TWI327585B - Production efficiency of superabsorbent polymer - Google Patents

Description

1327585 ' IX. Description of the invention: ' [Technical field to which the invention pertains] ^ - * #· - The present invention relates to a method for producing a super absorbent resin, in particular to a water-absorbent resin having a low soluble content. Production method. % [Prior Art] • Lu two water-absorbing reversal has a strong secret water force 'absorbs 100 times or even thousands of times its own weight of water' domain water can be swollen and has a state of non-flowing, shouting pressure will not seep Leaks, and the absorbed water can be slowly released in the atmosphere. Because of the above-mentioned characteristics, the soil water retaining agent which was first used in the agricultural forestry industry has been widely used in recent years due to the considerable advancement in the production technology of superabsorbent resins, and sanitary articles such as diapers and adults have been widely used. The wealth of the women's health (four) products and preservation applications for food preservation. (5) The component of the water-absorbent resin is a hydrolyzed starch_acryl〇nitrile graft polymer (Japanese Patent Publication No. 49(1974)-43,395) Propylene thorn graft polymer (Japanese Patent A a a σ σ 51 (1976)-125, 468), saponified ethylene propylene acetate propylene g copolymer (曰本专利专利公告 52 (10) 7H4, called hydrolyzed propylene guess copolymer Or acrylamide copolymer (Japanese Patent Publication No. Sho 53(10) H5 959), and partially neutralized ♦ propylene k (Japanese Patent Laid-Open Publication No. Sho 55(10), etc., which is obtained by crosslinking polymerization using propylene k and propylene salt. Superabsorbent resin accounts for the largest part of 6 1327585. It is also the most economical, and its dependence can be quickly obtained from the consumption, and the obtained:: - the age is high (four) Qianli, and (4) the county is the most economical and effective. It has become a universal superabsorbent resin. * · 'The method of forming superabsorbent resin from polymerized acrylic acid and _ acid salt has been widely used. It has been successfully developed and has been used in industrial production. The method includes a ruthenium film and a polymerization reaction (Japanese Patent Publication No. Sho 48 (1973) -42,466), polymerization reaction was carried out in a kneading machine on a conveyor belt (Japanese Patent Publication No. 58 (Lan), 714), and a pulverizing stirring blade (Japanese Patent Laid-Open Publication No. Sho 57 (1982)- 34, 1G1), performing reverse float liquid polymerization (Japanese Patent Publication No. 59 (Cong)-37, _) ' or polymerizing a monomer or coating on a fibrous substrate (Japanese Patent Publication No. 62 (Japanese Patent Publication) 1987)-53, 309). Most of the above polymerization methods are obtained by reacting a reaction raw material such as an acid group-containing monomer, a polymerization initiator and a crosslinking agent with a radical polymerization reaction, so that the entire polymerization reaction is difficult. In view of the above, the present invention provides a method for producing a super absorbent resin, wherein the polymerization process is relatively stable and the heat of reaction is not too high, in addition to improving the operating environment. The manufacturing method provided by the invention further comprises the following steps: 1) pre-polymerizing an aqueous solution of an acid-containing monomer with a neutralization rate of 50 mole% or more and prepolymerizing the polymerization initiator to obtain a sticky amount. , the acid group-containing monomer is selected From propylene or thiol propyl or 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ c hot air drying, smashing, screening 4) surface cross-linking agent coating treatment. , 5) / dish degree 80C to 230eC heating surface treatment. 6) Add inert inorganic salt powder. The above prepolymerization can be carried out in a prepolymerization reactor which is required to have a uniform mixing and prepolymerization of the polymerization raw materials; The prepolymerization reaction H can be used in addition to the vertical reaction tank of the stirring paddle. The horizontal cylindrical container can also be used, and the towel is rotated to make the material flow in one direction, and is mixed, single screw or juxtaposed. The twin-screw is used to ensure that the reaction material is unidirectionally moved to the month without the phenomenon of reflow. From (4) the non-polymerization, the reaction material stays in the reactor for a long time to form a gel-like solid. The above-mentioned type of reactor is usually in the form of a batch of human materials, which is disadvantageous to industrialization. In view of the above, the present invention resides in a method for continuously producing a super absorbent resin having a low soluble content, which is characterized in that The n solution is retained in the line towel, and the initiator can be added to the line to cause the acid group-containing monomer to undergo radical polymerization to become a viscous polymer. After the viscous prepolymer is mixed with the ternary epoxy compound, it can be continuously added to the belt reaction, and a high-intensity light source can be used above it (for example: mercury lamp, halogen 1327585

