TWI288140B - Method of manufacturing the super-absorbent polymer (SAP) which is powdery, insoluble in water, and able to absorb water, blood and urine and has slight soluble things - Google Patents

Abstract

A method of manufacturing the super-absorbent polymer (SAP) which is powdery, insoluble in water, and able to absorb water, blood and urine and has slight soluble things. The method includes the steps at least: by mixing a monomer solution having at least 50 mole% of neutralized acrylic acid with polymerization initiators, and a sticky precursor is synthesized. Monomers can be chosen from acrylic acid or methacrylic acid or 2-acrylamido-2-methylpropane sulfonic acid or their complexes. Mixing high hydrophile epoxy compounds and polymerization initiators with the precursor, and then produce the gel via UV crosslinking. Drying the gel in the temperature of 100 DEG C to 250 DEG C to become a polymer. Grinding and selecting the polymer with constant particle size. Coating the polymer with surface cross-linking agents. Heating the polymer in the temperature of 80 DEG C to 230 DEG C. And, coating the inert inorganic salt powder with the polymer.

Description

1288140

[Technical Field] The present invention relates to a method for producing a water-absorbent resin, in particular, a powder-like, water-insoluble, water-absorbable liquid, urine or blood with high water absorption and low water absorption. A method of producing a resin. [Prior Art] The south water-absorbent resin has a strong water retention capacity, can absorb water hundreds of times or even thousands of times its own weight, and can be inflated after being absorbed, and does not leak even if pressure is applied. And the absorbed water can be slowly released in the atmosphere. Due to the above characteristics, the soil water retaining agent that was first used in the agricultural forestry industry has been widely used in the production of water-absorbing resins in recent years, so it is widely used in money-saving products such as diapers and adult-type products. Water-absorbing agents for feminine hygiene products and preservation applications for preserving food. The component material of the Lu superabsorbent resin is a hydrolyzed starch-acrylonitrile graft polymer (Japanese Patent Laid-Open Publication No. Sho 49 (1974)-43,395), a neutralized starch acrylic acid graft polymer. (Japanese Patent Laid-Open Publication No. Sho 51 (1976)-125,468) 'Saponified ethylene propylene acetate copolymer (曰本专利利, Kai Gaz. 52 (1977). 14, 689), hydrolyzed acrylonitrile copolymer or acrylamide, = Polymer (Japanese Patent Publication No. Sho 53 (19-8) - 15, 959), and partially neutralized polyacrylic acid (Japanese Patent Laid-Open Publication No. Sho 55 (1980)-84,304) and the like. Among them, the superabsorbent chicks obtained by cross-linking polymerization using acrylic acid and acrylonitrile account for the largest part, and the most part is 1,288,140, which is obtained by rapidly obtaining acrylic acid (four), and has high water absorption capacity and high manufacturing cost. Low cost and most economical, it has become the most common superabsorbent resin. Aspirate _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ After the diameter, the surface of the # resin is further bridged. This surface cross-linking treatment utilizes a polyfunctional crosslinking agent having a dicarboxylic acid group. Many patents have been proposed before, for example: Dispersing superabsorbent resin Surface cross-linking treatment with a crosslinking agent in an organic solvent (JP-A-56-131608 > JP-A-57-44627 > JP-A-58-42602 > 58 117222), using inorganic powder directly The parent-linking agent and the cross-linking agent solution are mixed with a superabsorbent resin (JP_A60_163956, jp_A Qin 255814), and after adding a crosslinking agent, the surface is treated with steam (JP-A-1-113406), using an organic solvent, water, and a polyol. Treatment (JP-A-63-27〇74, JP-A_64_5〇7〇7, JP-A_l_292〇〇4), organic solution for spring, water and compound (jp_a_2-153903). This - the surface treatment method can increase the absorption rate of the resin or increase the water absorption rate under pressure, but it will cause the adverse effect of excessive retention of the retention force, and reduce the practical application. The method of polymerizing acrylic acid and acrylate to form a super absorbent resin has been successfully developed in various aspects' and various kinds have been applied to industrial production, and the polymerization method thereof has a ruthenium film polymerization reaction (Japanese Patent Publication Showa 48 (1973) · 42,466) On the conveyor belt 8 1288140 :. 二·· η

