CN100413894C - Preparation method of powdery, water-insoluble high hydroscopicity resin capable of adsorbing water, urine or blood and containing low content soluble substance - Google Patents

Preparation method of powdery, water-insoluble high hydroscopicity resin capable of adsorbing water, urine or blood and containing low content soluble substance Download PDF

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CN100413894C
CN100413894C CNB2005101241400A CN200510124140A CN100413894C CN 100413894 C CN100413894 C CN 100413894C CN B2005101241400 A CNB2005101241400 A CN B2005101241400A CN 200510124140 A CN200510124140 A CN 200510124140A CN 100413894 C CN100413894 C CN 100413894C
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absorbent resin
urine
blood
super absorbent
water
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CN1970588A (en
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施凯耀
吴政璋
钟宏宗
黎元中
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TAIWAN PLASTICS INDUSTRIAL Co Ltd
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TAIWAN PLASTICS INDUSTRIAL Co Ltd
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Abstract

The invention discloses a making method of powder-shaped, insoluble, water, urine or blood absorbable, low-nonreacted monomer high-hydroscopicity resin, which comprises the following steps: adding acid group monomer liquid with neutralizing rate over 50%; prepolymerizing with initiator to obtain viscous prepolymer; selecting acroleic acid or methyl acroleic acid or 2-acroleic amide-2-methyl propane sulfonic acid or mixture as monomer; adding long-chain, high-hydrophilicity polybasic epoxy radical compound and polymer initiator in the viscous prepolymer; generating gel solid; drying through hot wind at 100-250 deg.c; grinding; sieving; coating surface crosslinking agent; heating surface at 80-230 deg.c; adding inert inorganic salt powder.

Description

Powdery, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content
Technical field
The present invention relates to a kind of manufacture method of super absorbent resin, particularly a kind of powdery, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content.
Background technology
Super absorbent resin has powerful moisture holding capacity, can absorb hundred times even thousand times to the water of weight own, but and after the suction swelling have and keep immobilising state, can seepage even exert pressure also not, and absorbed water can gently disengage in atmosphere.Owing to have above-mentioned characteristic, so be used in the water-loss reducer of soil of agricultural forest industry the earliest, in recent years the production technology because of super absorbent resin has sizable progress, so also apply to the water-retaining agent of sanitary product such as diaper, adult-incontinence articles and women sanitary articles widely and preserve fresh-keeping application that food uses etc.
The composition material of super absorbent resin have hydrolysis starch acrylamide nitrile (hydrolyzedstarch-acrylonitrile) graftomer (the open communique clear 49 (1974)-43 of Japanese Patent, 395), neutral starch acrylamide acid graftomer (the open communique clear 51 (1976)-125 of Japanese Patent, 468), saponification ethene acetate propylene ester copolymer (the open communique clear 52 (1977)-14 of Japanese Patent, 689), hydrolyzed acrylonitrile multipolymer or acrylamide copolymer (Japanese patent gazette clear 53 (1978)-15,959), and partly and polyacrylic acid (Japanese Patent openly announces clear 55 (1980)-84,304) etc.Wherein account for maximum partly also economical with the super absorbent resin that uses vinylformic acid and acrylate to carry out the crosslinking polymerization gained, its former because vinylformic acid can be obtained by commercially available rapidly, and the super absorbent resin that makes has high water-retaining capacity, and have cheap for manufacturing cost and tool economic benefit, so become the super absorbent resin that generalizes most.
Absorbent resin is undissolved hydrophilic polymer, general resin inside has inhomogeneity bridge formation structure, in order to improve quality, for example improve uptake rate, improve colloid intensity, improve anti-caking effect and hydraulic permeability etc., fixedly can remake further bridge formation on the surface of resin behind the particle diameter in screening, this is surface-crosslinked be treated to utilize have can with the multi-group crosslink agent of acid-base reaction, existing many before this patents propose, for example: disperse super absorbent resin and linking agent to carry out surface-crosslinked processing (JP-A-56-131608 in organic solvent, JP-A-57-44627, JP-A-58-42602, JP-A58-117222), use inorganic powder directly linking agent and cross-linking agent solution to be sneaked into super absorbent resin processing (JP-A60-163956, JP-A-60-255814), add behind the linking agent with steam treatment (JP-A-1-113406), with an organic solvent, water and polyvalent alcohol carry out surface treatment (JP-A-63-270741, JP-A-64-50707, JP-A-1-292004), use organic solution, water and ether (ether) compound (JP-A-2-153903) etc.Though these surface-treated methods can improve the uptake rate of resin or the water absorbent rate under the pressurize, will cause the too much adverse consequences of its confining force decline, reduce the performance of practical application.
