200817464 九、發明說明： 【發明所屬之技術領域】 本發明係有關於-種高吸水性樹脂的製造方法，尤其是一種可 洛物含1低的吸水性樹脂的製造方法。 【先前技術】 ，高吸水性_具有強大的財力，可吸收百倍甚錄千倍於本 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 壓力也不會渗漏’且被吸收的水可緩緩地在大氣中釋出。由於具 有上述之雜’所以最早使祕農森林業的土麵糊，近年因 问吸水性觸的生產肋有相當大的進步，所以也歧地運用於 衛生用品如尿布、成人失糾品及婦女衛生用品的吸水劑及保存 食物用的保鮮應用等。 冑吸水性樹脂的成分材料有遇水分解型㈣粉丙稀猜 (hydrolyzed Starch-acryl〇nitrile)接枝聚合物（日本專利公^ 公報昭49(1974)-43,395)，中和之殿粉丙烯酸接枝聚合物（日本 專利公開公報昭51⑽6)-125,468)，皂化乙稀醋酸丙稀醋共〒 物（日本專利公開公報昭52⑽7M4, 689)，水解丙烯腈共聚物 或丙稀醯胺共聚物（日本專利公報昭53 (1978)-15, 959)，及呷 份中和聚丙烯酸（日本專利公開公告昭55(198〇)_84,3〇4)等。 其中以使用_酸及丙烯_進行交聯聚合所得之高吸水性樹月旨 6 200817464 ΓΓ大晶也取為經濟，其原因為丙稀酸可迅速由市售取得， =仔的:吸水性她具有高的吸水能力，及具有製造成本低廉且 取具經濟效並，故成為最普遍化的高吸水性樹脂。 來合丙烯酸及丙馳鹽形成高吸水性樹脂的方法已被多方面 功，且有多種已應用於4界生產，其聚合方法有铸膜 、Κ。Μ (日本專利公開公報昭48(1973)-42, 466)，於輪送帶上 ,進仃聚合反應（日本專利公開公報昭58(1983) _紙7⑷，粉碎之 授拌刀片的捏拌機中進行聚合反應（日本專利公開公報卞昭 57(1982)-34,101)，進行逆姆浮·合反應（日本專利公開公 =59(1984)—37，_)’或將單體或塗覆於纖維基質上進行 聚合反應（日本專利公開公報昭62(1987)-53, 3〇9)。 【擬解決之課題】 $ 合方献妓將聚合單體、聚糾發倾交聯劑等反應 原料同進行自由基聚合反應而成凝膠狀固體，如此整個聚合反 應不易控制，可溶物含量也較高。鑑於此，本發明提供一種高吸 水性樹脂㈣造方法，其聚合反應過程相對來說較為穩定，反應 熱也不致於過高，除了改善操作環境之外，更提高了產品質量。 本發明所提供的製造方法至少包括有·· 1)使中和率50 mole%以上之含酸基單體水溶液與聚合反應 引發劑作預聚合得到黏稠預聚物，其含酸單體係選自丙婦 7 200817464 酸或曱基丙烯酸或丙烯胺I曱基丙細酸或其混合物； 2)添加長鏈、高親水性❹元魏基化合物妙合引發劑於 钻稠預承物中，利用光起始聚合方式進一步生成凝膠狀固 3) 以/皿度100 c至250 C熱風進行乾燥、粉碎、篩選。 4) 表面交聯劑塗覆處理。 5) 再以溫度80°C至230°C加熱表面處理。 上述之預聚合反應可以在—個預聚合反應器中進行，該反應 器需具備關使聚合反應·混合钟且進行預聚合的作用。預 聚合反應器除了可以採用一般安裝有攪拌槳之直立式反應槽外，、 也可以制—觀式的筒狀容器，巾嫂财使物解向流動的 游漿、單錢狀雙轉，可以倾反祕料單向向 前運動而不出現回流的現象，從而避免了聚合反應物料在反應器 中停留時間過長而形成凝膠狀固體。細，上述類型之反應器通 常採用批次人料的方式，較不利於工業化生產。 【解決課題之技術手段】 釔於此本發明提供一種可連續生產具備低可溶物含量之高 吸水! 生树㈣方法，其特徵在於.1—，使單體溶液與聚合引發 通過於s夾套之—長管線巾進行自由絲合反應而成黏祠的高 分子；第二，控制管線出口流體溫度為15_8{rc ;第三，黏祠的預 聚物與多元環氧基化合物混合之後，可連續加入至皮帶反應器 200817464 上，其上方利用高強度之各式光源（例如：紫外線、紅外線或 射線等）進行光起始聚合方式使其轉變成凝膠狀固體。 於管線中進行減合反應除了較—般直立式反簡或筒狀容 器節省空間外，更能夠確保反應單體水溶液歧先出的原則，使 得預聚合·滅反應單體殘留於管射，進崎低聚合反應過 度的情形發生。反鮮體水溶液於管財的滞㈣暇控制預聚 合反應的重制素之-，如滯㈣間長，咖聚合反應越完全， 預聚物黏度與分子量也越高，成品的可溶份也較低，但較容易發 生=管線中過度聚合的現象；如滯留時間短，咖聚物黏度與分 子量較低，成品可溶份較高’但發生過度聚合的機會較少。此外， 反應單體水減絲合引㈣，乃賴歧縣之棘物與架橋 劑的混合均勻性也是影響預聚合反應與照光反應的重要因素。為 了提高上述各趙彼此之間的混合效果 ⑴於管線中通入惰性氣體，如:氮氣、或二氧==法或 減、或其混合髓，在工業界為節省成本及考慮便於取得，通 f使贼氣或二氧化碳或其混合氣體。此外，惰性氣體的壓力要 高於管線内壓力’才可使惰性紐_注人含單體水溶液管線内 而使各反麟體達觀合的效果⑵於管線巾域_葉片或具 混合效果的填絲如：㈣環、錢耳環⑶制汽㈣靜能混合 器。 〜 例如：塗裝、 光起始聚合技術發展純熟，應用也相當廣泛 9 200817464 =業、PCB/LO)製程、鞋業料。_照光引發聚合的方式具有 =優勢驗製程、提昇產能與節省能源料。光源義 ’、夕’包括紫外線、紅外線、x_射線或r_射線轉，—般以紫外 線最為大眾所制，它具有波長較短⑽—働nm)，穿透力強的特 it值得注意岐，—般製㈣的料線燈職度為1〜 2_/Cm，這往朗承載工作物的輸送帶造成嚴重的姉。如此一 來’輸送帶就必須經常性的更換，生產成本也跟著增加。鐘於此， =明_夾套保溫加熱的方式’提高通過於長管線中之反應流 =的溫度，以輸後段光聚合反應的時間。如此—來，不但照射 4間與光源使用功率降低，輸送帶與照光元件的使用期限也 延長。 取重要的是，由於自由絲合反應速率快，如果管線中的反 二流體溫度過高’極可能造成單體「爆聚」的現象而堵塞管線， 造成，個製程癱瘓。鑑於此’為了同時達到縮短照射時間與操作 上的文全性’管線出口之反應流體的溫度以㈣ 以20-401為佳。 ，、 本發明所製造之高吸水性樹脂㈣的含酸基單體除了丙稀酸 尚可個其它具有不飽合雙_水溶性單體，如：甲基丙稀 "、或馬林酸、或富馬酸、或2-丙烯胺Μ基丙垸错酸等。單體 選用不特定關只可—種，亦可合併多種單體:齊使用早亦 了視h況繼加具有不飽和雙鍵其他親水性的單體，如：丙稀酿 200817464 胺、甲基丙烯醯胺、丙烯酸2-烴基乙酯、甲基丙烯酸2_烴基乙酯、 丙烯酸曱酯、丙烯酸乙酯、二曱胺丙烯丙烯醯胺、氣化丙烯丙稀 基二甲叙但添加量以不破壞高吸水性樹脂之物性為原則。 在進行自由基聚合反應前，單體水溶液濃度宜控制在重量百分 比20wt%至55wt%間，適當濃度為30wt%至45wt%之間，濃度在重 量百分比20wt%以下時，聚合後水合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，中和劑為氫氧化鋰、氳氧化鈉、氫氧化鉀、碳酸鋰、 碳酸鈉、碳酸鉀、碳酸氫鋰、碳酸氫鈉、碳酸氫鉀及氨。含酸基 單體之羧酸基將部份中和成鋰鹽或鈉鹽或鉀鹽或銨鹽或兩種以上 .混合鹽類，中和濃度莫耳百分比為45m〇l%至85m〇l%，適當濃度為 、50mol%至75mol%，中和濃度莫耳百分比為45m〇1%以下時成品之pH 值會偏低’中和濃度莫耳百分比為85mol%以上時成品之pH值會偏 高’成品PH值若非呈中性或微雜時，不慎與人體接觸時均不太 適合也較不安全。 預聚合反應由聚合引發劑的分解產生自由基開始。聚合引發 划可遥用熱分解型起始劑，適合的熱分解型起始劑有過氧化物， 如.過氧化氫、一-第二丁基過氧化物、過氧化醯胺或過硫酸鹽(銨 鹽、驗金屬鹽）等，及偶氮化合物如：2· 2，_偶氮基雙(2_脉基丙院） 11 200817464 皿0，2·2-偶氮基雙(N，N-二伸甲基異丁脉)二鹽酸鹽；亦可 '用通原士使成為氧化還原型起始劑，如：酸性亞硫酸鹽、斧 代硫酸鹽、抗壞血酸或亞鐵鹽；或將氧化還原型起始劑和^分解L 里起=^1合併使用’首先氧化還馳始劑先進行反應產生自由 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 應進订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㈣始劑的分 =而=整個聚合反應更臻於完全。—般自由基聚合反應起始劑 l田用里為重量百分比為0. 〇〇1的%至1〇謂以中和丙稀酸鹽重量 為基準）’更適當用量則在〇.lwt%至5wt%之間，使用重量二分比 〇. ooiwmx下時，反應太慢不利經濟效益；使用重量百分比ι〇_ 以上時，反應域反應熱不級做容絲合過度㈣彡成凝膠狀° 固體。 ^ 進行光起料合反麟絲加交·於軸歸物巾，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(: _基)胺、N，N‘-次甲基雙丙職胺、N，N‘_次甲基雙甲基丙稀醯 知、丙稀酸丙烯g旨、乙二醇二丙烯_旨、聚乙二醇二丙稀酸醋、 乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸醋、甘油三丙烯 酸酉旨、甘油三甲基丙稀_旨、甘油附加環氧乙烧之三丙歸酸醋或 三甲基丙稀酸自旨、三曱醇丙燒附加環氧乙烧之三丙烯酸酉旨或三甲 基丙烯酸酉旨、三甲醇丙烷三甲基丙烯_旨、三甲醇丙烷三丙烯酸 200817464 酉曰、N，N，N-二（2-丙烯基）胺、二丙烯酸乙二醇酯、二丙烯三甘醇 酉曰等’亦可選用具有兩個或兩個以上環氧基的化合物，如山梨醇 縮水甘_、聚丙三醇聚縮水甘_、乙二醇二縮水甘油鱗、 二乙二醇二縮水甘油_、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 ㈣當的添加劑量在重量百分比Q•謝¥酿5wt%之間（以反應物 總固形份絲準），更適當_量重量百分比在G· 至㈣之 間，添加·在重量百纽G·则wt%町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5wt%以上吸水性太 低，降低樹脂性能。 黏稠預聚物可於輸送帶式反應H上或裝錢拌紅橫式反應 、器中進行光起始聚合反應，製備出之高吸水性凝賴先利用絞^ 機切成粒徑20mm以下小凝膠體，粒徑1〇麵以下更佳，再進行烘 乾。 。烘乾溫度可於HKTC至25{rc下進行乾燥，乾燥溫度則以12〇 C至18Gt進行縣為宜，當烘乾溫度溫度12Gt以下麟乾時間 太久不具經濟效益，烘乾溫度1801：以上烘乾使交聯劑提早進行交 聯反應，使得後續的乾燥過程中，因交聯度過高而無法有效的去 除殘存單體，達到降低低殘存單體之效果。 13 200817464 乾燥後進行粉碎、_定粒徑，再進行表面交聯劑塗覆處 理。篩選固定粒徑以〇〇6刪至1〇〇麵間為宜酿至 0. 850mm間㈣，粒徑請咖以下細粉使成品粉塵提高，粒徑 1. 00麵以上粒子使成品吸水速率變慢。 火f生树月曰為不/谷解化之親水性聚合體，樹脂内部具有均句性 的木y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、㈣滲透性等，會在樹脂絲面再作進一步 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 刈在此之刖已有許多專利提出；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—56-131608、 jp-A-57-44627、JP-A-58-426G2、JP-A58-117222)使用無機粉 末直接將交聯劑與交聯劑溶液混入高吸水性樹脂處理 (^60-删56、^魯255814)，添加交聯紐以蒸氣處理 (JP-A+11繼）’使时機溶劑、水及多元醇進行表面處理 (JP-A-63-27圓、】P+64-5_7、】p—A—；[._)使用有機 溶液、水、醚（ether)化合物（JP—A—2-1539〇3)等；這些表面 處理的方法雖能提高吸收速率提高壓力下吸水倍率，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。 _選固定粒徑後，根據本發明於可表面處理時能同時進行反應 的交聯劑可為多元醇如：丙三醇、乙二醇、二乙二醇、三乙二醇、 聚乙二醇、丙二醇、i，4 丁二醇、三烴基甲基丙烧、山梨醇等；或 14 200817464 可使用多it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偏上#<氧基的化合偏σ :山_聚縮水甘 油_、聚丙三醇聚縮水甘油鱗、乙二醇二縮水甘油鱗、二乙二醪 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：乙二醇碳酸酯、4—甲基一1，3_二氧 雜環戊烧-2-酮、4, 5-二甲基-1，3-二氧雜it戊燒|酮、4, 4_二甲 基-1，3-二氧_姐_2—_、4_乙基—^ 3二氧雜環姐U、 1，3-二氧雜環己烧|酮、4, 6_二曱基^ 3_二氧雜環己烧_2_嗣或 1，3-二氧雜環庚烧_2__。表面處交聯劑_法可單獨使用或雨 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. OOlwt%至iGwtLx反應物翻形份絲準），更適當的用量 在0.005wt%至5wU之間，表面處交聯劑添加劑量在重量百分比[Technical Field] The present invention relates to a method for producing a superabsorbent resin, and more particularly to a method for producing a water-absorbent resin having a low ketone content of 1. [Prior Art], high water absorption _ has strong financial resources, can absorb hundreds of times more than a thousand times its own weight of water, and can swell after water absorption to maintain a state of no flow, even if pressure is applied, it will not leak The absorbed water can be slowly released in the atmosphere. Because of the above-mentioned miscellaneous's, the soil batter of the secret forestry industry was the earliest. In recent years, due to the considerable progress in the production ribs of water-absorbing touches, it has also been applied to sanitary products such as diapers, adult distorted items and women's health. Water absorbing agent for products and fresh-keeping applications for preserving food. The constituent materials of the water-absorbent resin are water-decomposable (4) hydrolyzed Starch-acryl〇nitrile graft polymer (Japanese Patent Publication No. 49 (1974)-43,395), Neutral Hall Powder Acrylic Acid Grafted polymer (Japanese Patent Laid-Open Publication No. SHO 51(10)6)-125,468), saponified ethyl acetate propylene vinegar conjugate (Japanese Patent Publication No. Sho 52(10) 7M4, 689), hydrolyzed acrylonitrile copolymer or acrylamide copolymer ( Japanese Patent Publication No. Sho 53 (1978)-15, 959), and a portion of neutralized polyacrylic acid (Japanese Patent Laid-Open Publication No. Sho 55 (198〇) _84, 3〇4) and the like. Among them, the high water absorption of the cross-linking polymerization using _acid and propylene _ is intended to be economical, because the acrylic acid can be quickly obtained from the market, = aberde: water absorption It has a high water absorption capacity, and is inexpensive to manufacture and economical, so it is the most general superabsorbent resin. The method of forming a superabsorbent resin by combining acrylic acid and propylene salt has been widely used, and various methods have been applied to the production of the four layers, and the polymerization methods thereof include a cast film and a crucible. Μ (Japanese Patent Laid-Open Publication No. Sho 48 (1973)-42, 466), on a transfer belt, a polymerization reaction (Japanese Patent Publication No. Sho 58 (1983) _ paper 7 (4), a pulverizing mixing blade of a kneading machine The polymerization reaction is carried out (Japanese Patent Laid-Open Publication No. Sho 57 (1982)-34,101), and the reverse mfg-reaction reaction (Japanese Patent Publication No. 59 (1984)-37, _) is carried out or the monomer is coated or coated. Polymerization is carried out on a fibrous substrate (Japanese Patent Laid-Open Publication No. Sho 62 (1987)-53, 3〇9). [Problems to be Solved] $ 合 方 妓 妓 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合The radical polymerization is carried out to form a gelatinous solid, so that the entire polymerization reaction is difficult to control and the soluble content is also high. In view of the above, the present invention provides a method for producing a highly water-absorbent resin (IV), and the polymerization process is relatively speaking. It is relatively stable, and the heat of reaction is not too high. In addition to improving the operating environment, the product quality is further improved. The manufacturing method provided by the present invention includes at least 1) an acid group having a neutralization ratio of 50 mole% or more. The monomer aqueous solution and the polymerization initiator are prepolymerized A viscous prepolymer whose acid-containing single system is selected from the group consisting of B-Wang 7 200817464 acid or methacrylic acid or acrylamine I mercaptopropionic acid or a mixture thereof; 2) adding a long-chain, high-hydrophilic fluorene Wei-based compound The initiator is further formed into a gel-like solid by means of photoinitiating polymerization in the thick pre-filled product. 3) Drying, pulverizing and screening with a hot air of 100 c to 250 C. 4) Surface crosslinker coating treatment. 