The polymerization reaction was carried out in a t-mixer (Japanese Patent Laid-Open No. 57 (1982) _34, im), and the reverse phase fresh liquid age reaction was carried out (in Japanese Patent Publication No. 037). Japanese Patent Laid-Open No. 59 (1984)-37, No. 3), or a monomer is sprayed or coated on a fibrous substrate to carry out a polymerization reaction (Japanese Patent Laid-Open No. 62 (1987)-53,309). However, most of the above-mentioned polymerization methods are gel-like solid clocks in which a polymerization monomer, a polymerization initiator, and a parent-linking agent are reacted together, and a radical-polymerized reaction is carried out to form a water-absorbent resin, so that the entire polymerization reaction is not Miscellaneous, soluble content is also relatively south. SUMMARY OF THE INVENTION In view of the above, the present invention provides a method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content, and the polymerization process is relatively speaking. It is relatively stable and the heat of reaction is not too high. In addition to improving the operating environment, the product quality is improved. The method for producing a superabsorbent resin which is filled with powder, is insoluble in water, absorbs water, urine or blood and has a low soluble content, and at least comprises the following steps: providing a neutralization rate of 50 m More than a percentage of the aqueous acid group-containing monomer solution and the polymerization initiator are prepolymerized to obtain a viscous prepolymer, and the acid group-containing monomer is selected from acrylic acid or methacrylic acid or 2-propenylamine-2-mercaptopropane sulfonic acid. Or a mixture of the above groups; adding a long-chain polybasic epoxy compound and a polymerization initiator in the viscous prepolymer to further form a gel by photoinitiating polymerization; and repairing the gel at a temperature of 100 1288140 ( Further, it is being replaced with hot air of 250 ° C for drying, pulverizing, screening, coating surface crosslinking agent, controlling the degree of 80 C to 230 C for wire surface treatment and adding inert inorganic salt powder. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs aqueous liquid, urine or blood and has a low soluble content as described in the preferred embodiment of the present invention, wherein the viscous prepolymer is The viscosity is 1〇~1〇〇〇〇cp. The invention relates to a method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content, wherein the mouth-reacting hair styling agent is thermally decomposed. Type initiator or redox type initiator. , silk, the invention touches the description of the minerals, transferred to water, absorbable water, liquid or blood; night and soluble content is low, the principle of high water absorption, the pre-treatment can be used in women An upright reaction tank equipped with a stirring paddle, a center-mounted cylindrical container in which a material flows in one direction, a cylindrical container in which a single (double) screw is installed, or a pipe towel with a jacket and a nitrogen gas is used. The polymerization temperature is 5 to 80 ° C, and the prepolymerization time is 5 to 16 hours. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content according to a preferred embodiment of the present invention, and the initiating polymerization in the package is included in 1G. ~ diligence_complete, more included in 3g~6_complete 0 According to the preferred embodiment of the present invention, the powdery, water-insoluble, water-absorbable liquid, urine or money and high content of sweets The method, wherein the long-chain 702⁄4 oxy compound includes sorbitol polyglycidil test, polyglycerol polyglycidyl m, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl (IV), 1288140 factory-^. In September, it was replaced (more) with ethylene glycol diglycidyl ether and diglycerol polyglycidyl ether. A method for producing a superabsorbent resin which is powdery, insoluble in water, and absorbable water according to a preferred embodiment of the present invention, and which has a low content of soluble substances in the night, urine or blood, The condensed_post-particle size distribution surface is between _ and 1 filament (mm). a method for producing a superabsorbent resin which is powdery, water-insoluble, absorbable aqueous urine or blood and has a low soluble content according to the preferred embodiment, wherein the surface crosslinking agent is a polyol, or Polyethylene glycol diglycidyl _, or alkylene carbonate φ 酉曰 or a mixture of the above groups. The surface crosslinker is added in the range of 0 005 to 5.0 weight percent. A method for producing a superabsorbent resin having a low content of powder, water-insoluble, water-absorbable liquid, urine or blood-soluble soluble matter according to a preferred embodiment of the present invention, and wherein the inorganic bribe is Sulfur-, or oxo, or magnesium oxide, or oxidized/, or or south territories, or dioxide 11, or carbon-, or magnesium carbonate, or a mixture of the above. The inert inorganic salt powder is added in the range of 0·01 to 4·〇 by weight.