Polymeric acrylic acid and acrylate form the method for super absorbent resin and are succeeded in developing by many-sided, and the multiple industry member production that has been applied to is arranged, its polymerization process has the casting film polyreaction, and (Japanese patent laid-open publication gazette is clear and 48 (1973)-42,466), (Japanese Patent discloses clear and 58 (1983)-49 to carry out polyreaction on conveying belt, 714), (Japanese Patent discloses clear and 57 (1982)-34 to carry out polyreaction in the pug mill type mixer of the stirring blade of pulverizing, 101), (Japanese Patent discloses clear and 59 (1984)-37 to carry out the anti-phase suspension polymerization, 003), or monomer sprayed or be coated on and carry out polyreaction (Japanese Patent disclose clear and 62 (1987)-53,309) on the fibre substrate.
Yet, above-mentioned existing polymerization process is reaction raw materials such as polymerization single polymerization monomer, polymerization starter and linking agent together to be carried out Raolical polymerizable and the gelatinous solid that forms super absorbent resin mostly, whole polyreaction like this is wayward, and solubles content is also higher.
Summary of the invention
For solving above-mentioned problems of the prior art, the invention provides a kind of powdery, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, its polymerization process is comparatively stable comparatively speaking, it is too high that reaction heat also is unlikely, except improving operating environment, more improved quality product.
Powdery of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, at least may further comprise the steps: provide the above acidic group monomer solution that contains of neutralization ratio 50 molar percentages to react through prepolymerization with initiators for polymerization and obtain viscous prepolymer, and contain the mixture that the acidic group monomer is selected from acrylic or methacrylic acid or 2-allylamine-2-methyl propane sulfonic acid or above-mentioned group; Add polynary epoxy compounds of long-chain and initiators for polymerization in viscous prepolymer, utilize the light starting polymerization further to generate gelinite; And gelinite is carried out 80 ℃ to 230 ℃ of dryings, pulverizing, screening, coated surface linking agent, controlled temperature with 100 ℃ to 250 ℃ hot blasts of temperature carry out heating surface and handle and add the inert inorganic salt powder.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein the viscosity of viscous prepolymer is 10~10000cp.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein initiators for polymerization is thermolysis type initiator or oxidation-reduction type initiator.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein prepolymerization reaction can be equipped with in vertical type reactive tank, center that stirring rake is installed and make store list to the horizontal cylindrical container of mobile stirring arm, list (two) screw rod or chuck is housed and leads in the pipeline of nitrogen and carry out.And the temperature of prepolymerization reaction is 5~80 ℃, and the prepolymerization reaction times is 0.5~16 hour.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein the light starting polymerization was finished in 10~300 seconds, preferably finished in 30~60 seconds.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein the polynary epoxy compounds of long-chain is included as sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ether.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein gelinite screening back particle size distribution range is between 0.05 to 1 millimeter (mm).
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein surface crosslinking agent is the mixture of polyvalent alcohol or polyethyleneglycol diglycidylether or alkylene carbonate or above-mentioned group.And surface crosslinking agent interpolation scope is 0.005~5.0 weight percent.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, wherein the inert inorganic salt powder is the mixture of Tai-Ace S 150 or aluminum oxide or magnesium oxide or calcium oxide or kaolin or silicon-dioxide or lime carbonate or magnesiumcarbonate etc. or above-mentioned group.And the interpolation scope of inert inorganic salt powder is 0.01~4.0 weight percent.
The present invention re-uses the chemical reaction means of light starting polymerization because of adopting first prepolymerization, the polyreaction that makes the relative prior art of polymerization process of integral body of the present invention be adopted is more stable, it is too high that reaction heat also is unlikely, and except improving operating environment, more improved quality product.
Relevant feature of the present invention is described in detail as follows by most preferred embodiment.
Embodiment
Below enumerate specific embodiment to describe content of the present invention in detail.
Powdery proposed by the invention, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, at least may further comprise the steps: provide contain acidic group monomer solution and the initiators for polymerization of neutralization ratio molar percentage more than 50 to obtain viscous prepolymer, and contain the mixture that the acidic group monomer is selected from acrylic or methacrylic acid or 2-allylamine-2-methyl propane sulfonic acid or above-mentioned group through the prepolymerization reaction; Add polynary epoxy compounds of long-chain and initiators for polymerization in viscous prepolymer, utilize the light starting polymerization further to generate gelinite; And gelinite is carried out 80 ℃ to 230 ℃ of dryings, pulverizing, screening, coated surface linking agent, controlled temperature with 100 ℃ to 250 ℃ hot blasts of temperature carry out heating surface and handle and add the inert inorganic salt powder.
