CN101333274B - Method for making high water-absorbent resin - Google Patents
Method for making high water-absorbent resin Download PDFInfo
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- CN101333274B CN101333274B CN2007101235220A CN200710123522A CN101333274B CN 101333274 B CN101333274 B CN 101333274B CN 2007101235220 A CN2007101235220 A CN 2007101235220A CN 200710123522 A CN200710123522 A CN 200710123522A CN 101333274 B CN101333274 B CN 101333274B
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Abstract
Disclosed is a method for fabricating super hydrophilic resin; wherein the neutralization ratio is within the range of 45-85 mol% and the concentration of the unsaturated monomer solution is within the range of 20-55 proportions by weight; surface processing is carried out during the preparation process, thus getting super hydrophilic resin which is of good physical property, high retentivity and high absorption ratio under high pressure.
Description
Technical field
The present invention relates to a kind of super absorbent resin, it applies to the water retention agent of agricultural or gardening aspect, the anti-dewdrop condensing agent in the material of construction widely, remove the material of moisture content in the oil, or as the waterproof outer coating in the cable, and usefulness in sanitary product such as diaper, women sanitary articles, deserted wiping cloth etc.
Background technology
Material at tool super absorbent resin composition known in this field, starch-vinyl cyanide (hydrolyzed starchacrylonitrile) graftomer (day disclosure special permission communique clear 49 (1974)-43 of meeting the water decomposition type is arranged, 395), neutral starch-acrylic acid-grafted polymkeric substance (day disclosure special permission communique clear 51 (1976)-125,468), saponification ethene acetic acid-propylene ester copolymer (day disclosure special permission communique clear 52 (1977)-14,689), hydrolyzed acrylonitrile multipolymer or acrylamide copolymer (day disclosure special permission communique clear 53 (1978)-15,959), and partly and polyacrylic acid (day disclosure is speciallyyed permit communique clear 55 (1980)-84,304) etc.Wherein in the raw material of starch-acrylonitrile grafting polymkeric substance,, can cause the decomposition of putrescibility, so can't preserve for a long time because contain natural polymer-starch; Moreover its manufacture method is very complicated, so the preparation method of super absorbent resin accounts for maximum partly also economical with the super absorbent resin that uses vinylformic acid and acrylate to carry out the crosslinking polymerization gained now.It is former because raw material-the vinylformic acid of acrylate multipolymer can be rapidly by buying on the market, and the super absorbent resin that makes has very high water-retaining capacity, and have decomposition and tool economic benefit cheap for manufacturing cost and that can not cause putrescibility, so become the super absorbent resin that generalizes most.
The method that polymeric acrylic acid and acrylate form super absorbent resin can be made by several known methods, as aqueous solution polymerization reaction, anti-phase suspension polymerization, emulsion polymerization reaction or with the monomer sprinkling or be coated on methods such as carrying out polyreaction on the fibre substrate.In these methods, anti-phase suspension polymerization and emulsion polymerization reaction must use organic solvent, but if the temperature when effectively controlled polymerization reacts, organic solvent will cause the increase of reactive system temperature and pressure, produce on fire even explosion caused, and then threaten operation site personnel's safety and cause problem of environmental pollution, its finished product also has the doubt of organic solvent residual.
Super absorbent resin is the hydrophilic polymer of dissolving not, resin inside has inhomogeneity bridge formation structure, generally for improve quality as: improve uptake rate, improve colloid intensity, improve anti-caking effect, hydraulic permeability etc., can be when producing the super absorbent resin of polyacrylic, utilize heat treatment mode that crosslinking Treatment is carried out on the water-absorbent besin particles surface, formed gel and cohesion by the wetting back of waterborne liquid to reduce absorbent resin.When the absorbent resin surface forms gel, can block liquid from the absorbent resin surface to delivered inside, thereby reduced outside the receptivity of super absorbent resin to liquid, also can make absorbent resin produce the phenomenon of cohesion, further reduce the receptivity of absorbent resin.
