1275596 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的製造方法，特別是一種利 用多次中和的不飽和單體水溶液以製備高吸水性樹脂的製造方 法。 【先前技術】 高吸水性樹脂廣泛地運用於農業或園藝方面的水保持劑、建 築材料中的抗露珠凝結劑以及移除石油中水份的材料，或是電纔 線中的外層防水包覆劑以及喊生用品如尿布、婦女衛生用品、抱 棄式的擦巾等。 在上述的情況下，由於高吸水性樹脂會直接與人體接觸，所 以兩吸水性樹脂的安全性變得十分重要。一般而言，高吸水性樹 脂所須具備的物理性質包括吸收速率、吸收力、壓力下吸收倍率、 低單體殘留量以及吸收後的凝膠力。優良的高吸水性樹脂不僅要 滿足上述的物理性質，更重要的是必須具備良好的安全性。 技藝界已知的高吸水性樹脂的成分材料有遇水分解型的澱 粉〜丙烯腈(hydrolyzed starchacrylonitrile)接枝聚合物（日本專利公 開公報昭49(1974)-43,395)，中和之澱粉一丙烯酸接枝聚合物（曰 本專利公開公報昭51 (1976)-125,468)，皂化乙烯醋g复一丙烯酯共 聚物（日本專利公開公報昭52(1977)-14,689)，水解丙烯腈共聚 物或丙烯醯胺共聚物（曰本專利公報昭53 (1978)-15,959)，及部 伤中和來丙烯酸（日本專利公開公告昭55(198〇)_84,3〇4)等。其 7 1275596 中殿粉-丙烯腈接枝聚合物的原料中，因為含有天然的高分子一 澱粉’會引起腐爛性的分解，所以無法長時間的保存；再者，其 製造方去十分複雜，所以現今高吸水性樹脂之製備方式以使用丙 稀酸及丙烯酸鹽進行交聯聚合所得之高吸水性樹脂佔最大部份 也最為經濟，其原因為丙烯酸鹽共聚物的原料一丙烯酸可迅速由 商％上購得，且製得的高吸水性樹脂具有高的吸水能力，及具有 製造成本低廉骑具經濟效益以及不會引起腐爛性的分解，故成 為最普遍化的向吸水性樹脂。 ♦ 口娜-文及丙烯酸鹽形成高吸水性樹脂的方法可由數種 已知的方謂彳于，如水溶液聚合反應、逆相懸浮液聚合反應、乳 化聚合反賴將單體賴或塗覆於麟基質上進行聚合反應等方 法在化些方法中，逆相懸浮液聚合反應以及乳化聚合反應必須 使用到有H但;^若無法有效的控制聚合反應時的溫度，有 U將&成反應系統溫度以及壓力的增加，會產生 至將輯，進而威脅到操作現場人M的安全以及造成環境= 問題’其成品也有有機溶麵留的疑慮。 q吸水脂所需的水溶性不飽和單體中的丙稀酸二 量過高時，不卿合反應之進行，進而影響生 水性樹脂物理性曹# τ目，_ ^ ^ 表現’如：南殘存未反應單體、低保持力， 武二下的吸收倍率特性偏低；*高吸水性樹脂使用於衛生 未:應升=能直接和人體及食物接觸’較低的殘存 、 吏用上的安全性，因此近年來要求降低殘存 8 1275596 單體殘留量已成為一種趨勢。 旦至今仍有許多科學家—直為降低高吸水性樹月旨的單體殘留 里而努力，技藝界已有許多降低高吸水性樹脂的單體殘留量的方 法被開發出來’如:添加—種—級或二級胺類（日本專利公告昭和 33〇958) _2,646與日本專利公開昭和5〇(1975)_4_)，及添加亞 硫酸鹽和亞硫酸氳鹽（美國專利2,96G，486號和4，裏,955號）以 _單_留量’另有使用低溫分解型及高溫分解则發^ (曰 本專利公告昭和5〇(1975>44,28〇，日本專利公開昭和 53(1978)-141，388 )及合併使用氧化還原引發劑（日本專利公開昭 和5〇(i975)-96,689及美國專利Μ7·號），使殘留在高吸水 性樹脂表面的單體再次聚合，而達到單體殘留量的降低，亦有使 用微生物分解法分解殘留單體（日本專利公告昭和的 (⑽5)-29,523)及利用蒸汽預熱方式再進行烘乾（日本專利公告 Η口和62(1987)_刚，764及美國專利I·，2號）而達到單體殘 留量減少的目的，使用親水性溶劑轉取以及·二氧化碳進行 超臨界點萃取（美國專利4,794，116號），使用氯酸鹽或漠酸鹽類 氧化物進行重合反應以降低單體殘留量（美國專利5,629,377號 及美國專利6,914，’ #u)，更有利用有機填化合物（美國專利 f#u) 鹽類（麵專利 6,3i3,23i 號） 以降低水雜不鮮單财的，離子合計含量進而達到單體 殘留量減少的目的。 1275596 然而’添加氨、脸趣兀各 有效，但會造成財酸鹽對減低殘存單體含量相當 高吸水性樹腊，若& : '而且常常無法獲得PH值為尹性的 外，使用氨、胺類^不足對降低殘存單體的效果很有限；此 觸造成人體的損害， ^在水办液中，將會和人體接 降低在膠縣面的殘存二，:二。而使用引發劑的方法，只能 果，而且將耗費細 _，蹲_部的殘存單體則毫無效 過高且耗時仏=^=分輪財_成本 的方法，則有掣程繁珀、批去t ^ ，利用瘵气先預熱再烘乾 的缺點，·利irtir困難及現場機器設備損害折舊率高 低殘存單體含量的效臨界點萃取法來降 溶而有所限制；使用氯酸鹽或的=機溶劑不互 可財效的降低殘存單體含量，但是==== 問述，和人體接觸造成人體的損害，而且表面 :二會產生成本過高的缺點;利用有機 ^產生水質優氧化的環境問題，此外，添加量不足對降低殘ς單 體的效果财限’以及所製造之高吸水性樹脂的耐尿性不佳。 此外’高吸水性樹脂為不溶解化之親水性聚合體，翻旨内部 具有均勻性_橋結構，—般為了改善品質如:提高吸收速率 高膠體強度、提高抗結塊性、㈣滲紐等，會在樹脂的表面再 作進-步架橋’絲面交聯處理即糊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 10 1275596 月曰人又％^於有機溶劑巾進行表面交聯處理（Jp_Ami6⑽、 JP^57-44627 ^ JP^58-42602 ^ JP-A58-117222)， 接將父聯劑與交聯劑溶液混入高吸水性樹脂處理 (JP ΑόΟ I639%、吓备6〜2558〗4)，添加交聯劑後以蒸氣處理 、UP_A_1-1134G6)，使用有機溶劑、水及多元醇進行表面處理 、UP各1_29·4、美國專利Μ46%9號）使用有機溶液、水， (ether)化合物（爪^2七39〇3)彡；這些表面處理的方法雖能 籲提南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。 > 【發明内容】 鑒於以上的問題，本發明的主要目的在於提供—種利用多次 中和的不飽和單體水溶液以製備高吸水性樹脂的製造方法，藉以 解決先前技術所揭露之降低殘存單體的效果不佳，及所製造之高 _ 吸水性樹脂的耐尿性不佳的問題。 本表明之另一目的在提供一種粉狀、不溶於水，可吸收水液 • 或尿液及血液，具有低齡未反鮮體、高保持力，且在較高的 ' 動下具有較高魏倍轉性的高性能高吸水性樹脂。 本發明提出一種利用多次中和的不飽和單體水溶液以製備 南吸水性樹脂的製造方法，至少包括下列步驟··使用—次或多次 中和的不飽和單體水溶液，—次或多次中和不飽和酸單體水溶液 的pH值不低於8，在？11值不低於8之前的中和，中和後不飽和 11 Ϊ275596 水細__大於秒，完全中和完不飽和單 i 〇奋液pH值不低於Μ，不飽和單體水溶液中和比率在衫至 :莫耳％之範圍内且濃度在2()至55重量百分比之範圍；接著’ • 仃自由基知反£、亚提供賴後的凝膠體，將娜體利用溫 / WC至航額的熱風乾燥、粉碎、篩選、塗覆表面交聯劑及 、控制溫度贼至23〇t：進行加熱表面處理後成為 高吸水性樹脂。 • 柄明更提出一種利用多次中和的不飽和單體水溶液以f 傷高吸水性樹脂的製造方法，方法至少包括下列步驟：使用1 • ❹対和的不飽和單體水溶液，_次❹次作不飽和單體水 ‘溶液阳值不低於8,在PH值不低於8之前的中和，中和後不餘 和酸早體水溶液靜置時間須大於3⑻秒，完全作完成的不飽和 早體水溶液pH值不低於5.5，不飽和單體水溶液中和比率在衫 至85莫耳％之範圍内且濃度在2〇至％重量份之範圍，·接著，進 =由基聚合反應並提供篩選後的凝膠體，利用溫度議^至⑽ C乾圍的熱風賴、粉碎、篩選、添加惰性無難粉末、塗覆表 ' 时·溫度及控制贼至2聊進行域表面處理後成為高吸 ' 雜獅；添加林雜婦及轉胁“樣義，以進行 抗結塊處理；及前述之表面㈣觀於加熱表面處理時進行交聯 反應。 即 依照本發明較佳實施例所述之利用多次中和的不飽和單體 水溶液以製備高吸水性樹脂的製造方法，其中不飽和酸單體為^ 婦酸、甲基丙烯酸、馬林酸、富馬酸、2_丙稀胺_2_甲基丙淀石黃酸、 12 I275596 =溶液^製備高吸水性樹脂的製造方法，其中黏著劑為丙三醇、 t乙二醇、、山梨糖醇、聚乙稀亞胺或其衍生物，黏著劑的用法為 早獨使用或合併崎以上混合使用。黏㈣添加範圍在重量百分 比0.005至5.0之間。 轉月方法所製造的高吸水性樹脂為具有低殘存未反應單 肢、高保持力’且在較高的動下具有較高魏倍顿性的高性 t吸水性翻旨，適合做為衛錢品如尿布、婦女衛生用品、拋 棄式的彳祭巾等之使用材料。 有關本I明的特徵與實作，兹配合實施例詳細說明如下。 【實施方式] 以下舉出具體實施例以詳細說明本發明之内容。 古吸提ώ—翻用乡対和料飽和單體水溶液以製備 同吸水性樹脂的製造方法，包括： ⑻，用-次或多次中和的方式來產生不飽和單體水溶液， —次或多次中和不飽和單體水溶液pH值不低於8，在阳 ，不低於8之則的巾和，其巾和後不飽和酸單體水溶液 二置時間須大於300秒’中和完成的不餘和單體水溶液 =值不低於5.5 ’巾和比率在Μ至％料百分比之範 圍内，不飽和單體水溶液的濃度在2〇至55 t量百分比 之範圍。 )進仃自^絲合反應並提㈣選後的凝㈣，將凝膠 14 1275596 體利用溫度100 C至180 C範圍的熱風乾燥、粉碎、篩選、 塗覆表面交聯劑及控制溫度90°C至230°C進行加熱表面 處理後成為高吸水性樹脂。 本發明更提出一種利用多次中和的不飽和單體水溶液以製 備高吸水性樹脂的製造方法，包括下列步驟·· (a)使用一次或多次中和的不飽和單體水溶液，一次或多次 中和不飽和單體水溶液pH值不低於8，在？11值不低於 8之W的中和，中和後不飽和酸單體水溶液靜置時間須大 於300秒’完全中和完成的不餘和單體水溶液_值不低 於5.5 ’不飽和單體水溶液中和比率在衫至％ 比之範_且濃度在20至％重量百分比之範圍； ⑻添加水不溶性微粉及黏著舰高吸水性樹脂，以進行抗 ⑼進仃自由基聚合反應並提供篩選後的凝膠體，利用溫度 ⑽C至18CTC範圍的熱風乾燥、粉碎、篩選、添加情性 …、機鹽粉末、塗覆表面交聯航控制溫度9叱至挪。◦ 進行加熱表面處理後成為高吸水性樹脂； 行交聯反應。 及别述之表面3C聯劑能於加熱表面處理時進 上述之特徵，係利用中和時控制丙烯酸 鹽水溶性不飽和單體BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a super absorbent resin, and more particularly to a method for producing a super absorbent resin using a multi-neutralized unsaturated monomer aqueous solution. . [Prior Art] Superabsorbent resins are widely used in water retaining agents for agriculture or horticulture, anti-dew beads coagulants in building materials, and materials for removing moisture from petroleum, or outer waterproof coatings in electric wires. Agents and shouting supplies such as diapers, feminine hygiene products, and disposable wipes. In the above case, since the super absorbent resin directly contacts the human body, the safety of the two water absorbent resins becomes important. In general, the physical properties of the superabsorbent resin include absorption rate, absorption, absorption under pressure, low monomer residual, and gel strength after absorption. The excellent superabsorbent resin not only satisfies the above physical properties, but more importantly, it must have good safety. The constituent material of the superabsorbent resin known in the art is a hydrolyzed starch acrylonitrile graft polymer (Japanese Patent Laid-Open Publication No. Sho 49 (1974)-43,395), neutralized starch-acrylic acid. Grafted polymer (Japanese Patent Publication No. Sho 51 (1976)-125,468), saponified ethylene vinegar g-polypropylene copolymer (Japanese Patent Laid-Open Publication No. Sho 52 (1977)-14, 689), hydrolyzed acrylonitrile copolymer or propylene The guanamine copolymer (Japanese Patent Publication No. Sho 53 (1978) -15, 959), and the genus of the genus and the acryl (Japanese Patent Laid-Open Publication No. Sho 55 (198 〇) _84, 3 〇 4) and the like. The raw material of the 7 1275596 nave powder-acrylonitrile graft polymer, because it contains a natural polymer-starch, can cause decomposition of decay, so it cannot be preserved for a long time; furthermore, its manufacture is very complicated. Therefore, the preparation method of the super absorbent resin today is the most economical by using the superabsorbent resin obtained by crosslinking polymerization using acrylic acid and acrylate, and the reason is that the raw material of the acrylate copolymer can be rapidly liquefied. The highly water-absorbent resin is the most common one, and the obtained super absorbent resin