate, polyethylene glycol dimercapto acrylate, glycerol triacrylate, glycerol triterpenone 15 1342788 / year June> 曰Correct replacement of acrylic acid vinegar, glycerin plus ethylene oxide acrylate, trimethyl propyl acetonate, trimethyl methoxide, ethylene oxide triacrylate or tridecyl acrylate Ester, trimethylolpropane trimethacrylate, triterpene propane triacrylate, N,N,N_tris(2-propenyl)amine, ethylene glycol diacrylate, dipropylene triethylene glycol ester, etc. Compounds having two or more epoxy groups, such as sorbitol polyglycidyl ether, polypropylene glycol, and fine water, can be used. Scales, ethylene glycol diglycidyl times, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bis glycerol polyglycidyl ether and the like. After the radical reaction, the superabsorbent resin can have an appropriate degree of crosslinking, and the superabsorbent resin colloid can have appropriate processability. The radical polymerization crosslinking agent may be used singly or in combination of two or more. Free Radical Polymerization Crosslinking agent Suitable additive amount is between 0.001 and 5 by weight (based on total solids of the reactants). A more appropriate amount by weight is between 〇.1 to 3, and the amount of the additive is in the weight. After the polymerization of 0.001 or less, the hydrated body is too soft and viscous to be unfavorably mechanically processed, and the amount of the additive is too low in the water content of 5 or more to lower the resin property. The polymerization starts by the decomposition of the radical polymerization initiator to generate a radical. The free radical initiator can be selected from a thermal decomposition type initiator, and the suitable thermal decomposition initiator is a peroxide such as hydrogen peroxide, di-tert-butyl peroxide, amine peroxylate or persulfate. Salts (ammonium salts, alkali metal salts), etc., and azo compounds such as 2,2,-azobis(2-amidinopropane) dihydrochloride, 2,2,-azobis (v) , ν-di-methyl-isobutyl hydrazine) dihydrochloride; a reducing agent may also be used to make a hydrazine reduction-type initiator, such as acidic sulfite, thiosulfate, anti-bad or ferrous Salt; or the redox type from 1342788. June 彡曰 correction replacement page. The combination of the initiator and the thermal decomposition initiator, first oxidized and the initiator should first generate free radicals, when the free radicals are transferred to The polymerization is initiated on the monomer, and a large amount of heat is released during the polymerization to increase the temperature. When the temperature reaches the decomposition temperature of the thermal decomposition initiator, a second thermal decomposition type is initiated. The decomposition of the initiator causes the entire polymerization to be more complete. Generally, the radical polymerization initiator is suitably used in an amount of 0001 to 10 by weight based on the weight of the neutralized acrylate. 'More suitable amount is between 0.1 and 5 by weight, and when the weight is used, the percentage is less than 0.0 〇ι. The reaction is too slow and unfavorable economical. When the weight percentage is above 10, the reaction is too fast and the reaction heat is not easy to control. Drying temperature can be dried at 100C to 25 (TC, drying temperature is preferably 12〇°〇 to 180°Cit drying, when the drying temperature is below 12叱, the drying time is too long, it is not economical, pure Temperature (10). (3) Shangxian County, early cross-linking