Existing many methods at the surface-crosslinked processing of super absorbent resin are developed, as: disperse super absorbent resin and linking agent in organic solvent, to carry out surface-crosslinked processing (JP-A-56-131608, 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 vapour cure (JP-A-1-113406), with an organic solvent, water and polyvalent alcohol are heat-treated (JP-A-63-270741, JP-A-64-50707, JP-A-1-292004), use organic solution, water, ether (ether) compound (JP-A-2-153903), utilize many glycidyl ethers, this class difunctionality based compound (United States Patent (USP) 4 of multi-functional yl amine, 666, No. 983), and the interpolation polyvalent alcohol carries out the method (United States Patent (USP) 4 of crosslinking Treatment to absorbent resin as inert solvent, 507,438,4,541, No. 871), other has the high-speed mixer of use that surface-crosslinked solvent is mixed (United States Patent (USP) 5 with absorbent resin, 140, No. 076), also there is use N-(hydroxyalkyl)-methylamino propionic ester to be sprayed on the absorbent resin surface and heat-treats (United States Patent (USP) 5,229, No. 466), and the method (United States Patent (USP) 5 that uses alkylidene group carbonate to heat-treat, 409, No. 771) etc., other has disclosed the patent about the surface-crosslinked processing of super absorbent resin; As No. 4289814,4295978,4500670,4732968,4758617,4824901,4954562 and 5026800, United States Patent (USP), though these heat treated United States Patent (USP) methods can improve uptake rate, it is water absorbent rate under the pressurize, but will cause the too much adverse consequences of confining force decline, reduce the performance of practical application.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of super absorbent resin.
For achieving the above object, the manufacture method of super absorbent resin provided by the invention, this method comprises at least:
(a) use a kind of water-soluble unsaturated monomer that contains vinylformic acid (salt) and acrylamide (salt), neutralization ratio is in the scope of 45 to 85 moles of %, and the concentration of unsaturated monomer solution is in the scope of 20 to 55 weight parts;
(b) the gelinite chopping of reaction back generation is in 100 ℃ of warm air dryings to 180 ℃ of scopes of temperature, pulverizing, screening;
(c) carry out surface-crosslinked coating processing with cross-linking compounds and the phosphatic mixed aqueous solution of epoxy alkyl; And
(d) 120 ℃ to 230 ℃ heat hot of temperature are handled.
The manufacture method of described high-absorbable resin, wherein, the gelinite diameter of chopping is not more than 2.00mm.
The manufacture method of described super absorbent resin, wherein, cross-linking compounds is selected from diglycidyl ether compounds, alkylene carbonate compound or polyol compound.
The manufacture method of described super absorbent resin, wherein, the epoxy alkyl phosphate compounds is an oxyethane alkylphosphonic acid carboxylic acid salt compound, the surface tension value of the aqueous solution is not more than 36mN/m.
The manufacture method of described super absorbent resin, wherein, the scope of surface crosslinking agent aqueous solution addition is between weight percent 0.005wt% to 10.0wt%.
According to the obtained super absorbent resin of above-mentioned manufacture method, wherein, particle size distribution range is between 0.10 to 0.850mm, and average particle size range is 0.2 to 0.6mm; Particle length and width ratio are in 1.5 to 20 scopes, and particle length is in the 100-10000um scope, and width is in the 10-2000um scope.
Super absorbent resin of the present invention is characterized in that:
(a) a kind of water-soluble unsaturated monomer that contains vinylformic acid (salt) and acrylamide (salt), in it and ratio in the scope of 45 to 85 moles of %, the concentration of unsaturated monomer solution is in the reaction of the scope of 20 to 55 weight parts;
(b) with the warm air drying of 100 ℃ to 180 ℃ of temperature, pulverizing, screening (the reaction back generates) gelinite;
(c) the inert inorganic salt powder of interpolation 0.005wt% to 10.0wt%;
(d) cross-linking compounds and the phosphatic mixed aqueous solution of epoxy alkyl of coating 0.001wt% to 10.0wt%;
(e) the crosslinking reaction processing is carried out in 120 ℃ to 230 ℃ heating of temperature; Again
(f) add water-insoluble micro mist and sticking agent, carry out the agglomeration resistance processing and constitute.
