TW399062B - Process for producing superabsorbent polymer - Google Patents

Abstract

A method of producing the superabsorbent polymer powder insoluble in water, having low residual acrylic monomers, high absorbability and improved absorption under pressure when absorbing aqueous solutions and body fluids, wherein the method comprises the steps of: (a) polymerizing a solution containing cross-linking agents, free radical polymerized cross-linking agents, 0 to 5 wt% water-soluble polymers and at least 50 mole% neutralization of the carboxylic-containing monomers such as acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid of their complexes, (b) drying at temperature ranging from 100 DEG C to 155 DEG C, grinding and sizing, (c) coating the surface with crosslinking agents, (d) reacting the polymer with the surface crosslinking agents at temperature ranging from 155 DEG C to 230 DEG C, The crosslinking agents described in step (a) can either undergo crosslinking reactions when heated at step (d).

Description

V. Description of Invention ............................ ................................. ................................................... The invention relates to a super absorbent resin and a method for manufacturing the same. In particular, it is a water-absorbent resin with a small amount of residual monomers, high holding power and absorption under high pressure, and a method for producing the same. Super water-absorbent resin has strong water retention ability, can absorb water 100 times or even 1000 times its own weight, and can swell after absorbing water and maintain a non-flowing state, even if pressure is applied, it will not leak. Slowly released in the atmosphere. Due to the above characteristics, it was the first soil water-retaining agent used in agriculture and forestry. In recent years, due to the considerable progress in the production technology of super absorbent resins, it has also been widely used in sanitary products such as diapers, adult incontinence products and women's hygiene. Water absorbing agent for articles and fresh-keeping application for preserving food. The superabsorbent resin contains water-decomposable hydrolyzed starchacrylonitrile graft polymer (Japanese Patent Laid-Open Publication Sho 49 (1 974) -43,395), and neutralized starch acrylic polymer (Japan Patent Publication Gazette Sho 5 1 (197 6)-1 2 5,4 6 8), Saponified Ethyl Acetate • Propyl Ester Copolymer (Japanese Patent Gazette Sho 52 (1 977) -1 4, 689), Hydrolyzed propylene copolymer or acrylamide copolymer (Japanese Patent Publication Sho 53 (1 978) -1 5, 959), and partially neutralized polyacrylic acid (Japanese Patent Publication Sho 55 (1 980) -84, 304 )Wait. Among them, the superabsorbent resin obtained by cross-linking polymerization using acrylic acid and acrylate is the most economical. The reason is that acrylic acid can be quickly obtained from the market and the superabsorbent resin produced has a high water absorption capacity. And it has the lowest manufacturing cost and the most economic benefits, so it has become the most common super absorbent resin.

V. Description of the invention (2) The method of polymerizing acrylic acid and acrylate to form a super absorbent resin has been successfully developed in many ways, and has been used in industrial production, and its polymerization method includes cast film polymerization (Japanese Patent Publication Showa 48 (1973) -42, 466), polymerization is carried out on a conveyor belt (Japanese Patent Publication No. Showa 58 (1 983) -49, 714), and the kneading base of the pulverized stirring blade is subjected to polymerization (Japanese Patent Publication No. Showa 57 (1982) -34,101), performing reverse suspension polymerization reaction (Japanese Patent Publication No. Showa 59 (1 984) -37, 〇03)) or spraying or coating monomers on a cellulose substrate for polymerization Reaction (Japanese Patent Publication Showa 62 (1 987) -53, 309). The produced polyacrylic acid-based superabsorbent resin is used in sanitary products or food preservation. It may be in direct contact with the human body and food. The lower the residue, the soap body will be available, and the safety record of Shengli i will be required. Reducing the amount of residual monomers has become a trend. , * Μ ί ί I monomer residues of the same water-absorbent resin *, there have been many methods V :: adding ammonia and amines (Japanese patent publication Showa), and adding sulfites; = Kai Showa 50 (1 975) ~ 4 °, No. 689 and U0U55) t = gas salt (U.S. Patent 2,960,486 solution type and pyrolysis type W: (low-yield residual body mainly uses low-temperature separation and combined use of redox primers) Publication of Showa 53 (〖978) -141, ⑽8) 50 (1 975) -96, 689 and Mimo Nao '(Japanese Patent Publication Showa ^, jc a ^ ^ 4 / Λ3, ί 73,263 ^ 5 ^ ^ Dan- People polymerize and reduce the residual flow of monomers

