TW396173B - Method of preparing superabsorbent polymer - Google Patents

Abstract

A method of preparing the superabsorbent polymer powder insoluble in water, having low residual monomers, high absorbability and improved absroption under pressure when absorbing urine, aqueous solutions and body fluids, wherein the method includes the steps of: (a) polymerizing a solution containing hydrophilic and long-chain epoxy compounds 5 to 10 wt% water-soluble polymers and at least 50 mole% neutralization of the carboxylic containing monoers such as acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid or their complexes, (b) drying at the temperature ranging from 100 degree C to 180 degree C, grinding and sizing, (c) coating the surface cross-linking agents, (d) reacting the polymer with the surface cross-linking agents at the temperature ranging from 90 degree C to 230 degree C. The hydrophilic and long-chain epoxy compound corresponds to the formula : R1-{0[CH(R3)CH(R3)0] y-R2} x wherein : R1 is independently in each occurrence a C2-10 straight or branch chain alkyl moiety; R2 is independently in each occurrence a C2-10 straight or branch chain epoxy group; R3 is independently in each occurrence hydrogen, methyl or ethyl; x is independently in each occurrence 2 or greater, where x is 2, y is 3 to 15; where x is 3 or greater, y is 3 to 33.

Description

V. Description of the invention α) The present invention relates to a super absorbent resin and a manufacturing method thereof. In particular, it is a water-absorbent resin having low residual unreacted monomers, high retention, and high absorption rate under pressure, and a method for producing the same. Super 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 state of flowing, even if pressure is applied, it will not leak, and the absorbed water can 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 resin, 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. Highly water-absorptive (hydrolyzed Lee Publication Gazette Polymer (Saponified Ethyl Acetate 52 (1977) -14, (Japanese Patent Glycolic Acid (Japan specifically obtains by using acrylic acid esters for the largest portion) and manufacturing costs Low-cost resin. The component material of the resin is a water-decomposable starch-acrylonitrile starchecrylonitrile) graft polymer (Japanese Patent 49 (1 974) -43,395), and the starch acrylic acid is connected to this patent publication Sho 5 1 ( 1 976)-1 25,468), propylene ester copolymers (Japanese Patent Laid-Open Publication Sho 689) 'hydrolyzed acrylic copolymers or acrylamide copolymers Sho 53 (1 978) -1 5,959), and partially neutralized Polyclinic Public Announcement Zhao 55 (1 980) -84,304) and so on. The superabsorbent tree obtained by cross-linking polymerization of straight and acrylic salts is also the most economical. The reason is that acrylic acid can be quickly sold from commercially available superabsorbent resins with high water absorption capacity, and has and has the most economic benefits, so Becoming the most universal superabsorbent

Page 7 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 various aspects, and a variety of methods have been used in industrial production. The polymerization method is cast film polymerization (Japan) Patent Bulletin Showa 48〇973) -4 2,4 6 6) 'Polymerization is carried out on a conveyor belt (Japanese Patent Publication No. Showa 58 (1983) -49,714)' (Japanese Patent Publication No. Showa 57 (1 982) -34, 1 0 1), performing reverse suspension polymerization reaction (Japanese Patent Publication No. Showa 59 (1 984) -37, 003), or spraying or coating the monomer on Polymerization is performed on the fiber substrate (Japanese Patent Publication No. 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. Lower residual monomers will improve the safety in use. Therefore, in recent years, it is required to reduce the residual Monomer residue has become a trend. In order to reduce the residual amount of monomers in superabsorbent resins, many methods have been developed, such as the addition of ammonia and amines (Japanese Patent Publication Showa 33 (1958) -2,646 and Japanese Patent Publication Showa 50 (1975) -40,689), and the addition of beneficial sulfate and bisulfite (U.S. Patent Nos. 2,96,486, and 4'306,9,55) to reduce the residual amount of monomers, and the use of low temperature decomposition and high temperature Decomposition type initiator (Japanese Patent Publication Showa 50 (197.5) -44'280, Japanese Patent Publication Showa 53 (1978) -141,388) and combined use of redox initiator (Japanese Patent Publication Showa 50 (1 975 ) -96, 689 and National Patent No. 3,5 7 3, 2 6 3), the monomers remaining on the surface of superabsorbent resin are polymerized again to reduce the residual amount of monomers, and microbial decomposition method is also used Decomposition of residual monomers (Japanese Patent Publication Showa 60 (1 985))