The invention adopts the chemical reaction of the first pre-polymerization and the photo-initiated polymerization, and the overall polymerization process of the hand-month is relatively different from the conventional one. The last wish is not too high, and the reverse is not too high, except that the change I is improved. Product quality. ^Others The features and implementations of the present invention are as follows. [Embodiment] The following is a detailed description of the embodiment of the present invention. /α 11 1288140 (more) m! DETAILED DESCRIPTION OF THE INVENTION The contents of the present invention are described in detail. The powdery, water-insoluble, water-absorbable, urine or blood-soluble superabsorbent resin having a low soluble content is proposed. The manufacturing method comprises at least the following steps: providing an aqueous solution of an acid group-containing monomer having a neutralization ratio of 50 mol% or more and a polymerization initiator to obtain a viscous prepolymer, and the acid group-containing monomer is selected from the group consisting of propylene glycol Or methacrylic acid or 2-propyleneamine 2 • methyl propyl ketone or a mixture of the above groups "j, a long chain epoxide epoxy compound and a polymerization initiator in the cohesive polymer• Further generating a gel by photoinitiating polymerization And the condensate body is heated to a temperature of 25 to, hot air, pulverized, screened, coated with a surface crosslinking agent, controlled by C to 230 C for heating surface treatment, and an inert inorganic salt powder is added. In a prepolymerization reactor, the reaction needs to be able to make the polymerization reaction ride evenly and prepolymerize. The prepolymerization reaction H can be used in addition to the vertical reaction tank. Use the -type cylindrical container, the towel shouts (four) to make the solution to the flow of the rubbing mix, single screw or parallel twin screw, so as to ensure that the reaction material moves forward in one direction without reflow, thus avoiding The polymerization reaction material stays in the reactor for a long time to form a knee-shaped solid. In addition, the prepolymerization reaction can also be carried out in the tube and the road, and the outside of the pipeline is provided with a jacket for introducing the cooling medium f (such as Cooling water), remove the heat of reaction to ensure that the prepolymerization is carried out under 丨n. Nitrogen is introduced into the 'mouth' to continuously introduce an inert gas to prevent oxygen from affecting the free radical polymerization. Sticky level was continuously added to the people on the conveyor belt, above the conveyor belt with a high intensity ultraviolet, _, Lai Lin tear Queliao heteroaryl bonded so Dui mesh body.

12 1288140 The acid-containing monomer required for the super absorbent resin produced by the present invention can be made other than the bupropion acid, and can be made into other W-rich double bonds, such as: propyl benzoate or marinic acid. Or fumaric acid, or 2_propanylamine 2 methyl propyl succinate and the like. The monomer can be used without any specific limitation. It can also be used in combination with multiple frequencies. It is also possible to add other hydrophilic (tetra) monomers with unsaturated slits, such as: acrylamide, methacrylamide, acrylic acid. 2_hydrocarbyl ethyl ester, f-based acrylic acid 2_yanyl ethyl vinegar, propylene methyl & ethyl acrylate, dimethylamine propylene acrylamide, chlorinated amidoxime The physical properties of the superabsorbent resin are principles. Before the free radical polymerization, the concentration of the aqueous monomer solution should be controlled between 20 and 55 by weight. 'The appropriate degree is between 30 and 45 by weight. The concentration is in the case of heavy in 77 to 2G. The polymer is too soft after polymerization. And there is viscous unfavorable mechanical processing 'addition concentration is above 55% by weight, close to saturation concentration, difficult to mix and react too fast. The reaction heat is not easy to control. The carboxylic acid group of the acid group-containing monomer should be partially neutralized to control the pH of the finished product to make it neutral or slightly acidic. The towel and the agent are oxyhydrogen brain, sodium hydroxide, potassium hydroxide, lithium carbonate and sodium carbonate. , potassium carbonate, hydrogen carbonate clock, sodium carbonate, potassium hydrogencarbonate and ammonia. The acid-containing monomer reading wire will be a partial towel and a mixed salt or a potassium salt salt or a mixture of two or more salts, the concentration of the molar concentration of the molar % _%) is from 85 to 85, and the appropriate concentration is 5 〇 mol% to 75mol 〇 / 〇, the neutralization concentration of the molar percentage of 4S or less when the finished product pH will be low, the neutral concentration of the molar percentage of more than %, the positive value of the finished product will be higher, the finished product pH is not neutral or