5) Heat the surface treatment at a temperature of 80 ° C to 230 ° C. The above prepolymerization can be carried out in a prepolymerization reactor which is required to have a polymerization reaction and a mixing clock and carry out prepolymerization. In addition to the vertical reaction tank in which the stirring paddle is generally installed, the prepolymerization reactor can also be made into a cylindrical container of a view type, and the waste can be turned into a flowing slurry and a double-shaped double-turn. The phenomenon that the anti-critical material moves forward in one direction without reflow, thereby avoiding that the polymerization material stays in the reactor for too long to form a gel-like solid. Fine, reactors of the above type are usually used in batches, which is not conducive to industrial production. [Technical means for solving the problem] The present invention provides a method for continuously producing a high water absorption with low soluble content! The raw tree (four) method is characterized in that: -1, the monomer solution and the polymerization initiation are passed through the s clip The long-lined towel is free-filamented to form a sticky polymer; secondly, the temperature of the control line outlet fluid is 15_8{rc; third, after the viscous prepolymer is mixed with the poly-epoxy compound, It can be continuously added to the belt reactor 200817464, and it is converted into a gel-like solid by light-initiating polymerization using a high-intensity light source (for example, ultraviolet rays, infrared rays or rays, etc.). The reduction reaction in the pipeline not only saves the space compared with the vertical vertical reverse or the cylindrical container, but also ensures the principle of the first reaction of the aqueous monomer solution, so that the prepolymerization and the reaction monomer remain in the tube. Stagnation of excessive polymerization occurs. The anti-fresh aqueous solution in the control of the stagnation (four) 暇 control of the pre-polymerization of the heavy protein - such as lag (four) length, the more complete the coffee polymerization, the higher the viscosity and molecular weight of the prepolymer, the soluble fraction of the finished product is also Low, but more likely to occur = excessive polymerization in the pipeline; such as short residence time, low viscosity and molecular weight of the polymer, and higher soluble fraction of the finished product', but less chance of excessive polymerization. In addition, the reaction monomer water reduced wire combined (4), is the mixing uniformity of the spine and bridging agent in Laiqi County is also an important factor affecting the prepolymerization reaction and the photochemical reaction. In order to improve the mixing effect between the above-mentioned Zhaos (1) to introduce an inert gas into the pipeline, such as: nitrogen, or dioxin == method or subtraction, or a mixed pulp thereof, in order to save costs and consider easy to obtain in the industry, f makes thief gas or carbon dioxide or its mixed gas. In addition, the pressure of the inert gas is higher than the pressure in the pipeline, so that the inert gas can be injected into the pipeline of the monomer solution to make the anti-collars achieve the effect of the combination (2) in the pipeline area _ blade or mixed effect Silk such as: (four) ring, money earrings (3) steam (four) static energy mixer. ~ For example: coating, light-starting polymerization technology is well developed, and the application is quite extensive. 9 200817464 = industry, PCB / LO) process, footwear materials. _ Illumination-initiated polymerization has = superior inspection process, increased production capacity and energy saving materials. The light source meaning ', 夕' includes ultraviolet, infrared, x-ray or r-ray rotation, which is generally made by ultraviolet light. It has a shorter wavelength (10) - 働 nm), and the penetration is strong. The general line (4) of the line lamp is 1~ 2_/Cm, which causes serious smashing of the conveyor belt carrying the work. As a result, the conveyor belt must be replaced frequently, and the production cost is also increased. In this case, = bright_jacket insulation heating method 'increased the temperature of the reaction stream passing through the long line = to the time of the subsequent photopolymerization reaction. In this way, not only the illumination of the four sources and the light source are reduced, but also the service life of the conveyor belt and the illumination element is extended. It is important that, due to the fast rate of free silk fibroin reaction, if the temperature of the counter-fluid in the pipeline is too high, it is likely to cause the monomer to "explode" and block the pipeline, causing a process. In view of this, in order to simultaneously achieve a shortened irradiation time and operational fluency, the temperature of the reaction fluid at the outlet of the pipeline is preferably 40-401. The acid-containing monomer of the super absorbent resin (IV) produced by the present invention may have an unsaturated double-water-soluble monomer such as methyl propylene " or marinic acid in addition to acrylic acid. Or fumaric acid, or 2-acrylamine mercaptopropionic acid or the like. Monomer selection is not specific, only a variety, can also be combined with a variety of monomers: the use of the same as before, followed by the addition of other hydrophilic monomers with unsaturated double bonds, such as: propylene, 200817464 amine, methyl Acrylamide, 2-hydrocarbylethyl acrylate, 