V. Description of the invention (3) I ----------- ...................-.............. (................................ 29,523) And using the steam preheating method to dry the Showa 62 (1 98 7) — 104, 764) to reduce the residual amount of monomers ^ Announcement of the addition of ammonia, amines, sulfites, to reduce residual monomers = of. It is effective, but it will cause a decrease in water absorption. If the amount is not enough, it will reduce the effect of 2 meshes. In addition, the use of ammonia, amines, and thionyl in: solution will cause contact with the human body and cause damage to the human body; ：： > 5 dyeing》 and using the initiator method, the monomers of the ring bonds, but the residual monomers inside the colloid are effective and the three-sided residual J ... It is beneficial to the process: body = = = ; = High :: The process is complicated and the control is difficult and the depreciation rate of field equipment damage is the method I :; "in providing a high-performance superabsorbent resin manufacturing method, which is based on a long chain of acid-based monomer aqueous solution. Plurality, = The crosslinker is used to crosslink to produce a highly absorbent resin. The father said that the present invention is to provide a powdery, water-insoluble, holding solution and Μ, and have # 低 残存Manufacture of unreacted monomer and high-guaranteed superabsorbent resin: high-performance method for absorbing rate characteristics, the method includes at least: a ^ acid-based monomer aqueous solution, the concentration of which is adjusted to 20wt% to 55wt % ， / 二 # The neutralizing agent will neutralize the carboxylic acid group in the monomer to make the neutralization concentrated. The degree is above 50 mol%; (b) f front f is added with an acid group-containing monomer aqueous solution, and a hydrophilic long chain 70 oxy compound is used as a polymerization reaction crosslinking agent to perform free radical polymerization ... ............. " .......................... (4) I .............................. ............ Combined reaction 'to obtain a super absorbent resin; (C) After drying the obtained resin at a temperature of loot to 180 ° C Pulverize and screen to fix the particle size; U) apply the coating treatment of surface cross-linking agent to the resin particles with fixed particle size to make the particle surface and even the inside cross-linking reaction; (e) the surface cross-linking agent The resin after the coating treatment is heated at a temperature of 90 ° C. (: The surface treatment is performed by heating to 230C to obtain a high-performance and highly water-absorbent resin. Among these, the acid-group-containing single system is selected from acrylic acid, methacrylic acid, linacic acid, One of maleic acid, 2-propenylamine-2-methylpropanesulfonic acid, = mixtures thereof, monomer aqueous solution containing 0 to 5% by weight of water-soluble polymer, the hydrophilicity of the crosslinking agent has long-chain characteristics Polyvalent epoxy compounds-{〇 [C H (R3) CH (Rjj) 〇] y one group, 卩 ^ / 1 composition is C2_1 ° linear or branched alkyl-functional alkyl radical or branched alkyl substituted ring 2 when the = = Methyl or ethyl; x can be greater than or equal to X Wy from 3 to 15, if x > 2 then the above characteristics are used before polymerization: 33: polyhydric epoxy compounds, and hydrophilic It is a highly water-absorbent resin with long-chain specialties. It has low residual monomers based on the polymerization reaction. The high water-absorbency produced by the water absorption obtained through the characteristics of the monomer content of the present invention is high, so that the resin can be more suitable for the resin. ， Because it has low residual safety, it can be used in various types of sanitary products

V. Description of the invention (5), absorbent for agriculture and food preservation. In addition to acrylic acid, the acid-containing monomer required for the superabsorbent resin manufactured by the present invention can also use other water-soluble monomers with unsaturated double bonds, such as: methacrylic acid, maleic acid, rich Maleic acid, 2 ~ acrylamine_2-methylpropanesulfonic acid, etc. 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-Nicotinyl ethyl vinegar, methacrylic acid 2-Nicotinyl ethyl ester, methyl acrylate, ethyl acrylate, dimethylamine propylene acrylamide, vaporized propylene acrylamine trimethylammonium but the amount is added so as not to destroy The physical properties of super absorbent resin are the principle. Before the radical polymerization reaction is performed, the concentration of the monomer aqueous solution should be controlled between 20% by weight and 55% by weight, and the appropriate concentration is 30% by weight and 45% by weight. When the concentration is below 20% by weight, the polymerization The post hydrate is too soft and viscous, and it is unfavorable for machining. The added concentration is more than weight percent, which is close to the saturation degree. It is not easy to mix and the reaction is too fast. The reaction heat is not easy to control. The acid-containing monomer should be partially neutralized to control the p Η value of the finished product, so that the neutralizing agent is neutral or slightly acidic. The neutralizing agent is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, hydrogen carbonate. Sodium, potassium bicarbonate and ammonia. The acid group of the acid-containing monomer neutralizes the sodium salt or potassium salt or ammonium salt. The neutralization mole ratio is 45inol% to 85mol%, preferably 50mol% to 75mol%. The neutralization concentration is molar. When the percentage is below 45mol%, the PH value of the finished product will be low. When the neutralization concentration Mohr percentage is above 85mol%, the PH value of the finished product will be high. When the pH value of the finished product is not neutral or slightly acidic, Not suitable for contact