micro When acidic, 13 1288140 is unsuitable and unsafe when inadvertently in contact with the human body. Λ The prepolymerization starts with the generation of free radicals by the decomposition of the polymerization initiator. The polymerization initiator may be selected from a thermal decomposition type initiator, and a suitable thermal decomposition type initiator is a peroxide such as ruthenium peroxide, di-tert-butyl peroxide, guanidinium peroxide or persulfate. (ammonium salt, alkali metal salt), etc., and azo compounds such as: 2.2, -azobis(2-amidinopropane) monohydrochloride, 2.2-azobis(Ν,Ν-dimethyl) Isobutyl hydrazine) dihydrochloride; a reducing agent can also be used to make a redox initiator, such as an acid sulfite, thio sulphate, ascorbic acid or ferrous salt; or a redox-type initiator The agent and the thermal decomposition type initiator are used in combination. First, the redox initiator starts to react to generate a radical, and when the radical is transferred to the monomer, the polymerization reaction is initiated, and a large amount of heat is released due to the polymerization reaction. When the temperature is raised, when the temperature reaches the decomposition temperature of the thermal decomposition type initiator, the decomposition of the second stage thermal decomposition type silking agent is caused, and the entire polymerization is completely inhibited. The amount of the free silk reaction reaction initiator is 0.001 to 10 by weight (based on the weight of the neutralized acrylate), and more suitable. #The amount is between 5% and 5, and the weight percentage is _1 or less. When the reaction is too slow, the economic benefit is unfavorable; when the weight percentage is 10 or more, the reaction is too fast, the reaction is too fast, and the polymerization is excessive to form a gelatinous solid. For photoinitial polymerization, a cross-linking agent is added to the viscous prepolymer. The cross-linking agent can be selected from compounds having two or more unsaturated double bonds, such as ruthenium, osmium (2-propenyl). Amine, hydrazine, Ν'·methine bis acrylamide, hydrazine, Ν'_methine dimethyl propyl amide, acryl acrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, 1288140 ethylene glycol dimercaptopropyl acrylate, polyethylene glycol dimethacrylate _, glycerol triacrylate, acid ester, glyceryl tridecyl acrylate, glycerin plus ethylene oxide triacrylate or • three Methyl acrylate vinegar, trimethyl propylene propylene singly epoxidized triacetin or trimethyl propyl hydrazine 曰 甲醇 甲醇 甲醇 院 二 二 二 二 二 二 曱 曱 、 、 、 、 、 、 、 、 、 , N-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 ether, two Φ ethylene glycol diglycidyl ether, polyethylene glycol Ether, glycerol polyglycidyl bis glycidyl ether and the like. After the radical reaction, the superabsorbent resin can have an appropriate degree of crosslinking, and the superabsorbent resin colloid can have appropriate processability. Radical polymerization The parent crosslinking agent may be used singly or in combination of two or more. Free Radical Polymerization Crosslinking agent Suitable additive amount is between 0.001 and 5 by weight (based on the total solids of the reactants). A more appropriate amount by weight is between 〇·〇1 and 3, and the amount of the additive is in the weight. After the polymerization of 0.001 or less, the hydrate is too soft and sticky. The mechanical additive is too low in water absorption of 5 or more to lower the resin properties. The viscous prepolymer can be photoinitiated in a conveyor belt reactor or a horizontal reactor equipped with a stirring blade, and the prepared highly water-absorbent gel is first cut into a shredder. A gel having a diameter of 20 mm or less, preferably 10 mm or less in diameter, and then dried. The drying temperature can be dried at 10 (TC to 250 °c, and the drying temperature is preferably 120 to 180 °C. When the drying temperature is below 120 °C, the drying time is too long. 15 1288140 Benefit, drying temperature. (3) The crosslinking reaction is carried out early in the second reaction, so that in the subsequent drying process, the crosslinking degree is too high to be effective, and the residual body can be reduced to achieve the effect of reducing the low residual monomer. After the pulverization, screening the wire diameter, and then the fine cross-linking agent coating treatment. The screening fixed particle size is preferably between 0.06 mm and J 〇〇 mm, preferably between _ brewing and 0.850 mm, and the particle size is 0.06. The following fine powder improves the finished dust, and the particle size of 1.00 mm or more makes the water absorption rate of the finished product slow. After screening the fixed particle size, the cross-linking agent capable of simultaneously reacting when surface-treating according to the present invention can be plural Alcohol such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, M butanediol, trisylmethylmethyl dahro, sorbitol, etc.; Amines such as: ethylenediamine, diethylenediamine, triethylenediamine, polyethylenediamine; or can be used