has high water absorption capacity, and has economical benefits such as low cost of manufacturing, and decomposition without causing rot. ♦ The method of forming a superabsorbent resin from the genus and the acrylate can be carried out by several known methods, such as aqueous solution polymerization, reverse phase suspension polymerization, emulsion polymerization, or monomer coating. In the method of conducting polymerization on the substrate, the reverse phase suspension polymerization and the emulsion polymerization must use H; if the temperature cannot be effectively controlled, U will be & The increase in system temperature and pressure will result in a series of threats that threaten the safety of the operator M at the site and cause environmental problems. q When the amount of acrylic acid in the water-soluble unsaturated monomer required for the water-absorbing fat is too high, the reaction does not proceed, which affects the physical properties of the water-based resin. _ ^ ^ Performance ' Residual unreacted monomer, low retention, low absorption rate characteristics under Wuji; *Superabsorbent resin used in sanitation: should be raised = can directly contact human body and food 'lower residual, use Safety, so in recent years it has become a trend to reduce the residual amount of 8 1275596 monomer residues. There are still many scientists who have been working hard to reduce the monomer residue of the high water absorption tree. There have been many methods in the art world to reduce the monomer residue of superabsorbent resins. - Grade or secondary amines (Japanese Patent Publication Showa 33〇958) _2,646 and Japanese Patent Publication Showa 5 (1975)_4_), and the addition of sulfite and barium sulfite (US Patent 2,96G, 486) No. 4, ri, No. 955) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 1978)-141,388) and a combination of a redox initiator (Japanese Patent Publication No. 5(i975)-96,689 and U.S. Patent No. 7/7) to repolymerize the monomer remaining on the surface of the superabsorbent resin to reach The reduction of the residual amount of the monomer is also caused by the decomposition of the residual monomer by the microbial decomposition method (Japanese Patent Publication (Show) ((10) 5)-29, 523) and the drying by the steam preheating method (Japanese Patent Publication Sakaguchi and 62 (1987) _ Gang, 764 and US Patent I·, No. 2) and achieve monomer For the purpose of reducing the amount of residues, use hydrophilic solvent transfer and carbon dioxide for supercritical point extraction (U.S. Patent No. 4,794,116), using a chlorate or a salt acid oxide to carry out a recombination reaction to reduce the monomer residual amount ( U.S. Patent No. 5,629,377 and U.S. Patent 6,914, '#u), the use of organic filler compounds (US Patent f#u) salts (face patents 6, 3i3, 23i) to reduce water and impurities, ions The total content further achieves the purpose of reducing the residual amount of the monomer. 1275596 However, 'addition of ammonia and face fun are effective, but it will cause the acid salt to reduce the residual monomer content to a relatively high water absorption of the wax, if & : 'and often If the PH value is not acceptable, the use of ammonia and amines is insufficient to reduce the residual monomer; this touch causes damage to the human body. ^ In the water solution, it will be lowered to the human body in Jiao County. The residual of the surface is two: two. The method of using the initiator can only be fruitful, and it will consume fine _, the residual monomer of the 蹲 _ part is too inefficient and time consuming = ^ = 轮 财 _ cost Method, there are rumors, Go to t ^, use the disadvantages of preheating and then drying the helium, · Litir difficulty and on-site machine equipment damage depreciation rate high and low residual monomer content effect critical point extraction method to reduce solubility; use chlorate Or = machine solvent does not mutually reduce the residual monomer content, but ==== ask, human body damage caused by contact with the human body, and surface: two will produce the disadvantage of excessive cost; use organic ^ to produce water quality The environmental problem of excellent oxidation, in addition, the insufficient amount of addition is insufficient for reducing the effect of the residue monomer, and the high water-absorptive resin produced has poor urine resistance. In addition, the 'superabsorbent resin is a hydrophilic polymer that is insoluble, and has a uniform internal _ bridge structure. Generally, in order to improve the quality, such as: improving the absorption rate, high colloid strength, improving anti-caking property, (4) osmosis, etc. It will be further processed on the surface of the resin - the bridge cross-linking treatment, that is, the paste has a polyfunctional crosslinking agent capable of reacting with the acid group, and many patents have been proposed before; for example, dispersing the superabsorbent tree 10 1275596 Months and other people are surface-crosslinked with an organic solvent towel (Jp_Ami6(10), JP^57-44627^ JP^58-42602^ JP-A58-117222), and the parental agent is mixed with the crosslinker solution. Superabsorbent resin treatment (JP 639 I639%, scare 6~2558) 4), after adding a crosslinking agent, steam treatment, UP_A_1-1134G6), surface treatment with organic solvent, water and polyol, UP 1_29· 4, US patent Μ 46% No. 9) using organic solution, water, (ether) compound (claw ^ 2 7 39 〇 3) 彡; these surface treatment methods can call the South absorption rate to increase the water absorption rate under pressure, but will Causes the adverse consequences of excessive retention, reducing the actual Application performance. SUMMARY OF THE INVENTION In view of the above problems, it is a primary object of the present invention to provide a method for producing a superabsorbent resin using a multi-neutralized unsaturated monomer aqueous solution, thereby solving the problem of reducing the residual property disclosed in the prior art. The effect of the monomer is not good, and the high water-absorbent resin produced has a problem of poor urine resistance. Another object of the present invention is to provide a powdery, water-insoluble, water-absorbable liquid or urine and blood, which has a low age, no anti-fresh, high retention, and a high A high-performance, high-absorbency resin that is doubling. The invention provides a method for preparing a south water-absorbent resin by using a multi-neutralized unsaturated monomer aqueous solution, which comprises at least the following steps: using one or more neutralized unsaturated monomer aqueous solutions, one or more times The pH of the secondary neutralized unsaturated acid monomer aqueous solution is not less than 8, in? 11 value is not lower than 8 before neutralization, after neutralization, unsaturated 