2-hydrocarbylethyl methacrylate, decyl acrylate, ethyl acrylate, diamine propylene acrylamide, vaporized propylene propylene dimethyl sulphate It is a principle to destroy the physical properties of the super absorbent resin. Before carrying out the radical polymerization reaction, the concentration of the aqueous monomer solution is preferably controlled between 20% by weight and 55% by weight, and the appropriate concentration is between 30% by weight and 45% by weight. When the concentration is less than 20% by weight, the hydrated body is too soft after polymerization. And the viscosity is unfavorable mechanical addition, the work 'addition concentration is above 55^ by weight, close to the saturation concentration, it is difficult to mix 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 of the finished product to make it neutral or slightly acidic. The neutralizing agent is lithium hydroxide, sodium bismuth oxide, potassium hydroxide, lithium carbonate or sodium carbonate. , potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and ammonia. The carboxylic acid group of the acid group-containing monomer is partially neutralized into a lithium salt or a sodium salt or a potassium salt or an ammonium salt or a mixture of two or more salts, and the concentration of the neutralizing concentration is 45 m〇l% to 85 m〇l. %, the appropriate concentration is 50mol% to 75mol%, and the pH value of the finished product will be lower when the percentage of neutralization concentration is below 45m〇1%. The pH value of the finished product will be partial when the percentage of neutral concentration is 85mol% or more. If the high-finished PH value is not neutral or slightly mixed, it is not suitable or safe to contact with the human body. The prepolymerization starts by the decomposition of the polymerization initiator to generate a radical. The polymerization initiation can be carried out by using a thermal decomposition type initiator, and a suitable thermal decomposition type initiator is a peroxide such as hydrogen peroxide, mono-second butyl peroxide, guanidinium peroxide or persulfate. (ammonium salt, metal salt), and azo compounds such as: 2·2, _ azobis (2_脉基丙院) 11 200817464 皿0,2·2-azobis(N,N - bis-methyl isobutyl hydride) dihydrochloride; can also be used as a redox initiator, such as: acid sulfite, alkaloid sulfate, ascorbic acid or ferrous salt; or The redox initiator is combined with the decomposition of L. The combination of 'first oxidation and the initiator first reacts to generate a radical'. When the radical is transferred to the monomer, the polymerization is initiated, because the polymerization should proceed. When the order is set, a large amount of heat is released to raise the temperature. When the temperature reaches the decomposition temperature of the thermal decomposition type initiator, the second stage of thermal decomposition is caused. (4) The amount of the initiator is = and the whole polymerization reaction is more ambiguous. complete. The average amount of the radical polymerization initiator is 0. 〇〇1% to 1〇 is based on the weight of the neutralized acrylate, and the appropriate amount is 〇.lwt% to Between 5wt%, use the weight ratio 〇. ooiwmx, the reaction is too slow, unfavorable economic benefits; when using the weight percentage ι〇_ or more, the reaction domain reaction heat is not good, the silk is excessive (4) gelatinized solid . ^ For the light-feeding and anti-column addition, the shaft-returning towel, the cross-linking agent may be a compound having two or more unsaturated double bonds, such as: n, n-bis(: _yl)amine , N, N'-methine dipropionamine, N, N'-methine dimethyl propyl amide, propylene propylene g, ethylene glycol dipropylene, polyethylene glycol Acrylic vinegar, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triglyceride, trimethyl propylene triglyceride Vinegar or trimethyl propylene acid from the purpose, tridecyl alcohol, propylene oxide, triethyl acrylate or trimethyl acrylate, trimethylolpropane trimethyl propylene, trimethylolpropane triacrylate 200817464酉曰, N, N, N-bis(2-propenyl)amine, ethylene glycol diacrylate, dipropylene triethylene glycol oxime, etc. may also be selected from compounds having two or more epoxy groups. Such as sorbitol shrinkage _, polyglycerol polycondensation _, ethylene glycol diglycidyl scale, diethylene glycol diglycidyl _, polyethylene glycol diglycidyl ether, diglycerol poly Glycidyl 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 reaction crosslinking agent may be used singly or in combination of two or more. Free radical polymerization cross-linking (4) When the amount of the additive is between 5% by weight and Q% by weight (according to the total solid fraction of the reactants), more appropriate _ by weight percentage between G· and (iv), add · The hydrated body is too soft and viscous to be unfavorably mechanically processed after weighting in the weight of G. G., and the amount of the additive is too low in water absorption of 5 wt% or more to lower the resin property. The viscous prepolymer can be subjected to photoinitiation polymerization on the conveyor