with two or More than one epoxy group compound such as: sorbitol polyglycoside, polyglycerol polycondensation (IV), ethylene glycol diglycidyl, diethylene glycol diglycidyl ether, polyethylene glycol dimerized glycine _ , diglycerol polyglycidyl ether, etc.; alkylene carbonate such as: ethylene glycol carbon_, 4-methyl-1,3-dioxolane-2-one, 4,5_ Dimethyl·α-dioxole·2-ketone, 4,4-dimethyl-1,3-dioxacyclohexane-2,4•ethyl#dioxole _fine 1,3: dioxohane-2-one, 4,6•dimethyl(dioxanone) or oxebufen-2-one, etc. The usage may be used singly or in combination of two or more. The appropriate amount of the crosslinking agent at the surface is between 〇〇〇1 and 1〇 by weight (based on the total solids of the reactants), and the appropriate amount is in the weight. f percentage 16 1288140 ratio _5 to 5, the amount of cross-linking agent additive at the surface can not be _ effect when the weight percentage of the tank, cross-linking at the surface _ plus (four) in the weight of more than 100 〇 ,, water absorption Too low to reduce resin properties. Surface crosslinker coating When the time is left, the addition of the surface cross-linking may be directly added to the surface crosslinking agent, or added to the surface crosslinking agent aqueous solution, or adjusted to form a surface crosslinking agent aqueous organic solvent solution, hydrophilic organic solvent such as methanol, ethanol, The propanol, isobutanol, acetone, methyl ether, diethyl ether and the like are not particularly limited, and a solution may be formed, wherein methanol and ethylene are preferably added. When the surface is added to the side, the inert inorganic salt powder may be added to the high water absorption. To help the solution to disperse, the inert inorganic salt powder may be sulphuric acid, or sulphur dioxide, or oxidized, or oxidized or the like or a mixture thereof. Among them, sulphuric acid and cerium oxide are preferred. The inert inorganic salt powder is added in the weight range. The percentage 〇〇〇 is between 5 and 10.0, with 〇〇1 to 4 重量 by weight. After the surface crosslinking agent coating treatment, heat treatment is carried out at 8 TorrS23 〇t to allow the surface crosslinking agent to undergo a crosslinking reaction, and the internal crosslinking agent is subjected to a crosslinking reaction to attain the effects of the present invention. Treatment temperature 8 (the crosslinking reaction time below TC is too long, it is not economical.) When the treatment temperature is g230 °C, the resin is easily deteriorated and affects the quality. The treatment time is preferably 2 to 150 minutes, depending on the treatment temperature, and the temperature is high. The time is short, the temperature is low, and the time is long. Since the super absorbent resin has the phenomenon of agglomeration after moisture absorption, in order to avoid the use of the super absorbent resin in the high humidity region, the agglomeration after moisture absorption may result in unsatisfactory processing, generally in 17 1288140. With a pro: 丨生:: two sides coated with an inorganic salt powder or surfactant, so that the surface is a little machine ( (5) water-absorbent resin retains _ after the characteristics of not easy to agglomerate, this inert t machine ^ sulphur _, Red oxygen cut, or oxygen, or oxidized town, ==, or kaolin, or carbon _ or the like or a mixture thereof; _, the end of the month is not related to the size of the powder noodles, if;;: Li Wei: u, regardless of the specific surface area of the powder, so effective inert inorganic salt; 塁 丨 inert inorganic salt powder is added in the range of weight ratio 〇·〇〇5 to dynamic, wherein the weight percentage _ to 4G is preferred, inert Yi machine salt powder its particle size is please 1 / ZM to Qing M, if the inorganic salt powder with a particle size less than 0 Gu/zM is used for the industrial production of high-yield cakes, if the inorganic salt powder with particles larger than 100//M is used, the excessive addition amount will affect the absorption capacity of the super absorbent resin. The inert inorganic salt powder may be added alone or may be accompanied by a surfactant or a dry organic compound, and the interface may be HLA (hydmphile_lip〇phile balance) value 12 The above nonionic surfactant, or water-soluble anionic surfactant, or cationic surfactant, or y-yang-type surfactant, or a mixture thereof, usually has 9 界面 or a dry organic compound. Use glycerin, ethylene glycol, hexahexaol, polyoxyethylene alcohol, or polyethylene glycol, or polyethylene glycol stearate, or polyethylene glycol hexahexyl stearate, or polyoxyethylene benzene Ether, or polyoxyethylene octyl phenyl ether, or polyoxyethylene sesquiphenyl ether, or polyoxyethylene alkyl ether, or polyethylene oxide lauryl ether, etc., or a viscosity organic compound can be formulated into water The liquid form is added or added separately, and the appropriate surfactant or viscosity organic compound additive is between 1288140 篁 and 0.001 to 5 (based on the total solids of the reactants), and the appropriate amount is 0% by weight. Between 01 and 3. The