11 Ϊ 275596 water fine __ is greater than second, completely neutralized unsaturated single i stimulating liquid pH is not lower than Μ, unsaturated monomer aqueous solution neutralization The ratio is in the range of the shirt to: % of the mole and the concentration is in the range of 2 () to 55 weight percent; then the ' 仃 仃 仃 知 、 、 、 、 、 、 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚The hot air drying, pulverizing, screening, coating surface cross-linking agent to the flight amount, and controlling the temperature thief to 23〇t: after heating surface treatment, it becomes a super absorbent resin. • The handle further proposes a method for producing a superabsorbent resin by fusing a neutralized aqueous solution of an unsaturated monomer, the method comprising at least the following steps: using 1 • an aqueous solution of an unsaturated monomer, _ times ❹ The secondary non-saturated monomer water' solution has a positive value of not less than 8, and the neutralization before the pH value is not less than 8, the neutralization time after the neutralization and the acid early solution aqueous solution must be more than 3 (8) seconds, completely completed. The pH of the aqueous solution of the unsaturated early solution is not less than 5.5, the neutralization ratio of the aqueous solution of the unsaturated monomer is in the range of from 5% to 5% by weight of the shirt, and the concentration is in the range of from 2 Å to % by weight, and then, the polymerization is carried out. React and provide the filtered gel body, using the temperature to the (10) C dry circumference of the hot air, crushing, screening, adding inert powder, coating the table 'time · temperature and control the thief to 2 chat after the surface treatment Become a high-absorption 'mixed lion; add a forest mixed woman and turn the threat to "anti-caking treatment; and the surface (4) of the foregoing is subjected to a cross-linking reaction when heated surface treatment. That is, according to a preferred embodiment of the present invention Said to utilize multiple neutralized unsaturated monomer water a solution for preparing a superabsorbent resin, wherein the unsaturated acid monomer is potassium methacrylate, methacrylic acid, marinic acid, fumaric acid, 2-propyleneamine 2 -methyl methicillin, 12 I275596=Solution ^Preparation method for preparing super absorbent resin, wherein the adhesive is glycerol, t ethylene glycol, sorbitol, polyethyleneimine or a derivative thereof, and the adhesive is used as early as possible. Or the combination of the above and above. The viscosity (4) is added in the range of 0.005 to 5.0 by weight. The high water-absorbent resin produced by the moon-turning method has a low residual unreacted single limb, high retention force' and is under high movement. The high-quality t water-absorbing reversal with high Weibenton is suitable for use as a protective material such as diapers, feminine hygiene products, disposable abalone towels, etc. Regarding the characteristics and implementation of this I, The following is a detailed description of the following examples. [Embodiment] The following is a detailed description of the present invention to explain the contents of the present invention in detail. An ancient suction extraction method - a method for preparing a water-absorbent resin by using a saturated aqueous solution of a nos. , including: (8), with - times or more a secondary neutralization method to produce an aqueous solution of an unsaturated monomer, one or more times of neutralizing the aqueous solution of the unsaturated monomer, having a pH of not less than 8, in the yang, not less than 8 and the towel and the The aqueous solution of the saturated acid monomer must be set to more than 300 seconds. The neutralization is completed and the aqueous monomer solution = the value is not less than 5.5. The ratio of the towel and the ratio is from the range of Μ to % of the percentage of the aqueous solution of the unsaturated monomer. In the range of 2〇 to 55 t by percentage.) The enthalpy from the ^spinning reaction and (4) the selected coagulation (4), the gel 14 1275596 body is dried, pulverized, screened, by hot air at a temperature ranging from 100 C to 180 C. The surface crosslinking agent is coated and the temperature is controlled from 90 ° C to 230 ° C to form a super absorbent resin after heating and surface treatment. The present invention further provides a method for preparing a super absorbent resin by using a multi-neutralized aqueous solution of an unsaturated monomer. The manufacturing method comprises the following steps: (a) using one or more neutralized aqueous solutions of unsaturated monomers, and neutralizing the aqueous solution of the unsaturated monomer one or more times with a pH of not less than 8, in? Neutralization of 11 values of not less than 8 W, after the neutralization, the aqueous solution of the unsaturated acid monomer must be allowed to stand for more than 300 seconds 'completely neutralized and the monomer aqueous solution _ value is not less than 5.5 'unsaturated single The aqueous solution neutralization ratio is in the range of shirt to % and the concentration is in the range of 20 to % by weight; (8) adding water-insoluble fine powder and adhesive ship super absorbent resin for anti-(9) radical polymerization and providing screening After the gel, the hot air is dried, pulverized, screened, and added with temperature (10) C to 18 CTC range, machine salt powder, coated surface cross-linking control temperature 9 叱 to move.进行 After heating and surface treatment, it becomes a highly water-absorptive resin; And the surface 3C crosslinking agent described above can be used to control the surface of the heated surface to control the acrylate unsaturated polyunsaturated monomer during neutralization.
二聚體在水溶性不飽和單體中的含 的ρΗ值’或是在pH值不低於8之前的中: 酸單體水溶液I秦罢卩主p目.. 15 1275596 量，以利於進;6 體中，，4 丁目由基聚合反應；因為丙烯酸鹽水溶性不飽和單 ㊅机—聚體的含餘低時，可使躲合反應較完全，進 调低殘存單體且具有高物理性質的高吸水性樹脂。 本發明中若中和時無法有效控制丙烯酸鹽水溶性不飽 體的pH值，式η + ττ ^The ρΗ value of the dimer in the water-soluble unsaturated monomer is either in the middle of the pH value not lower than 8: the acid monomer aqueous solution I Qin 卩 卩 main p mesh.. 15 1275596 amount, in order to facilitate ;6, in the body, 4 butyl-based polymerization; because the acrylate salt water-soluble unsaturated single-fibre-polymer has a low content, the hiding reaction can be more complete, lower residual monomers and high physics Highly water-absorbent resin of nature. In the present invention, if the neutralization is not effective, the pH value of the acrylate salt water-soluble unsaturated can not be effectively controlled, and the formula η + ττ ^