• Light, infrared (V, ·, or T-ray, etc.) is used to initiate the polymerization to form a gel-like solid. Gas ♦ This feature is characterized by the use of partially neutralized acrylate in the pipeline, and the polymerization (10) agent is added to the line towel to carry out free radical polymerization of the acid group-containing monomer to form a polymer. The shaft prepolymer is then combined with bridging navigation to illuminate the light: it should be gelatinized. The pre-polymerization in the pipeline not only saves the m-like vertical reaction tank or the same-shaped container, but also ensures that the aqueous solution of the reaction monomer is advanced. The __principle' makes no reaction monomer remain in the pipeline during the county-integration process, thereby reducing Κ δ excessive reaction occurs. The residence time of the aqueous solution of the reaction monomer in the pipeline is an important factor of the pre-combination reaction. If the residence time is long, the more complete the prepolymerization reaction, the higher the viscosity and molecular weight of the prepolymer, and the soluble fraction of the finished product. It is also lower, but it is expected to occur in the county (four) degree polymerization; if the residence time is checked, the viscosity and molecular weight of the prepolymer are lower, and the finished product can be higher, but the chance of excessive polymerization is less. In addition, the mixing uniformity of the aqueous solution of the reaction monomer with the polymerization initiator and even the prepolymer and the bridging agent before the photoreaction is also an important factor affecting the prepolymerization reaction and the photoreaction reaction. In order to improve the contact effect of the above fluids with each other, the following methods can generally be used: (1) The tube is sprayed with a human inert gas. Such as: nitrogen, or carbon dioxide, or helium, or helium, or a mixture thereof (10). In order to save costs and considerations in the industry, it is common to use nitrogen or carbon dioxide or a mixture thereof. In addition, the pressure of the inert gas should be 13⁄4 in the f-line pressure, so that the inert gas paste can be filled with the monomer aqueous solution line _ to make each reaction Zhao achieve the mixing effect, (2) in the f-shooting agricultural snail 9 % 1327585 Mixed-effect correcting fillers such as: Raschig rings or wave earrings, (3) using a vapor-liquid static mixer. In addition to the acid group-containing mono-acrylic acid required for the production of a super absorbent resin, other water-soluble monomers having unsaturated double bonds, such as methyl-acid or marolinic acid, may be used. Or fumaric acid, or 2-propenylamine-2-methylpropanin, such as tartaric acid. Monomers can be used without any specific limitation. They can also be combined with multiple fresheners. It is also possible to add other hydrophilic monomers with unsaturated double bonds, such as acrylamide or methacrylic acid. Amine, 2-hydrocarbyl ethyl acrylate, 2-hydrocarbyl ethyl acrylate, ruthenium acrylate, acrylic acid, diamine propylene acrylamide, chlorinated propylene amide amide, but not heavy The physical properties of the superabsorbent resin are principles. i Before the radical polymerization, the concentration of the aqueous monomer solution should be controlled between 20% by weight and 55% by weight, the appropriate concentration is between 3〇wt% and 45rt%, and the concentration is less than 20wt% by weight. The combination is too soft and sticky. Unfavorable mechanical processing 'addition concentration is above 55 wt% by weight'. It is close to saturation concentration, difficult to formulate and the reaction is too fast. The reaction heat is not easy to control. The carboxylic acid group of the acid group-containing monomer should be partially neutralized to control the pH of the finished product, so that the neutral or slightly acidic 'neutralizer is hydrogen peroxide, sodium hydroxide, potassium hydroxide, 5 carbonic acid clock, Sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and ammonia. The carboxylic acid group of the acid group-containing monomer is partially neutralized to a lithium salt or a sodium salt or a potassium salt or an ammonium salt or a mixture of two or more kinds, and the percentage of the molar amount is 45 mol% to 85 mol%, suitable wave Degree is 1327585

When the percentage of neutralization concentration of 50mol% to 75mol% is 45mol% or less, the pH value of the finished product will be low. When the percentage of neutralization concentration is 85mol% or more, the pH value of the finished product will be high, and the finished product PH value is not present. In case of sexual or sputum acidity, inadvertent contact with human body is not suitable or safe. The prepolymerization starts by the decomposition of the polymerization initiator to generate a radical. The polymerization initiator may be selected from a thermal decomposition type initiator. Suitable thermal decomposition type initiators include peroxides such as hydrogen peroxide, di-tert-butyl peroxide, guanidinium peroxide or persulfate ( Ammonium salt, alkali metal salt, etc., and azo compound such as: 2·2'-azobis(2-amidinopropane) dihydrochloride, 2. 