Above-mentioned prepolymerization reaction can be carried out in a pre-polymerization reactor, and this reactor need possess can be made the polyreaction raw material mix and carry out prepolymerized effect.Pre-polymerization reactor is except can adopting the vertical type reactive tank that stirring rake generally is installed, also can adopt a kind of horizontal cylindrical container, the center is equipped with and makes store list to mobile stirring arm, single screw rod or twin screw arranged side by side, the phenomenon that can guarantee unidirectional the travelling forward of reaction mass like this and not occur refluxing, thus polyreaction material overstand and form gelatinous solid in reactor avoided.In addition, prepolymerization reaction also can be carried out in pipeline, and chuck is equipped with in the pipeline outside, is used for feeding heat-eliminating medium (as water coolant) and guarantees that prepolymerization is reflected under the constant temperature and carry out to remove reaction heat.Nitrogen inlet is equipped with in inside, can feed rare gas element continuously in case block gas influences Raolical polymerizable.At last, the heavy-gravity prepolymer is added on the travelling belt continuously, and the travelling belt top utilizes the high-intensity ultraviolet irradiating machine to carry out the light starting polymerization and makes the gel solid.
What the super absorbent resin of manufacturing of the present invention was required contains the acidic group monomer except vinylformic acid, still can use other to have the water-soluble monomer that two keys are closed in insatiable hunger, as: methacrylic acid or Malin's acid or fumaric acid or 2-allylamine-2-methyl propane sulfonic acid etc.Monomer selects for use not specific limited to use a kind of only, also can merge multiple monomer uses simultaneously, also can depending on the circumstances or the needs of the situation add and have other hydrophilic monomer of unsaturated double-bond, as: acrylamide, Methacrylamide, vinylformic acid 2-alkyl ethyl ester, methacrylic acid 2-alkyl ethyl ester, methyl acrylate, ethyl propenoate, dimethylamine acrylic acid-acrylamide, propylene dichloride acrylamido TMA (TriMethylAmine) but addition is a principle with the rerum natura of not destroying super absorbent resin.
Before carrying out Raolical polymerizable, monomer solution concentration should be controlled at 20 to 55 of weight percents, proper concn is weight percentage between 30 to 45, concentration is when weight percent 20 is following, too soft and the unfavorable mechanical workout of toughness of hydrated body after the polymerization, add concentration at weight percent more than 55,, be difficult for allotment and react that too fast response heat is wayward near saturation concentration.
Contain the monomeric carboxylic acid group of acidic group and should partly neutralize with the pH value of control finished product, make to be neutrality or subacidity, neutralizing agent is lithium hydroxide, sodium hydroxide, potassium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus and ammonia.Contain the monomeric carboxylic acid group of acidic group part is neutralized into lithium salts or sodium salt or sylvite or ammonium salt or two or more mixing salt, in and concentration molar percentage (mol%) be 45 to 85, proper concn is 50mol% to 75mol%, in and the concentration molar percentage be that the pH value of 45 finished products when following is understood on the low side, in and the concentration molar percentage be that the pH value of 85 finished products when above is understood higher, if not when finished product pH value is neutrality or subacidity, all not too be fit to also more dangerous when contacting with human body accidentally.
The prepolymerization reaction is begun by the decomposition generation free radical of polymerization starter.Polymerization starter can be selected thermolysis type initiator for use, the thermolysis type initiator that is fit to has superoxide, as: hydrogen peroxide, two-tert-butyl peroxide, peroxidation acid amides or persulphate (ammonium salt, an alkali metal salt) etc., and azo-compound is as two (N, N-two the stretches the methyl NSC 18620) dihydrochlorides of two (2-amidine propane) dihydrochloride, the 2.2 '-azo-groups of: 2.2 '-azo-group; Also can use reductive agent, making becomes the oxidation-reduction type initiator, as: acid accumulator sulfite, thiosulphate, xitix or ferrous salt; Or with oxidation-reduction type initiator and thermolysis type initiator merging use, at first the redox initiator reacts the generation free radical earlier, when radical transfer is the carrying out of initiated polymerization to monomer, can discharge a large amount of heats when carrying out owing to polyreaction elevates the temperature, when temperature arrives the decomposition temperature of thermolysis type initiator, can cause the decomposition of second section thermolysis type initiator again, and whole polyreaction is more attained in fully.The general suitable consumption of Raolical polymerizable initiator be weight percentage 0.001 to 10 (with in and acrylate weight be benchmark), more suitable consumption is then between weight percent 0.1 to 5, when operating weight per-cent 0.001 is following, react too slow unfavorable economic benefit; When operating weight per-cent 10 was above, reacting too, the wayward and easy polymerization of fast response heat excessively formed gelatinous solid.