反應’使得後續的乾燥過程巾，因㈣度過高而無法有效的去除 殘存単體，達到降低低殘存單體之效果。 … —乾燥後進行粉碎、定粒徑’再進行表面交聯劑塗覆處 理。歸選固定粒徑以_mm至⑽_間為宜，更可以為㈣ 至〇.850mm間，粒徑_mm以下細粉使成品粉塵提高，粒徑 1.00mm以上粒子使成品吸水速率變慢。 $^年6月夕曰更正替換頁 二乙二醇、聚乙二醇 '丙二醇、1，4 丁二醇、三烴基曱基丙烷、山 梨醇等；或可使用多元胺如：乙二胺、二乙二胺、三乙二胺、聚 乙二胺；或可使用具有兩個或兩個以上環氧基的化合物如：山梨 醇聚縮水甘油醚、聚丙三醇聚縮水甘油醚、乙二醇二縮水甘油趟、 二乙二醇二縮水甘油醚、聚乙二醇二聚縮水甘油醚、雙丙三醇聚 縮水甘油醚等；亦可使用碳酸亞烴酯如：乙二醇碳酸g旨、4_甲基 -1，3-二氧雜環戊烧-2-酮、4,5-二曱基-1，3-二氧雜環戍烧_2_酮、4,4_ 一甲基-1,3-二氧雜環戊烧-2-綱、4-乙基-1，3-二氧雜環戊烷_2•鲷、 13_二氧雜環己烧-2嗍、4,6-二曱基胃1，3-二氧雜環己、烷_2嗍或u_ 一氧雜環庚烷-2·酮等。表面處交聯劑的用法可單獨使用或兩種以 上混合使用。表面處交聯劑的適當添加劑量在重量百分比〇〇⑴ 至10之間(以反應物總固形份為基準），更適當的用量在重量百八 比0.005至5之間，表面處交聯劑添加劑量在重量百分比〇 〇〇1 2 下時無法顯出效果，表面處交聯劑添加劑量在重量百分比1〇以上 時’吸水性太低，降低樹脂性能。 表面交聯舰覆處理時’絲交咖之添加可為表面交聯巧 直接添加，或調成表面交聯劑水溶液添加，或調成表面交聯織 水性有機關水溶祕加，親雜有機溶㈣曱醇、乙醇、丙^、 異丁醇、醜、甲醚、乙_沒有特殊限制，可形成溶液即可，、 其中以甲醇、乙醇雛。表面交聯麻加時高财樹脂 惰性無機餘末，的祕齡散，舰無機鹽粉材Μ酸^ 娜年6月彡曰更正替換頁 或二氧化碎’或氧她’或氧化鎂等或其混合物Γ其中以硫酸銘— 一氧化石夕較佳。惰性無機鹽粉末添加範圍在重量百分比0.005至 10.0之間，更可以為重量百分比0 01至4〇。 進行表面交聯劑塗覆處理後，再以80。(：至230°C加熱處理， 使表面父聯劑能進行交聯反應，並使内部交聯劑進行交聯反應而 達到本發明之效果。處理溫度8(rc以下交聯反應時間太久，不具 經濟效益，處理溫度^230。(：時，樹脂易劣化影響品質。至於處理 時間則以2〜150分鐘為宜，依處理溫度調整，溫度高則時間短， 溫度低則時間長。 由於高吸水性樹脂具有吸濕後結塊的現象，為避免在高濕度 地區使用兩吸水性樹脂會有吸濕後結塊導致加工不順，一般會在 向吸水性樹脂表面塗附惰性無機鹽粉末或界面活性劑，使表面略 具親油性而使高吸水性樹脂保有吸濕後不易結塊的特性，此惰性 無機鹽粉末可選用硫酸鋁、或二氧化矽、或氧化鋁、或氧化鎂、The reaction is such that the subsequent drying process towel cannot effectively remove the residual carcass due to the high degree of (4), thereby achieving the effect of reducing the low residual monomer. ... - pulverization, particle size after drying, and surface crosslinking agent coating treatment. The selected fixed particle size is preferably between _mm and (10)_, and may be between (4) and 850.850mm. The fine powder with a particle size of _mm or less improves the finished dust, and the particles with a particle size of 1.00 mm or more slow the water absorption rate of the finished product. $^年月月月曰曰 Replacement page diethylene glycol, polyethylene glycol 'propylene glycol, 1,4 butanediol, trihydrocarbyl mercaptopropane, sorbitol, etc.; or polyamines such as ethylenediamine, Diethylenediamine, triethylenediamine, polyethylenediamine; or compounds having two or more epoxy groups such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol Diglycidyl hydrazine, diethylene glycol diglycidyl ether, polyethylene glycol dimer glycidyl ether, diglycerol polyglycidyl ether, etc.; an alkylene carbonate such as ethylene glycol carbonate may also be used. 4-methyl-1,3-dioxol-2-one, 4,5-dimercapto-1,3-dioxanthene-2-one, 4,4-monomethyl- 1,3-dioxolane-2-yl, 4-ethyl-1,3-dioxolane-2•鲷, 13_dioxane-2嗍, 4,6 - Diterpenoid stomach 1,3-dioxan, alkane 2 oxime or u_ oxacycloheptane-2 ketone. The crosslinking agent at the surface may be used singly or in combination of two or more. The appropriate amount of the crosslinking agent at the surface is between 重量(1) and 