2'-azobis (N, N- Dihydroxanthyl dihydrochloride; dihydrochloride; may also be used as a redox initiator, such as acid sulfite, thiosulfate, ascorbic acid or ferrous salt; or redox The type of initiator and the thermal decomposition initiator are used in combination. First, the redox initiator first reacts to generate a radical, and when the radical is transferred to the monomer, the polymerization proceeds, and the polymerization reaction is released. A large amount of heat increases the temperature, and when the temperature reaches the decomposition temperature of the thermal decomposition type initiator, decomposition of the second stage thermal decomposition type initiator is caused, and the entire polymerization reaction is more complete. Generally, the radical polymerization initiator is suitably used in an amount of from 〇〇〇1% to 〇wt% (based on the weight of the neutralized acrylate), and more suitably in the range of l. lwt% to 5% by weight. Between 0.001 wt% or less, the reaction is too slow to be uneconomical; when the weight percentage is more than 10% by weight, the reaction is too fast. The reaction heat is not easily controlled and is easily polymerized to form a gel-like solid. 11 Ϊ 327585 To add light to the viscous prepolymer before the start of the polymerization, the crosslinker may be a compound with two or more unsaturated double bonds, such as ❹-雔 (2—two Amine, oxime methyl propylene diamine, methine dimethyl propyl amide, acryl acrylate, ethylene glycol diacrylate vinegar, polyethylene glycol dipropylene _, _ _ Alcohol dimercapto acrylate, polyethylene glycol dimethacrylate, glycerol triacetate vinegar, trimethyl propyl glycerol, glycerin plus epoxy acetonitrile, her brewing or dimethyl propylene Sour vinegar, trimethyl propylene sulphate, epoxy sulphur triacetate or tris, acrylate, trimethyl propylene trimethacrylate, trimethyl propylene triacrylate = bis(2-propenyl)amine, Dipropylene glycol vinegar, dipropylene triethylene glycol: 曰, can also choose compounds with two or more epoxy groups, such as sorbitol: glycosaminoglycan (tetra), polyglycerol polycondensation _ , ethylene glycol diglycidyl, : ethylene glycol dihydrated _, polyethylene glycol dihydrated _, diglycerin polycondensed 2 oil it [in freedom The reaction can after having suitably Superabsorbent = degree of crosslinking, the superabsorbent polymer additive # Suitable colloids of the guard. The radical polymerization inverse == agent may be used singly or in combination of two or more. Free radical polymerization cross-linking = when the amount of additive in the weight percentage Q • hidden _ to 5w version just as the reactant ^ shape material fresh) '(four) when _ «quantity percent please thank you (four) 2 add seam in the weight percentage please (4) After the following polymerization, the hydrated body is too soft and has: unfavorable mechanical processing, and the amount of the additive is in the weight percentage - the above water absorption is too _, and the resin property is lowered. The horizontal reaction of the stirring blade can be used to carry out the polymerization initiation reaction on the conveyor belt reactor or in T327585-, and the high water-absorbent gel is prepared by firstly using the grounding. A small gel having a particle size of 2 g or less, preferably m or less, and then dried.卞 < -. Then the temperature can be HO (TC to 25 (drying under TC, drying temperature is 12〇; ^ to 18叱 for the county, when the county temperature is below 12 () t below the dry time • too long * Qixin's silk temperature 18Gt^x_U secretly makes the exchanges early and cross-linking, so that the subsequent dry process, because the degree of cross-linking is too high, can not effectively remove the residual monomer, to achieve low residual The effect of the monomer. After drying, the pulverization, _ grading the particle size, and then the surface cross-linking agent coating treatment. Screening the fixed particle size from 0 to m to U0 is appropriate, to 〇.1〇„ 0. 850mm Between the #又仏, 粒〇〇.〇6 delete the following fine powder to improve the finished dust, particle size 1. 00mm or more particles make the product water absorption rate slower. Water-absorbent resin Lin riding chemical-like polymer, fine The uniform structure of the bridge structure is generally used to improve the quality, such as: improving the absorption rate, increasing the strength of the colloid, increasing the resistance to joints, and (4) the permeability, etc., and the surface of the grease is further advanced into the step bridge. That is, having a polyfunctional crosslinkable d capable of reacting with an acid group has been proposed in the prior art. The aqueous resin and the crosslinking agent are subjected to surface crosslinking treatment in the organic solvent #1 up+56_i3, JP_A_57_44627, JP-AI42·, JP-A58-117222) using inorganic powder: 纟 directly bonding the parent and the crosslinking agent solution Mixed with superabsorbent resin treatment 'UP-A6G-163956, 疋韵_验4), after adding cross-linking agent, steam treatment 13 1327585 (JP 'Al-113406) 'surface treatment with organic solvent, water and polyol (_JP A-63-27G741, IP-A-64-5G7G7, IP+1-292GG4) use organic cold liquid, water, ether compound '(: ρ_Αϋ9()3), etc.; these surface treatment methods are mixed Increasing the absorption rate under the lifting force, but it will cause the adverse effect of excessive retention and reduce the performance of the powder.