和萨1 ^疋在_值不低於8之前的中和，其中和後不飽 广早豆水錢靜置時間，則丙騎鹽水溶性侦和單體聚合後 :传到，顧鹽聚合物會具有下列缺點：含有大量的丙稀酸二 ^體1 合物隨後進行熱處理或是在高温的環境下使用時，聚 2 g產生新的殘存單體，增加殘存單體的含量，使得丙稀酸鹽 聚合物進行表面交聯處理時，表面交聯劑無法有效的改善丙稀酸 鹽聚合物的各種物理性質。 丙稀酸鹽聚合物中，中和時控制丙烯酸鹽水溶性不飽和單體 的pH值或靜置時間，即可以有效降低殘存單體含量，目前為技 藝界所接受的推論為··由於丙騎二聚體巾續乙基的…氮原子 在驗性條件下，會進行Ε2脫除反應，形成2分子的丙稀酸鹽， 田中和後丙烯酸鹽水溶性不飽和單體的ρΗ值越接近14，丙烯酸 -本體進行Ε2脫除反應的速率就越快，丙烯自請水溶性不飽和 單體中丙：)#酸二聚體的含量就越低；而中和後丙烯酸鹽水溶性不 飽和單體的靜置時間越長，也會使丙烯酸鹽水溶性不飽和單體中 丙烯酸二聚體分解成丙烯酸鹽的量就越多，使得丙烯酸鹽水溶性 不飽和單體中丙烯酸二聚體的含量越少，當聚合物隨後進行熱處 16And Sa 1 ^ 疋 in the _ value is not less than 8 before the neutralization, and after the time is not full, the early bean water money rest time, then the C salt salt water soluble detection and monomer polymerization: passed, Gu salt polymerization The material has the following disadvantages: when a large amount of the acrylic acid compound is subsequently subjected to heat treatment or when used in a high temperature environment, the poly 2 g generates a new residual monomer, and the residual monomer content is increased to make C When the dilute acid polymer is subjected to surface crosslinking treatment, the surface crosslinking agent cannot effectively improve various physical properties of the acrylic acid polymer. In the acrylic acid polymer, the pH value or the standing time of the unsaturated water-soluble unsaturated monomer of the acrylate is controlled during neutralization, which can effectively reduce the residual monomer content, and the inference that is currently accepted by the art industry is due to Riding the dimerized towel to renew the ethyl ... nitrogen atom under the test conditions, will carry out the Ε 2 removal reaction to form 2 molecules of acrylate, the closer the ρ Η value of the acrylate unsaturated monomer in the field and after 14, the faster the rate of acrylonitrile-substrate Ε2 removal reaction, the lower the content of propylene:)#acid dimer in propylene-free water-soluble unsaturated monomer; and the water-soluble unsaturated acrylate after neutralization The longer the standing time of the monomer, the more the amount of the acrylic acid dimer in the acrylate water-soluble unsaturated monomer is decomposed into the acrylate, so that the acrylic acid dimer of the water-soluble unsaturated monomer in the acrylate The less the content, when the polymer is subsequently subjected to heat 16
1275596 理或疋在高溫的環境下使 體，增加殘存單㈣人⑤* ^物便不g產生新的殘存單 質的高吸水性樹^ 細細_單體且具有高物理性 =她而言，僅須控制中和時丙烯酸鹽水 _ ^歧在PH值不低於8之前的中和 = 酸單體水溶液靜詈眛門，如叮‘ 後不飽和 酸1·^ΑΘ Β °有效降低水雜讀和單體中丙歸 來製備合於此敘義水雜獨和單體的 步驟只需_—種多対和的方式來產生，每次單體添 不大於總添加量之—半，中和劑、純水與單體中和方式可分為下 列方法(1)-(3)最能展現本發明的特點： w ⑴一種包括如下步驟的方法··射和劑與純水充分混合， 然後將單體加入混合水溶液中，將其充分混合而得。 (2) -種包括如下步驟的方法：將單體與純水充分混合，然 後將得到的混合水溶液與中和劑充分混合而得。…、 ⑶-種包括如下步驟的方法··射和顺純水充分混合， 然後將得_混合水溶液加人單财，將其充分混合而 得0 本發明所製造之高吸水性樹脂所需的水溶性不飽和單體除 了丙烤酸外，尚可使㈣錢有雜基_不飽和魏的水溶性 單體，如:f基丙烯酸、馬林酸、富馬酸、2·丙烯胺_2_甲基丙烷磺 酸、順丁烯二酸、順丁烯二酸酐、反丁烯二酸、反丁烯二酸酐等: 17 1275596 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 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-羧基乙酯、曱基丙烯酸2_ 竣基乙§曰、丙烯酸甲酯、丙烯酸乙酯、二甲胺丙稀丙_胺、氣 丙烯丙烯基二甲銨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時，不飽和單體水溶液濃度並沒 別=限制，但濃度宜控制在重量百分比如至％間，適當濃度為寺 重里百77比30至45之間，濃度在重量百分比2()以下時，聚合 後尺破膠太叙且有黏性不利機械加工，添加濃度在重量百分比％ 以上，接近飽和濃度’ Μ調配狀應太快反應熱不易控制 飽和單體水溶液阳值不低於1 2·2，若ΡΗ低於5.5時，聚合後水 凝膠體内殘存單體含量過高，會導致高吸水性樹脂之物性不佳。 18 1 體之触基應該部份中和以控制成品之阳值，使 2 :是碳 碳酸氫納、碳料料、减崎、碳咖、碳酸鉀、 種混合使用。含駿中和劑可單獨使用一種或多 9，中和濃;駿基部份+和油贱鉀鹽或兹 ;耳百 ⑽ 比為85«上喊觀，作敍莫耳百分 曰扁阿成口口 pH值非呈中性或微酸 1275596 性時’若不慎與人體接觸時均不太適合，也較不安全。 在進行自由基聚合反應前單體水溶液中，亦可添加水溶 降低成本，此等水溶性高分子如：部份4化或完全妻化的 Γ乙喊、聚乙二醇、聚丙稀酸、聚丙_胺、㈣或殺粉衍生 ，如甲基纖維素，丙烯酸甲基纖維素，乙基纖維素等聚合物，·此 等水溶性高分子的好量並補舰定，射紐的水溶性高分 子為殿粉、部份皂化或完全皂化㈣乙_料獨姐合使用。 兩吸水性翻旨含鱗水雜高分子㈣#添加制如為重量百 分比為G至20 ’更例如為重量百分比G至1()，尤可例如為重量 百分比0至5，當添加量超過重量百分比2()時會影響物性，使高 吸水性樹脂的物性變差。 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，K2_丙烯基廉、n，n，_ 次曱基雙丙烯醯胺、N，N，-次甲基雙曱基丙烯醯胺、丙烯酸丙烯 酯、乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、乙二醇二曱基丙 烯酸酯、聚乙二醇二曱基丙烯酸酯、甘油三丙稀酸酯、甘油三曱 基丙烯酸酯、甘油附加環氧乙烷之三丙烯酸酯或三曱基丙烯酸 酉曰、二曱醇丙：!：元附加環氧乙燒之三丙烯酸酯或三曱基丙烯酸酉旨、 二曱醇丙少元二曱基丙烯酸醋、三曱醇丙烧三丙烯酸酯、 三(2-丙烯基)胺、二丙烯酸乙二醇酯、三丙烯酸聚氧乙烯甘油酯、 19 1275596 二丙烯酸一乙基聚氧乙烯甘油酯、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、 ♦丙二g子聚縮水甘油醚、乙二醇二縮水甘油醚、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 吸水性樹轉體有適當的加讀。自由絲合反應交聯劑可單獨 使用或兩伽上混合朗。自由基聚合反應交聯劑適當的添加劑 謀重量百分比aocu至5之間(以反應物總_份絲準），更 適當的㈣重量百分比在_至3之間，添加缝在重量百分比 0.001曰以下聚合後水合體太軟且有黏性不利機械加玉，添加劑量 在重里百Μ 5以上财性太低，降低高吸水性樹脂性能。 ^合反應由自由絲合反應起始劑的分解產生自由基開 2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 氧化物’如.·過氧化氫、二_第三丁基過氧化物、過氧化 3或過硫酸鹽(銨鹽、驗金屬鹽)等，及偶氮化合物如·· 2.2，-偶 鼠基雙㈣基丙垸)二鹽酸鹽、22，_偶氮基雙⑽ 脒)二鹽酸鹽；亦可使用還原南J /、 酸性亞硫_、蝴_、b_糊，如： 抗权血酸或亞鐵鹽；或將氧化還屌 型齡㈣併如，首錄傾轉始劑= L ^丨發聚合反應的進 £、進购會釋放出大量的熱量而使溫度升高，當 20 1275596 溫度到達熱分解型起始_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《合反應更赫完全。而自由基聚合 反應，始劑適當用量為重量百分比為〇顧至1〇(以中和丙騎 鹽重量為基準），更適當用量則在(U至5之間，當使用量在重量 百分比o.ooi以下時，反應太慢不利轉效益，當使用量在重量 百分比10以上時，反應太快反應熱不易控制。 根據本發明所述之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 一醇丙一®予、1，4 丁二醇、三脞基甲基丙烷、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 使用具有兩個或兩伽上環氧基的化合物如··山梨_縮水甘油 醚來丙二％聚縮水甘油醚、乙二醇二縮水甘油醚、二乙二醇二 、、很水甘油_、聚乙二醇二縮水甘油醚、雙丙三醇聚縮水甘油鍵 等，、亦可使用碳酸亞烴酯如··乙二醇碳酸酯、4_甲基七^工氧雜 5衣戊：1：兀2’、4,5-二曱基-1，3-二氧雜環戊烧酮、4,4-二曱基4,3_ -氧趣狀_2_酮、4_乙基，❾：氧雜環姐I酮、以工氧雜 ί衣己:)：兀-2_酮、4,6_二曱基-i，3-二氧雜環己烷冬酮或U•二氧雜環 庚烷-2·_。交聯劑_法可使用或兩種以上混合使用。交 聯劑的適當添加劑量在重量百分比_1至10之間(以反應物總 固形伤為基準），更適當的用量在重量百分比0·0〇5至5之間，交 如▲加刻里在重1百分比議丨以下時無法顯出效果，交聯劑 21 1275596 添加劑量在重量百分比10以上時，吸水性太低，降低樹脂性能。 本發明之聚合反應可於傳統批次反應容器中，或於輸送帶式 反應裔上進行反應，反應所得之高吸水性樹脂，先利用絞碎機切 成直徑20mm以下凝膠體，更可以切成直徑1()mm以下凝膠體 後，再進行篩選。 # 篩選固定粒徑之凝膠體直徑以2·00 mm以下為宜，以〇.05 mm至1.50 mm間較佳，粒徑大於2.00 mm之凝膠體則重新送回 紋碎機進行再次切碎。粒徑〇 〇3mm以下之凝膠體進行烘乾、粉 碎處理後，易產生成品細粉量提高，粒徑2 〇〇mm以上之凝膠體 進行烘乾時，容易因為熱傳導效果不佳，導致成品在殘存單體偏 高，其他物性表現不佳之缺點。依據本發明，丙烯酸鹽凝膠體的 顆粒大小分佈越窄，不僅可使凝膠體在烘乾後物性表現達到最佳 狀態，而且有利於控制烘乾的時間及溫度，篩選完成後再進行烘 •乾。 烘乾溫度以溫度10(TC至180°c進行烘乾為宜，烘乾溫度 100 C以下烘乾時間太久，不具經濟效益，烘乾溫度180它以上烘 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，達到降低殘存單體之效果。 乾燥後進行粉碎、篩選固定粒徑，再進行表面交聯劑塗覆處 22 I275596 =:ΤΓΓ至UOmm間為宜，更可以在❹― 〇獅麵間’ _ Q.G6mm以下細粉使成品 1.00mm以上粒子使成品吸水速率變 捉门祖位 聚合物的顆粒大小分佈越窄越好&。依據本發明’丙稀酸鹽 表面交聯敝航_，表岭㈣之添㈣ 面交聯劑的種類’分成表面交聯·接添加，或調成表面交聯劑 添力…觸表面交聯舰水性有機溶劑水溶液添加，親 =性有機溶劑如帽、乙醇、丙醇、異丁醇、_ ,、乙鍵 4沒有特殊關，可形成溶液即可，其中以甲醇、乙醇較 =利6849665號）。表面交聯劑添加時高吸水樹脂中可添加惰 I機鹽粉末，以幫助溶液分散，恤無機鹽粉末可為硫酸铭、 或了乳切，或氧修或氧化鎂等或其混合物。其中以硫酸紹、 -=切較佳。惰性無频粉末_法可單獨使用或合併兩種以 上混合使用。惰性無機鹽粉末添加範圍在重量百分比〇至 10.0之間，更可以為重量百分比⑽丨至4.〇。 進行表面交聯劑塗覆處理後，再以9(rc s 23(rc範圍内進行 加f歧，使表面交聯舰均勻而且快速的進行交聯反應，並使 P父％背彳進行父聯反應而達到本發明之效果。熱處理溫度9〇。〇 =下父聯反應時間太久，不具經濟效益，熱處理溫度23〇。〇以上 樹月曰易劣化影響品質，熱處理時間以2分鐘至150分鐘為宜，依 …奴獲侍到的表面處理效果做熱處理溫度調整，熱處理溫度高則 23 1275596 熱處理時間短，熱處理溫度低時，則熱處理溫度時間長。 本發明使用普通的乾燥器或加熱爐即可完成熱處理的步 驟士’適麟本發明的祕理裝置實·括：騎式混合乾燥器、 轉鼓式乾燥H、臺式觀H、流化床乾燥器、氣流式乾燥器以及 紅外線乾燥器。 • >表面交聯熱處理後，於高吸水樹脂中添加水不溶性微粉，進 打抗結塊處理，目的在增加高吸水樹脂麵之__，使高吸 - 顿脂在吸㈣驗仍有高流雛；林溶性微粉添加方式為直 ' 細加’再糊麟舰林溶性微錄著於高财樹脂表面； 水不溶性微粉包括硫酸銘、硫酸鎮、氧化 侧'_、魏鋇他、軟土、黏土、滑石粉: :土、膨土、活性碳、二氧切、二氧化鈦之無機鹽粉末，及 繼末、聚㈣乙㈣氯乙稀、聚苯乙稀之有機粉末。 .水不溶性微射，縣加無鐘粉末的效果較好，而益機 ^末的用法可早獨制或合併兩_上混合使用。水不溶 加範祕梅梅_錢㈣，更可量 【==。水不溶性微粉之粒子大小最好不大於1。麵， 更適當的大小為0.6mm以下。 上述之黏著财為多辑如：丙三醇 或可使用紅触胺。__碰_讀兩=/上 24 1275596 混合使用。黏著劑的適當添加劑量在重量百分比至⑺之間 (以反應物總H]形份為基準），更可以在重量百分比至5之 間’黏著劑添加劑量在重量百分比_丨以下時無法使惰性益機 鹽粉末完錄著於高吸水翻旨絲，而當黏著齡加劑量在重量 百分比10以上時，高吸水樹脂吸水性太低，降低樹脂性能。