V. Description of the invention (3) ................. ........................................ ................. low, also use microbial decomposition Resolving residual monomers, non-humiliating, 1 Showa 60 (1 98 5) -29, 523) and re-entry using steam preheating method "A. Japanese Patent Publication Showa 62 (1 987) -1 04, 764 ) And ^ __ Auntie (reduction purpose. &Amp; Machine heavy addition of ammonia, amines, sulfites, effective to reduce the residual strict T dry content of ginseng, but will cause a reduction in water absorption, if the amount added Insufficient effect on reducing the body is very limited; In addition, 'using ammonia, amines, and sulfites in aqueous solution' will cause human damage and pollution due to contact with the body. The method of using initiators, only Can reduce the monomers on the colloidal surface: monomers, but the residual monomers inside the colloid are ineffective and will consume: the cost of; the method of relying on microbial decomposition of monomers will be unfavorable because the cost is too high and the consumption = too long Application in process; ^ method using steam preheating and drying, It has the disadvantages of tedious manufacturing process, difficult control and high damage to on-site equipment. + Water-absorbent resin is used in sanitary products such as baby diapers, adult diapers, women's hygiene products, etc. In the early days, only the ability to absorb liquids was required, but = soon It was later discovered that it is not only the amount of liquid that is absorbed, but also the water absorption ^ It is as important as the absorptivity under pressure, because when the resin has insufficient absorption under pressure, the resin becomes incapable of being stressed (such as the load on the body). Disperses and absorbs liquid, so the special absorption under pressure load becomes an important performance index.% At the same time, for environmental protection (reduction of waste), aesthetics, cost and other factors, shrinking 1. The size and thickness of sanitary products have become a trend. The only way to meet this trend is to reduce the bulk of fluffy pulp in the diaper and increase the water absorption tree

Page 8 V. Description of the invention (4) .............. ........ '' '' The amount of fat used at this time was originally replaced by the expensive liquid transfer wheel of fluffy pulp, which cannot be replaced by traditional water-absorbent resin, so new: high: ^ water-absorbent The tree can be replaced. " One of the objects of the present invention is to provide a high-performance water-absorbing tree shrew with high holding power and high absorption speed under pressure, making it suitable for ultra-thin applications of sanitary products. The water-absorbent resin is an insoluble hydrophilic polymer with a uniform bridging structure inside the resin. Generally, in order to improve the quality, such as: increase the absorption rate, increase the strength of the cross-section, improve the blocking resistance, liquid permeability, etc., Further bridge the resin surface. This surface cross-linking treatment uses a polyfunctional cross-linking agent that can react with acid groups. Many patents have been proposed before; such as: dispersing super absorbent resin and cross-linking agent. Surface cross-linking treatment in organic solvents (4-56-1 31 608,]?-Person ~ 57-44627, ??? 1 " 58-42602, JP-A-58-117222) using inorganic powder The cross-linking agent and the cross-linking agent solution are directly mixed into the super absorbent resin treatment (JPH0 — 1 63596, Jp_ A-60-2558 1 4), and the cross-linking agent is added and then treated with steam (JP-A-1-113406) '' Surface treatment with organic solvents, water, and polyols (JP-A-63-270741, jp — A —64-50707, JP-A ~ 1 -2920〇4) using organic rolls, water, _ (ether) compounds (Jp — a-2-153903), etc. Although these surface treatment methods can increase the absorption rate and increase the water absorption under pressure 'But will result in the holding force drops too much adverse consequences, reduce the performance of the practical application. The object of the present invention is to provide a powdery, insoluble in water, which can absorb water or urine and blood ’has low residual unreacted monomer, high retention and high