According to the present invention, the cross-linking agent can be a poly/alcohol such as glycerol, ethylene glycol, diethylene glycol or triethylene glycol. , polyethylene glycol, propylene glycol,! , 4 butanediol, trihydrocarbylmethyl propylene, sorbitol, etc.; or polyamines such as ethylenediamine, diethylenediamine, triethylenediamine, polyethylenediamine; or two or two Like the Wei-based orbital compound such as ···························································· Glycerol polyglycidyl sulphate; may also use acetonic acid carbonate such as: ethylene glycol carbonate, 4_mercapto 43-dioxolane-2, 4, 5-dimethyl-!, 3_dioxole, 4,4-dimethyldioxolane, 4-ethylindole-3-dioxacyclopentanone, u-dioxane-2, 4,6_m 3 dioxolane or 1,3-dioxane-2, and the like. The crosslinking agent at the surface may be used singly or in combination of two or more. The appropriate amount of the crosslinking agent at the surface is between 0. ooiwn and iGwt% (based on the total _ parts of the reactants), more appropriate amount 〇 _ run 5wt%, cross-linking at the surface _ When the dosage is less than 百分.〇_%, the effect is not obvious. When the amount of cross-linking agent additive is more than 1321,237,585 knives and more than lOwU, the water absorption is too low, and the resin performance is lowered. . The surface is 乂t峨, and the surface cross-linking batch can be added as a surface cross-linking agent. Add or adjust the surface to be added to the aqueous solution, or adjust the surface crosslinking agent to add a hydrophilic organic solvent aqueous solution. Hydrophilic organic solvent For example, methanol, ethanol, propanol, alcohol, and _H are not particularly limited, and a solution can be formed. Preferably, sterol and ethanol are used in .2. Table • Surface cross-linking agent added in superabsorbent resin _ ; Φ = 1 ± no paving Tai ' to help the solution to disperse 'inert inorganic sputum can be sulfuric acid Ming, or 'fossil eve' or oxidation Ming, or oxidation town Etc. or a mixture thereof. Among them, the name of sulfuric acid, one emulsifying bribe. , New York salt powder is added in the range of: t amount percentage G. 〇〇 5wt% • to 1〇. 〇Wt%, wherein 〇. Olwt% to 4·Owt% is preferred. After entering the surface of the lamp, the X-foaming treatment is carried out, and then the surface is heated to 2 wrists to make the surface into contact with the surface, and (4) the cross-linking reaction is carried out to achieve the effect of the present. Treatment temperature 8 "c below the cross-linking reaction time is too long, do not have a good effect, processing temperature ^ 230. When 〇, the resin is easily deteriorated and affects the quality. As for the treatment time, _m 2~15G minutes is appropriate, depending on the processing temperature, the temperature is high, the temperature is low, and the temperature is low. Since the application of the water-absorbent essence has the advantage of hiding after caking, in order to avoid the use of superabsorbent resin in high-humidity areas, there will be aggravation after moisture absorption, and the surface will be coated on the high-absorbing XI±M. Inert inorganic salt powder or surfactant, so that the surface is slightly sister-friendly, so that the water-absorbing resin retains the characteristics of not easy to agglomerate after moisture absorption. This inert no 15 1327585 machine salt powder can be selected with sulfuric acid chain, or dioxide; Either, or oxidized, or magnesium oxide, or calcium oxide, or kaolin, or calcium carbonate, or magnesium carbonate, or a mixture thereof; usually, the amount of the inert inorganic salt powder is related to the particle size of the inorganic salt powder particles, The granules having a smaller particle size and a larger specific surface area of the inorganic salt powder, the amount of the inert inorganic salt powder may be less, and the inert inorganic salt powder is added in a weight ratio of 〇. 005 wt% to 10. Owt% between Oi. oiwt% to 4. 