里 /為顯示本發明之高吸水性樹脂_力下吸水倍率，本發明利 ^ ^壓吸收重(M力負荷·’ 2〇g/em2及卿―來測定，受墨吸收 ，係根據歐洲翻咖你A號賴書第七頁巾所描述的方法測 定；將初始重量的高吸水性樹脂放在依據有軸底部的圓柱體 中’對粉體加以2〇_2及49g/em2的動，接著將此圓柱體置 於吸收n収②上’讓此高吸水性樹脂吸收&9%的氯化納 水溶液-小時’再將測吸水重量將所得數值除以高吸水性樹脂的 重量，即得受壓吸收重數值。 本發明之保持力係利用茶袋試驗法測定，並以五次量測結 =，絲最紐以及最低值後，取平均值；將G.2g的高吸水性樹 脂裝在茶袋裡，並魏於〇.9%的NaC1水驗2G分鐘，然後將 b又泡後的余衣置於離心機巾離^(直徑、轉速㈣m) #刀知後秤重。所得之數值先減去未充填高吸水性樹脂的空白組 茶袋重(以相同步作)再除妓合物重即得保持力數值。 低殘存單體的測定是利用液相層析儀分析，先精秤取0.500g 25 1275596 冋吸水性樹脂於15〇cc錐形瓶中，加入〇·524% Naa水溶液ι〇% 及2cm的授拌子一顆，以5⑻印㈤轉速攪拌一小時，加入 20%Al2(SO4)3水溶液5g，再利用2阿濾、紙過濾、，將遽液打入液 相層析儀内分析’把所得之訊號和校正曲線相比對即可得到殘存 單體量。 以下詳細地列出參考工作實例，以便說明本發明；但本發明 範圍不完全由這些實例所代表。 實例一： 1) 取48%氫氧化鈉水溶液802g及1〇69 2g的水於4〇〇〇c c圓錐瓶 中’緩慢加入330g丙烯酸，氳氧化鈉/丙烯酸的滴加比率在〇.衫 至〇·95範圍内，並保持瓶内中和反應系統的溫度在4〇。〇，中和 後水溶性不飽和單體pH值為12.6，靜置5分鐘後，再將660g 丙烯酸加入部份中和完成的水溶性不飽和單體中，完全中和後 水溶性不飽和單體pH值為5.6，此時得水溶性不飽和單體濃度 42wt%水溶液，其中70mol%(莫耳比)丙烯酸部份中和為丙烯酸 2) 再加入1.518 g的n，N，-次曱基雙丙烯醯胺於水溶性不飽和單體 溶液’並維持溫度於2〇°C左右。 3) 加入0.528g雙氧水，6.62 g亞硫酸氫鈉及6.62 g過硫酸銨以起 始反應。 26 1275596 4) 利用切式粉碎機將反應後的凝膠體切碎，並篩選出粒徑大小為 2mm直徑以下的凝膠體。 5) 以130 C概度乾燥2小日守，利用師網篩選Q imm〜〇 固定 粒徑，得粉狀高吸水性樹脂。 6) 秤取此高吸水性樹脂i〇〇g，加入硫酸鋁粉末lg，待混合均勻 後再加入乙二醇碳酸酯:水:甲醇=1:1:1(重量比)溶液3.6g，以 215°C溫度加熱處理1〇分鐘。 7) 冷卻後，秤取此咼吸水性樹脂5〇g，加入水不溶性微粉氧化鎂 粉末0.5g，待混合均勻後再加入聚乙烯亞胺:水=1:3(重量比)溶 液6 g ’進行抗結塊處理’即得南性能南吸水性樹脂，測定保持 力為29.42g/g，20g/cm2壓力下吸水倍率28.69g/g，49g/cm2壓力 下吸水倍率17.34g/g，殘存單體16.3ppm。 實例二： 重覆實例一，但中和方法先利用48%氳氧化鈉水溶液802g 及1069.2g水的混合水溶液，再加入200g丙烯酸，並保持瓶内中 和反應系統的溫度在40°C，待充分混合並靜置5分鐘，此時水溶 性不飽和單體pH值為13.3，再將790g丙烯酸加入。其餘同實例 一’得高吸水性樹脂，測定保持力為29.52g/g，20g/cm2壓力下吸 水倍率29.41g/g，49g/cm2壓力下吸水倍率17.89g/g，殘存單體 12·4ρριη 〇 27 !275596 實例三： 重覆實例一，但一次中和後靜置6〇分鐘。其餘同實例一， 知向吸水性樹脂，測定保持力為29 22g/g，2〇g/cm2壓力下吸水 倍率29.1〇g/g，49g/cm2壓力下吸水倍率17.84g/g，殘存單體 12·1ρριη 〇 實例四： 重覆實例一，但中和方法先利用33〇g丙烯酸及1069e2g的水 充分混合後，再加入48%氫氧化鈉水溶液8〇2g，待充分混合並 #置5分鐘’並保持瓶内中和反應系統的溫度在4〇。〇，此時水溶 陡不飽和單體pH值為12.6，再將660g丙烯酸加入。其餘同實例 —’可得高吸水性樹脂，測定保持力為29.13g/g，20g/cm2壓力 下吸水倍率28/74g/g，49g/cm2壓力下吸水倍率I6.81g/g，殘存單 體 l9.7ppm。 實例五： 重覆實例一，但中和方法先利用330g丙烯酸置於4000cx 圓錐瓶中，並保持瓶内中和反應系統的溫度在4〇°C，再加入48% 氫氧化鈉水溶液802g及1069.2g水的混合水溶液，待充分混合並 靜置5分鐘，並保持瓶内中和反應系統的溫度在40°C，此時水溶 28 1275596 =不餘和單體pH值為U.6，再將_g丙烯酸加人。其餘同實例 —，得高吸水性樹脂，測定保持力為29.ng/g，20g/cm2壓力下 吸水倍率29.06g/g ’ 49g/cm2墨力下吸水倍率16.33g/g，殘存單體 17.9ppm。 實例六： 重覆貫例-，但添加水不溶性微粉為硫酸铭粉末lg。其餘同 實例-’得高吸水性樹脂，測定保持力為28.llg/g ，20g/cm2 壓力 下吸水倍率28.15g/g，49g/em2壓力下吸水倍率16 73g/g，殘存單 體 21.3ppm。 炫以比較例及一，來作為實例一至六比較的對象，以突顯 出本發明之效果。 比較例一： 重覆貫例一，但將48%氫氧化鈉水溶液g〇2g及i〇69.2g的 水充分混合後，再緩丨艾加入990g丙烯酸，此時水溶性不飽和單 體pH值為5.8。其餘同實例一，得高吸水性樹脂，測定保持力為 27.61g/g，20g/cm2壓力下吸水倍率25.32g/g，49g/cm2壓力下吸水 倍率14.53g/g，殘存單體183.6ppm。 比較例二: 29 1275596 ^重覆實例一，但一次中和後直接將660g丙烯酸加入，並無 静置。其餘同實例一，得高吸水性樹脂，測定保持力為25.04g/g， 2〇g/cm2壓力下吸水倍_ %.馳，49一2麼力下吸水倍率 13.59g/g ’ 殘存單體 2〇6 7ppm。 •、本《明的方法可提供—種粉狀、不溶於水，可吸收水液或尿 液及血液’具有_存未反鮮體、高雜力，且在較高的麗力 • τ具有較高吸收倍率特性的高性能高吸水性樹脂 —經由本發贿製造的高吸水性_，由於具有低殘存單體含 量的雜，所以可提高使用上的安全性，經由本發明所得之高吸 .水性樹脂將能更適用於各種型式的衛生用品、農業用及食品保鮮 用的吸水劑。 —雖然本發明以前述之較佳實施觸露如上，财並非用以限 疋本發明，任何熟習相像技藝者，在不脫離本發明之精神和範圍 >内’當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。 301275596 疋 or 疋 使 使 高温 高温 高温 高温 高温 高温 高温 高温 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋It is only necessary to control the neutralization of the acrylic acid brine during neutralization. _ The neutralization before the pH value is not lower than 8 = the acid monomer aqueous solution is static, such as 叮 ' after the unsaturated acid 1 · ^ ΑΘ Β ° effectively reduce the water miscellaneous reading And the preparation of the monomer in the monomer to the water and the monomer and the monomer are only required to be produced in a multi-plutonium manner, each time the monomer is added no more than the total amount of added - half, neutralizer The pure water and monomer neutralization method can be divided into the following methods (1)-(3) to best demonstrate the characteristics of the present invention: w (1) A method comprising the following steps: · The shotant is thoroughly mixed with pure water, and then The monomer is added to the mixed aqueous solution and sufficiently mixed. (2) A method comprising the steps of: thoroughly mixing a monomer with pure water, and then thoroughly mixing the obtained mixed aqueous solution with a neutralizing agent. ..., (3) - a method comprising the following steps: · shot and cis pure water are thoroughly mixed, and then the obtained mixed aqueous solution is added to the monopoly, and the mixture is sufficiently mixed to obtain 0 water-soluble resin required for the super absorbent resin produced by the present invention. In addition to the acrylic acid, the unsaturated monomer can also make (4) money with a hetero-based unsaturated water-soluble monomer, such as: f-based acrylic acid, marlinic acid, fumaric acid, 2·acrylamide_2_ Methylpropane sulfonic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, etc.: 17 1275596 Monomers can be used without particular limitation, and can also be combined with a plurality of monomers. It is also necessary to add other hydrophilic monomers having unsaturated double bonds, such as acrylamide, methacrylamide, 2-carboxyethyl acrylate, methacrylic acid 2 竣 乙 乙 曰, acrylic acid Ester, ethyl acrylate, dimethylamine propylamine, and propylene propylene dimethylammonium are added in such a manner that the physical properties of the superabsorbent resin are not impaired. In the radical polymerization, the concentration of the unsaturated monomer aqueous solution is not limited, but the concentration should be controlled between the weight percentage and the %, and the appropriate concentration is between 77 and 30 to 45 in the temple weight, and the concentration is in the weight percentage. When 2() is below, after the polymerization, the rubber breaks too much and the viscosity is unfavorable mechanical processing. The added concentration is above the weight percentage, close to the saturated concentration. Μ The configuration should be too fast. The reaction heat is not easy to control the positive value of the saturated monomer solution. Below 1 2·2, if ΡΗ is less than 5.5, the residual monomer content in the hydrogel after polymerization is too high, resulting in poor physical properties of the superabsorbent resin. 18 1 The contact group of the body should be partially neutralized to control the positive value of the finished product, so that 2: is carbon sodium bicarbonate, carbon material, sub-salt, carbon coffee, potassium carbonate, and a mixture of species. The containing neutralizing agent can be used alone or in combination with 9 or less; the base part + and the oil sputum potassium salt or the sputum; the ear hundred (10) ratio is 85 «speaking, the syllabus When the pH of the mouth is not neutral or slightly acidic 1275596, it is not suitable or insecure if it is inadvertently contacted with the human body. In the aqueous solution of the monomer before the radical polymerization, water solubility may be added to reduce the cost. Such water-soluble polymers are, for example, partially or completely devoid of sputum, polyethylene glycol, polyacrylic acid, polyacrylic acid. _ amine, (four) or powder-derived, such as methyl cellulose, methyl cellulose methacrylate, ethyl cellulose and other polymers, · these water-soluble polymers are good and make up the ship, the water solubility of the injection is high The molecule is a temple powder, partially saponified or completely saponified (4). The two water-absorbing scaly water-containing polymer (IV) # is added in a weight percentage of G to 20', for example, by weight G to 1 (), especially for example, 0 to 5 by weight, when the amount exceeds the weight When the percentage is 2 (), the physical properties are affected, and the physical properties of the super absorbent resin are deteriorated. 