invention adopts the method of pre-polymerization and further polymerization in the whole polymerization reaction, the viscosity of the pre-polymerized product relative to the liquid reaction material is obviously improved, the fluidity is lowered, and the belt reactor is more likely to be used later. Matching, and improving the stability of the entire polymerization reaction, the heat of reaction is not too high. The method for producing the super absorbent resin provided by the present invention has greatly improved the quality of the product in addition to improving the operating environment, especially for reducing the content of soluble matter. Obvious effect. In order to show the characteristics of the low soluble content of the superabsorbent resin in the present invention, the determination of the soluble content is as follows: firstly, 5 g of a highly water-absorbent resin is weighed, and then 185 g of 〇9 % brine is added at 500 rpm. After stirring for one hour, the SAP extract was filtered through a filter paper. Finally, the extract was weighed 2 〇 g, first titrated with 〇1N sodium hydroxide (NaOH), and then back titrated with 〇·1Ν hydrochloric acid (HC1) to determine the content of SAp solubles. The working examples are listed in detail below to illustrate the invention, but the scope of the invention is not limited by these examples. Example 1 (1) Add i76〇g acrylic acid and 2263.7g of water to a container replaced by a rat gas in 6000c.c, and then weigh 1476 3g of 45% aqueous sodium hydroxide solution, and hydrogen under ice cooling. The sodium oxide aqueous solution was slowly added to the aqueous solution of acrylic acid for neutralization; at this time, an aqueous solution containing an acid group of a single-detailed 38% by volume was obtained, and the +-containing 68 md% of the internal phase 19 1288140 acid was neutralized to sodium acrylate. • (2) Adding the above neutralized acid-based monomer aqueous solution to o.lg potassium persulfate: sodium sulfite = 1:1 (weight ratio) to a jacketed horizontal cylindrical prepolymerization reactor Mixing and prepolymerization are carried out. The reaction temperature was 20 ° C, the reaction time was - 60 min, and the obtained prepolymer viscosity was 100 cp. * (3) Add the viscous prepolymer, lg azobisisoheptacene and 768.768g glycerol polyethylene glycol diglycidyl i|(n=7) to the conveyor belt. • A high-intensity ultraviolet ray irradiator is used to irradiate the mixed liquid for 40 seconds (illuminance = 7.1 J/cm2) to cause cross-linking reaction to form a colloid. (4) Cut into a gel of 2 mm or less diameter using a cutter. (5) Drying at a temperature of 130 ° C for 2 hours; screening a fixed particle diameter of 0.1 mm to 0.85 mm by a sieve to obtain a powdery superabsorbent resin. (6) Weighing this superabsorbent resin i〇g, adding sulfuric acid|Lu powder 〇jg, after mixing evenly, then adding ethylene glycol carbonate: water: methanol=1 soil 1 (weight ratio) solution 〇.4g, Heat treatment at φ 215 ° C for 10 minutes. (7) After cooling, a high-performance superabsorbent resin is obtained, and the retention is determined to be 29.2 g/g, and the water absorption ratio under pressure of 20§/〇112 is 29.5 8/8, and the water absorption ratio under pressure of 49§/〇112=22.5 g/g, soluble content = 5.1%. Examples 2 to 4: (1) The operation method is the same as that in the first embodiment, but the prepolymerization time is I80min, 420min and 720min, respectively, and the obtained prepolymer viscosity is 370cp, 1350cp, 20 1288140 ^〇0〇ct (). St holding force is 32.3 ^, 34.5 ^, depreciation, 20 〆, pressure ϋ water magnification are 32.7 g / g, 31.5 g / g, 28 7 W, 39 pressure water rate fraction 24. 丨 g / g, 22.9 g / g, l9 8g / g, soluble content of 5.3%, 6.1%, 7.6%. Example 5 to VIII. U) The operation method is the same as Φ 25 ° C and 35 ° C, l 〇 5 〇 cP 〇 Example 1, but the prepolymerization temperature is 15t: respectively, and the obtained prepolymer viscosity is 15cp, 80cp, 270cp, (2) measured, holding capacity of 2λ1 g / g, 28 6 , 317 g / g, 33 4 w, 20 g coffee pressure under water pressure ratio of 27 3 g / g, 28 7 The water absorption ratios of g/g, g/g, and children's 5 gg 39g/cm are respectively heart, (4) Μ, ·, and 23·6 g/g, and the soluble contents are 2 peaches, 34%, and 5, respectively. 2%, 6 ι%. Example 92: • f, 乍方胡实关一, but the polymerization hair styling agent is ammonium persulfate and sulfite sulfonate (weight ratio - 1:1), hydrogen peroxide, hydrogen peroxide Diisopropyl ester, ^ 2,2·azobis(2-mercaptopropenyl) dihydrochloride. (2) The measurement holding power is 3〇.丨/ W 2y·7 g/g, 30.5 g/g, 31·0 g/g, and the water absorption ratio under pressure of 20 g/cm 2 'A~2. /g, 30·0 g/g, 28·9 g/g, 3 i ·6 g/g, and the water absorption rate under the pressure of 39 g/cm 2 was 23.0 g/g, 22.5 g/g, 29.9 g/ respectively. g, 23·6 g/g, soluble matter content y丨i 杳# / Knife is 5.1.1%, 6.2%, 5.4%, 5.7%. Example 13 to 15: 21

Alcohol trihydrate