〇wt% is preferred, the inert inorganic salt powder has a particle size of 〇. 001 βΜ to 100. If the inorganic salt powder with a particle size smaller than 〇. ooi y Μ is used, the cost is too high for industrial production. If using particles 100 # Μ inorganic salt in the powder, there are added in an amount excessive impact force absorbing superabsorbent polymer. The inert inorganic salt powder may be added alone or may be added with a surfactant or a viscosity organic compound, and the surfactant or the viscosity organic compound may be selected from a value of 12 or more of a nonionic surfactant or a water-soluble anionic surfactant, Or a cationic surfactant, or an yin-yang amphoteric surfactant, or a mixture thereof, usually a surfactant or a viscous organic compound may use glycerin, ethylene glycol, hexahexaol, polyoxyethylene glycol, or polyethylene Alcohol, or polyethylene glycol stearate, or stearic acid ♦ hexitol hexaacetate, or polyethylene oxide benzophenone, or polyoxyethylene octyl phenyl ether, or polyoxyethylene dodecyl ether, or Polyoxyethylene alkyl ether, or polyethylene oxide laurel, etc., such a surfactant or a viscous organic compound may be formulated into an aqueous solution or added separately, and a suitable surfactant or viscosity organic compound additive in a weight percentage 〇 Between OOlwt% and 5% by weight (based on the total solids of the reactants), a more appropriate amount by weight is between 〇1wt% and 3% by weight. 1327585 SUMMARY OF THE INVENTION The present invention provides a method for continuously searching for a high water-absorbent resin having a low soluble content, which is a reaction monomer fresh start initiator prior to prepolymerization, prepolymer and ring. The oxy compound is then illuminated to form a gelatinous solid. Through this production method, the viscosity of the prepolymer relative to the liquid reaction material is remarkably improved, and the fluidity is lowered' more easily matched with the subsequent belt reactor, and the stability of the entire polymerization reaction is lowered. The heat of reaction is not too high. It is important to use the pipeline reaction to save space and to ensure the principle of first-in-first-out of the reaction fluid, and to achieve continuous production. The high-absorbent female fat manufacturing method provided by the present invention not only improves the production operability and In addition to the working environment, the quality of the product is also greatly improved, especially for reducing the content of soluble matter. For the characteristics of the low soluble content of the present invention to the water-absorbent resin, the measurement steps of the soluble matter are as follows: first, take a Q. 5 g high water-absorbent contact and then add 〇. 9 % saline 185 g After stirring at 500 rpm for one hour, the SAP extract was filtered through a filter paper. Finally, the extract was taken up to 20 g, first titrated with 0. IN NaOH, and then back titrated with 0. IN HC1 to determine the content of SAP solubles. 17 1327585 [Embodiment] The following is a description of the present invention, but the patents and technical scope of the present invention are not limited by these examples. Example 1: (1) 1760 parts by weight of acrylic acid and 2263.7 parts by weight of water were added to the neutralization tank, and then 1476.3 parts by weight of an aqueous sodium hydroxide solution (concentration: 45%) was slowly added to the above under ice bath. In an aqueous solution of acrylic acid. At this time, an aqueous solution having a monomer concentration of 38.6 rt% was obtained, in which 68 mol% of acrylic acid was neutralized to sodium acrylate. (2) After the neutralization order is completed, the temperature of the aqueous sodium sulphate solution neutralized in the control section is about 20 °C. (3) Adjust the flow rate of the above monomer solution to 1 〇〇 liter / hr, and pass it through a non-mineral steel pipe with a straight position of 5 cm and a total length of 26.35 m. In addition, a stainless steel pipe with a diameter of 〇. 5 and 〇. 9 cm is connected to the side of the steel pipe at a distance of 5 cm and 10 cm. In the former, nitrogen gas was introduced, and the flow rate was controlled to 2 liters/hour, while the latter was passed through potassium persulfate/sodium hydrogensulfite = 1/1 (weight ratio), and the flow rate was controlled to 2 ml/hr. The prepolymerization and reaction temperatures were controlled at 20 ° C, and the resulting prepolymer viscosity was 80 cps. (4) Connect two diameters of 9 cm from the outlet end of the pipeline to the side of the pipeline. 9 cm of non-scale steel pipe, one imported dioxane, and the flow rate is controlled to 20 ml/hr. Two §? 5 ^ B- ol diglycidil test (n = 7), flow control 1327585 is 15 ml / hour. (5) The reaction fluid described in (4) is placed on a conveyor belt, and a high-strength ultraviolet ray irradiation device is disposed above the conveyor belt, and the mixed liquid is irradiated by the device for 20 seconds (illuminance = 13.9 J/cm2) to carry out the reaction. The cross-linking reaction forms a colloid. (6) Cut into a gel of 2 mm or less diameter using a cutter. (7) Drying at 130 C for 2 hours; using a sieve to screen 〇·imin~〇. g5mm fixed granules to obtain powdered T§j water-absorbent resin.