V. Description of Invention ........................................ .........-...................................... .........................................., high performance of water absorption rate under force Water-absorbent resin, prepared by method 1, which at least includes: (1) the following 4 methods (a) containing a crosslinking agent and a radical polymerization reaction crosslinking agent%) above the aqueous solution containing an acid group monomer free ( Molar acid-based monomers can be selected from acrylic acid, dimerized alpha reaction, containing amine-2-methylpropanesulfonic acid, or a mixture thereof, and propylene ~ 5 wt% water-soluble polymer. Each solution of early vessel water contains 0 == The temperature is 100. (: to 155. (: hot air drying, powder (c) surface cross-linking agent coating treatment. Pan division (d) temperature 155 ° C to 23 (TC heating surface treatment. A) cross-linking The agent can be cross-linked in the step (addition.), Depending on the characteristics described above. It is a cross-linking agent that is added before polymerization to perform a cross-linking reaction, and can be absorbed under high pressure during low-temperature heat treatment. Amount of super absorbent resin. The superabsorbent resin with low residual water absorption rate and low water absorption rate manufactured by the present invention :: 3 force and high roofing force characteristics, so the safety in use can be improved = quantitative :::: water absorption rate characteristics under force '$ 能Improve this superabsorbent resin: the superabsorbent resin obtained by the present invention will be more suitable; / type absorbent for sanitary products, agricultural and food preservation. ^ Contains the superabsorbent resin required by the invention In addition to propylene. Acid-based monomers, other water-soluble monomers with unsaturated double bonds can be used, such as: methacrylic acid, maleic acid, fumaric acid, 2-propenylamine-2 monomethylpropane

5. Description of the invention (6) Tank acid. There are no specific restrictions on the choice of monomers. Only one kind can be used, and multiple monomers can be used together. If necessary, other hydrophilic monomers with unsaturated double bonds can be added, such as acrylamide, methacrylamide, and acrylic acid. 2-Nicotinylethyl_, 2-Hydroxyethyl Methacrylate, Methyl Acrylate, Ethyl Acetate, Dimethylamine, Propylene Acrylate, Vaporized Acrylic Acid, Acrylic Acid, Trimethylamine, but added in order not to destroy the high water absorption The physical properties of the resin are the principle. Prior to the radical polymerization reaction, the concentration of the monomer aqueous solution should be controlled between 20% by weight and 55% by weight, and the appropriate concentration is between 30% and 45% by weight. When the concentration is below 20% by weight, the hydrate after polymerization is too soft And it has viscosity and is not suitable for mechanical processing. If the concentration is more than 55% by weight, the concentration is close to the saturation concentration, which is difficult to adjust and the reaction is too fast. The reaction heat is not easy to control. The carboxylic acid group of the acid-containing monomer should be partially neutralized to control the PH value of the finished product to make it neutral or slightly acidic. The neutralizing agent is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium carbonate, sodium bicarbonate. , Hydrogen carbonate If and ammonia. The acid group-containing monomer is neutralized to form a sodium or potassium salt or an ammonium salt. When the ear percentage is less than 45mol%, the PΗ value of the finished product will be low. When the neutralization concentration Mohr percentage is more than 85mol%, the value of the finished product will be high. When the PΗ value of the finished product is not neutral or slightly acidic, They are not suitable for human contact and are not safe. In the monomer aqueous solution before the radical polymerization reaction, water-soluble polymers can also be added to reduce costs. Polypropylene V. Description of the invention (7) Polymers such as amines, powders, or powder-derived derivatives such as methyl cellulose; these waters are limited to 'the preferred water-soluble and highly saponified polyvinyl alcohol, etc., added alone or in combination The proper weight of the water-soluble polymer is preferably 10% by weight, and 0 to 5% by weight is particularly preferable, so that the physical properties are deteriorated. When performing radical polymerization reaction in unreacted monomer solution, use two or more unsaturated 2-propenyl) amines, N, N '~ methacrylamide, propyl methacrylate Glycol Diacrylate, Glycol Diyl Acrylate, Glycerin Triacrylic Acid, Ethylene Oxide, Tri-Dilute Acrylic Acid, Triethylene Glycol, Propyl Tripropene, Trimethacrylic Acid Tris (2-propenyl) amine, dipropylene & can also be used with more than two cycloglycidyl ethers, polyglycerol polyglycidyl, monoethylene glycol monoglyceride, triol polyglycidyl hydrazone, etc. The advanced resin has a proper degree of cross-linking while being processable. The molecular weight of free-radical polymerization cross-linked cellulose, acid methyl cellulose, and ethyl-soluble polymer is not special. The molecule is starch, partially saponified, or completely combined. The super absorbent resin contains the same percentage of 0 to 20% by weight. However, if the addition exceeds 20% by weight, the radical polymerization reaction should be added before adding the radical polymerization reaction. Compounds such as: N, N-bis (bisacrylamide, N, r-methine diester, ethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethyl ester, glycerol Trimethacrylate, glyceride or trimethacrylate, trimethacrylate or trimethacrylate, trimethylolpropane triacrylate, N, N, N-ethylene glycol ester, dipropylene triethylene glycol Esters and other oxy compounds, such as sorbitol polyglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol diglycidyl, and dipropylene glycol radical reaction can make the superabsorbent resin and the superabsorbent resin colloid suitable. Can be used alone or in combination of two or more