10 (based on the total solids of the reactants), and more suitably between 8% and 0.005 to 5 by weight. The added dose does not show an effect when the weight percentage is 〇〇〇1 2 , and the amount of the cross-linking agent additive at the surface is more than 1 重量, the water absorption is too low, and the resin property is lowered. When the surface cross-linking ship is treated, the addition of silk coffee can be added directly to the surface cross-linking, or it can be added to the surface cross-linking agent aqueous solution, or the surface cross-linking woven water can be added to the water-soluble solution. (4) sterol, ethanol, propylene, isobutanol, ugly, methyl ether, and B are not particularly limited, and a solution may be formed, wherein methanol and ethanol are used. Surface cross-linking Ma Jiashi Gaocai resin inert inorganic residual, the secret age scattered, ship inorganic salt powder tannic acid ^ Na Nian June correction correction page or dioxide dioxide 'or oxygen her' or magnesium oxide, etc. The mixture is preferably sulphuric acid - nitric oxide. The inert inorganic salt powder is added in a range of from 0.005 to 10.0 by weight, more preferably from 0 01 to 4 Å by weight. After the surface cross-linking agent coating treatment, it was again 80. (: heat treatment at 230 ° C, the surface parent crosslinking agent can be cross-linked, and the internal crosslinking agent is subjected to a crosslinking reaction to achieve the effect of the present invention. The treatment temperature is 8 (the crosslinking reaction time is less than rc, too long, It is not economical, and the treatment temperature is ^230. (: When the resin is easily deteriorated, the quality is affected. As for the treatment time, it is suitable for 2~150 minutes, according to the treatment temperature adjustment, the temperature is high, the time is short, and the temperature is low, the time is long. The water-absorbent resin has a phenomenon of agglomeration after moisture absorption. In order to avoid the use of the two water-absorbent resin in a high-humidity region, the agglomeration caused by moisture absorption may cause processing, and an inert inorganic salt powder or interface may be applied to the surface of the water-absorbent resin. The active agent makes the surface slightly oleophilic and the superabsorbent resin has the property of not easily agglomerating after moisture absorption. The inert inorganic salt powder may be selected from aluminum sulfate, or cerium oxide, or aluminum oxide or magnesium oxide.
或氧化鈣、或咼嶺土、或碳酸鈣、或碳酸鎂等或其混合物；通常 此惰性無機鹽粉末的添加量與無機鹽粉末顆粒粒徑大小有關，若 顆粒粒徑較小其無機鹽粉末比表面積較大，所以有效惰性無機鹽 粉末用量可較小，其惰性無機鹽粉末添加範圍為重量百分比〇 〇〇5 至10.0之間，更可以為重量百分比0.01至4 〇 ’惰性無機鹽粉末 其粒徑為0.001//M至i〇〇aM，若選用顆粒小於〇 〇〇1#M的無 機鹽粉末則成本過高不利於工業化生產，若選用顆粒大於1〇〇#M 1342788 '. Μ年6月夕曰更正替換頁 . 的無機鹽粉末則有添加量過高影響高吸水性樹脂吸收力的問題。 惰性無機鹽粉末可單獨添加或可伴隨界面活性劑或具粘度有機化 口物加入，其界面活性劑或具粘度有機化合物可選用值12 以上非離子性界面活性劑、或水溶性陰離子型界面活性劑、或陽 離子型界面活性劑、或陰陽兩性型界面活性劑、或其混合物，通 常界面活性劑或具枯度有機化合物可使用甘油、乙二醇、己六醇、 t氧乙稀醇、或聚乙一醇、或硬脂酸聚乙二醇g旨、或硬脂酸聚 • 乙二醇己六酯、或聚氧化乙烯壬苯醚、或聚氧化乙烯辛苯醚、或 聚氧化乙針n絲氧化乙狀細、絲氧化乙稀月桂 謎等此界面活性劑或具點度有機化合物可調配成水溶液型態力口入 或單獨加入’適當的界面活性劑或具枯度有機化合物添加劑量在 重里百刀比0.001至5之間(以反應物總固形份為基準），更適當的 用量重量百分比在〇.01至3之間。 