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,K2_propenyl, n,n,_ decyl bis acrylamide, N,N,-methine bis decyl acrylamide, propylene acrylate, ethylene glycol diacrylate, Polyethylene glycol diacrylate, ethylene glycol dimercapto acrylate, polyethylene glycol dimercapto acrylate, glycerin triacrylate, glyceryl tridecyl acrylate, glycerin plus ethylene oxide triacrylate Ester or tridecyl acrylate, diterpene propyl C:!: element added with epoxy triacetate or tridecyl acrylate, dinonol, propylene, diacetate, acetal, propylene glycol Burning triacrylate, tris(2-propenyl)amine, ethylene glycol diacrylate, polyoxyethylene glyceryl triacrylate, 19 1275596 monoethyl oxyethylene glyceryl diacrylate, dipropylene triethylene glycol ester, etc. Compounds having two or more epoxy groups, such as Yamanashi, may also be used. Polyglycidyl ether, ♦ propylene diglycidyl polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycerol polyglycidyl ether, etc. . After the radical reaction is carried out, the superabsorbent resin can be appropriately crosslinked, and the superabsorbent dendrimer can be appropriately read. The free-knit reaction crosslinker can be used alone or in combination with two gamma. Free radical polymerization crosslinker appropriate additives to achieve a weight percentage between aocu to 5 (based on the total reactants of the reactants), more appropriate (four) weight percentage between _ to 3, adding seams below 0.001 重量After the polymerization, the hydrated body is too soft and sticky, and the mechanical addition of jade is unfavorable. The amount of the additive is in the range of more than 5, and the financial property is too low, thereby lowering the performance of the superabsorbent resin. The reaction is generated by the decomposition of the free silk reaction initiator to generate a radical. The 2 radical initiator is optionally selected from a thermal decomposition type initiator, and a suitable thermal decomposition type starting oxide such as hydrogen peroxide. _ tert-butyl peroxide, peroxidized 3 or persulfate (ammonium salt, metal salt), and azo compounds such as 2.2,-iso-m-bis(tetra)ylpropionamidine dihydrochloride, 22, _ azobis(10) hydrazine) dihydrochloride; may also be used to reduce south J /, acidic sulphur _, butterfly _, b_ paste, such as: anti-cortic acid or ferrous salt; or will also oxidize屌 age (4) and, for example, the first recorded tilting agent = L ^ burst polymerization reaction, the purchase will release a large amount of heat to increase the temperature, when the temperature of 20 1275596 reaches the thermal decomposition type of initial decomposition At the temperature, the decomposition of the second stage thermal decomposition type initiator is initiated, and the whole reaction is more complete. In the free radical polymerization, the appropriate amount of the starting agent is about 1% by weight (based on the weight of the neutralized C salt), and the appropriate amount is between (U and 5, when the amount is in the weight percentage o) When the concentration is below oo, the reaction is too slow, and the benefit is not good. When the amount is more than 10% by weight, the reaction is too fast, and the reaction heat is difficult to control. According to the invention, the crosslinking agent capable of simultaneously reacting at the surface treatment can be used. It is a polyhydric alcohol such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylidene propionate®, 1,4 butanediol, trimethylolpropane, sorbitol, etc.; Or a polyamine such as ethylenediamine, diethylenediamine, triethylenediamine, polyethylenediamine may be used; or a compound having two or two ethoxy groups of epoxy groups such as sorbitol _ glycidyl ether may be used.丙二% polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol dihydrate, very glycerol _, polyethylene glycol diglycidyl ether, diglycerol polyglycidyl bond, etc. An alkylene carbonate such as ethylene glycol carbonate, 4_methyl sulphate, oxalate 5: 兀2 can be used. , 4,5-dimercapto-1,3-dioxolone, 4,4-dimercapto 4,3-oxo-like 2-ketone, 4-ethyl, oxime: oxocycle Sister I, ketone, and oxyethylene:): 兀-2-ketone, 4,6-dimercapto-i,3-dioxanone or U•dioxane- 2·_. The crosslinking agent_method may be used alone or in combination of two or more. The appropriate amount of the cross-linking agent is between _1 and 10 by weight (based on the total solids of the reactants), and a more appropriate amount is between 0 and 0 〇 5 to 5 by weight. When the weight is less than 1%, the effect is not exhibited. When the crosslinking agent 21 1275596 is added at a weight of 10 or more, the water absorption is too low, and the resin property is lowered. The polymerization reaction of the invention can be carried out in a conventional batch reaction vessel or on a conveyor belt type reaction, and the superabsorbent resin obtained by the reaction is first cut into a gel having a diameter of 20 mm or less by a mincer, and can be cut. After forming a gel having a diameter of 1 () mm or less, screening is performed. #Screening the diameter of the gel with a fixed particle size of 2·00 mm or less, preferably between 〇.05 mm and 1.50 mm, and the gel with a particle size larger than 2.00 mm is sent back to the granulator for re-cutting. broken. When the gel having a particle size of 〇〇3 mm or less is dried and pulverized, the amount of fine powder of the finished product is easily increased, and when the gel having a particle diameter of 2 〇〇 mm or more is dried, it is easy to cause poor heat conduction. The finished product has the disadvantage that the residual monomer is high and other physical properties are not good. According to the invention, the narrower particle size distribution of the acrylate gel body not only enables the gel body to perform in an optimal state after drying, but also facilitates controlling the drying time and temperature, and then drying after the screening is completed. •dry. Drying temperature is preferably carried out at a temperature of 10 (TC to 180 °c, drying time is below 100 C for too long, no economic benefit, drying temperature above 180, drying to crosslink the crosslinking agent early The