5. Description of the invention (6) Unsafe. In the monomer aqueous solution before the radical polymerization reaction, water-soluble polymers can also be added to reduce costs. Such water-soluble polymers such as: partially saponified or fully saponified polyvinyl alcohol, polyethylene glycol, polyacrylic acid, Polyacrylamide, starch or starch derivatives such as polymers such as amyl cellulose, acrylic methyl cellulose, ethyl cellulose; etc .; the molecular weight of these water-soluble polymers is not particularly limited, and the preferred ones are high in water solubility The molecules are starch, partially saponified or fully saponified polyvinyl alcohol, etc., used alone or in combination. The appropriate weight percentage of super absorbent resin containing these added water-soluble polymers is 0 to 20% by weight, but preferably 0 to 10% by weight, especially 0 to 5% by weight. Adding more than 20% by weight will affect physical properties and change physical properties. difference. Before the radical polymerization reaction, a radical polymerization crosslinking agent should be added to the unreacted monomer solution. The radical polymerization crosslinking agent can be selected from compounds having two or more surplus and double bonds. For example: N, N -bis (2-propenyl) amine, N, N'-methinebispropenamide, N, N'-methinebismethacrylamide, acrylic acrylate, ethylene glycol Diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethyl acrylate, glycerol triacrylate, glycerol trimethyl acrylate, glycerin Triacrylate or trimethacrylate with ethylene oxide, trimethylolpropane Triacrylate or trimethacrylate with ethylene oxide 'trimethylolpropane trimethacrylate, trimethylolpropane triacrylate , Ν, Ν, Ν ~ tris (2-propenyl) amine, ethylene glycol diacrylate, dipropylene triethylene glycol ester, etc., or compounds having two or more epoxy groups, such as sorbitol Polyglycidyl ether'Polyglycerol polyglycidyl ether, ethylene glycol diglycidyl

Page 12 5. Description of the invention (7) Glyceryl ether, diethylene glycol diglycidyl ether, polyhexanediol diglycidyl ether, diglycerol polyglycidyl ether, and the like. After the radical reaction is carried out, the super absorbent resin can have an appropriate degree of crosslinking, and the super absorbent resin colloid can have appropriate processability. The radical polymerization crosslinking agent may be used singly or as a mixture of two or more kinds. Appropriate addition amount of free-radical polymerization cross-linking agent is between 0.001% by weight and 5% by weight (based on the total solids content of the reactant). A more appropriate amount is from 0.1% by weight to 3% by weight. %, The added amount is less than 0.001 wt%. After polymerization, the hydrate is too soft and viscous, which is disadvantageous for mechanical processing. If the added amount is more than 5 wt%, the water absorption is too low, which reduces the resin performance. In order to increase the retention of super absorbent resin, a longer-chain bridging agent can be selected. For example, as shown in US Patent No. 5,506, 324, a long-chain 2-ethylglycerol tripolyethylene glycol acrylate is added. The characteristics of this long chain will effectively improve the retention of super absorbent resin. However, the superabsorbent resin 'obtained by using the above-mentioned free-radical polymerization crosslinker can not take into account both its holding power, absorption rate under high pressure, and low residual AA physical properties; and US Patent No. 5,506, 324 It shows that long-bond 2-ethyl glycerol triethylene glycol acrylate is added. Although the obtained super absorbent resin has the characteristics of high retention and low residual AA, it cannot obtain a high absorption rate under pressure, and Reduced practicality of superabsorbent resin. In order to achieve the goals of high retention, absorption rate under high pressure, and low residual AA of the super absorbent resin of the present invention, the free-radical polymerization crosslinker used in the present invention should have long-chain characteristics. Characteristics will increase the retention of superabsorbent resin 'and can effectively improve the subsequent surface modification steps

Page 13 V. Description of the invention (8) Absorption ratio under rising pressure; therefore, the present invention adds a compound having long chain characteristics and containing two or more epoxy groups before performing a radical polymerization reaction. Such as: long-chain glycerol polyethylene glycol triglycidyl ether, long-chain 2-ethyl glycerol polyethylene glycol triglycidyl ether, polyethylene glycol diglycidyl ether, long-chain hexahexyl polyethylene 01 wt% 至 3wt。 Glycol hexaglycidyl ether, etc .; the appropriate added dosage is between 0.0001 wt% to 5wt% (based on the total solids content of the reactant), more appropriate dosage is 0.01 wt% to 3wt %between. Polymerization begins with the generation of free radicals by the decomposition of a radical polymerization initiator. As the free radical initiator, a thermal decomposition type initiator may be used. Suitable thermal decomposition type initiators include peroxides, such as: hydrogen peroxide, di-third butyl peroxide, ammonium peroxide or persulfuric acid. Salts (ammonium salts, alkali metal salts), etc., and azo compounds such as: 2.2'-azobis (2-fluorenylpropane) dihydrochloride, 2.2'-azobis (N, N-Dimethylidene isobutyrate) dihydrochloride; reducing agents can also be used to make redox-type initiators, such as: acid sulfite, thiosulfate, ascorbic acid or ferrous salt; or The redox initiator and the thermal decomposition initiator are used in combination. First, the redox initiator is first reacted to generate free radicals. When the free radicals are transferred to the monomer, the polymerization reaction is initiated. A large amount of heat is released to increase the temperature. When the temperature reaches the decomposition temperature of the thermal decomposition initiator, the second stage of the thermal decomposition initiator is decomposed, and the entire polymerization reaction is completed. Lwt% 至 5wt% 之间 ， 用 The appropriate amount of general free radical polymerization initiator is a weight percentage of 0.00lwt% to 10wt% (based on the neutralization of acrylic acid weight) When the weight percentage is less than 0. 0 0 1 wt%, the reaction is too slow and the economic benefits are not good.