Page 12 V. Description of the invention (8) ................. ........................................ .................................. Used together. The appropriate addition amount of the free-radical polymerization cross-linking agent is between 0.001 wt% and 5 wt% (based on the total solid content of the reactant), and the more weight percentage is between 0.01 wt% and 3 wt%, ^ The added amount is less than 0.001 Wt%. After polymerization, the hydrate is too stiff and sticky. Mechanical processing is not effective. The added amount is 5wt% or more, and the water absorption is too low. The resin performance is reduced. A polymerization reaction starts with the decomposition of a radical polymerization initiator to generate free radicals. Free radical initiators can be selected from thermal decomposition type initiators.: Decomposition type initiators include peroxides, such as: hydrogen peroxide, dioxides, ammonium peroxide, or persulfates (ammonium salts, alkali metals). Salts), etc., and azo compounds such as: 2.2, -azobis (2-crylpropane) dihydrochloride, 2'2'-azobis ((N, N-dimethylidene) Ding) dihydrochloride; reducing agents can also be used to make emulsification-reducing initiators, such as: acid sulfites, thiosulfates, ascorbic acid or ferrous salts; or redox starting, and The thermal decomposition type initiators are used in combination. First, the advanced reaction of the redox initiators generates free radicals. When the free radicals are transferred to the monomer, the polymerization reaction is initiated. When the temperature reaches the decomposition temperature of the thermal decomposition-type initiator, the decomposition of the f-stage thermal decomposition-type initiator is initiated, and the entire polymerization reaction is completed. Lwt% 至 5wt Generally suitable amount of free radical polymerization initiator is weight, the knife ratio is 0, OOlwt% to i0wt% (based on the neutralization of acrylate weight) If the weight percentage is less than or equal to wt%, the reaction is too slow, which is unfavorable for economic benefits. When the weight percentage is greater than w U, the reaction is too fast and the heat of reaction is not easy to control.

Page 13 V. Description of Invention ............................ .......---............................ .................................................. ........................................ ........................................ ...... > W ^ According to the present invention, it can be simultaneously reversed when it can be surface-treated; & ίΛ Father Union Sword can be helmeted; ^-给 ,, ten_ heart-specific diol if many? Alcohols such as glycerol, ethylene glycol ... diols, triethyl ethane-ferment, propylene glycol, I 4 butanediol, trihydrocarbylmethanine. Sorbitol, etc .; or polyamines such as: ethylenediamine, di, dipropyl, polyethylene diamine; or compounds with two or two such as: oxygen ^ such as: sorbitol polyglycidyl ether = Oil yell, ethylene glycol diglycidyl ether, diethylene glycol: water-supply water glycerol ^ 〇-drunk fine glycerol, alcohol monomethyl glyceryl ether, diglycerol polyglycidyl ether, etc .; Hydrocarbon esters such as: ethylene glycol carbonate, 4-methyl 3-dioxane m ... yl-u dioxolane_2 also 4 = 1,3-dioxolane-2_one , 丨, 3-dioxane-, 4 / -dimethyl-1 ^ -dioxane_2_one or ι > 3-dioxan-2-one, and the like. The crosslinker can be used alone or in combination of two or more. The appropriate addition amount of the cross-linking agent is between 0.00% and 10% by weight (based on the total solid content of the reactant), and more suitably between 0.005wt% and 5wt%. When the added amount is less than 0.01% by weight, the effect cannot be exhibited. When the added amount of the crosslinking agent is more than 1% by weight, the water absorption is too low, which reduces the resin performance. The polymerization reaction can be carried out in a traditional batch reaction container or on a conveyor belt reactor. The super absorbent resin obtained by the reaction is first cut into small gels with a diameter of 20 mm or less and a diameter of 10 or less by using a machine. = OK to dry. Go to Ran Drying temperature is 100 ° C. (: To 155. (;: Drying is appropriate, drying temperature below 100 ° C is too long, not economical, drying temperature / degree)