Described super absorbent resin, wherein, the water-insoluble micro mist can be the inorganic salt powder of Tai-Ace S 150, lime carbonate, magnesium oxide, zeolite, kaolin, titanium dioxide or silicon-dioxide, the water-insoluble micro mist can use or merge two or more mixing separately and use, and the interpolation scope is between weight percent 0.01wt% to 4.0wt%.
Described super absorbent resin, wherein, the size of particles of water-insoluble micro mist is not more than 0.6mm.
Preparation method provided by the invention can make product have under high absorbing power and the high pressure to absorb multiplying power, and low gel blockage phenomenon, makes absorbing products have easy drying property and low leaks.
Embodiment
Make the required water-soluble unsaturated monomer of super absorbent resin of the present invention, except vinylformic acid, still can use other insatiable hunger to close the water-soluble monomer of two keys with acidic-group, as: methacrylic acid, Malin's acid, fumaric acid, 2-allylamine-2-methyl propane sulfonic acid, maleic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, FUMARIC ACID TECH GRADE acid anhydride etc.The monomeric specific limited of selecting for use is not used a kind of only, also can merge multiple monomer uses simultaneously, also can depending on the circumstances or the needs of the situation add other hydrophilic monomer with unsaturated double-bond, as: acrylamide, Methacrylamide, vinylformic acid 2-carboxyl ethyl ester, methacrylic acid 2-carboxyl ethyl ester, methyl acrylate, ethyl propenoate, the dimethylamine acrylic acid-acrylamide, propylene dichloride acrylamido TMA (TriMethylAmine) (United States Patent (USP) 4,057, No. 521,4,062, No. 817,4,525, No. 527,4,286, No. 082 and 4,295, No. 987), 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 between weight percent 20wt% to 55wt%, proper concn is between the 30wt% to 45wt%, concentration is when weight percent 20wt% is following, hydrated body is too soft and the unfavorable mechanical workout of stickiness arranged after the polymerization, add concentration more than weight percent 55wt%,, be difficult for allotment and react that too fast response heat is wayward near saturation concentration.
Containing the monomeric carboxylic acid group of acidic group should partly neutralize with the pH value of control finished product, make and be neutrality or subacidity, neutralizing agent is the oxyhydroxide or the carbonate compound of alkali metal group or alkaline earths in the periodictable, as: sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniac compounds; Neutralizing agent can be used alone or multiple mixing is used.Contain the monomeric carboxylic acid group of acidic group and partly be neutralized into sodium salt or sylvite or ammonium salt, in and the concentration molar percentage be 45mol% to 85mol%, be preferably 50mol% to 75mol%, in and the concentration molar percentage be that the pH value of 45mol% finished product when following is understood on the low side, in and the concentration molar percentage be that the pH value of 85mol% finished product when above is understood higher, finished product pH value is non-when being neutrality or subacidity, if all not too suitable, also more dangerous when contacting with human body accidentally.
Before carrying out Raolical polymerizable, also can add water-soluble polymer in the monomer solution to reduce cost, these water-soluble polymers are as partly saponification or fully saponified polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid, polyacrylamide, starch or starch derivative such as methylcellulose gum, the vinylformic acid methylcellulose gum, polymkeric substance such as ethyl cellulose; The molecular weight of these water-soluble polymers is not particularly limited, and wherein preferable water-soluble polymer is a starch, partly saponification or fully saponified polyvinyl alcohol etc. are used alone or as a mixture.It is 0 to 20wt% that super absorbent resin contains these suitable weight percents that add water-soluble polymers, but with 0 to 10wt% preferable, 0 to 5wt% is good especially, and adding when surpassing 20wt% to influence rerum natura, makes the rerum natura variation.