Page 14 V. Description of the invention (9) When the ratio is above 1 Owt%, the reaction is too fast and the reaction heat is not easy to control. Super absorbent resin is an insoluble hydrophilic polymer. The resin has a uniform bridging structure. Generally, in order to improve the quality, such as: increase the absorption rate, increase the colloidal strength, improve the blocking resistance, liquid permeability, etc. The surface of the resin is further bridged. 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 in Surface crosslinking treatment in organic solvents (JP-A-56-131608, JP-A-57-44627, JP-A-58-42602, JP-A58-117222) Use inorganic powder to directly crosslink the crosslinking agent with the crosslinker Agent solution mixed with super absorbent resin treatment (]?-Person 6 0-1 6 3 9 5 6,]?-A- 6 0-25 58 1 4), adding a crosslinking agent and steam treatment (JP-A- 1-113406), surface treatment using organic solvents, water, and polyols (JP-A-63-270741, JP-A-64- 5 0 70 7, JP-A-Bu 292004) using organic solutions, water, ( ether) compounds (JP-A-2-153903), etc .; although these surface treatment methods can increase the absorption rate and increase the water absorption rate under pressure, To retain power drops too many adverse consequences, reduce the performance of the practical application. According to the present invention, the cross-linking agent capable of carrying out simultaneous reactions during surface treatment may be a polyhydric alcohol such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol, trihydrocarbylmethylpropane, sorbitol, etc .; or polyamines such as ethylenediamine, diethylenediamine, triethylenediamine, polyethylenediamine; or two or Two or more epoxy-based compounds such as: sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, poly

Page 15 V. Description of the invention (10) Ethylene glycol diglycidyl ether, diglycerol polyglycidyl ether, etc .; alkylene carbonates such as ethylene glycol carbonate, 4-methyl-1, 3 -dioxolane-2-one, 4, 5-dimethyl-1,3-dioxolane-2-one, 4, 4-dimethyl-1,3-dioxo Cyclopentane-2 -one, 4-ethyl_1,3-dioxetan-2-_, 1,3 ~ dioxane-2-one, 4,6-dimethyl -L, 3-dioxane-2-fluorene or 1,3-dioxepane-2-one and the like. The cross-linking agent can be used alone or in combination of two or more. The appropriate addition amount of the cross-linking agent is between 0.001 wt% to 1 Owt% (based on the total solid content of the reactant). A more appropriate amount is between 0 0 0 5wt% to 5wt%, cross When the dosage of the coupling agent is less than 0.001 wt%, the effect cannot be exhibited. When the dosage of the parent coupling agent is more than 10wt%, 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 reaction. The super absorbent resin obtained by the reaction can first be cut into small gels with a diameter of 201ΗΠ1 or less by using a mincer. The drying temperature is preferably from 10001 to 1801 for drying. The drying time for drying along C and C is too long, and it is not economical. Drying temperature production i 8 = drying Make 2 agents cross-linking reaction early to make the follow-up: dry 4 reduce the residual: Si; high and unable to effectively remove the residual monomers, reach the surface cross-linking agent mm, the following fine powder to dry the finished product and crush it 1. Screen the fixed particle size, and then apply coating. The screened fixed particle size is preferably between 0.06 mm and 1.00 0'10 mm to 0.850 mm, and the particle size is 0.06.

V. Description of the invention (11) ---............................ ........................................ ......—— Dust increase, the particle size is 1. 00mm or more, the finished product absorbs water at a fixed speed, and then the table is taken for the heat. Parent linker coating treatment, can be used as a surface cross-linking agent can be a polyol such as: two = 8 & 1 PV side, ethylene glycol, alcohol 'triethylene glycol, polyethylene glycol, propylene glycol, 1,4 Butanol-methyl propane, sorbitol, etc .; or polyamines such as ethylene diamine monoamine, diethylene monoamine, polyethylene diamine; or compounds having an epoxy group such as sorbitol polyglycidyl Glycidyl ether, 6 diol diglycidyl, double bond, polyethylene glycol-polyglycidyl, dipropylene =; carboxylates such as ethylene glycol diethyl two or two oil Ether, polyglycerol, polyethylene glycol, diglycidyl alcohol, polyglycidyl ether, etc., ethylene glycol carbonic acid, 4 ~ methyldioxane-2-one, 4,5 ~ dimethyl-1 ^ -dioxo Heterocyclopentanone, 4,4-dimethyl-1,3-dioxolane_2__ , 4_dioxolane-2-one, 1,3_dioxane-2__ ,: 'diyl-1,3-dioxane-2-one or 1 3_ -hydrogen M. Fu Shi 'wi' d dioxan-2-one calculation. The use of a cross-linking agent at the surface can be used alone for two or more people. The proper dosage of the cross-linking agent at the surface is between # I wn ° ^ and the weight percentage of 0.001wt% $ 10wt% (based on the total solid content of the reactant, which is based on the true solid and pseudo horse). More suitable between 0.005wt% and 5wt% 'surface at the end of the M fine' Table l such as, the weight of the use of double parent joint agent dosage. When less than 0. OOlwt% can not show the effect, the amount of 100 knives in When the weight percentage is above 10Wt%, the water absorption surface is too high: Additive dosage can. % And water is too low, reduce the resinous cross-linking surface = when the cross-linking agent is coated, the surface cross-linking agent is added directly, or the surface cross-linking agent solution is added to the surface surface cross-linking agent, and the hydrophilic organic solvent aqueous solution is added. Or into