Page 14 V. Description of the invention (10) ......... ........................................ ........................................ ........................................ ........................................ ................................................. ........-…-“… — Drying above C allows the cross-linking agent to perform the crosslinking reaction early, and loses the effect of virtue === reaction, and can not achieve low residual at the same time I: keep it between ^ and 咼The effect of water absorption rate under pressure. Sub-soap body, smashed after drying, screening fixed particle size, coating. Screening fixed particle size is increased by one to = residual: particles with a particle size of 1.00 or more make the water absorption rate of the finished product slow.叩 Dust can be used as ethylene dihydrocarbyl Λ ^ ® ^ ^ Γ and then applied to the surface. Parental crosslinking agent coating treatment. The surface crosslinking agent can be a polyhydric alcohol such as glycerin. Triethylene glycol, polyethylene glycol, Propylene glycol, "ί:;: A: Propylene sorbitol, etc .; or you can use polyamines such as: di-month female, diethylene diamine, poly 7-epoxy compounds such as Can be used with two or two to shrink ..., ethylene glycol dihydrate glycerol, polyglycerol polyether, polyethylene glycol dimer glycidol'-ethylene glycol monoglycidyl, · glycerine carbonate can also be used Polyglycidyl hydrazone dioxolane-2—_ ,: V alcohol carbonate, [methyl], 3-, 4,4-dimethyl—], 3-dioxodi-5-1, 3 Dioxol-2-oneoxetane-2-one, ketone, 4-ethyl-13-di-1,3-dioxane_2 ~ 蜩 or ^ ', ring The use of —hexane-2-ketone, 4, 6-dimethyl surface cross-linking agent can be monooxan-2-one and the like. Suitable additives for the cross-linking agent at the surface are used, or two or more are used in combination. Table 10 wt% (to the total solids of the reactant = 0.00% wt% to 0.05 wt% to 5wt%, as a benchmark), a more appropriate amount of cross-linking agent on the surface The added dosage is in weight five. Description of the invention (11) .............. .—.—......................................- '— .. ....... -............................................ ---................................................ ......., 'The effect cannot be exhibited when the percentage is less than 0.001 wt%' When the weight of the crosslinker additive at the surface is above 0 wt%, the water absorption Too low, low energy. Λ said surface cross-linking agent straight surface cross-linking such as methanol, special limited surface cross-linking agent to help the solution, or oxidized silicon oxide than 0.05% by weight treatment, so that during the cross-linking cross-linking reaction, the fat is easily degraded. Retention power and agent, hygienic water agent and Baowei machine are not good. At the end of the table, it is better to use the oxidized stone name and two ratios. C. When heating the coupling agent into the following trees, it is better to apply the coating treatment of the parent body, high soil water-retaining product, the surface crosslinking agent can be added or the surface crosslinking agent solution can be added, and the agent is hydrophilic. Adding an organic solvent aqueous solution, hydrophilicity can be ethanol, propanol, isobutanol, acetone, methyl ether, ether, can be formed into a solution, in which methanol and ethanol can be added to the water-absorbing resin to disperse the inert inorganic salt powder to disperse The inert inorganic salt powder may be aluminum sulfate, Erming or magnesium oxide, or a mixture thereof. Among them, sulfuric acid is a good-purifying inorganic salt powder, and the addition range is between 100% by weight and 0.001% by weight, and 001% to 40% by surface cross-linking agent after coating treatment, and then 155 to 230. The surface cross-linking agent can perform a cross-linking reaction and internally interact to achieve the effect of the present invention. The processing temperature of 1 55 ° c is too long, and it is not economical. The processing temperature is 230 3 grades! The processing time is from 2 minutes to 150 minutes: the temperature is still short and the temperature is low for a long time. Ancient :: The super absorbent resin has a low residual unreacted single water rate, and is suitable for the preservation of agricultural and forestry soils, adult incontinence products, and women's hygiene. Shows the water absorption rate under pressure of the super absorbent resin of the present invention.