丄 140 140 (1) ==! Example 1, but the cross-linking agent is C. The lower water absorption ratio is 3U g / g, 27.9 g / g, 28 7 g ' 2 〇 2 2, the pressure is not 5.7%, 3 5%, 3 9%. Φ T dissolved content is divided into sixteen to nineteenth examples: 〇 (1) = Saki's but the material _ marriage 30, 20, 1 sec, illuminance is divided into 60, L7W. Do not be 1 〇.2 fine 2,5."/ gamma 2, 3.5 test 2, (7) measure the simple force division π.6 g / g, 29 6 , - (d) pressure absorption rate of 3, / ' 2〇g/g , 39 e/cm2 厌 ★ g § 仏 办), 30.4 g/g, 32·9 _ (four) lower water absorption ratio of 24.9g / g, 26.3g / g, 243 heart 9 wall solubles The contents were 6.3%, 7.1% and 8.1%, respectively. Referring to Comparative Examples - to 2, the effects of Experimental Examples 1 to 19 were highlighted. Comparative Example 1: (1) In the 6_ex (10) gas-substituted Rongcaijia·g-propyl benzoic acid and 2263.7 g of water'· additionally weighed 1476 45 45% sodium hydroxide aqueous solution, and the sodium hydroxide aqueous solution was cooled under ice cooling. Slowly adding to the aqueous solution of acrylic acid, at this time, a monomer concentration of 38.6 wt% aqueous solution was obtained, in which 08 m〇l% of the acrylic acid was neutralized as sodium acrylate. 22 1288140 (2) 0.768 g of glycerol polyethylene glycol triglycidyl ether (n = 20) was added to the above neutralized monomer solution, and the temperature was maintained at about 20 C. (3) Add 1.9 g of hydrogen peroxide, 3.0 g of sodium persulfate and 1.0 g of 2. azobis(2-amidinopropane) dihydrochloride to initiate polymerization, and let it stand for 1 hour to form a gel. shape. (4) Cut into a gel of 2 mm or less diameter using a cutter. (5) Drying at a temperature of 130 C for 2 hours; using a sieve to screen a fixed particle size of 0.1 mm to 0.85 mm to obtain a powdery superabsorbent resin. (6) Take this super absorbent resin l〇g, add aluminum sulfate powder 〇.lg, and then add the ethyl citrate after mixing: water: fermentation = 1:1:1 (weight ratio) solution〇 .4g, heat treated at 215 ° C for 1 〇 minutes. (7) After cooling, a high-performance superabsorbent resin is obtained, and the retention is determined to be 331 g/g, and the water absorption ratio under pressure of 20 g/cm 2 is 32. 〇, the water absorption ratio under pressure of 49 g/cm 2 = 22.1 g/g, soluble Content = 12.1% 〇 • Comparative Example 2 (1) Add 176 〇g of acrylic acid and - 2263 Jg of water to a vessel replaced with nitrogen at 6000 C.C; and further weigh 45 〇 / 〇 sodium hydroxide solution 1476.3g, in ice · · cold 1 ^ hydroxy sin aqueous solution slowly added (four) acid aqueous solution for neutralization; this time to obtain a monomer concentration of 38.6wt% aqueous solution, which has 68 mol% of acrylic acid neutralization * for C Sodium citrate. (2) Add 768 kg of diol glycol triglycidyl triglycidyl bond (4) 2) to the monomer solution neutralized in the above section, and maintain the temperature at about 2 Torr. 23 I2S8140 95. 曰Other repairs (X. (3) Adding 1. 9 g of hydrogen peroxide, 3·g of sodium persulfate and 1〇g22-azobis(2_mercaptopropenyl) dihydrochloride The polymerization reaction was started, and it was allowed to form a colloidal form after being placed for a few hours. (4) The gel was cut into a size of 2 mm or less by a slitting machine. (5) Drying at a temperature of C for 2 hours; screening 〇jmm using a sieve ~ Q.85mm fixed - particle size, get powdery super absorbent resin. (6) Weigh this water-absorbing resin l〇g, add sulfuric acid Ming powder 〇 lg, to be mixed evenly φ, then add ethylene glycol carbonate: water : sterol = 1:1:1 (by weight) solution 〇.4g, heat treatment at 215 ° C for 10 minutes. (7) After cooling, that is, high performance superabsorbent resin, measuring retention, 20 g / Water absorption ratio under cm2 pressure = 31 · 5 g / g, water absorption ratio under pressure of 49 g / cm 2 = 24.7 g / g 'soluble matter content = ι〇 · 5%. As described above, a powder disclosed in the present invention The method for producing a superabsorbent resin which is insoluble in water, absorbs water, urine or blood and has a low soluble content has at least the following advantages: 1. High water absorption provided by the present invention The manufacturing method of the fat, in addition to improving the operating environment, the product quality is also greatly improved, and the invention has been confirmed through various experimental tests - particularly effective for reducing the content of soluble matter. 2. The present invention uses chemical techniques, The conventional polymerization reaction is replaced by: first using *prepolymerization' and then using light to initiate polymerization. The viscosity of the prepolymer of the present invention is significantly improved relative to other liquid reaction materials, and the fluidity is lowered, which is easier and later. The conveyor belt reactor is matched, and the overall polymerization stability is 24 1288140, and the heat of reaction is not too high. 乍 许 许 许 许 更 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 许 本 本 本 本 本 本 本 本 本 本Although the present invention has been disclosed in the foregoing preferred embodiments, it is not intended to limit the scope of the present invention.