belt reaction H or the money-mixed red cross-flow reaction, and the prepared high-absorbency condensate is first cut into a particle size of 20 mm or less by using a twisting machine. The gel has a particle size of 1 以下 or less, and is then dried. . The drying temperature can be dried under HKTC to 25{rc, and the drying temperature is preferably from 12〇C to 18Gt. When the drying temperature is below 12Gt, the drying time is too long and has no economic benefit. The drying temperature is 1801: Drying causes the cross-linking agent to crosslink the reaction early, so that in the subsequent drying process, since the degree of crosslinking is too high, the residual monomer cannot be effectively removed, and the effect of lowering the residual monomer is achieved. 13 200817464 After drying, it is pulverized, sized, and then subjected to surface crosslinking agent coating treatment. The fixed particle size is selected from 〇〇6 to 1〇〇. It is suitable to be brewed to 0. 850mm (4). The particle size is required to increase the finished dust by the fine powder below the particle size. slow. The fire-floating tree is a hydrophilic polymer that is not/solventized, and the resin has a homogenous wooden y structure inside. In order to improve the quality, such as: increasing the absorption rate, increasing the strength of the colloid, and improving the anti-caking property, (4) Permeability, etc., will be further bridged on the surface of the resin. This surface crosslinking treatment uses cross-linking of polyfunctional groups capable of reacting with acid groups. Many patents have been proposed here; for example, dispersion and high water absorption The resin and the crosslinking agent are surface-crosslinked in an organic solvent (JP-A-56-131608, jp-A-57-44627, JP-A-58-426G2, JP-A58-117222) using an inorganic powder directly Mix the cross-linking agent and the cross-linking agent solution into the superabsorbent resin (^60-cut 56, ^Lu 255814), add cross-linking to steam treatment (JP-A+11), make the timing solvent, water and Polyol for surface treatment (JP-A-63-27 round, P+64-5_7, p-A-; [._) using organic solution, water, ether compound (JP-A-2- 1539〇3), etc.; these surface treatment methods can increase the absorption rate and increase the water absorption rate under pressure, but will cause the adverse effect of excessive retention. The actual performance of the application. _ After selecting a fixed particle size, the crosslinking agent capable of simultaneously reacting in the surface treatment according to the present invention may be a polyhydric alcohol such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol Alcohol, propylene glycol, i, 4, butanediol, trihydrocarbylmethylpropane, sorbitol, etc.; or 14 200817464 polyamines such as ethylenediamine, diethylenediamine, triethylenediamine, polyethylenediamine can be used. Or may use a compound partial σ having two or two uppers of an oxy group: mountain _ polyglycidol _, polyglycerol polyglycidol scale, ethylene glycol diglycidil scale, diethyl hydrazine condensate Glycerol ether, polyethylene glycol dimer glycidyl ether, diglycerol polyglycidyl ether, etc., may also use alkylene carbonate such as ethylene glycol carbonate, 4-methyl-1,3-dioxa Cyclopentan-2-one, 4, 5-dimethyl-1,3-dioxa-ethene ketone|ketone, 4,4-dimethyl-1,3-dioxo_sister_2-_, 4_ethyl-^ 3 dioxane, U, 1,3-dioxanone, ketone, 4,6-dimercapto^3_dioxane_2_嗣 or 1, 3-dioxane _2__. The cross-linking agent at the surface can be used alone or in combination with rain. The appropriate amount of the crosslinking agent at the surface is in the weight percentage 〇. OOlwt% to iGwtLx reactants, and the appropriate amount is between 0.005wt% and 5wU, and the amount of the crosslinking agent additive at the surface is in the weight percentage.
OlrU以下日^^法喊出效果，表面處交聯劑添力α劑量在重量百 刀比10wt%以上時，吸水性太低，降低樹脂性能。 表面交聯繼航_，表面交·之添加可為表面交聯劑直 接添加絲面交·水溶液添加，或調成表面交聯劑親水 性有機溶劑水溶液添加，親水性有機溶劑如曱醇、乙醇、丙醇、 :丁醇、丙_、甲醚、乙醚等沒有特殊限制，可形成:液即二 =中以曱醇、乙醇較佳。表面交聯劑添加時高吸水樹脂中可添加 惰性無機聽末’㈣祕液分散’惰性域贿材為硫酸^ 或二氧切，或氧他，或氧化麟或其混合物。其中以硫酸銘、 15 200817464 ^ 較^土 &性媒機鹽粉末添加範圍在重量百分比〇〇5wt% 至1〇· 〇Wt%之間，其中以〇· Olwt%至4· Owt%較佳。 如丁表面塗覆處理後，再以8(Tt至230°c加熱處理，使 义又U月匕進行父聯反應，並使内部交聯劑進行交聯反應而達 本㈣之效果。處理溫度8『c以下交聯反麟間太久，不具經 4效应’處理溫度説叱時，樹脂易劣化影響品質。至於處理時 間則以2〜⑽分鐘為宜，域理溫度滅，溫度高則時間短，溫 度低則時間長。 由於高吸水性樹脂具有賴後結塊的現象，為避免在高濕度地 £使用㈣雜樹齡有賴後概導致加工不順，-般會在高 ° w _日表面細惰性無機餘末或界面活性劑，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㈣ 機鹽粉末可選用硫酸鋁、 …、 ^ 及—虱化矽、或氧化鋁、或氧化鎂、或 =化鈣$同領土、或碳酸約、或碳酸鎂等或其混合物；通常此 6性無機藤末的添加量麵機歸末顆姉徑大小有關，若顆 t粒錄小其無難穌比㈣積較大，_极雜無機鹽粉On the following day, OlrU shouted the effect. When the surface of the cross-linking agent added force α dose was more than 10% by weight, the water absorption was too low, and the resin performance was lowered. Surface cross-linking relay _, surface cross-addition can be added directly to the surface cross-linking agent, silk surface, aqueous solution, or surface-crosslinking agent, hydrophilic organic solvent aqueous solution, hydrophilic organic solvent such as decyl alcohol, ethanol , propanol, butanol, propyl ketone, methyl ether, diethyl ether, etc. are not particularly limited, and can be formed: liquid, ie, succinyl alcohol, ethanol is preferred. When the surface cross-linking agent is added, an inert inorganic listener may be added to the superabsorbent resin, which is a sulfuric acid or a dioxate, or an oxygen, or an oxidized lin or a mixture thereof. The salt powder is added in the range of 〇〇5wt% to 1〇·〇Wt% by weight of sulphuric acid, 15 200817464 ^, and preferably 〇· Olwt% to 4·Owt%. . After the surface coating treatment of Ding, the heat treatment is carried out at 8 (Tt to 230 °c, the parental reaction is carried out, and the internal crosslinking agent is cross-linked to achieve the effect of (4). 