Carry out in viscous prepolymer, to add linking agent before the reaction of light starting polymerization, the optional usefulness of linking agent has the compound of two or more unsaturated double-bonds, as: N, N-two (2-propenyl) amine, N, N '-methylene-bisacrylamide, N, N '-methylene-bis Methacrylamide, vinylformic acid propylene ester, glycol diacrylate, polyethyleneglycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycerol tri-acrylate, the glycerine trimethacrylate, the triacrylate or the trimethacrylate of glycerine additional ring oxidative ethane, the triacrylate or the trimethacrylate of trihydroxymethyl propane additional ring oxidative ethane, the trihydroxymethyl propane trimethacrylate, the trihydroxymethyl propane triacrylate, N, N, N-three (2-propenyl) amine, ethylene glycol diacrylate, two propylene triethyleneglycol ester etc., also optional usefulness has the compound of two or more epoxy group(ing), as the sorbyl alcohol polyglycidyl ether, the polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, the Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers etc.After carrying out free radical reaction, just can make super absorbent resin have suitable degree of crosslinking, and make the super absorbent resin colloid that suitable processibility be arranged.The Raolical polymerizable linking agent can be used alone or mixed use of two or more.Raolical polymerizable linking agent suitable additive amount is (is benchmark with the total solid of reactant) between weight percent 0.001 to 5, more suitable consumption is weight percentage between 0.01 to 3, additive capacity is the too soft and unfavorable mechanical workout of toughness of hydrated body after weight percent 0.001 following polymerization, additive capacity is too low in weight percent 5 above water-absorbents, reduces resin property.
Viscous prepolymer can be on the conveyer belt type reactor or is equipped with in the horizontal type reactor of paddle and carries out the reaction of light starting polymerization, the superabsorbent gels body of preparing utilizes pulverizer to be cut into the following gelinite of diameter 20mm earlier, better below the diameter 10mm, dry again.
Bake out temperature can carry out drying under 100 ℃ to 250 ℃, drying temperature is then dried with 120 ℃ to 180 ℃ and is advisable, when 120 ℃ of bake out temperatures are not had an economic benefit too for a long time with next drying time, bake out temperature is dried more than 180 ℃ and is made linking agent carry out crosslinking reaction ahead of time, make in the subsequent drying process, can't effectively remove remaining monomer because of degree of crosslinking is too high, reach and reduce low remaining monomeric effect.
Pulverize, screen fixedly particle diameter after the drying, carry out the surface crosslinking agent coating processing again.Fixedly particle diameter is to be advisable between 0.06mm to 1.00mm in screening, and with preferable between 0.10mm to 0.850mm, the following fine powder of particle diameter 0.06mm improves the finished product dust, and the above particle of particle diameter 1.00mm makes the finished product rate of water absorption slack-off.
Screening is fixedly behind the particle diameter, can be polyvalent alcohol as glycerol, ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, 1,4 butyleneglycol, trialkyl methylpropane, sorbyl alcohol etc. according to the linking agent that can react simultaneously when the surface treatment of the present invention; Maybe can use polyamine as quadrol, two quadrols, Triethylene Diamine, polyethyene diamine; Maybe can use compound as sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyoxyethylene glycol two polyglycidyl ethers, two glycerol polyglycidyl ethers etc. with two or more epoxy group(ing); Also can use alkylene carbonate as ethylene carbonate, 4-methyl isophthalic acid, 3-dioxolane-2-ketone, 4,5-dimethyl-1,3-dioxolane-2-ketone, 4,4-dimethyl-1,3-dioxolane-2-ketone, 4-ethyl-1,3-dioxolane-2-ketone, 1,3-dioxane-2-ketone, 4,6-dimethyl-1,3-dioxane-2-ketone or 1,3-Dioxepane-2-ketone etc.The usage of surface crosslinking agent can be used alone or mixed use of two or more.The suitable additives amount of surface crosslinking agent is (is benchmark with the total solid of reactant) between weight percent 0.001 to 10, more suitable consumption is between weight percent 0.005 to 5, the surface crosslinking agent additive capacity can't show effect when weight percent 0.001 is following, the surface crosslinking agent additive capacity is when weight percent 10 is above, water-absorbent is too low, reduces resin property.
During the surface crosslinking agent coating processing, the interpolation of surface crosslinking agent can be surface crosslinking agent and directly adds, or the furnishing surface crosslinking agent aqueous solution adds, or the furnishing surface crosslinking agent hydrophilic organic solvent aqueous solution adds, hydrophilic organic solvent such as methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol, acetone, methyl ether, ether etc. do not have particular restriction, can form solution and get final product, wherein preferable with methyl alcohol, ethanol.Can add the inert inorganic salt powder in the High hydrophilous resin when surface crosslinking agent adds, disperse to help solution, the inert inorganic salt powder can be Tai-Ace S 150 or silicon-dioxide, or aluminum oxide, or magnesium oxide etc. or its mixture.Wherein preferable with Tai-Ace S 150, silicon-dioxide.The inert inorganic salt powder adds scope between weight percent 0.005 to 10.0, and is wherein preferable with weight percent 0.01 to 4.0.