(8) Weigh the water-absorbent resin i〇〇g and add aluminum sulfate powder k. After mixing, add ethylene glycol carbonate to the solution of water/methanol/methanol=1/1/1 (weight ratio). Heat treatment at 215 ° C for 1 Torr. (9) After cooling, 'Add 1 § carbon_Former Company's product name: faint and 鸠 2 g of glycerin aqueous solution, all of which are mixed to obtain high-performance superabsorbent resin. Measurement guarantee

= :g'49g/cm2 Under pressure, 篁 = 10. 1%. Example 2: (1) Repeated Example -' but the length of the single steel (four) was changed to a viscosity of 210 cps. The superabsorbent resin was maintained at a pre-polymerization pressure under water absorption ratio = 23 fields, soluble matter '8 Example 3: (1) Example 1 was repeated, but the total length of the individual steel pipe was changed to * viscosity was 370 CPS. Highly water-absorbent tree. 2%。 The long, the resulting engraving force is 35.4g / g, 49g / c 1327585 under water pressure absorption ratio = 25. 2g / g, soluble content = 7.2%. Example 4: ψ- (1) Before adding 1760 wt of acrylic acid to 2263. 7 parts by weight of water in the neutralization tank, then 1476. 3 parts by weight of sodium hydroxide aqueous solution (concentration is 45%) was slowly added to the above aqueous acrylic acid solution. At this time, an aqueous solution having a monomer concentration of 38.6 wt% was obtained, in which 68 mol% of acrylic acid was neutralized as sodium acrylate. (2) After the completion of the neutralization procedure, the temperature of the aqueous sodium acrylate solution neutralized in the control section is about 20 °C. (3) Adjust the flow rate of the above monomer solution to 1 〇〇 liter / hr, and pass it through a stainless steel official with a diameter of 5 cm, a total length of 26.35 m and a diameter of 5 zippered inner ring. In addition, a stainless steel tube with a diameter of 〇·5 and 〇.9 cm is connected to the side of the stainless steel tube at a distance of 5 cm and a side of 1 cm. The former was introduced with nitrogen, the control was 200 liters/hour, and the latter was passed through potassium persulfate/sodium hydrogen sulfite = 1/1 (weight ratio). The flow rate was controlled to 2 ml/hr. The prepolymerization and reaction temperature were controlled at 2 〇 c ' and the resulting prepolymer viscosity was n5 cps. (4) Two diameters are connected to the side of the exit line of the official line at 85 cm. 9 cm of stainless steel sputum is introduced into the azo diisoheptane, the flow rate is controlled to 20 ml/hr, and the other is introduced into the glycerol. Ethylene glycol triglycidyl ether (n=7) with a flow rate control of 15 ml/hr. (5) The reaction fluid described in (4) is placed on a conveyor belt, and a high-intensity ultraviolet ray irradiator is disposed above the conveyor belt, and the mixed liquid is irradiated by the apparatus for 2 sec seconds (illuminance of 1327585 = 13.9 J/cm2) for crosslinking reaction. The colloidal β V (6) was cut into a gel having a diameter of 2 or less by a cutter. (7) Drying at I30 C for 2 hours; using a sieve to screen 〇. 1 coffee ~ 〇 · 85 surface fixed particle size 'to obtain a powdery superabsorbent resin. (8) Weigh 100g of this superabsorbent resin and add lg powder lg. After mixing, add 4g of ethylene carbonate/water/methanol = 1/1/1 (weight ratio) solution to 215 C. The temperature was heat treated for 1 minute. • (9) After cooling, add 12 carbon (Taiwan company product name: NS-2000) and 20% glycerin solution 2g, and mix high-performance superabsorbent resin. Determination of retention = 31.3g / g, water absorption at 49 g / on2 pressure = 23 5g / g, soluble content = 8.9% » Example 5: (1) repeated real butterfly -, but the total length of the woman is 52 The resulting prepolymer had a viscosity of 302 cPS. The retention of the superabsorbent resin is a crime, 49 - the water absorption ratio under pressure = 24. 5g / g, the soluble content of diterpene iodine. Example 6: (1) The example was repeated - but the total amount of the secret steel pipe was changed to (10) meters long, and the obtained prepolymer viscosity was yang CPS. The retention of the superabsorbent resin was 36. She, 49 g of heart 2 under water pressure absorption ratio = 24.3 g / g, soluble content. Example 7: Acid and 2263. 7 parts by weight of (1) 1760 parts by weight of propane 21 Ϊ 327585 water was added to the neutralization tank, and then 1476. 