8 "The following cross-linking is not too long, and there is no effect of 4 when the temperature is not treated. The resin is easily deteriorated to affect the quality. The processing time is preferably 2 to 10 minutes, the temperature is off, and the temperature is high. Short, low temperature and long time. Because of the phenomenon of agglomeration after superabsorbent resin, in order to avoid the use of high humidity, (four) the age of the tree depends on the processing is not smooth, it will be fine on the surface of high ° w _ day The inert inorganic residue or surfactant makes the surface slightly oleophilic and the superabsorbent resin retains the characteristics of not easily agglomerating after moisture absorption. The inert (4) machine salt powder can be selected from aluminum sulfate, ..., ^ and 虱 虱Or alumina, or magnesium oxide, or = calcium, the same territory, or carbonic acid, or magnesium carbonate, or a mixture thereof; usually the addition of the six inorganic inorganic vines is related to the size of the last diameter, if The t-grain recorded that it is not difficult to compare with the (four) product, _ very hetero-inorganic Salt powder
末用量可較小，其惰性I …、機末添加範圍為重量比百分比 〇· 005wt%至1〇· 〇社％之間，发由 ，、中以〇· 〇lwt%至4· Owt%較佳，惰性無 概末其粒徑為〇〇1減至，若選用顆粒小於0鳥 的热機餘末軸柄高邱敎#化生產，若顆粒大於 ^的無频粉末财添加量過高群高吸水性細旨吸收力的 200817464 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 有栈化合物加入，其界面活性劑或具粘度有機化合物可選用沿上 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， 通常界面活性織具減有機化合物可使用甘油、乙二醇、己六 鮮、聚氧乙稀醇、或聚乙二醇、或硬脂酸聚乙二醇酯、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?κ氧化乙烯十二苯_、或聚氧化乙烯絲_、絲氧化乙稀月 桂醚等此界面活性劑或具粘度有機化合物可調配成水溶液型態加 入或單獨加入，適當的界面活性劑或具粘度有機化合物添加劑量 在重1百分比〇· 〇〇lwt%至5wt%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· Olwt%至3wt%之間。 【發明内容】 本發明是提供一種可連續生產具低可溶物含量之高吸水性樹 月曰的方式，其特徵在於：第一，使單體溶液與聚合引發劑通過於 έ夾套之長官線中進行自由基聚合反應而成黏稠的高分子丨第 一，控制管線出口流體溫度為15-80°C ;第三，黏稠的預聚物與多 元％氧基化合物混合之後，可連續加入至皮帶反應器上，其上方 利用回強度之各式光源(例如：紫外線、紅外線或χ-射線等）進行 光起始聚合方式使其轉變成凝膠狀固體。透過本發明所提供的生 產方式具有下列優點··（1)預聚物相對於液體反應物料的黏度明 17 200817464 ’’、、員提同〜紐降低’更容易與之後的皮帶反應器相匹配，而且 使正個聚合反應敎度提高，反應熱不至於過高⑵使用-長管 線反應器除了節省空料，且更能夠德反應流體先進先出的原 :，而翻連續式生顏目的⑶制夾套加鮮線中的反應流 體並控制其出π溫度為15册，可以縮短後段照射時間並延長輸 送帶與照光元件的使用壽命。本發明所提供之高吸水性樹脂製造 方法除了提高生產操作性與工作環境外，產品質量也大大提高， 尤其對於降低可溶物含量具有彳__效果。 為頒不本發明中高吸水性樹脂的低可溶物含量之特性，可溶 物含量的測定步驟如下：S秤取G. 5 g高吸水性樹脂，再加入^ =鹽水185 g，在5GGrpm轉速下勝，時後，以濾紙過濟 出AP卒取液。最後，秤取該萃取液2〇 g，先以〇. 1N _滴定， 再使用G· IN HC1進行反滴定以求出SAp可溶物的含量。 【實施方式] 以下以實施例說明本發明，但本發明之技術及專 μ 些實施例所限制。 又14 實施例一： ⑴先於中和槽中加入重量份的丙烯酸及2263 7重量份的 於冰浴下將1476.3麵的氫物液(濃料 、友、、歲加入上述丙烯酸水溶液中。此時得到單體濃度為 200817464 38.6禮的水溶液，其中有68蝴的丙婦酸中和為丙稀酸納。 ⑵中和程序完成後，湘水継控制部分中和之㈣義鹽水溶 液為20°C左右。 ⑶調整上料齡_流4為公升/辦，使其通過一支含 夹套、直徑為5公分、總長度為26. 35米的不鑛鋼管。此外， 不鏽鋼管入端5公分與1〇公分處侧邊分別連接一支直徑〇 5 ， 與〇. 9公分的不鏽鋼管。前者導入氮氣，流量控制為2〇〇公升 /小時，後者則通入過硫酸鉀/亞硫酸氫鈉=1/1(重量比），流 重控制為2毫升/小時。 (4)距離官線出口端85公分處侧邊連接二支直徑〇· 9公分的不鏽 鋼管，一支導入偶氮二異庚月青，流量控制為2〇毫升/小時， 另一支則導入丙三醇聚乙二醇三縮水甘油醚(n=7)，流量控制 為15耄升/小時。最後，管線出口流體的溫度為2〇。〇 K (5)將（4)所述之反應流體加入到傳送帶上，傳送帶上方裝置有言 強度紫外線照射機，利用該裝置照射上述混合液體25秒（照 度= 15.18 J/cm2)使之進行交聯反應而成膠體。 (6) 利用切式絞碎機切成2腿直徑以下的凝膠體。 (7) 以13(TC溫度乾燥2小時；利用篩網篩選〇·丨腿〜〇· 85_固定 粒徑，得粉狀高吸水性樹脂。 (8) 科取此高吸水性樹脂i〇〇g，加入硫酸鋁粉末lg，待混合均句 後再加入乙二醇壤酸醋/水/曱醇=1/1/1(重量比）溶液知，以 19 200817464 215t：溫度加熱處理忉分鐘。 ⑼冷卻後，加入1§碳_台塑公司生產品名：ns__)及· 甘油水办液2g ’均勻混合後即得高性能高吸水性樹脂。測定保 持力’ _ ’ 49 g/W壓力下吸水倍率=22. 8g/g，可溶物 含量= 13.4%。 實施例二： ⑴紐貫關…但錄出σ溫度為25t錢段崎時間調整為 20秒（照度= 13.99 J/cm2)，結果所得吸水樹脂的保持力= 3L 5g/g，49 —壓力下吸水倍率=23·的，可溶 10.0%。 實施例三： ⑴重複實_-’但管線一溫料3(rc且後段照射時 15秒（照度= 9.35 ’結果所得吸水樹脂的二 30. 7g/g，49 g/on2壓力下吸水倍率=23.崎，可溶物人二 \ 8.1%。 3 里 > 實施例四： ⑴重複實麟卜但管線出π溫度為阶錢舰 10秒（照度=6.36關，結____:整為 30· lg/g，49 g/cm2壓力下吸水倍率=24 ig/ 口 ，、持力： 7.3%〇 H落物含量： 實施例五： 20 200817464 (l)重複貫施例一，伯总細 5秒（^1=線心溫度為4Q°C且紐照射時_整為 9Q ^又3.03 j/cm2)，結果所得吸水樹脂的佯拄六 29· 5g/g，49 s/cm2 颅 7 保持力= 5.4%。 勤下吸水倍率=23.2的，可溶物含量= 貫施例六： ⑴重複實施例―，但不鏽鋼管總長度改為犯米長。 ,=的保持力則為35. Vg，49 壓力下吸水倍^水性樹 • 3g/g，可洛物含量= 11. 2%。 貫施例七： ⑴重複實施例六，但管線出口溫度為25t且後_射 2〇秒(照度= 13. 99 J/W)，結果所得吸水樹脂的二正為 8= 49 * M力下吸水倍率=23. Vg ’可溶物含量= 貫施例八： ⑴重複實施例六，但管線出口溫度為机 15秒（照度⑽補，結果所得吸水樹脂:^ 32· 〇g/g，49 g/cm2壓力下吸水倍率=〇以 ’、、~ 6.4%。 . g’可溶物含量= 實施例九： ⑴_實_六’但管糾π溫度為阶且後触、射护1 10秒（照度= 6.36 J/Cm2)，結果所得吸水樹斤/間兩整為 曰9保持力= 21 200817464 3L 8g/g，49 g/cm、力下吸水倍率喷阶，可溶 5.1%。 實施例十： ⑴重複實施例六’但管線出口溫度為靴且後段照射時間調整為 5秒（照度H/W)，結果所得吸水樹脂的保持力= 30. 9g/g ’ 49 g/cm2麗力下吸水倍率=24.响，可溶物含量= 3篇。 比較例一： ⑴重複實施例-，但步驟⑶所述之反應單體溶·通氮氣(流量 &制在2GG a升/小日t)下注人—直立式反應槽並在高速授掉下 反應反應30min左右，所得預聚物黏度為14〇cps，但出料後發 現攪拌葉片上有少許聚合物。高吸水性樹脂的保持力則為 33.4g/g，49 g/cm2壓力下吸水倍率=23· lg/g，可溶物含量= 13.7%。 比較例二： ⑴重複貫施彳和’但步驟⑶所述之反鮮體紐_氮氣（流量 控制在200公升/小時）了注入一直立式反應槽並在高速授摔下 反應反應60min左右’所得預聚物黏度為255cps，但出料後發 現攪拌葉片和反應槽内有部分聚合物殘留的現象。高吸水性樹 22 200817464 脂的保持力則為36. lg/g，49 g/cm2壓力下吸水倍率= 23. 4g/g，可溶物含量= 13. 5%。 