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Claims (1)

1288140 X. Patent application scope: 』修 (more) is replacing 1. A method for producing a water-absorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content, and the method comprises at least the following steps: And a rate of 50 mole percent or more of an aqueous acid group-containing monomer solution and a polymerization initiator are subjected to a prepolymerization reaction to obtain a viscous prepolymer, and the acid group-containing monomer is selected from the group consisting of acrylic acid or methacrylic acid or acrylamine. Methylpropane sulfonic acid or a mixture of the above groups; 10 adding a long-chain polybasic epoxy compound and the polymerization initiator in the viscous prepolymer, further forming a gel by a photoinitiation polymerization; The gel is dried at a temperature of 10 (TC to 25 Torr, pulverized, screened, coated with a surface crosslinking agent, controlled at a temperature of 80 ° C to 230 ° C for a heated surface treatment and an inert inorganic salt is added. Powder. 2. According to the patent application, the powdery, water-insoluble, absorbable liquid, urine or blood and low-absorbent resin with low soluble content are manufactured. Prepolymer The viscosity is 1〇~(8). 3. Superabsorbent resin in powder form, transferred to water, absorbable liquid, urine or blood and low in soluble content according to the scope of patent application. a manufacturing method, wherein the polymerization reaction (f) is a thermal decomposition hair styling agent or a redox type annihilation initiator. /, -4. Powdery, water-insoluble, absorbable according to the third application of the patent application. A method for producing a superabsorbent resin having a low water content, urine or blood and a low soluble content, wherein the thermal decomposition initiator comprises ruthenium peroxide, chlorine peroxide, and di-third 26 1288140 peroxides, peroxy-amines or persulfates (ammonium salts, metal salts) peroxides or 2,2-azobis(2-mercaptopropane) dihydrochloride, 2.2,-Azobis(R); an azo initiator of (N,N-dimethylammonium) dihydrochloride. .5. A method for producing a superabsorbent resin having a powdery content, transferred to water, absorbable aqueous liquid, urine or blood and having a low soluble content according to item 3 of the special job application, wherein the oxidation type The initiator is an acidic sulfite, thiosulfate, ascorbic acid, ferrous sulfate or persulfate. • 6. A method for producing a powdery, water-insoluble, absorbable aqueous liquid, urine or money and a high soluble content in accordance with the scope of the patent application, wherein the prepolymerization is carried out. The vertical reaction tank with the paddle is installed, the center is equipped with a slurry for one-way flow of the material, the horizontal cylindrical container of the single (double) screw, or the pipe with the jacket and nitrogen gas. 7. According to the above-mentioned item i, please refer to the superabsorbent dendritic manufacturing method of powdery, secret water, absorbable water, urine or blood and low soluble content, _ where the prepolymerization The temperature is 5~8 (rc. 8. According to the special application, the method of manufacturing the superabsorbent resin which is insoluble in water, absorbs water, urine or blood and has low soluble content. The prepolymerization reaction time is 〜·5~16 hours. 9. According to the application of the shed, the powder, the water, the absorbable liquid, the urine or the blood and the soluble content is low. The method for producing a super absorbent resin, the towel is rotated to include the K) filament, and is further included in 3 to 60 seconds. 27 1288140 10'Manufacturing method of superabsorbent resin according to the special wealth, please refer to the powder, water, absorbable water, liquid, urine or blood and low soluble content according to the first item, % / Wherein the long-chain polybasic epoxy compound comprises sorbitol polyglycidyl ether, polypropylene glycol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl shunt, t ethylene glycol diglycidyl ether , diglycerol polyglycidyl ether. 11. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbable aqueous liquid, urine or blood and has a low soluble content according to the scope of claim 1 of the patent application, wherein the gel is screened The post particle size distribution ranges between 005 and i millimeters (mm). 12. The method for producing a superabsorbent resin having a powdery, poplar, absorbable aqueous liquid, urine or blood and having a low soluble content according to the above application, wherein the surface parent agent It is a polyol, or polyethylene glycol diglycidyl ether, or an alkylene carbonate or a mixture of the above groups. 13. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbable aqueous liquid, urine or blood and has a low soluble content according to the application of the special fiber circumference item i, wherein the surface cross-linking The agent can be added in the range of 〇〇〇5~5 〇 by weight. 14. The method for producing a superabsorbent resin which is powdery, insoluble in water, absorbable aqueous liquid, urine or blood and has a low soluble content according to the first aspect of the patent application, wherein the lysine inorganic salt powder is Or oxygen, or magnesium oxide, or calcium oxide or sinter, or cerium oxide, or carbonic acid, or magnesium carbonate, or a mixture of the above. 15. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs urine or blood, and has a low soluble content according to the patent of the patent (4), 28 1288140 wherein the inert inorganic salt The powder is added in the range of 0.01 to 4.0% by weight.