V. Description of the invention (12) ................. ........................................ ........................................ ........................................ .....................-, it means that the pressure absorbs the weight (pressure load: 2 〇g / cirf & 49g / crrf) to measure tritium, and the double pressure absorption is determined according to the method described on page 7 of European Patent No. 0339461A specification; the initial weight of the superabsorbent resin is placed in Yi, with a sieve In the cylinder at the bottom of the net, apply 20g / c m2 and 49§ / c πί to the powder, and then press the cylinder on the absorbent demand tester to allow the water-absorbent resin to absorb q. 9%. Sodium chloride aqueous solution for one hour, and then reset the water absorption j to divide the obtained value by the weight of the super absorbent resin, and press the absorption value. The holding force of the present invention is measured by a tea bag test method, and an average value of five times is used. The superabsorbent resin of 0.2 g is packed in a tea bag, and is dissolved in a 0.9% NaCl aqueous solution for 20 minutes. The soaked tea bag was centrifuged in a centrifuge (23 cm in diameter and 140 ° rpm) for three minutes and then weighed. The calculated value is obtained by subtracting the weight of the blank tea bag without filling the super absorbent resin (in the same procedure), and then dividing by the polymer weight to obtain the retention value. The determination of low-residual monomer was analyzed by liquid chromatography. First, weigh 0.50 g of water-absorbent resin in a 150 cc Erlenmeyer flask, add 0.524% NaCl, 100 g of cereal, and 2 cm of Add one spice and stir for one hour at 500 rpm. Add 5 g of 2HA1 SO aqueous solution, and then filter it with 2um filter paper. Put the filtrate into a liquid chromatograph for analysis. Compare the obtained signal with the calibration curve. The amount of residual monomer can be obtained. Reference working examples are listed in detail below to illustrate the present invention; however, the scope of the present invention is not limited by these examples. Example 1: A UWOc.c Erlenmeyer flask was charged with 30 g of acrylic acid and 32,4 g of water;

Page 17 V. Description of the invention (13) 1 0 0c. C Weigh a 24.3 g 48% sodium hydroxide aqueous solution in a conical flask, and slowly add the sodium hydroxide aqueous solution to the acrylic acid aqueous solution under ice cooling to neutralize it; at this time An aqueous solution with a monomer concentration of 42 wt% was obtained, in which 70 moU (mole ratio) of acrylic acid was partially neutralized to sodium propionate. 2) Add 0.03 g of N, N'-methacrylamide and 0.046 g of polyethylene glycol diglycidyl ether (η di 9) in a partially neutralized acrylic acid solution 'and maintain the temperature at 20 . (: Left and right. 3) 0.016 g of L-ascorbic acid, 0.2 g of sodium persulfate and 0.2 g of 2.2-azobis (2-ylpropane) dihydrochloride were added to initiate the reaction. 4) After the reaction, the super absorbent resin is cut into a gel having a diameter of 2 minutes or less by a cutter mill. 5) drying at a temperature of 130 ° C for 2 hours; screening with a sieve of 0.1 to 0.85 mm fixed particle diameter to obtain a powdery superabsorbent resin. 6) Weigh out 10g of this super absorbent resin, add ethylene glycol carbonate / water / methanol = 1/1/1 (weight ratio) solution 0.4g, and heat-treat at a temperature of 21 ° C for 10 minutes. After cooling, a high-performance superabsorbent resin was obtained. The measured retention was 34g / g, the water absorption rate under the pressure of 20g / Crrf was 30.5§ / §, and the water absorption rate under the pressure of '49g / cjrf was 20g / g.' Residual monomer 70 ppm. Comparative example one: Example 1 is repeated, but step 2) is changed to use 0.05 mg NN, _ = melamine, without addition of polyethylene glycol diglycidyl. U = 9), which is the same as example 1, A super absorbent resin was obtained, and the measured retention was 29 g / g, 20 g / g

V. Description of the invention (14) Water absorption ratio under 49 g / c iri pressure 15 § / § cm2 Water absorption ratio under this pressure to 450 ppm of residual monomer. Comparative example two: JH, but step 5) was changed to i8 (rc drying, the rest is the same as the example-, coax = «water-based resin, measurement retention is 26 · 3g / g, 2 water absorption rate 26g / g, 49g / cnfs m Lower body 6 50ppm. Hair knife absorbs water by 16g / g, and the remaining list is Example 2: 30.02 acrylic acid is added to the iMOOc.c conical flask; 48% sodium hydroxide solution 26.0g & is added to the 100cc conical flask. 36.2 g of water, slowly add acrylic acid to an aqueous solution of sodium hydroxide under ice cooling, and then; at this time, obtain a 40% by weight aqueous solution of monomer concentration, of which? 5 moi% (molar ratio) acrylic acid is partially neutralized It is sodium acrylate. 2) Add 0.035 g of trimethylolpropane triacrylic acid and 0.8 g of polyethylene glycol 300 in a partially neutralized acrylic acid solution, and maintain the temperature at about "^. 3) Add 0 016g L-ascorbic acid, 0.2% sodium persulfate and 0.2g 2 2-azobis (2-amidinopropane) dihydrochloride to initiate the reaction. 4) This super absorbent resin was used after the reaction. Lmm〜 0.85mm 固 粒。 Cut powder ^ machine cut into gels with a diameter of less than 2mm. 5) Dry at 130 ° C for 2 hours; use a sieve to screen 0.1 mm ~ 0.85mm fixed particles To give powdered superabsorbent polymer. 6) to take this still-scale water-absorbent resin 10g 'addition of glycerol / water = 1 / Shu (wt.