【圖式簡單說明】 無0 【主要元件符號說明】 無0 23The amount of the final amount can be small, the inertia I ..., the end of the machine is added in the range of weight ratio 〇 · 005wt% to 1 〇 〇 % % , , 发 、 、 、 、 、 、 〇 〇 〇 wt wt wt wt wt wt wt wt wt wt wt wt wt wt 较 较Good, inert, no particle size is reduced to 〇〇1, if the particle is less than 0 bird heat engine shaft shank Gao Qiu 敎# chemical production, if the particle is greater than ^, the frequency of the powder is too high The highly absorbent nature of the 200817464 issue. The inert inorganic salt powder may be added alone or may be added with a surfactant or a viscosity-containing stacking compound, and the surfactant or the viscosity organic compound may be selected from a nonionic surfactant having a value above 12 or a water-soluble anionic interface. An active agent, or a cationic surfactant, or an yin-yang amphoteric surfactant, or a mixture thereof, usually an interface active woven organic compound can be used with glycerin, ethylene glycol, hexahexanol, polyoxyethylene glycol, or poly Ethylene glycol, or polyethylene glycol stearate, or polyethylene glycol hexahexyl stearate, or polyoxyethylene decyl ether, or polyoxyethylene octyl phenyl ether, or ? oxyethylene dodecene _, or polyoxyethylene wire _, wire oxidized ethylene lauryl ether and other such surfactants or viscous organic compounds can be formulated into an aqueous solution form or added separately, the appropriate surfactant or viscosity organic compound additive weight 1% 〇· 〇〇1wt% to 5% by weight (based on the total solids of the reactants), a more appropriate amount by weight of 〇· Olwt% to 3% by weight. SUMMARY OF THE INVENTION The present invention provides a method for continuously producing a highly water-absorbent tree sorghum having a low soluble content, characterized in that: first, a monomer solution and a polymerization initiator are passed through the scorpion Free radical polymerization in the line to form a viscous polymer crucible. First, the fluid temperature at the outlet of the control line is 15-80 ° C. Third, after the viscous prepolymer is mixed with the polyvalent oxy compound, it can be continuously added to On the belt reactor, a light-initiated polymerization method is used to convert it into a gel-like solid by a light source of various kinds of light sources (for example, ultraviolet rays, infrared rays, or xenon rays). The production method provided by the present invention has the following advantages: (1) The viscosity of the prepolymer relative to the liquid reaction material is clearly 17 200817464 '', the member is the same as the lower limit', and it is easier to match the belt reactor afterwards. And the positive polymerization temperature is increased, the heat of reaction is not too high (2) use-long pipeline reactor in addition to saving empty material, and more capable of reacting fluid first-in-first-out original:, and continuous continuous skin-building purposes (3) The reaction fluid in the jacket and the fresh wire is controlled and the temperature of the π is 15 volumes, which can shorten the irradiation time of the rear section and prolong the service life of the conveyor belt and the illumination component. In addition to improving the operability of the production and the working environment, the method for producing a super absorbent resin provided by the present invention greatly improves the quality of the product, and particularly has an effect of reducing the content of soluble matter. In order to demonstrate the low soluble content of the superabsorbent resin of the present invention, the determination of the soluble content is as follows: S scales G. 5 g of superabsorbent resin, and then adds =1 g of salt water at 5 GG rpm. After the victory, after the time, use the filter paper to survive the AP stroke fluid. Finally, the extract was weighed 2 〇 g, first titrated with 〇. 1N _, and then back titrated with G· IN HC1 to determine the content of SAp solubles. [Embodiment] The present invention will be described below by way of examples, but the invention and the specific examples thereof are limited. 14) Example 1: (1) Adding a part by weight of acrylic acid and 2263 7 parts by weight of a hydrogen solution (concentrated material, friend, and aged) to the aqueous acrylic acid solution in an ice bath prior to the neutralization tank. At the time of obtaining an aqueous solution having a monomer concentration of 200817464 38.6 ritual, 68 of which is neutralized with sodium acrylate. (2) After the completion of the neutralization process, the neutralized (4) aqueous solution of the salt water of the control zone of Xiangshui is 20°. (3) Adjust the upper age of the material _ flow 4 is liters / office, so that it passes through a non-mining steel pipe with a jacket, diameter of 5 cm and a total length of 26.35 meters. In addition, stainless steel pipe inlet 5 cm Connect a stainless steel tube with a diameter of 〇5 and 〇.9 cm to the side of 1 cm. The former is introduced with nitrogen and the flow rate is controlled to 2 liters/hour. The latter is introduced with potassium persulfate/sodium hydrogen sulfite. =1/1 (weight ratio), the flow weight is controlled to 2 ml/hr. (4) Two stainless steel tubes with a diameter of 〇·9 cm are connected to the side of the exit of the official line at 85 cm, and one is introduced with azo Gengyueqing, flow control is 2〇ml/hr, and the other is imported into glycerol Alcohol triglycidyl ether (n=7), the flow rate is controlled to 15 liters/hour. Finally, the temperature of the outlet fluid of the pipeline is 2 〇. 