Before carrying out Raolical polymerizable, should add the Raolical polymerizable linking agent earlier in unreacted monomer solution, the optional usefulness of this Raolical polymerizable linking agent has the compound of two or more unsaturated double-bonds, as: N, N '-two (2-propenyl) amine, N, N '-methyne bisacrylamide, N, the two Methacrylamides of N '-methyne, 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, three vinylformic acid polyoxyethylene glycerides, three vinylformic acid diethyl polyoxyethylene glycerides, 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 0.001wt% to 5wt%, and more suitable consumption weight percent is between 0.01wt% to 3wt%.Additive capacity hydrated body after the following polymerization of weight percent 0.001wt% is too soft and the unfavorable mechanical workout of stickiness is arranged, and additive capacity is too low in the above water-absorbent of weight percent 5wt%, reduces resin property.
Polyreaction of the present invention is begun by the decomposition generation free radical of Raolical polymerizable initiator.Free radical starting agent can be selected thermolysis type initiator for use, the thermolysis type initiator that is fit to has superoxide, as: hydrogen peroxide, two-Di tributyl superoxide, 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 suitable consumption of general Raolical polymerizable initiator be weight percentage 0.001wt% to 10wt% (with in and acrylate weight be benchmark), more suitable consumption is then between 0.1wt% to 5wt%, when operating weight per-cent 0.001wt% is following, react too slow unfavorable economic benefit, when operating weight per-cent 10wt% is above, react that too fast response heat is wayward.
Polyreaction of the present invention can be in the conventional batch reaction vessel, or reacts on the conveyer belt type reactor, and the super absorbent resin of reaction gained utilizes pulverizer to be cut into the following little gelinite of diameter 20mm earlier, and is better below the diameter 10mm, screens again.
Fixedly the gelinite diameter of particle diameter is to be advisable below the 2.00mm in screening, and with preferable between 0.05mm to 1.50mm, particle diameter is then sent pulverizer again back to greater than the gelinite of 2.00mm and shredded once more.The following gelinite of particle diameter 0.03mm is dried, after the pulverization process, easily producing the finished product fine powder amount improves, when the above gelinite of particle diameter 2.00mm is dried, because thermal conduction effect is not good, cause the shortcoming that the remaining monomer of finished product is higher and other rerum natura is performed poor easily.
According to the present invention, the particle size dispersion of acrylate gelinite is narrow more, not only can make gelinite rerum natura performance after oven dry reach optimum regime, and help controlling the time and the temperature of oven dry, dries after screening is finished again.
Bake out temperature is dried for 100 ℃ to 180 ℃ with temperature and is advisable.Bake out temperature is dried below 100 ℃, time can not had economic benefit too for a long time, and bake out temperature is dried more than 180 ℃, can make 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 and reach the remaining monomeric effect of reduction.
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.According to the present invention, the particle size dispersion of acrylate polymer is narrow more good more.
Super absorbent resin is the hydrophilic polymer of dissolving not, resin inside has inhomogeneity bridge formation structure, generally for improve quality as: improve uptake rate, improve colloid intensity, improve anti-caking effect, hydraulic permeability etc., can remake further bridge formation on the surface of resin.
According to the present invention, the reaction of when thermal treatment, building bridge simultaneously, its surface crosslinking agent is for can be polyvalent alcohol as glycerol, ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, 1,4-butyleneglycol, trialkyl methylpropane, sorbyl alcohol etc.; 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 suitable additives amount of this linking agent is (is benchmark with the total solid of reactant) between weight percent 0.001wt% to 10wt%, more suitable consumption is between 0.005wt% to 5wt%, the linking agent additive capacity can't show effect when weight percent 0.001wt% is following, the linking agent additive capacity is when weight percent 10wt% is above, water-absorbent is too low, reduces resin property.