After carrying out the surface crosslinking agent coating processing,, make surface crosslinking agent can carry out crosslinking reaction, and make internal crosslinking agent carry out crosslinking reaction and reach effect of the present invention again with 80 ℃ to 230 ℃ heat treated.Treatment temp cross-linking reaction time below 80 ℃ is too of a specified duration, does not have an economic benefit, and during treatment temp 〉=230 ℃, the easy deterioration of resin influences quality.Then be advisable as for the treatment time with 2~150 minutes, according to the treatment temp adjustment, the temperature height then the time short, the low then time of temperature is long.
Because super absorbent resin has the phenomenon of luming after the moisture absorption, caking causes processing to have some setbacks after the high humidity area uses super absorbent resin to have moisture absorption in order to avoid, generally can be at super absorbent resin coated inert inorganic salt powder in surface or interfacial agent, make slightly tool lipophilicity and make super absorbent resin possess the characteristic of prevented from caking after the moisture absorption of surface, this inert inorganic salt powder can be selected Tai-Ace S 150 or silicon-dioxide or aluminum oxide or magnesium oxide or calcium oxide or kaolin or lime carbonate or magnesiumcarbonate etc. or its mixture for use; Usually the addition of this inert inorganic salt powder is relevant with inorganic salt powder particle size, if less its inorganic salt specific surface area of grain diameter is long-pending bigger, so effectively inert inorganic salt powder consumption can be less, its inert inorganic salt powder interpolation scope is between the weight ratio per-cent 0.005 to 10.0, wherein preferable with weight percent 0.01 to 4.0, its particle diameter of inert inorganic salt powder is 0.001 μ M to 100 μ M, if select for use particle less than the inorganic salt powder of the 0.001 μ M too high suitability for industrialized production that is unfavorable for of cost then, if select for use particle the too high problem that influences the super absorbent resin absorbing power of addition then to be arranged greater than the inorganic salt powder of 100 μ M.The inert inorganic salt powder can add separately maybe can follow interfacial agent or tool viscosity organic compound to add, its interfacial agent or tool viscosity organic compound can be selected HLB (hydrophile-lipophile balance for use, wetting ability-lipophilicity equilibrium) value 12 above non-ionic surfactants, or water soluble anion type interfacial agent, or cationic interfacial agent, or negative and positive amphoteric interfacial agent, or its mixture, usually interfacial agent or tool viscosity organic compound can use glycerine, ethylene glycol, hexan-hexol, Volpo S 10, or polyoxyethylene glycol, or stearic acid macrogol ester, or oneself six esters of stearic acid polyoxyethylene glycol, or polyoxyethylene nonylbenzene ether, or the hot phenylate of polyoxyethylene, or polyoxyethylene ten phenyl ether, or polyethylene oxide alkyl ethers, or this interfacial agent or tool viscosity organic compound such as polyoxyethylene bay ether, can be formulated into aqueous solution kenel adds or adds separately, suitable interfacial agent or tool viscosity organic compound additive capacity between weight percent 0.001 to 5 (is benchmark with the total solid of reactant), more suitable consumption weight percent is between 0.01 to 3.
The present invention adopts the first prepolymerization reaction mode of further polyreaction again with whole polyreaction, the prepolymerization product obviously improves with respect to the viscosity of liquid reactions material, the mobile reduction, easier and belt reactor afterwards is complementary, and whole polyreaction stability is improved, it is too high that reaction heat is unlikely to.Preparation method of high-hydroscopicity resin provided by the present invention is except improving operating environment, and quality product also improves greatly, especially has clearly effect for reducing solubles content.
For showing the characteristic of the low solubles content of super absorbent resin among the present invention, the determination step of solubles content is as follows: take by weighing the 0.5g super absorbent resin earlier, add 0.9% salt solution 185g again, after stirring one hour under the 500rpm rotating speed, go out the SAP extraction liquid with filter paper filtering.At last, take by weighing this extraction liquid 20g,, re-use 0.1N hydrochloric acid (HCl) and carry out back titration to obtain the content of SAP solvend earlier with 0.1N sodium hydroxide (NaOH) titration.
Below at length list the reference work example so that the present invention is described, but the scope of the invention is not limited by these examples.
Embodiment one:
The water that in 6000 milliliters of containers of crossing with nitrogen replacement, adds 1760g vinylformic acid and 2263.7g; Take by weighing 45% aqueous sodium hydroxide solution 1476.3g in addition again, neutralize in the acrylic acid aqueous solution in ice-cold down aqueous sodium hydroxide solution slowly the adding; Must contain the aqueous solution of acidic group monomer concentration weight percent (wt%) 38.6 this moment, wherein has the vinylformic acid neutralization of 68mol% to be sodium acrylate.