〇K (5) The reaction fluid described in (4) is added to the conveyor belt. The device above the conveyor belt has a high-intensity ultraviolet ray irradiator, and the device is used to illuminate the mixed liquid for 25 seconds (illuminance = 15.18 J/cm2) to carry out cross-linking reaction to form a colloid. (6) Cut into 2 legs by a cutter mincer Gels below the diameter. (7) Dry at a temperature of 13 (TC for 2 hours; use a sieve to screen the 粒径·丨 leg~〇·85_ fixed particle size to obtain a powdery superabsorbent resin. (8) Superabsorbent resin i〇〇g, add aluminum sulfate powder lg, after mixing the sentence, add ethylene glycol vinegar / water / sterol = 1 / 1 / 1 (weight ratio) solution, to 19 200817464 215t : Temperature heat treatment for 忉 minutes. (9) After cooling, add 1 § carbon _ Formosa Plastics product name: ns__) and · Glycerin water solution 2g 'High-performance superabsorbent resin after uniform mixing. Determination of retention ' _ ' The water absorption ratio under the pressure of 49 g/W = 22. 8 g / g, soluble content = 13.4%. Example 2: (1) New Zealand Guan... but recorded The σ temperature was adjusted to 25 seconds (25 illuminance = 13.99 J/cm 2 ), and the obtained water-absorbent resin retention force was 3 L 5 g/g, 49 - the water absorption ratio under pressure = 23 ·, and the solubility was 10.0%. Example 3: (1) Repeating the actual _-' but the line-temperature material 3 (rc and 15 seconds after the subsequent irradiation (illuminance = 9.35 ' results in the water-absorbing resin of 20.7 g / g, water absorption ratio under the pressure of 49 g / on 2 = 23. Saki, soluble matter 2 8.1%. 3 里> Example 4: (1) Repeat the actual lining but the π temperature of the pipeline is 10 seconds for the money carrier (illuminance = 6.36, knot ____: 30. lg/g, water absorption at 49 g/cm2) =24 ig / mouth, holding capacity: 7.3% 〇H falling material content: Example 5: 20 200817464 (l) Repeat the first example, the total thickness of 5 seconds (^1 = core temperature is 4Q ° C and When the illuminating _ is 9Q ^ and 3.03 j/cm 2 ), the obtained water-absorbent resin has a 佯拄62.9·g/g, 49 s/cm2 cranial 7 retention force = 5.4%. The submerged absorption ratio = 23.2, Solution content = Example 6: (1) Repeat the example -, but the total length of the stainless steel tube is changed to the length of the rice. The retention of the = is 35. Vg, 49 water absorption under pressure ^ water tree • 3g / g, can Loose content = 11. 2%. Example 7: (1) Repeat Example 6, but the outlet temperature of the pipeline is 25t and the latter is 2 sec (illuminance = 13.99 J/W). Positive 8 = 49 * M force under water absorption ratio = 23. Vg 'soluble matter content = Example 8: (1) Repeat Example 6, but the line outlet temperature is 15 seconds (illuminance (10), the resulting water-absorbing resin: ^ 32· 〇g/g, 49 g/cm2 Absorbency under pressure = 〇 is ',, ~ 6.4%. g' soluble content = Example 9: (1) _ real _ six 'but the tube is corrected for π temperature and then touched, shot 1 10 seconds (illuminance) = 6.36 J/Cm2), the result of the water-absorbing tree jin / between the two is 曰 9 retention = 21 200817464 3L 8g / g, 49 g / cm, under the force of water absorption rate spray, soluble 5.1%. Example 10: (1) Repeat Example 6', but the outlet temperature of the line is the shoe and the irradiation time of the latter stage is adjusted to 5 seconds (illuminance H/W), and the retention of the obtained water-absorbent resin is 30. 9g/g ' 49 g/cm2 =24. Loud, soluble content = 3. Comparative Example 1: (1) Repeat Example -, but the reaction monomer described in step (3) is dissolved in nitrogen (flow & in 2GG a liter / small day t) The bet was placed in a vertical reaction tank and the reaction was carried out at a high speed for about 30 minutes. The viscosity of the obtained prepolymer was 14 〇 cps, but after the discharge, a small amount of polymer was found on the stirring blade. The retention of the superabsorbent resin was 33.4 g / g, water absorption at 49 g / cm 2 pressure = 23 · lg / g, soluble content = 13.7%. Comparative Example 2: (1) repeated application and 'but step (3) Anti-fresh new _ nitrogen (flow control at 200 liters / hr) was injected into the vertical reaction tank and the reaction reaction was carried out for about 60 minutes under high-speed drop. The obtained prepolymer viscosity was 255 cps, but the stirring blade and reaction were found after discharge. There is a phenomenon of partial polymer residue in the tank. Superabsorbent tree 22 200817464 The retention of grease is 36. lg / g, water absorption at 49 g / cm 2 pressure = 23. 4g / g, soluble content = 13. 5%. [Simple description of the diagram] No 0 [Description of main component symbols] No 0 23