Surface crosslinking agent is when coating processing, and the addition manner of its surface crosslinking agent is divided into surface crosslinking agent and directly adds, or the interpolation of the furnishing surface crosslinking agent aqueous solution, 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 to get final product, and be 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, and is wherein preferable with Tai-Ace S 150, silicon-dioxide.The usage of inert inorganic salt powder can be used or merge two or more mixing separately and use.The inert inorganic salt powder adds scope between weight percent 0.005wt% to 10.0wt%, and is wherein preferable with 0.01wt% to 4.0wt%.
After carrying out the surface crosslinking agent coating processing,, make the surface crosslinking agent can be evenly and carry out crosslinking reaction fast, and make internal crosslinking agent carry out crosslinking reaction and reach effect of the present invention again to carry out heat treated in 120 ℃ to the 230 ℃ scopes.Thermal treatment temp cross-linking reaction time below 120 ℃ is too of a specified duration, do not have an economic benefit, thermal treatment temp more than 230 ℃ the easy deterioration of resin influence quality, heat treatment time was advisable with 2 minutes to 120 minutes, do the thermal treatment temp adjustment according to the thermal effectiveness of desiring to acquire, thermal treatment temp height then heat treatment time is short, and when the thermal treatment temp temperature was hanged down, then the thermal treatment temp time was long.
After the surface-crosslinked thermal treatment, in High hydrophilous resin, add the water-insoluble micro mist, carry out agglomeration resistance and handle.The present invention makes High hydrophilous resin still have high workability after absorbing moisture for increasing the gap between the High hydrophilous resin particle.Water-insoluble micro mist addition manner is directly to add, or utilizes sticking agent that the water-insoluble micro mist is attached to the High hydrophilous resin surface again.The water-insoluble micro mist comprises; The inorganic salt powder of Tai-Ace S 150, sal epsom, aluminum oxide, magnesium oxide, zinc oxide, lime carbonate, calcium phosphate, barium phosphate, diatomite, weak soil, clay, talcum powder, zeolite, kaolin, swollen soil, activated carbon, silicon-dioxide, titanium dioxide reaches the organic dust as cellulose powder, polyester, polyethylene, polyvinyl chloride, polystyrene.In the above-mentioned water-insoluble micro mist, best with the effect of adding the inorganic salt powder.The usage of inorganic salt powder can be used or merge two or more mixing separately and use.The interpolation scope is between weight percent 0.001wt% to 10.0wt%, and is wherein preferable with 0.01wt% to 4.0wt%.The size of particles of water-insoluble micro mist preferably is not more than 10mm, and more suitable size is below the 0.6mm.Sticking agent can be polyvalent alcohol as glycerol, polyoxyethylene glycol, sorbyl alcohol etc.; Maybe can use polymine.The usage of sticking agent can be used or merge two or more mixing separately and use.The suitable additives amount of sticking agent is (is benchmark with the total solid of reactant) between weight percent 0.001wt% to 10wt%, more suitable consumption is between 0.005wt% to 5wt%, and the sticking agent additive capacity can't make the inert inorganic salt powder be attached to the High hydrophilous resin surface fully when weight percent 0.001wt% is following.The sticking agent additive capacity is when weight percent 10wt% is above, and the water-absorbent step-down reduces resin property.
The mixing device that is utilized in the process of hybrid resin of the present invention and inorganic salt must can produce big mixing force, and it mixes the beginning can be full and uniform.Being used for mixing device of the present invention can V-type mixing tank, column mixer, high-speed stirring mixer, helical mixer, fluidized bed mixer, double arm kneading mixer, both arms cone mixer, ribbon blender, close wall type mixing tank, pulverize kneader, impeller and screw extrusion press.