3 parts by weight of sodium hydroxide aqueous solution (concentration of 45) under ice. %) slowly added to the above aqueous acrylic acid solution. At this time, an aqueous solution having a monomer concentration of 38.6 wt% was obtained, in which 68 m〇i% of the acrylic acid was neutralized to sodium acrylate. (2) After the neutralization process is completed, the temperature of the aqueous sodium sulphate solution neutralized in the temperature control section is about 20 °C. (3) Adjust the flow rate of the above monomer solution to 1 〇〇 liter / hour, and pass it through a gas-liquid static mixer (label: NORITAKE) with a diameter of 5 cm and a total length of 27.2 meters. The length of the mixing section is 3 cm. In addition, a stainless steel pipe having a diameter of 〇. 5 and 0.9 cm is connected to the side of the non-ferrous steel pipe at a distance of 5 cm and a side of 1 cm. The former introduces nitrogen gas and the flow rate is controlled to 2 liters per hour. The latter is introduced with persulfate desorption/hydrogen sulfite = 1/1 (weight ratio), and the flow rate is controlled to 2 ml/hr. The prepolymerization and reaction temperatures were controlled at 2 ° C, and the resulting prepolymer viscosity was 95 cps. (4) Two stainless steel pipes of diameter 〇. 9 cm are connected to the side of the outlet end of the pipeline at a distance of 85 cm, one is introduced with azobis-iso-gumamine, the flow rate is controlled to 20 ml/hr, and the other is introduced into C3. Alcohol polyethylene glycol triglycidyl ether (n = 7), flow control of 15 ml / hour. (5) The reaction fluid described in (4) is placed on a conveyor belt, and a high-intensity ultraviolet ray irradiator is placed above the conveyor belt, and the mixed liquid is irradiated by the apparatus for 20 seconds (illuminance = 13.9 J/cm2) to be delivered. The reaction is a colloid. (6) Cut into a gel having a diameter of 2 or less using a cutter. 22 1327585 (7) Drying at 130 °C for 2 hours; using sieve mesh 遝 t, 0.1 咖~〇.85mm fixed particle size' to obtain a powdery superabsorbent resin. r (8) Weigh this superabsorbent resin i〇〇g, add sulphur bismuth molybdenum powder 1 ^ _ and then add ethylene glycol carbonate / water / methanol = 1 / 1 / 1 (heavy denier ratio six, t 〇 Heat treatment at 215 ° C for 1 〇 minutes. (9) After cooling, 'add lg calcium carbonate (formed by Formosa Plastics Co., Ltd.: NS-2000) and 20% glycerin aqueous solution 2g, evenly mixed to obtain high-performance ancient

bTBJ and waterborne resin. The holding power was determined to be 31.2 g/g, and the water absorption ratio under the pressure of 49 g/cm 2 was 2+g/g, and the soluble matter content was 6.1%. Example 8: (1) Repeat the actual situation...but the total length of the non-mineral pipe is 53 meters long, and the obtained prepolymer viscosity is 285 cPS. The retention of the superabsorbent resin was % under water pressure absorption ratio = 24.9 g/g, and the soluble matter content was 521%. Example 9: (1) The Example -' was repeated except that the total length of the stainless steel tube was changed to (10) meters long, and the obtained prepolymer had a viscosity of 410 cPS. The superabsorbent resin has a holding power of 35 8 , and the water absorption ratio under the pressure of 49 2 = 26. 4 g / g, and the soluble matter content is compared with the first example: (1) the reaction sheet described in the step (3) is repeated. The body solution was injected into the vertical reaction tank under nitrogen gas (flow rate control at 200 MfV hours) and the reaction reaction was carried out for about 30 minutes under high-speed drop. The viscosity of the prepolymer obtained was 14〇cps, but it was issued after the discharge. There is a little polymer on the mixing blade. The retention of the superabsorbent resin was 33.4 g / ^ ' 49 g / cm 2 under water pressure capacity = 231 § / §, soluble content = 13.7% gas... Comparative Example 2: (1) Repeat Example 1, but The reaction monomer solution described in the step (3) is injected into the vertical reaction tank under nitrogen gas (flow rate control at 200 liters/hour) and the reaction reaction is carried out for about 60 minutes under high-speed mixing, and the obtained prepolymer viscosity is 255 cps. However, after the discharge, there is a phenomenon that some of the polymer remains in the stirring blade and the reaction tank. The retention of the superabsorbent resin was 36. lg/g, the water absorption ratio under a pressure of 49 g/cm2 > 23.4 g/g, and the soluble matter content = 13 5%. [Simple description of the picture] Blood No. [Main component symbol description] jfek 〇 } ”, v 24

Claims (1)