-Organic soluble #J

V. Description of the invention (12) For special restrictions such as methanol and ethanol, surface cross-linking agent can be added to aid solution dispersion, or alumina. 0.005wt% to 10% for surface treatment to make the surface cross-linking and the reaction time is too long. It is easy to deteriorate and affect the temperature adjustment of the texture. Through the retention of the hair and the high-pressure industry, the soil and water retaining sanitary products absorb propanol and isobutyl. Alcohol, acetone, methyl ether, ethyl, and the like do not have a f-shaped solution. Among them, methanol and ethanol are preferred. In the table, an inert inorganic salt powder may be added to the superabsorbent resin. The inert inorganic salt powder may be aluminum sulfate, stone dioxide, magnesium oxide, or a mixture thereof. Among them, aluminum sulfate, amphiphilic inorganic salt powder is added in a range of weight percent to .00 wt%, and from 0.01 to 4.0 wt% is preferred. After the cross-linking agent is coated, it is heated at 90 ° C to 230 ° C. The cross-linking agent can carry out the cross-linking reaction, and the internal cross-linking agent & achieves the effect of the present invention. Cross-linking at a processing temperature below 90 ° C ‘No economic benefits’ Processing temperature 2 3 0 t: Above resin is suitable for a processing time of 2 minutes to 150 minutes, depending on the high temperature and short time, and low temperature and long time. Mingzhi Super Absorbent Resin has low residual unreacted monomers, high absorption rate under high power, etc., so it is suitable for agricultural and forestry agents, sanitary products such as diapers, adult incontinence products and women's aquatics and food preservation applications. In order to show the water absorption ratio under pressure of the super absorbent resin of the present invention, the present invention uses a pressure absorption weight (pressure load: 20 g / crrf and 49 g / crrf) to determine the 'pressure absorption amount according to the European Patent No. 0339461A specification No. Measured in the method described on page 7; put the initial weight of superabsorbent resin in a cylinder based on the bottom of the screen, and apply pressure to the powder at 20g / CIrf and 49g / cm2 to hold the cylinder The body was placed on an absorbance demand tester, and this super absorbent resin was allowed to absorb 0.9% aqueous sodium gas solution for one hour, and then

V. Description of the invention (13) ~ Measure the water absorption weight and divide the value obtained by the weight of the super absorbent resin to obtain the pressure absorption weight value. The holding force of the present invention is measured by a tea bag test method, and an average value is obtained from five measurements; 0.02 g of a super absorbent resin is packed in a tea bag, and the fan is immersed in a 0.9% NaCl aqueous solution for 20 minutes. Then the soaked tea bag was placed in a centrifuge and centrifuged (23 cm in diameter and 1 400 rpm) for three minutes and then weighed. The value obtained is obtained by subtracting the weight of a blank group of tea bags not filled with superabsorbent resin (in the same procedure), and then dividing by the polymer weight to obtain the retention value. The determination of low and existing monomers is analyzed by liquid chromatography. First, weigh 500 grams of two water-absorbent resins into a 150-degree Erlenmeyer flask and add a "ο aqueous solution 100g and a 2Cm stirrer. Stir for one hour at 500 rpm. 'Add 5 g of 20% A12S04 aqueous solution, and then use 2 to filter from m filter paper, and analyze the filtrate into the liquid chromatograph.' The remaining signal can be compared with the calibration curve to obtain the residual. The amount of monomer. The reference working examples are listed in detail below to illustrate the present invention; but the scope of the present invention is not limited by these examples. Example one: 1) 100c. C Erlenmeyer flask was added 30g acrylic acid and 32.4g In addition, a 48% sodium oxynitride aqueous solution 2438 was weighed out in a 100 ° C conical flask, and the sodium hydroxide aqueous solution was slowly added to the acrylic acid aqueous solution under ice and neutralization; at this time, a 42% by weight monomer solution was obtained. In which, 70 mol% (molar ratio) of acrylic acid is partially neutralized to sodium acrylate. 2) 2 = ^ 〇46β glycerol polyethylene glycol triglycidyl ether in «Kanawa acrylic acid solution, and maintain the temperature Around 20 ot.

R " ········· ........................... ........................................ ........................................ ... 1 ..........................-------------------- -V. Description of the invention (14) .......................... ........................................ .............................. .-............................................ ........................................ 3) Add 0.16gL ~ ascorbic acid nitrogen-based bis (2-fluorenylpropanone, —Waki &. Zg sodium persulfate and 0.2g 2 2- Even 4) After the reaction, this super absorbent tree salt is used to start the reaction. The following gels. Cut into 2ηππ diameter mm 0. 85ηππ 5 with a cutter grinder 5) Dry at 130 ° C for 2 hours; Ligugang 'to get a powdery superabsorbent tree: choose ° "6) Weigh this water-absorbent resin 1 〇 After homogenization, add human B: ^ g, to be mixed ratio) solution 0.4 g, at 215 ° C Μ select I Μ methanol = 1/1 / 丨 (weight 7, person) from ZlbC 纟 dishes Heat treatment for 10 minutes. 7) After cooling, 'high performance and high water absorption σ / σ, 90fT / 2 2 t tree shrew' determination retention force is 30. 1 g / g Z〇S / CDl suction and pull 9 π c / 呦 skin supply plate 99 K / rate 9.5g / g, 49g / cirf pressure and water magnification 22.45g / g, residual monomer 152 {) {) 111. Example 2: > Repeat example 1 but 48g / g。 Step 2) instead added 0.046g of glycerol polyethylene glycol triglycidyl ether (n = 1 2), the rest is the same as in Example 1, a super absorbent resin can be obtained, the determination retention is 32. 48g / g The water absorption rate under the pressure of 20g / cirf is 30,24 home / 莒, the water absorption rate under the pressure of 49 Gong / 〇111 is 21.76 叾 / ^, and the residual monomer is 1 27ppm. Example 3: Repeat Example 1, but step 2) instead add 0.046g of glycerol polyethylene glycol triglyceride (n = 1 5), the rest is the same as in Example 1 to obtain a super absorbent resin. The measured holding force is 33. 73g / g, the water absorption ratio under pressure of 20g / cm2 is 32.7 8g / g, and the water absorption ratio under pressure of 49g / cirf is 21.16g / g. Body 94ppm °