reaction makes the residual monomer unable to effectively remove the residual monomer during the subsequent drying process, thereby reducing the residual monomer. After drying, pulverizing, screening and fixing the particle size, and then coating the surface crosslinking agent. Where 22 I275596 =: ΤΓΓ to UOmm is appropriate, you can also use 细 〇 面 面 ' ' _ Q. G6mm below the fine powder to make the finished product 1.00mm or more particles to make the product water absorption rate change the particle size distribution of the ancestral polymer The narrower the better &. According to the invention, the surface of the 'acrylic acid salt cross-linking _, the crown (4) of the (four) surface cross-linking agent 'divided into surface cross-linking, or added to the surface cross-linking agent Adding force...The surface-crosslinking ship is added with an aqueous solution of aqueous organic solvent. The organic solvent such as cap, ethanol, propanol, isobutanol, _, and B bond 4 is not specially closed, and a solution can be formed, in which methanol is used. , ethanol is more = profit 6846665). When the surface crosslinking agent is added, an inert salt of the inert salt may be added to help the solution to be dispersed. The inorganic salt powder may be sulfuric acid, or milk cut, or oxygen or magnesium oxide or the like or a mixture thereof. Among them, sulfuric acid and -= cut are preferred. The inert frequency-free powder method can be used singly or in combination of two or more. The inert inorganic salt powder is added in a range of from 〇 to 10.0 by weight, more preferably from 10% by weight to 4. After the surface cross-linking agent coating treatment, the cross-linking reaction is performed uniformly and rapidly on the surface cross-linked ship by 9 (rc s 23 (r s rc range), and the P-parent is backed up for parenthood. The reaction achieves the effect of the invention. The heat treatment temperature is 9 〇. 〇 = the lower parent reaction time is too long, and has no economic benefit, the heat treatment temperature is 23 〇. The above-mentioned tree 曰 is easily deteriorated to affect the quality, and the heat treatment time is 2 minutes to 150 minutes. It is advisable to adjust the heat treatment temperature according to the surface treatment effect of the slave, and the heat treatment temperature is high. 23 1275596 The heat treatment time is short, and when the heat treatment temperature is low, the heat treatment temperature is long. The present invention uses a common dryer or furnace. The step of heat treatment can be completed. The principle of the invention is: the riding type mixing dryer, the drum drying H, the table top H, the fluidized bed dryer, the airflow dryer and the infrared dryer. • > After surface cross-linking heat treatment, water-insoluble fine powder is added to the superabsorbent resin, and the anti-caking treatment is carried out in order to increase the surface of the superabsorbent resin, so that the high-suction grease is sucked. There are still high-flow chicks; the method of adding forest-soluble micropowder is straight 'fine-added', and the solubility of the forest is microscopically recorded on the surface of Gaocai resin; the water-insoluble micropowder includes sulfuric acid, sulfuric acid, oxidation side '_, Wei Wei, Soft soil, clay, talcum powder:: soil, bentonite, activated carbon, dioxo, titanium dioxide inorganic salt powder, and organic powder of the end, poly (tetra) ethyl (tetra) chloroethylene, polystyrene. Water insoluble Micro-shot, the county plus no bell powder effect is better, and the use of Yi machine ^ end can be used alone or combined two _ on the mix. Water insoluble plus Fan Mi Mei _ money (four), more quantifiable [==. The particle size of the water-insoluble fine powder is preferably not more than 1. The surface, the more appropriate size is 0.6 mm or less. The above-mentioned sticky money is a plurality of series such as: glycerin or red-touch amine. __Touch_read two=/ Mixing the above 12 1275596. The appropriate amount of additives for the adhesive is between weight percentage to (7) (based on the total H content of the reactants), and more preferably between 5 and 5% by weight of the adhesive additive. Under the following conditions, the inertia salt powder cannot be recorded in the high water absorption Silk, and when the adhesion age is more than 10% by weight, the superabsorbent resin has too low water absorption and lowers the performance of the resin. The liquid/water absorption ratio of the superabsorbent resin of the present invention is shown in the present invention. Absorption weight (M force load · ' 2 〇 g / em 2 and Qing ― to measure, absorbed by the ink, according to the method described in the European page, the seventh page towel of the A Lai book; the initial weight of the high water absorption The resin is placed in a cylinder according to the bottom of the shaft, and the powder is subjected to 2〇_2 and 49g/em2, and then the cylinder is placed on the absorption n 2 to make the superabsorbent resin absorb & The % sodium chloride aqueous solution - hour' will be measured by the water absorption weight divided by the weight of the superabsorbent resin, that is, the pressure absorption weight value. The retention force of the present invention is determined by the tea bag test method, and the knot is measured in five times, and the average value and the lowest value are taken, and the average value is taken; G.2g of the super absorbent resin is placed in the tea bag, and Wei Yu 〇 9% of NaC1 water test for 2G minutes, then put the b after the bubble is placed in the centrifuge towel away ^ (diameter, speed (four) m) #刀知, weigh. The obtained value is first obtained by subtracting the weight of the blank group tea bag which is not filled with the super absorbent resin (to be synchronized) and then removing the weight of the composition to obtain the retention value. The determination of the low residual monomer was carried out by liquid chromatography. First, 0.500 g of 25 1275596 冋 water-absorbent resin was placed in a 15 〇 cc flask, and 〇·524% Naa aqueous solution ι〇% and 2 cm were added. One stirrer, stir at 5 (8) printing (five) speed for one hour, add 5 g of 20% Al2(SO4)3 aqueous solution, and then use 2 AI filter, paper filtration, and sputum into liquid chromatograph for analysis. The signal is compared to the calibration curve to obtain the amount of residual monomer. The working examples are listed in detail below to illustrate the invention; however, the scope of the invention is not fully represented by these examples. Example 1: 1) Take 48g of 48% sodium hydroxide solution and 1〇69 2g of water in a 4〇〇〇cc conical flask, slowly add 330g of acrylic acid, and the ratio of sodium bismuth oxide/acrylic acid is in the range of 衫. • Within 95 limits, and maintain the temperature of the neutralization reaction system in the bottle at 4 〇. 