Containing the Potassium Persulphate of acidic group monomer solution with 0.1g after the above-mentioned neutralization: S-WAT=1: 1 (weight ratio) together joins and mixes in the pre-polymerization reactor of the horizontal tubular of being furnished with chuck and the prepolymerization reaction.Temperature of reaction is 20 ℃, and the reaction times is 60 minutes (min), and the prepolymer viscosity of gained is 100 centipoises (cp).
Blue or green together join on the travelling belt the two different moons in heptan of viscous prepolymer, 1g azo with 0.768g glycerol polyoxyethylene glycol triglycidyl ether (n=7), travelling belt top device has the high-intensity ultraviolet irradiating machine, utilizes 40 seconds (illumination=7.1J/cm of this device above-mentioned mixing liquid of irradiation 2) make it to carry out crosslinking reaction and form colloid.
Utilize the cut pulverizer to be cut into the following gelinite of 2mm diameter.
With 130 ℃ of temperature dryings 2 hours; Utilize fixedly particle diameter of screen cloth screening 0.1mm~0.85mm, get the powdery super absorbent resin.
Take by weighing this super absorbent resin 10g, add Aluminium Sulphate usp (powder) 0.1g, the ethylene carbonate that adds again after evenly to be mixed: water: methyl alcohol=1: 1: 1 (weight ratio) solution 0.4g, with 215 ℃ of temperature heat treated 10 minutes.
After the cooling, promptly get high-performance high absorbent resin, measure confining force=29.2g/g, 20g/cm 2Water absorbent rate=29.5g/g under the pressure, water absorbent rate=22.5g/g under the 49g/cm2 pressure, solubles content=5.1%.
Embodiment two~four:
Working method is with embodiment one, but the prepolymerization reaction times be respectively 180min, 420min and 720min, the prepolymer viscosity of gained is respectively 370cp, 1350cp, 5000cp.
Measure confining force and be respectively 32.3g/g, 34.5g/g, 37.1g/g, 20g/cm 2, water absorbent rate is respectively 32.7g/g, 31.5g/g, 28.7g/g, 39g/cm under the pressure 2Water absorbent rate is respectively 24.1g/g, 22.9g/g, 19.8g/g under the pressure, and solubles content is respectively 5.3%, 6.1%, 7.6%.
Embodiment five~eight:
Working method is with embodiment one, but the prepolymerization temperature of reaction is respectively 5 ℃, 15 ℃, 25 ℃ and 35 ℃, and the prepolymer viscosity of gained is respectively 15cp, 80cp, 270cp, 1050cp.
Measure confining force and be respectively 27.1g/g, 28.6g/g, 31.7g/g, 33.4g/g, 20g/cm 2, water absorbent rate is respectively 27.3g/g, 28.7g/g, 30.9g/g, 31.5g/g, 39g/cm under the pressure 2Water absorbent rate is respectively 18.2g/g, 19.8g/g, 22.8g/g, 23.6g/g under the pressure, and solubles content is respectively 2.5%, 3.4%, 5.2%, 6.1%.
Embodiment nine~12:
Working method is with embodiment one, but polymerization starter is respectively ammonium persulphate and sodium bisulfite mixture (weight ratio=1: 1), hydrogen peroxide, peroxidation carbonic acid diisopropyl ester, 2, two (2-amidine propane) dihydrochlorides of 2-azo-group.
Measure confining force and be respectively 30.1g/g, 29.7g/g, 30.5g/g, 31.0g/g, 20g/cm 2, water absorbent rate is respectively 29.6g/g, 30.0g/g, 28.9g/g, 31.6g/g, 39g/cm under the pressure 2Water absorbent rate is respectively 23.0g/g, 22.5g/g, 29.9g/g, 23.6g/g under the pressure, and solubles content is respectively 5.1%, 6.2%, 5.4%, 5.7%.
Embodiment 13~15:
Working method is with embodiment one, but linking agent is respectively glycerol polyoxyethylene glycol triglycidyl ether (n=20), three propenyl amine and ethylene glycol diacrylates.
Measure confining force and be respectively 33.2g/g, 26.5g/g, 27.8g/g, 20g/cm 2, water absorbent rate is respectively 31.3g/g, 27.9g/g, 28.7g/g, 39g/cm under the pressure 2Water absorbent rate is respectively 24.9g/g, 22.5g/g, 23.6g/g under the pressure, and solubles content is respectively 5.7%, 3.5%, 3.9%.