本發明係在聚合前將含交聯劑之單體與聚合引發劑於一並 列之雙螺桿混合機切留，透麵整滯留賴可贿反應單體與 觸媒充分混合而提高反應料性之外，也可使反應物料在混合機 巾進盯如同預聚合的作用。如此一來，整個聚合反應均句度與穩 定度相對提南不少’而且所製備出的高吸水性樹脂更具備低可溶 份的特性。 為顯示本發明中局吸水性樹脂(SAP)的低可溶份的特性，可溶 物含量的測定步驟如下：先秤取0.5 g高吸水性樹脂，再加入〇.9 1342788 ____ ^ . 年6月彡曰更正替換頁 . %食鹽水185 g ’在500rpm轉速下攪拌一個小$後厂以遽紙過g一' 出SAP萃取液。最後，科取該萃取液20 g，先以ο,ιν氫氧化鈉 (NaOH)滴定’再使用0.1N鹽酸(HC1)進行反滴定以求出SAP可溶 物的含量。 四、發明之實施例 以下詳細地列出參考工作實例以便說明本發明，但本發明範圍 φ 不受這些實例所限制。 貫例一： 1)先於100L(升)反應槽中加入49%氫氧化鈉水溶液17 35kg及 30.52kg的水，之後於冰浴下將丙烯酸22 53吆緩緩加入氫氧 化鈉水溶液中進行中和；此時得單體濃度38.6wt%水溶液，其 中68mole0/〇丙烯酸部份中和為丙烯酸鈉。 • 2)再加入33柳的丙三醇聚乙二醇三縮水甘油啡=7)於部分中 和的丙烯酸水溶液，並維持溫度於劝七左右。 3) 控制上述丙烯酸納溶液流量為70.4kg/hr，使其由第1圖之入料 管進入雙螺桿混合機體中。 4) 刀別控制L-抗壞A酸、過硫酸納及2,2_偶氮基雙(2·脒基丙烧） 里為12.99g/hr、脱卿/^與162 4〇g/hf，使其經由發明 詳細相ϋ示2·之人料管進人雙螺桿混合機體中。 )利用並列之雙螺桿將上述__溶液與聚合引發劑均句混 21 1342788 4 . @年6月；^日更正替換頁 • 合’控制螺桿轉速使反應物料的滯留時間為10秒，排出之反 應物料黏度為7.0cp (以B型黏度計測得）。 6) 將均勻混合後的反應物料連續地排入皮帶反應器中完成聚合 反應。結果顯示，聚合反應溫度穩定，而且雙螺桿混合機内部 並無任何聚合物。 7) 將膠體利用切式粉碎機切成2mm直徑以下的凝膠體。 8) 以170C溫度乾燥1小時’利用篩網篩選〇 imm〜〇別爪爪固定 鲁 粒控’得粉狀高吸水性樹脂。 9) 秤取此高吸水性樹脂i〇〇g，加入乙二醇碳酸酯/水/曱醇= 1/1/1(重量比)溶液4g，以215°C溫度加熱處理10分鐘。 1〇)冷卻後，加入lg碳酸約(台塑公司生產品名：NS 2〇〇〇)及2〇% 甘油水溶液2g，均勻混合後即得高性能高吸水性樹脂，分析 可溶物含量為2.5%。 ^ 實例二： 重覆實例一，但步驟5)的滯留時間改為2〇秒，排出之反應物 黏度為12.5卬，拆開雙嫘桿混合機觀察内部雖無發現任何^人 物，但因黏度較實例一高，於皮帶反應器上分散較不易，有1部 分局部反應熱較高的現象；其餘步驟同實例一复 /、所侍尚吸水性樹 脂的可溶份經分析為3 6%。 實例三： 22 1342788Or calcium oxide, or kaolin, or calcium carbonate, or magnesium carbonate or the like or a mixture thereof; usually, the amount of the inert inorganic salt powder is related to the particle size of the inorganic salt powder, and if the particle size is small, the inorganic salt powder The specific surface area is large, so the effective inert inorganic salt powder can be used in a small amount, and the inert inorganic salt powder is added in the range of 〇〇〇5 to 10.0 by weight, and more preferably 0.01 to 4 重量 by weight of the inert inorganic salt powder. The particle size is from 0.001//M to i〇〇aM. If the inorganic salt powder with particle size less than 〇〇〇1#M is used, the cost is too high, which is not conducive to industrial production. If the particle size is greater than 1〇〇#M 1342788 '. In June, the inorganic salt powder of the replacement page has a problem that the excessive addition amount affects the absorption capacity of the superabsorbent resin. The inert inorganic salt powder may be added alone or may be added with a surfactant or a viscosity organicating port, and the surfactant or the viscosity organic compound may have a value of 12 or more of a nonionic surfactant or a water-soluble anionic interface. Or a cationic surfactant, or an yin-yang amphoteric surfactant, or a mixture thereof, usually a surfactant or a dry organic compound may use glycerin, ethylene glycol, hexahexaol, t-oxyethylene glycol, or Polyethylenol, or stearic acid polyethylene glycol g, or stearic acid poly(ethylene glycol hexahexate), or polyoxyethylene decyl ether, or polyoxyethylene octyl phenyl ether, or polyoxyethylene needle n Wire oxidized sigmoid, silk oxidized ethylene, laurel mystery, etc. This surfactant or scented organic compound can be formulated into an aqueous solution type or added alone with 'appropriate