Page 20 V. Description of the invention (15) Example 4: Repeat Example 1 but add 0.046g of glycerol polyethylene glycol triglycidyl ether (n = 20). First, a highly water-absorbent resin was obtained, and the retention was determined to be 35.73 g / g '20 g / crri under 33.78 g / g, 49. g / ciri under 20.20 g / g of residual monomer, and 62 ppm of residual monomer. Example 5: Weight 73g Covering the first example, but step 2) was instead added to 0. 046g of glycerol polyethylene glycol triglycidyl ether (n = 25) 'The rest is the same as in Example 1, to obtain a super absorbent resin, the retention is determined to be 36.73g / g, 20g / crri water absorption rate 32.78g / g '49g / cm2 water absorption rate 19.93g / g under pressure, residual monomer 27 7ppm 〇 Example 6: Repeat Example 1, but step 2) instead add 〇〇〇46g of glycerin polyethylene glycol triglycidyl ether (n = 50) 'The rest is the same as in Example 1, to obtain a super absorbent tree purpose' The retention is determined to be 38. 14g / g, 20g / cm2 pressure Water absorption rate 31.94 舀 / ^ '49 £ / (: Water absorption rate 17.16 under 1112 pressure / this, residual monomer 10 Example 7: Repeat Example 1, but step 2) instead add 〇46g of 2-ethylglycerol polyethylene glycol triglycidyl ether (n = 7), the rest is the same as in Example 1, a superabsorbent resin can be obtained. The measured retention is 29.9g / g, 20g / The water absorption rate under the pressure of cni was 28.24 g / g, the water absorption rate under the pressure of 49 g / crri was 23.29 g / g, and the residual monomer was 164 ppm.

Page 21 V. Description of the invention (16) Example 8: Repeat Example 1, but step 2) instead add 0.046 & 2-ethylditriol polyethylene glycol diglycidyl hydrazone (n = l2 ), The rest is the same as in Example 1. A water-absorbent resin can be produced. The measured holding force is 32.59g / g, the water magnification is 31.0 3g / g under the pressure of 20g / crrf, and the water absorption magnification is 20.95 g under the pressure of 49g / ciri. Monomer 121 ppm. Example 9: Repeat Example 1 ', but step 2) was changed to add 0.046g of 2-ethyl propane = alcohol polyethylene glycol triglycidyl ether (n = 5), the rest is the same as in Example 1, to obtain high water Resin, measuring retention force is 34.25g / g '20g / CIrf under the pressure of water absorption, the rate is 32.7g / g, 49g / crrf under the water absorption rate of 20i 99g / g, monomer 89ρρπ ^ Example 10 · Repeated example One, but step 2) was instead added with 0.046 g of 2-ethylpropanetri-degree polyethylene glycol triglycidyl ether (n = 20), the rest was the same as in Example 1, and a superabsorbent resin was obtained. 36. I3g / g, water absorption rate under pressure of 20g / cni 34. 58g / g '49g / cm2 water absorption rate under pressure 20. 5 9 g / g, remaining in monomer 39Ppffl. Example 11: Example 1 is repeated, but step 2) is replaced by 0.046g of 2-ethylpropane three polyethylene glycol triglycidyl ether (n = 25), and the rest is the same as in Example 1, which is highly absorbent. = Resin, measured retention force is 37, 14g / g, water absorption under pressure of 20g / crrf ^ 33. 14g / g '49g / ciri pressure absorption rate of 20. 13g / g, residual " " body 32ppm.