Page 19 V. Description of Invention (15) .............. ........................................ ........................................ .......-............. ratio) solution 0.35g, heating at 20 (TC temperature) After processing for 45 minutes, after cooling, a high-performance super absorbent resin was obtained. The retention force was 38 g / g, the water absorption rate under pressure of 20 g / CIrf was 31 g / g, 49 g / crf, the water absorption rate under force was 18 g / g, and the residual monomer 9 〇ρριη Comparative Example 3: Repeat Example 2, but step 2) was changed to improve the use of 0.05g trimethylolpropane diacrylate and no polyethylene glycol 300, the rest is the same as in Example 2, get == For water-based resins, the measured retention was 27 g / g, water absorption under 20 g / crrf pressure 彳 2 7 g / g, water absorption ratio i 6 g / g under 49 g / c rri pressure, and residual monomer σ '' 550 ppm. Comparative Example 4: Example 2 was repeated, but step 6) was changed to heat treatment at a temperature of 2800 t. The rest was the same as in Example 2 to obtain a super absorbent resin. The measured holding force was 24 g / g. g, water absorption rate under 49g / cnf pressure 7 / 450ppm of residual monomer. Example three:

UlOOc.c conical flask was filled with 30,000 g of acrylic acid and 20.7 g of 2-acrylamine methylpropane sulfonic acid. In addition, 50 c.c beaker was added. ^ Polyvinyl alcohol and 14 g of water were added for dissolution; A 100cc conical flask was charged with 32.6g and 58.8g of 48% sodium hydroxide solution, and the polyvinyl alcohol aqueous solution was mixed with acrylic acid and 2-acrylamine-2-methylpropane under ice-cooling. • Add slowly to the sodium hydroxide aqueous solution for neutralization; at this time, the monomer concentration is 38% by weight and the acid is partially neutralized. 2) Add 0.035 g of N, N, N-tri- (2-propenyl) amine and 0.3 g of ethylenediamine

Page 20 V. Description of the invention (16) ......... .......-.............-............ ........................................ ...........--...................................... ........................................ ........................................ . Alcohol carbonates are around 0 ° C. And acrylic acid> valley, and maintaining the temperature at 203.) ^ 016.16 g of L-ascorbic acid, 0.02 g persulfide .. ^ propane) dihydrochloride to start the reaction. 4) After the reaction, the super-absorbent tender rape 丨 丨 Tian Dou, ',, M ci τ ^ ^ steep tree% is cut into a gel with a diameter of 2 mm or less using a cutting mill. 5) at 130 ° C Dry at temperature for 2 hours; sieve with a fixed mesh size of _ ~ 〇.85mm to obtain a powdery superabsorbent resin. 6) Weigh out 10g of this superabsorbent resin, add 0.15g of silica, and add Polyethylene glycol alcoholic acid ester / water = 1/1 (weight ratio) solution, heat-treated at a temperature of 60 ° C for 60 minutes. After cooling, a high-performance super-absorbent resin was obtained with a measurement retention of 33§ / g. Water absorption rate under pressure of 20 g / c 32 g / g, water absorption rate under pressure of 49 g / c 23 g / g, residual monomer 80 ppm. Comparative Example 5: Example 2 is repeated, but step 6) is changed to 1 4 〇 Heat treatment at ° C for 120 minutes, the rest is the same as in Example 3 to obtain a superabsorbent resin. The measured retention is 3, 20g / cirf, water absorption rate 18§ / §, 49g / crf pressure 7g / g, remaining Monomer 75ppm.