1327585 April 28, 2010 Revision X. Patent application scope: 1. 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 includes The following steps: 1) The aqueous solution of the acid group-containing monomer having a neutralization rate of 50 m〇ie% or more is retained in the pipeline and prepolymerized to obtain a viscous prepolymer, and the acid group-containing monomer is obtained. Is selected from the group consisting of acrylic acid or methacrylic acid or 2-propenylamine-2-mercaptopropenic acid or a mixture thereof; 2) adding a long chain, highly hydrophilic polybasic epoxy compound to the viscous prepolymer, using light The initial polymerization mode further produces a gelatinous solid; 3) drying, pulverizing, and screening at a temperature of 1 〇 (TC to 250. 〇 hot air; 4) surface crosslinking agent coating treatment; 5) temperature 8 (TC to 23 ( TC heating surface treatment; 6) Adding an inert inorganic salt powder 2. A powdery water-insoluble water-absorbable liquid, urine or blood and low water-absorbent content as described in claim 1 of the patent scope The method for producing a resin, the viscosity of the viscous prepolymer is 10 lOOOOcps 3. 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, as described in claim 1, wherein the polymerization initiator can be used. It is a thermal decomposition type initiator or a redox type initiator. 4. A powdery, water-insoluble, water-absorbable urine or blood and a low soluble content as described in claim 1 or 3. A method for producing a water-absorbent resin, which is a thermal decomposition type initiator, which may be hydrogen peroxide, ruthenium peroxide, or a second-third butyl 25 1327585 Λ • V. April 28, 2010 amendment - base peroxide, peroxidation a peroxide such as a guanamine or a persulfate (ammonium salt, an alkali metal salt), or a 2,2-azobis(2-amidinopropane) dihydrochloride, 2.2, an azobis An azo initiator such as methyl isobutyl hydrazine dihydrochloride. 5. A method for producing a superabsorbent resin which is powdery, insoluble in water, absorbable, effluent urine or blood and has a low soluble content, as described in claim 1 or 3, The type initiator ' may be an acidic sulfite, thiosulfate, ascorbic acid, ferrous sulfate or persulfate. 106. A method for producing a superabsorbent resin according to the above-mentioned item 1 which is powdery, insoluble in water, absorbable aqueous liquid, urine or blood and has a low soluble content, and the pipeline may be A line containing an inert gas, a line containing a spiral vane, a line equipped with a filler for mixing effect or a gas-liquid static mixer. 7. The method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water, urine or blood and has a low soluble content, as described in the patent application, the temperature of the prepolymerization reaction It is 5~8〇〇c. Lu 8. 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, as described in claim i, wherein the prepolymerization time is 0.5. ~16 hours. 9. A method for producing a superabsorbent resin which is described in the first paragraph of the patent application, which is insoluble in water, absorbs water, urine or blood, and has a low soluble content. Completed in 30~60 seconds. 1. 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 as described in claim 1 of the patent scope, the length of which is 26 1327585 V 2010 Revised on April 28th, the lysine compound can be a mountain bribe water (4), polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol Glycidyl ether, diglycerol polyglycidyl ether, and the like. U. 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, as described in the first application of the patent scope, The distribution of the grain is between 0. 05mm to 1 leg. Φ 12. 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, as described in the first paragraph of the patent scope, the surface parent-linked agent It is a polyol, or polyethylene glycol diglycidyl _, or an alkylene carbonate or a mixture thereof. 13. For example, the scope of the patent application! The 5% by weight of the 5% by weight of the 5% by weight of the 5% by weight of the 5% by weight of the 5% by weight of the 5% by weight of the 5% by weight of the 5% by weight of the 5% by weight. ~5. Owt%. Φ 14. 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, as described in item j of the patent scope, the inertia: '... The end may be aluminum sulfate, or aluminum oxide, or magnesium oxide, or oxidized mother, or sulphur, or sulphur dioxide, or carbonic acid, or carbonic acid, or the like. The method for producing a superabsorbent powder which is powdery, insoluble in water, absorbable water, sputum or blood and has a low content of soluble matter according to the first aspect of the patent scope of the patent application, the inert inorganic salt powder is added in the range of «Percentage is 0. Glwt%~4. (4). 27