〇, after neutralization, the water-soluble unsaturated monomer has a pH of 12.6. After standing for 5 minutes, 660 g of acrylic acid is added to the partially neutralized water-soluble unsaturated monomer to completely neutralize the water-soluble unsaturated single. The pH value of the body is 5.6, and a water-soluble unsaturated monomer concentration of 42 wt% aqueous solution is obtained, wherein 70 mol% (mole ratio) of the acrylic acid is partially neutralized to acrylic acid 2) and then 1.518 g of n, N,-decyl group is added. The bis acrylamide is in the water-soluble unsaturated monomer solution' and maintains the temperature at about 2 °C. 3) 0.528 g of hydrogen peroxide, 6.62 g of sodium hydrogen sulfite and 6.62 g of ammonium persulfate were added to initiate the reaction. 26 1275596 4) The gel after the reaction was chopped by a cutter mill, and a gel having a particle size of 2 mm or less was selected. 5) Dry the 2 small day shovel with 130 C. Use the screen to screen the Q imm~〇 fixed particle size to obtain a powdery superabsorbent resin. 6) Weigh this super absorbent resin i〇〇g, add aluminum sulfate powder lg, and mix it evenly, then add ethylene glycol carbonate: water: methanol = 1:1:1 (weight ratio) solution 3.6g, Heat treatment at 215 ° C for 1 Torr. 7) After cooling, weigh 5 〇g of this 咼 water-absorbent resin, add 0.5 g of water-insoluble fine powder magnesium oxide powder, and mix it evenly and then add polyethyleneimine: water = 1:3 (weight ratio) solution 6 g ' Anti-caking treatment is carried out, that is, the south performance water-absorbent resin is obtained, and the retention is 29.42 g/g, the water absorption ratio is 28.69 g/g under the pressure of 20 g/cm2, and the water absorption ratio is 17.34 g/g under the pressure of 49 g/cm2, and the residual sheet is The body is 16.3 ppm. Example 2: Repeat Example 1, but the neutralization method firstly uses a mixed aqueous solution of 48% sodium bismuth oxide aqueous solution 802g and 1069.2g water, and then adds 200g of acrylic acid, and keeps the temperature of the neutralization reaction system in the bottle at 40 ° C. The mixture was thoroughly mixed and allowed to stand for 5 minutes, at which time the pH of the water-soluble unsaturated monomer was 13.3, and 790 g of acrylic acid was further added. The rest of the same example was obtained as a highly water-absorptive resin with a retention of 29.52 g/g, a water absorption ratio of 29.41 g/g under a pressure of 20 g/cm2, a water absorption ratio of 17.89 g/g under a pressure of 49 g/cm2, and a residual monomer of 12·4ρριη. 〇27 !275596 Example 3: Repeat example 1, but let it sit for 6 minutes after a neutralization. The same as the first example, the known water-absorbent resin, the measured retention force was 29 22 g / g, the water absorption rate under the pressure of 2 〇 g / cm 2 29.1 〇 g / g, the water absorption ratio under the pressure of 49 g / cm 2 17.84 g / g, residual monomer 12·1ρριη 〇 Example 4: Repeat example 1, but the neutralization method is first mixed with 33〇g acrylic acid and 1069e2g water, then add 8〇2g of 48% sodium hydroxide solution, and mix well and set for 5 minutes. 'And keep the temperature of the neutralization reaction system inside the bottle at 4 〇. 〇 At this time, the pH of the water-soluble steeply unsaturated monomer was 12.6, and 660 g of acrylic acid was added. The rest of the same example - 'a superabsorbent resin can be obtained, the retention is 29.13g / g, the water absorption ratio under the pressure of 20g / cm2 28 / 74g / g, the water absorption ratio under the pressure of 49g / cm2 I6.81g / g, residual monomer L9.7ppm. Example 5: Repeat Example 1, but the neutralization method first uses 330g of acrylic acid in a 4000cx conical flask, and keeps the temperature of the neutralization reaction system in the bottle at 4 °C, and then adds 48% sodium hydroxide solution 802g and 1069.2. a mixed aqueous solution of g water, to be thoroughly mixed and allowed to stand for 5 minutes, and keep the temperature of the neutralization reaction system in the bottle at 40 ° C, at which time the water soluble 28 1275596 = not more than the monomer pH value of U.6, and then _g acrylic plus people. The rest of the same example - the superabsorbent resin was obtained, the retention was 29. ng / g, the water absorption ratio under the pressure of 20 g / cm 2 29.06 g / g ' 49 g / cm 2 under the ink absorption ratio of 16.33 g / g, residual monomer 17.9 Ppm. Example 6: Repeatedly--, but add water-insoluble micropowder to sulfuric acid Ming powder lg. The rest of the same example - 'to obtain a highly water-absorptive resin, the retention is 28.llg / g, the water absorption rate under the pressure of 20g / cm2 28.15g / g, the water absorption ratio under the pressure of 49g / cm2 16 73g / g, the residual monomer 21.3ppm . The comparison example and the first one are used as objects of the first to sixth comparisons to highlight the effects of the present invention. Comparative Example 1: Repeated Example 1, except that 48% aqueous sodium hydroxide solution g〇2g and i〇69.2g water were thoroughly mixed, then 990g of acrylic acid was added, and the pH value of the water-soluble unsaturated monomer was obtained. It is 5.8. The same as in the first example, a highly water-absorptive resin was obtained, and the retention was 27.61 g/g, the water absorption ratio under a pressure of 20 g/cm2 was 25.32 g/g, the water absorption ratio under a pressure of 49 g/cm2 was 14.53 g/g, and the residual monomer was 183.6 ppm. Comparative Example 2: 29 1275596 ^ Repeat Example 1, but add 660g of acrylic acid directly after neutralization, without standing. The same as the first example, the superabsorbent resin was obtained, and the retention was determined to be 25.04 g/g, and the water absorption ratio under the pressure of 2〇g/cm2 was _%. Chi, and the water absorption ratio under the force of 49-2 was 13.59 g/g 'Residual monomer 2〇6 7ppm. • This method of Ming can provide - powdery, insoluble in water, absorbs water or urine and blood. 'has not stored in fresh, high-heavy, and has a higher Lili•τ A high-performance superabsorbent resin having a high absorption rate characteristic - a high water absorption property produced by the present bribe - has a low residual monomer content, so that the safety in use can be improved, and the high absorption by the present invention can be achieved. The water-based resin will be more suitable for various types of sanitary products, water-absorbing agents for agricultural and food preservation. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Therefore, the scope of patent protection of the present invention is defined by the scope of the patent application attached to the specification. 30