surfactant or with a dry organic compound additive amount The weight ratio is between 0.001 and 5 (based on the total solids of the reactants), and the more appropriate amount by weight is between 〇.01 and 3. The invention cuts the monomer containing the crosslinking agent and the polymerization initiator in a twin-screw mixer which is juxtaposed before the polymerization, and the surface is completely stagnated, and the reaction monomer is mixed with the catalyst to improve the reaction property. In addition, the reaction material can also be used as a prepolymerization in the mixing machine. As a result, the overall polymerization reaction has a relatively high degree of stability and stability, and the prepared superabsorbent resin has a lower solubility characteristic. In order to show the low-soluble characteristics of the water-absorbent resin (SAP) in the present invention, the determination of the soluble content is as follows: 0.5 g of a highly water-absorbent resin is first weighed, and then 〇.9 1342788 ____ ^. Lunar New Year Correction Replacement Page. % Saline 185 g 'Agitate a small $ at 500 rpm and then use a paper to pass the g's out of the SAP extract. Finally, 20 g of the extract was taken, first titrated with ο,ιν NaOH (NaOH) and then back titrated with 0.1 N hydrochloric acid (HC1) to determine the content of SAP solubles. IV. Examples of the Invention The following is a detailed description of the working examples to illustrate the invention, but the scope of the invention is not limited by these examples. Example 1: 1) Adding 17 35 kg of water and 49.52 kg of 49% aqueous sodium hydroxide solution to the 100 L (liter) reaction tank, and then slowly adding 22 53 hydrazine to the aqueous sodium hydroxide solution in an ice bath. And; at this time, a monomer concentration of 38.6 wt% aqueous solution was obtained, in which 68 mole of O/acrylic acid was partially neutralized to sodium acrylate. • 2) Add 33 glycerol glycerol triglycidyl = 7) to partially neutralize the aqueous acrylic acid solution and maintain the temperature at about seven. 3) The flow rate of the above sodium acrylate solution was controlled to be 70.4 kg/hr, and it was introduced into the twin-screw mixing body from the feed pipe of Fig. 1. 4) The knife is controlled by L-anti-A acid, sodium persulfate and 2,2-azobis(2·mercaptopropene) in 12.99g/hr, deqing/^ and 162 4〇g/hf It is introduced into the twin-screw mixing body through the invention. The side-by-side twin-screw is used to mix the above __ solution with the polymerization initiator. 21 1342788 4 . @年月月;^日正正换页•合'Control screw speed so that the residence time of the reaction material is 10 seconds, discharge The viscosity of the reaction material was 7.0 cp (measured by a B-type viscosity meter). 6) The uniformly mixed reaction materials are continuously discharged into a belt reactor to complete the polymerization. As a result, the polymerization temperature was stable, and there was no polymer inside the twin-screw mixer. 7) The gel is cut into a gel having a diameter of 2 mm or less by a cutter. 