Embodiment 16~19:
Working method is with embodiment one, but uviolizing machine irradiation time was respectively 60,30,20,10 seconds, and illumination is respectively 10.2J/cm 2, 5.1J/cm 2, 3.5J/cm 2, 1.7J/cm 2
Measure confining force and be respectively 27.6g/g, 29.6g/g, 30.2g/g, 36.1g/g, 20g/cm 2, water absorbent rate is respectively 31.3g/g, 32.5g/g, 30.4g/g, 32.9g/g, 39g/cm under the pressure 2Water absorbent rate is respectively 24.9g/g, 26.3g/g, 24.3g/g, 19.7g/g under the pressure, and solubles content is respectively 4.2%, 6.3%, 7.1%, 8.1%.
With reference to comparative example one to two, to highlight the effect of experimental example one to 19.
Comparative example one:
The water that in 6000 milliliters of containers of crossing with nitrogen replacement, adds 1760g vinylformic acid and 2263.7g; Take by weighing 45% aqueous sodium hydroxide solution 1476.3g in addition again, neutralize in the acrylic acid aqueous solution in ice-cold down aqueous sodium hydroxide solution slowly the adding; Get the monomer concentration 38.6wt% aqueous solution this moment, wherein has the vinylformic acid neutralization of 68mol% to be sodium acrylate.
0.768g glycerol polyoxyethylene glycol triglycidyl ether (n=20) is joined above-mentioned part neutral monomer solution, and holding temperature is about 20 ℃.
Add the 1.9g hydrogen peroxide, two (2-amidine propane) dihydrochlorides of 3.0g Sodium Persulfate and 1.0g 2.2-azo-group react with starting polymerization, place to make it form colloidal naturally in 1 hour.
Utilize the cut pulverizer to be cut into the following gelinite of 2mm diameter.
With 130 ℃ of temperature dryings 2 hours; Utilize fixedly particle diameter of screen cloth screening 0.1mm~0.85mm, get the powdery super absorbent resin.
Weigh this super absorbent resin 10g, add Aluminium Sulphate usp (powder) 0.1g, the ethylene carbonate that adds again after evenly to be mixed: water: methyl alcohol=1: 1: 1 (weight ratio) solution 0.4g, with 215 ℃ of temperature heat treated 10 minutes.
After the cooling, promptly get high-performance high absorbent resin, measure confining force=33.1g/g, 20g/cm 2Water absorbent rate=32.0g/g under the pressure, 49g/cm 2Water absorbent rate=22.1g/g under the pressure, solubles content=12.1%.
Comparative example two:
The water that in 6000 milliliters of containers of crossing with nitrogen replacement, adds 1760g vinylformic acid and 2263.7g; Take by weighing 45% aqueous sodium hydroxide solution 1476.3g in addition again, neutralize in the acrylic acid aqueous solution ice-cold down aqueous sodium hydroxide solution slowly the adding; Get the monomer concentration 38.6wt% aqueous solution this moment, wherein has the vinylformic acid neutralization of 68mol% to be sodium acrylate.
0.768g glycerol polyoxyethylene glycol triglycidyl ether (n=12) is joined above-mentioned part neutral monomer solution, and holding temperature is about 20 ℃.
Add the 1.9g hydrogen peroxide, two (2-amidine propane) dihydrochlorides of 3.0g Sodium Persulfate and 1.0g 2.2-azo-group react with starting polymerization, place to make it form colloidal naturally in 1 hour.
Utilize the cut pulverizer to be cut into the following gelinite of 2mm diameter.
With 130 ℃ of temperature dryings 2 hours; Utilize fixedly particle diameter of screen cloth screening 0.1mm~0.85mm, get the powdery super absorbent resin.
Take by weighing this super absorbent resin 10g, add Aluminium Sulphate usp (powder) 0.1g, the ethylene carbonate that adds again after evenly to be mixed: water: methyl alcohol=1: 1: 1 (weight ratio) solution 0.4g, with 215 ℃ of temperature heat treated 10 minutes.
After the cooling, promptly get high-performance high absorbent resin, measure confining force=31.7g/g, 20g/cm 2Water absorbent rate=31.5g/g under the pressure, 49g/cm 2Water absorbent rate=24.7g/g under the pressure, solubles content=10.5%.
In sum, a kind of powdery disclosed in this invention, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, has following advantage at least:
1. the manufacture method of super absorbent resin provided by the present invention, except improving operating environment, quality product also improves greatly, via every experiment test, confirms that the present invention especially has clearly effect for reducing solubles content.
2. the present invention is substituted by existing polyreaction with the chemical technology means: use the prepolymerization reaction earlier, re-use the reaction of light starting polymerization.Make prepolymer of the present invention obviously improve with respect to the viscosity of other liquid reactions material, the mobile reduction, easier and conveying belt reactor afterwards is complementary, and whole polyreaction stability is improved, and it is too high that reaction heat is unlikely to.