Page 22 V. Description of the invention (17) — ——: — — — Example 12: Example 1 was repeated, but step 2) was changed to 0.046 g of 2-ethylglycerol polyethylene glycol three Glycidyl ether (n = 50), the rest is the same as in Example 1, and a super absorbent resin was obtained. The retention was determined to be 38.73g / g, the water absorption ratio under the pressure of 20g / cnf was 33.14g / g, and the water was absorbed under the pressure of 49g / crri. Magnification 19.8 / monomer 12PPm. # Example 13: Repeat Example 1, but step 2) instead add 0.046g hexahexamethylene triglyceride hexaglycidyl ether (n = 20) 'The rest is the same as in Example 1 to obtain a super absorbent tree shrew 'The measured holding force was 34.15 g / g, the water absorption rate under the force of 20 g / cm8 was 25.67 8 / z, the water absorption rate under the force of 49 words / 〇1112 was 12.92 / 2, and the residual monomer 581) 1) 111. Example 14: Example 1 was repeated, but step 2) was replaced by adding 0.046 g of hexahexanyl triethylene glycol hexaglycidyl ether (n = 50). The rest was the same as in Example 1, and a super absorbent resin was obtained. 'The measured holding force is 36.94 g / g, the water absorption ratio under pressure of 20 g / cm2 is 29.81, which is 8,49, and the water absorption ratio under pressure is 20.9, 7 home / £, and the residual monomer is 29 ppm. Example 15: Weight Example 1 was repeated, but step 2) was changed to adding 0.046 g of hexahexyl triethylene glycol hexaglycidyl ether (n = 100). The rest was the same as in Example 1, and a superabsorbent tree Jfe was obtained. The force is 3 8 · 37 g / g, 20 g / c ηί The rate of water absorption under pressure is 30 '26g / g' 49g / cm2 The rate of water absorption under pressure is π. 23g / g, and the residual is 1 Oppm. Example sixteen:

Page 23 V. Description of the invention (18) 1) Add 30g acrylic acid and 32.4g water to 100c.c conical flask; weigh 24.3g of 48% sodium nitroxide solution in 100c.c conical flask. The aqueous solution of sodium oxynitrate was slowly added to the aqueous solution of acrylic acid for neutralization; at this time, a 42 wt% aqueous solution of monomer concentration was obtained, of which 70 mol% (mole ratio) of acrylic acid was partially neutralized to sodium acrylic acid. 2) Add 0.046 g of hexahexanol tripolyethylene glycol hexaglycidyl ether (11 = 20) to a partially neutralized acrylic acid solution, and maintain the temperature at about 20 ° C. 3) 〇 '〇16gL-ascorbic acid' 0.2g sodium persulfate and 0.2g 2.2 ~ azobis (2-methyl propane) dihydrochloride were added to start the reaction. 4) After the reaction, the two water-absorbent resins are cut into a gel having a diameter of 2 min or less by a cutter mill. 5) Dry at 130 ° C for 2 hours; sieve 0.1 mm ~ 0.85_ with a sieve to fix the particle diameter to obtain a powdery super absorbent resin. 6) Weigh out this super absorbent resin i〇g, add silicon dioxide powder, and after mixing well, add ethylene glycol diglycidyl ether / water = 1/5 (weight ratio) solution 0.2 g '以9 0 t: temperature heat treatment for 15 minutes. ΌAfter cooling, a high-performance super absorbent resin is obtained. The measured holding force is 36. gg / g, water absorption rate under pressure of 20g / crrf is 32.54g / g, water absorption rate under pressure of 49g / cni is 17.12g / g, and the remaining list Volume 15ppm. Example 17: Example 16 was repeated, but step 2) was replaced by 〇46g of hexahexyl tri, ethanedipyl hexaglycidyl ether (n = 50), and the rest was the same as in Example 16 to obtain high absorption, Resin, measuring retention force is 37. 84g / g, water absorption rate under 20g / cnf pressure is 30. 10g / g, water absorption rate under 49g / CIrf pressure is 17 '15g / g, remaining

Page 24 V. Description of the invention (19) .............. ........................................ ........................................ ........................................ ....... Monomer 8ppm. Comparative Example 1: Example 1 was repeated, but step 2) was replaced by 〇46gN, N, N_tri (2-propenyl) amine, the rest was the same as in Example-to obtain a super absorbent resin, and the retention was determined to be 27.89g / The water absorption rate under g '20g / ciri pressure is 26.17 § / §, the water absorption rate under 49g / crri pressure is 12.76g / g', and the residual monomer is 597ppm. Comparative example two: Example 1 was repeated, but step 2) was changed to add 0.046 g of N, N-methinepropylamine, the rest is the same as in Example-, # super absorbent resin, the measurement retention was 26 '46 g / g, water absorption rate under pressure of 20g / cni 25.24g / g, water absorption rate under pressure of 10.17§ / § 'residual monomer 546 pm. Comparative Example 3: Repeat: Example-, but step 2) was replaced by 〇46g of 2-ethyl glycerol diethylene glycol acrylate (n = 15), the rest is the same as in Example 1, resin, the retention is determined as 34.15g / g, 20g / cnf pressed 2222 25. 67g / g, 49g / CIrf pressure water absorption ratio of 10 () 0 / Γ times hard and hard 58. Section 1U9g / g, residual monomer Comparative Example 4: Example 16 was repeated, but step 2) was replaced by 0.0046g of n NN-tris (2-propenyl) amine. Water-absorbent tree: The fixed holding force is 30. 16g / g '20g / cm2. The water absorption rate under 49g / crri pressure is I3.63g / g. The remaining list ^ · 4g / g,

Page 25

Claims (1)