8) Dry at 170C for 1 hour. Screening by 筛mmm~〇Claws are fixed by granules to obtain a powdery superabsorbent resin. 9) The superabsorbent resin i〇〇g was weighed, and 4 g of a solution of ethylene glycol carbonate/water/nonanol = 1/1/1 (weight ratio) was added, and heat treatment was carried out at 215 ° C for 10 minutes. 1〇) After cooling, add lg carbonic acid (former product name: NS 2〇〇〇) and 2〇% glycerin aqueous solution 2g, uniformly mixed to obtain high-performance superabsorbent resin, analysis of soluble content of 2.5 %. ^ Example 2: Repeat example 1, but the retention time of step 5) is changed to 2 〇 seconds, and the viscosity of the discharged reactant is 12.5 卬. When the double mast mixer is disassembled, no internal characters are found, but the viscosity is Compared with the first example, it is not easy to disperse on the belt reactor, and there is a phenomenon that the partial reaction heat is high in one part; the remaining steps are the same as the example, and the soluble fraction of the water-absorbent resin is analyzed to be 3 6%. Example 3: 22 1342788
重覆實例-度為6.8 cp， 但因滞留時間： 反應較快的現 可溶份經分析马8.7%。 實例四： 但步驟5)的滯留時間改為40秒， 重覆實例一， 物附著於螺桿上；其餘步驟同實例一 份經分析為5.1%。 實例五： 黏度祕W ’術繼桿混錢_咖_部分黏麵聚 其所得高吸水性樹脂的可溶 重覆實例-，但步驟5)的滯留時間改為9〇秒，排出之反摩物 赌為聽cp，拆開雙螺桿混合機觀察内部發現有部分膠體附 著於螺桿上；其餘步·實例—細得高吸水雜_可溶份經 分析為11.3%。 二 實例六·· 1) 先於100L反應槽中加入49%氫氧化鈉水溶液23 93吆及 44.07kg的水，之後於冰浴下將丙烯酸32 〇〇kg緩緩加入氫氧 化鈉水溶液中進行中和；此時得單體濃度38.44wt%水溶液， 其中66mole%丙烯酸部份中和為丙烯酸鈉。 2) 再加入98.45g的丙三醇聚乙二醇三縮水甘油醚(n=2〇)於部分 23 1342788 年6月J日更正替換頁 中和的丙烯酸水溶液，並維持溫度於20°C左右。 3) 控制上述丙烯酸鈉溶液流量為60.5kg/hr’使其由第1圖之入料 管進入雙螺桿混合機體中。 4) 分別控制L-抗壞血酸、二-第三丁基過氧化氫及過硫酸鉀的流 量為 11.25g/hr、139.13g/hr 與 139.13g/hr，使其經由第 1 圖之 入料管進入雙螺桿混合機體中。 5) 利用並列之雙螺桿將上述丙烯酸鈉溶液與聚合引發劑均勻混 合’控制螺桿轉速使反應物料的滯留時間為10秒，排出之反 應物料黏度為13.1cp (以B型黏度計測得）。 6) 將均勻混合後的反應物料連續地排入皮帶反應器中完成聚合 反應。結果顯示’雖然無任何聚合物附著於螺桿上，但因黏度 稍稍偏高，於皮帶反應器上分散較不易，有少數局部反應熱較 面的現象。 7) 將膠體利用切式粉碎機切成2mm直徑以下的凝膠體。 8) 以170°C溫度乾燥1小時；利用筛網篩選〇lmm〜〇85mm固定 粒徑，得粉狀高吸水性樹脂。 9) 秤取此高吸水性樹脂i〇0g，加入乙二醇碳酸酯:水：曱醇= 1出1(重量比)溶液4g，以215¾溫度加熱處理1〇分鐘。 10) 冷卻後，加入lg碳酸柯台塑公司生產品名：卿2〇〇〇)及2〇〇/〇 甘油水溶液2g，均勻混合後即得高性能高吸水性樹脂，分析 可溶物含量為4.2%。 24 1342788 ___ ^ 年<s月夕曰更正替換頁 . 實例七： ----- f覆實例六’但步驟5)的滯留時間改為2G秒，排出之反應物 黏度為18.3 cp，有局部反應熱較高的現象；其餘步驟同實例一其 所得高吸水性樹脂的可溶份經分析為4 5%。 實例八： 重覆實例六’但步驟5)的滯留時間改為3秒，排出之反應物黏 度為8.2 cp，拆開雙螺桿混合機觀察内部雖無發現任何聚合物， 籲但因滯留時間過短’反應單體與聚合引發劑未充分混合，有局部 反應較快的現象發生；其餘步糊實例—其所得高吸水性樹脂的 可溶份經分析為9.2%。 實例九： 重覆實例六，但步驟5)的滯留時間改為70秒，排出之反應物 黏度為105.1 cp，拆開雙螺桿混合機觀察内部發現有部分膠體附 著於螺桿上；其餘步驟同實例一其所得高吸水性樹脂的可溶份經 •分析為12.1%。 比較例一： 重複實例一，但聚丙烯酸鈉溶液與聚合引發劑並未通過雙螺 桿混合機，而是利用衝擊與流動的方式進行混合。結果顯示，後 段聚合反應溫度經常跳動’有局部反應熱過高的現象；其餘步驟 同實例一其所得高吸水性樹脂的可溶份經分析為14·6%。 比較例二： 25 1J4Z/60 重〜 I训年j日更正替換頁 機，滞Γ時二=丙稀酸納與聚合引發劑通過單螺桿混^ 但有部分絲魏，後郷妓歧度雖穩定’ # " , ; Ί干上，其餘步驟同實例一其所得高吸水性 树脂的可溶份經分析為4.7%。 你人^發狄錄、不雜水、可°聽核、紐或血液且可溶 3置低的高财性樹脂之製造方法，絲合反驗為均勻，反 〜’、也不致於過π ’除了能夠提高製程穩定性與改善操作環境之 #外本發明所製備出的高吸水性樹脂更具備低可溶份的特性。 〜雖穌發明以前述之較佳實施觸露如上，然其並非用以限 定本發明，任何熟習相像技藝者，在不脫離本發明之精神和範圍 内田可作些許之更動與潤飾，因此本發明之專利保護範圍須視 本說明書所附之申請專利範圍所界定者為準。 【圖式簡單說明】 第1圖為本發明實施例粉狀、不溶於水、可吸收水液、尿液 • 或血液且可溶物含量低的高吸水性樹脂之製造方法之雙螺桿混合 機設備簡圖。 ° 【主要元件符號說明】 1含交聯劑之反應單體入料管 2聚合反應引發劑入料管 3雙螺桿 4反應物料排出口 5驅動馬達 26 1342788 _ - ' ^^年6月3曰更正替換頁 、 6.