Though the present invention with aforesaid preferred embodiment openly as above; yet it is not in order to limit the present invention; any those of ordinary skill in the art; without departing from the spirit and scope of the present invention; can modify and change, therefore scope of patent protection of the present invention should be as the criterion with the scope that this specification sheets appending claims is defined.

Claims (16)

1. powdery, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, may further comprise the steps:
Provide neutralization ratio 50 molar percentages above one containing the acidic group monomer solution and react through a prepolymerization with an initiators for polymerization and obtain a viscous prepolymer, describedly contain the mixture that the acidic group monomer is selected from acrylic or methacrylic acid or 2-allylamine-2-methyl propane sulfonic acid or above-mentioned group;
In described viscous prepolymer, add a polynary epoxy compounds of a long-chain and an initiators for polymerization, utilize a smooth starting polymerization further to generate a gelinite; And
Described gelinite is carried out 80 ℃ to 230 ℃ of dryings, pulverizing, screening, coating one surface crosslinking agent, controlled temperature with 100 ℃ to 250 ℃ hot blasts of temperature to carry out a heating surface and handles and add an inert inorganic salt powder.
2. powdery according to claim 1, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that the viscosity of described viscous prepolymer is 10~10000 centipoises.
3. powdery according to claim 1, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described initiators for polymerization is a thermolysis type initiator or an oxidation-reduction type initiator.
4. powdery according to claim 3, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that, described thermolysis type initiator comprises the superoxide of hydrogen peroxide, two-tert-butyl peroxide, peroxidation vinegar amine or persulphate, or 2, the azo-initiator of two (N, N-two the stretches the methyl NSC 18620) dihydrochlorides of two (2-amidine propane) dihydrochloride, the 2.2 '-azo-groups of 2 '-azo-group.
5. powdery according to claim 3, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described oxidation-reduction type initiator is acid accumulator sulfite, thiosulphate, xitix, ferrous sulfate or persulfuric acid salt.
6. powdery according to claim 1, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that, described prepolymerization react on vertical type reactive tank, center that stirring rake is installed be equipped with make store list to the horizontal cylindrical container of mobile stirring arm, single screw rod or twin screw or chuck is housed and the pipeline of logical nitrogen in carry out.
7. powdery according to claim 1, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that, the temperature of described prepolymerization reaction is 5~80 ℃.
8. powdery according to claim 1, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that the described prepolymerization reaction times is 0.5~16 hour.
9. powdery according to claim 1, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described smooth starting polymerization was included in 10~300 seconds to be finished.
10. powdery according to claim 9, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described smooth starting polymerization was included in 30~60 seconds to be finished.
11. the manufacture method of super absorbent resin according to claim 1, it is characterized in that the polynary epoxy compounds of described long-chain is included as sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ether.
12. powdery according to claim 1, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that, described gelinite screening back particle size distribution range is between 0.05 to 1 millimeter.
13. powdery according to claim 1, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described surface crosslinking agent is the mixture of polyvalent alcohol or polyethyleneglycol diglycidylether or alkylene carbonate or above-mentioned group.
14. powdery according to claim 1, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described surface crosslinking agent interpolation scope is 0.005~5.0 weight percent.
15. powdery according to claim 1, water insoluble, can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described inert inorganic salt powder is the mixture of Tai-Ace S 150 or aluminum oxide or magnesium oxide or calcium oxide or kaolin or silicon-dioxide or lime carbonate or magnesiumcarbonate etc. or above-mentioned group.
16. powdery according to claim 1, water insoluble can absorb the manufacture method of the low super absorbent resin of water liquid, urine or blood and solubles content, it is characterized in that described inert inorganic salt powder interpolation scope is 0.01~4.0 weight percent.
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CN101333274B (en) * 2007-06-29 2010-11-03 台湾塑胶工业股份有限公司 Method for making high water-absorbent resin
CN101333261B (en) * 2007-06-29 2012-07-04 台湾塑胶工业股份有限公司 Method for making high water absorption resin
CN101333260B (en) * 2007-06-29 2012-07-04 台湾塑胶工业股份有限公司 Method for making high water absorption resin
CN101955680B (en) * 2009-07-13 2013-03-20 台湾塑胶工业股份有限公司 Preparation method of resin with high property and high water absorbability
CN102408510B (en) * 2011-09-09 2013-09-18 宜兴丹森科技有限公司 Preparation method for super absorbent resin
CN104788871A (en) * 2015-04-16 2015-07-22 江门市高力依科技实业有限公司 Preparation method of surface-treated super absorbent resin
CN108641045A (en) * 2018-05-07 2018-10-12 浙江卫星新材料科技有限公司 The preparation method of height water conservation super absorbent resin

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