丨 Winter winter; Sat '1. t patent scope ............ ........................................ ........................................ .....................--1-.- ....................... .........: .............................. ....... A manufacturing method of high-performance super-absorbent resin, used to manufacture powder that is insoluble in water, can absorb water or urine and blood, Application :; high retention and high water absorption rate under high pressure The method includes at least the following processes: (a) preparing an acid group-containing monomer aqueous solution, the concentration of which is adjusted to m and neutralizing the carboxylic acid group portion of the monomer with a neutralizing agent so that the neutralization concentration is above 50 mole% ; Adding a hydrophilic long adduct as a polymerization reaction cross-linking agent to the intermediate (b) f precursor monomer aqueous solution to perform a radical polymerization reaction to obtain a water-absorbent resin; (C) =: of = = After drying at a temperature of 10 ° m8rC, it is crushed and selected to fix the particle size. (D) The resin particles with a fixed particle size are coated with a surface cross-linking agent to make the surface of the particles even Crosslinking reaction unit; to (e) after the coating treatment of the surface crosslinking agent resin temperature households. 23 ° in 1 =: surface treatment, high performance and high performance: water-based resin; acid-based polymers in the age can be selected from acrylic acid, methyl acrylic acid, maleic acid, s-maleic acid, 2-propene Any of amine-2-methylpropanesulfonic acid, or a mixture of two, monomers are water-soluble and the solution contains 0 to 5% by weight of water-soluble i ::: == the hydrophilicity of the agent has long-chain characteristics and multiple epoxy groups { 〇 [CH (R3) CH (R3) 〇] y-R2} x Page 26 396173 VI. In the scope of the patent application, the composition of I is c2 "] () linear or branched alkyl functional group, R2 composition can be substituted by c2_1 () linear or branched alkyl group Epoxy group is a hydrogen atom or a methyl group or an ethyl group; X may be greater than or equal to 2, y is 3 to 15 when x = 2, and y is 3-33 if x > 2. According to the patent application The manufacturing method of the first item, wherein the water-soluble polymer is polyvinyl alcohol, starch, or a starch derivative or a mixture thereof. 3 · The manufacturing method according to the first item of the patent application range, wherein the high content is used as a crosslinking agent. Hydrophilic polyvalent epoxy compounds with long-chain characteristics can be added in the range of 0.05% by weight to 5.0% by weight. 4. The manufacturing method according to item 1 of the scope of patent application, wherein the high hydrophilicity has a long chain The characteristic polyhydric epoxy compound may be a long-chain glycerol polyethylene glycol triglycidyl ether, and its molecular weight distribution ranges from 350 to 5000. 5. The manufacturing method according to item 1 of the patent application scope, wherein the high Hydrophilic polyvalent epoxy compounds with long-chain properties may be 2-methylpropane Alcohol polyethylene glycol triglycidyl ether has a molecular weight distribution range of 400 to 5100. 6. The manufacturing method according to item 1 of the scope of patent application, wherein the highly hydrophilic polyhydric epoxy compound having long-chain properties may be It is 2-ethyl glycerol triethylene glycol triglycidyl ether, and its molecular weight distribution range is from 400 to 5 1 0. 7. The manufacturing method according to item 1 of the scope of patent application, wherein the high Hydrophilic polyvalent epoxy compounds with long chain properties can be hexamethylene triethylene glycol Page 27 6. Scope of patent application The molecular weight distribution of hexaglycidyl ether is between 800 and 6000. 8. The manufacturing method according to item 1 of the scope of patent application, wherein the neutralizing agent used in the neutralization process is any one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium nitrate. One or more mixtures. 9. The manufacturing method according to item 1 of the scope of patent application, wherein the particle size distribution range of the screening is between 0.10 mm and 0.8 50 min. 10. The manufacturing method according to item 1 of the scope of patent application, wherein the surface cross-linking agent used in the coating process is a polyvalent enzyme or ethylene glycol diglycidyl ether or an alkylene carbonate or a mixture thereof. 1 1. The manufacturing method according to item 11 of the scope of patent application, wherein the addition range of the surface cross-linking agent is between weight percent (K 0 0 5wt% to 5. Owt%. 1 2, according to the scope of patent application No. 1 The manufacturing method of item (b), between the process of screening the fixed particle size in (c) and the process of coating the surface cross-linking agent in (d), further includes a process of adding an inert inorganic salt powder to the above-mentioned resin particles, whereby The crosslinking agent used in the process can be subjected to a crosslinking reaction during the surface treatment in step (d), and the crosslinking agent may be a polyol, a polyethylene glycol diglycidyl ether, or an alkylene carbonate. 1 3. According to the application Olwt% 至 4. Owt% 之间。 1 Manufacturing method according to the scope of the patent No. 12, wherein the inert inorganic salt powder may be aluminum sulfate or silicon dioxide, the addition range is between weight percent 0. Olwt% to 4. Owt%. 1 or 12 of the manufacturing method, Page 28 396173 6. The superabsorbent resin obtained in the scope of patent application has the following characteristics: (a) its liquid retention value is at least 32-g per gram of resin under a 0.9% aqueous solution of sodium gasification; (b) at 0. The absorption of 9% aqueous sodium gas solution and pressure of 20 g / cm² is at least 28 grams per gram of resin; (c) Its absorption of 0.9% aqueous sodium gas solution and pressure of 49 g / cm2 is · A gram of resin is at least 17 grams. Page 29