混合機機座Repeated example - the degree is 6.8 cp, but due to the residence time: the readily soluble fraction of the soluble fraction was analyzed by 8.7%. Example 4: However, the residence time of step 5) was changed to 40 seconds, and Example 1 was repeated, and the object was attached to the screw; the remaining steps were analyzed to be 5.1%. Example 5: Viscosity secret W 'successive cross-pumping money _ _ _ part of the sticky surface of the superabsorbent resin obtained by the soluble repeat example - but the retention time of step 5) was changed to 9 〇 seconds, the anti-friction The gambling was to listen to cp, and the twin-screw mixer was disassembled to observe that some of the colloids were attached to the screw; the rest of the steps were as follows: the fine water-absorbent _ soluble fraction was analyzed to be 11.3%. Second example six·· 1) Add 49 93 氢氧化钠 sodium hydroxide solution and 93.07 kg of water in a 100 L reaction tank, then slowly add 32 〇〇kg of acrylic acid to the sodium hydroxide aqueous solution under ice bath. And; at this time, a monomer concentration of 38.44% by weight aqueous solution was obtained, wherein 66 mole% of the acrylic acid was partially neutralized to sodium acrylate. 2) Add 98.45g of glycerol polyethylene glycol triglycidyl ether (n=2〇) to the part of 23, and replace the acrylic acid aqueous solution in the page on June J, 1342788, and maintain the temperature at around 20 °C. . 3) The flow rate of the above sodium acrylate solution was controlled to be 60.5 kg/hr' to be introduced into the twin-screw mixing body from the feed pipe of Fig. 1. 4) The flow rates of L-ascorbic acid, di-tert-butyl hydroperoxide and potassium persulfate were controlled to be 11.25 g/hr, 139.13 g/hr and 139.13 g/hr, respectively, and passed through the feed pipe of Fig. 1 Twin screw mixing in the body. 5) The sodium acrylate solution and the polymerization initiator were uniformly mixed by the parallel twin screw. The control screw rotation time was 10 seconds, and the discharged reaction material viscosity was 13.1 cp (measured by a B type viscosity meter). 6) The uniformly mixed reaction materials are continuously discharged into a belt reactor to complete the polymerization. The results show that although there is no polymer attached to the screw, the viscosity is slightly higher, the dispersion on the belt reactor is less likely, and there is a small amount of local reaction heat. 7) The gel is cut into a gel having a diameter of 2 mm or less by a cutter. 8) Drying at 170 ° C for 1 hour; screening the 粒径lmm~〇85mm fixed particle size by a sieve to obtain a powdery superabsorbent resin. 9) Weigh this superabsorbent resin i〇0g, add 4g of ethylene carbonate: water: decyl alcohol = 1 out of 1 (weight ratio) solution, heat treatment at 2153⁄4 temperature for 1 〇 minutes. 10) After cooling, add lg carbonate Kotai Plastics Co., Ltd. product name: Qing 2〇〇〇) and 2〇〇/〇 glycerin aqueous solution 2g, evenly mixed to obtain high-performance superabsorbent resin, analysis of soluble content of 4.2 %. 