Claims (1)

........ it .................. 'ΑΑ »,, ....« Mody, u no 6. Scope of patent application1. A high performance and high water absorption 1. Tree version-unmanageable ^ None 'The method is as small as 4 Including the following steps: Acid-group-containing monomers with more than mol%) of water-soluble monomers / neutralization ratios of 50 (yes, where the acid-group-containing monomers may be selected from the group consisting of propyl, m, and acetic acid, or 2-propanamine-2-methyl two-burning continuation: acid = propylene monomer aqueous solution containing 0 to 5% by weight of water-soluble high content ^ Guang Qu · Mouthpiece '(b) the above reactant at a temperature of 100% 77 'Crush and sieve into powder;… air-dry, powder (c) apply the surface cross-linking agent coating treatment to the surface of the powder, and then apply: 155. (: To 23〇. (: Heating for surface treatment; obtain powdery and insoluble water-absorbing water or urine and blood and high-performance super absorbent tree with high retention and high water absorption rate under high pressure. Therefore, the cross-linking agent is a polyhydric alcohol or polyethylene or alkylene bicarbonate or a mixture thereof. In step (a) The cross-linking agent can be connected to the parent / 5 during the surface treatment in step (d), .14-six ^ ,, ι ^ '..., glycol diglycidyl ether 2. According to item 1 of the scope of patent application Manufacturing method, wherein the water-solubility is 3 · S: 5 enol, starch or starch derivative or a mixture thereof. * Zhongao & = manufacturing method of patent fanyuan item 1, wherein step (a) is the parent The addition ratio of the polyhydric alcohol of the cross-linking agent is between 0.05% and 5.0% by weight. Malari black 4. According to the manufacturing method of claim 1 in the patent scope, in step U) Page 22 `` 99062 VI. Patent Application Range ............... ........................................ ..... The added range of polyethylene glycol diglycidyl scale as the parent linker is between 0.05% by weight and 5.0% by weight. 5. The manufacturing method according to the scope of claim 1, wherein the addition range of the alkylene carbonate as the cross-linking agent in step (a) is 0.005 wt% to 5.0 wt%. 6. The manufacturing method according to claim 3, wherein the polyhydric alcohol is glycerol or polyethylene glycol. 7. The manufacturing method according to item 4 of the patent application range, wherein the polyethylene glycol has a molecular weight distribution range of 62 to 2000. 8-The manufacturing method according to item 5 of the application, wherein the alkylene carbonate may be a glycol carbonate. 9. The manufacturing method according to item 6 of the scope of patent application, wherein the polyethylene glycol diglycidyl ether has a molecular weight distribution ranging from 176 to 13,000. 10. The manufacturing method according to item 1 of the scope of patent application, wherein the neutralizer used in step (3) is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. One or more of them. 11. The manufacturing method according to item 1 of the scope of patent application, wherein the screening in step (b) has a particle size distribution ranging from 0.10 mm to 0.85 mm. 1 2. The manufacturing method according to item 1 of the scope of patent application, wherein the surface cross-linking agent used in step (c) is a polyol or a polyethylene glycol diglycidyl ether or an alkylene carbonate or a mixture thereof. 1 3. The manufacturing method according to item 2 of the scope of the patent application, wherein the surface crosslinking agent is added in a range of 0.05% by weight to 5.0% by weight. 14 4. The manufacturing method according to item 1 of the scope of patent application, wherein step (b) is a powder Page 23 6. After the patent application scope screening, in order to promote the dispersion of the solution when the surface crosslinking agent is adjusted to an aqueous solution, an inert inorganic salt powder is added, and then the surface crosslinking agent coating treatment in step (C) is applied, and the step ( d) Heated surface treatment. 1 5. The manufacturing method according to item 14 of the scope of patent application, wherein the inert inorganic salt powder may be aluminum sulfate or silicon dioxide. 16. The manufacturing method according to item 15 of the scope of patent application, wherein the inert inorganic salt powder may be aluminum sulfate or silicon dioxide, and the addition range is between 0.1% by weight and 4.0% by weight. 1 7. The high-performance and highly water-absorbent resin prepared by the method of the first item of the scope of patent application has low residual unreacted monomers and high retention power, and is suitable for agricultural and forestry soil water retaining agents, general and feminine hygiene products. Water absorbent, and water absorbent for food preservation. Page 24