24 1342788 ___ ^ Year <s month 曰 曰 correction replacement page. Example 7: ----- f over the example six 'but the step 5) retention time is changed to 2G seconds, the discharge of the reactant viscosity is 18.3 cp, there The phenomenon of high local heat of reaction was observed; the remaining steps were the same as those in Example 1, and the soluble fraction of the obtained superabsorbent resin was analyzed to be 45%. Example 8: Repeat the case six' but the retention time of step 5) was changed to 3 seconds, and the viscosity of the discharged reactant was 8.2 cp. Although the inside of the twin-screw mixer was disassembled, no polymer was found, but the retention time was exceeded. The short 'reaction monomer and the polymerization initiator were not sufficiently mixed, and a local reaction occurred quickly; the remaining step paste--the soluble fraction of the obtained superabsorbent resin was analyzed to be 9.2%. Example 9: Repeat example six, but the residence time of step 5) was changed to 70 seconds, and the viscosity of the discharged reactant was 105.1 cp. When the twin-screw mixer was disassembled, some colloids were found to adhere to the screw; the remaining steps were the same as the examples. The soluble fraction of the obtained superabsorbent resin was analyzed to be 12.1%. Comparative Example 1: Example 1 was repeated, but the sodium polyacrylate solution and the polymerization initiator were not passed through a twin screw mixer, but were mixed by impact and flow. As a result, it was revealed that the polymerization temperature in the latter stage was often hopped by the phenomenon that the partial reaction heat was too high; the remaining steps were the same as those in the first example, and the soluble fraction of the obtained superabsorbent resin was analyzed to be 14.6%. Comparative example 2: 25 1J4Z/60 weight ~ I training year j day correction replacement page machine, stagnation time two = sodium acrylate and polymerization initiator through a single screw mixed ^ but some silk Wei, after the 郷妓 difference Stabilized ' # ",; Ί dry, the remaining steps of the same as the first example of the obtained high-absorbent resin soluble fraction was analyzed to 4.7%. You can make a high-quality resin that can be used to make a record of the high-acid resin that can be used to listen to the nuclear, neo- or blood, and soluble 3, and the silk-reverse test is uniform, anti-~, not too π 'In addition to the ability to improve process stability and improve the operating environment, the superabsorbent resin prepared by the present invention has a lower solubility characteristic. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The scope of patent protection shall be subject to the definition of the scope of the patent application attached to this specification. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a twin-screw mixer for manufacturing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine, or blood and has a low soluble content. Equipment sketch. ° [Main component symbol description] 1 Reaction monomer containing crosslinking agent Feeding tube 2 Polymerization initiator Inlet pipe 3 Twin screw 4 Reaction material discharge port 5 Drive motor 26 1342788 _ - ' ^^年月月曰3曰Correct replacement page, 6. Mixer base
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