Powdery provided by the invention, water insoluble, can absorb water liquid or urine and blood, and have on equipment and reduce thermal treatment temp, and shorten the super absorbent resin of its heat treatment time, have high confining force, and under higher pressure, have the higher absorption multiplying power property.Manufacture method of the present invention comprises at least:
(a) use a kind of water-soluble unsaturated monomer that contains vinylformic acid (salt) and acrylamide (salt), neutralization ratio is in the scope of 45 to 85 moles of %, and the concentration of unsaturated monomer solution is in the scope of 20 to 55 weight parts;
(b) the gelinite chopping of reaction back generation is in 100 ℃ of warm air dryings to 180 ℃ of scopes of temperature, pulverizing, screening;
(c) carry out surface-crosslinked coating processing again with cross-linking compounds and the phosphatic mixed aqueous solution of epoxy alkyl; And
(d) 120 ℃ to 230 ℃ heat hot of temperature are handled:
The surface tension value that is used for cross-linking compounds of the present invention and the phosphatic mixed aqueous solution of epoxy alkyl preferably is not higher than 36mN/m, preferentially selects for use between the 30-35m N/m.If the surface tension value of mixed aqueous solution is higher than 36mN/m, then can cause when being sprayed on absorbent resin, absorbent resin has the expansible phenomenon to take place, make absorbent resin have the accumulative phenomenon to produce, because when the surface tension value of mixed aqueous solution is higher than 36mN/m, mixed aqueous solution just can't be scattered in the surface of absorbent resin uniformly, after causing surfaction, the absorbent resin water-retaining capacity reduces.
For the present invention, the cross-linking compounds and the phosphatic mixed aqueous solution of epoxy alkyl that utilize surface tension value to be lower than 36mN/m are sprayed on absorbent resin, and via 120 ℃ to 230 ℃ thermal treatments of temperature, can make and have high confining force, and the super absorbent resin that has the higher absorption multiplying power under higher pressure is maximum characteristics of the present invention.Be used for preparing closing and there is no special restriction in the step of above-mentioned water-soluble unsaturated monomer, as long as make the super absorbent resin of gained via method of the present invention, the sanitary product, agricultural that can be applicable to various types with and the water-retaining agent used of food fresh keeping.
Be water absorbent rate under the pressure that proves super absorbent resin of the present invention, the inventor utilizes pressurized absorbed dose (pressure load: 20g/cm
2And 49g/cm
2) measure.Its pressurized absorbed dose system measures according to the method described in the 7th page in the European patent 0339461 A specification sheets; The super absorbent resin of initial weight is placed in the right cylinder of sieve shading portion, to powder 20g/cm in addition
2And 49g/cm
2Pressure, then this right cylinder is placed on the absorptivity demand tstr, allow this super absorbent resin absorb 0.9% sodium chloride aqueous solution one hour, will survey the weight that absorbs water again, with the weight of institute's value, promptly get pressurized absorbed dose numerical value divided by super absorbent resin.
The confining force that the present invention is alleged utilizes the tea bag test method determination, then remove maximum and Schwellenwert with five measurements after, average; The super absorbent resin of 0.2g is contained in the tea bag, and was soaked in 0.9% the NaCl aqueous solution 20 minutes, the tea bag after then this being soaked places whizzer centrifugal (diameter 23cm, rotating speed 1400rpm) weighing after three minutes.The numerical value of gained deducts not earlier, and the blank group tea bag heavy (with the same steps as operation) of filling super absorbent resin heavily promptly gets confining force numerical value divided by polymkeric substance again.
The surface tension that the present invention is alleged, utilize KRUSS K-100 type surface tension apparatus; get measured liquid and place the cup of containing sample; this sample cup is placed on the sample table of surface tension apparatus; hang hold cleaning the platinum plate on the cantilever of surface tension apparatus; the sample table that raises then to platinum plate place makes the platinum plate under fluid surface, presses the mensuration switch, can obtain the surface tension value of measured liquid; Surface tension value unit is mN/m, and measuring temperature is 23 ± 2 ℃, and replication at least 3 times is got its mean value.
Below with preferred embodiment explanation the present invention, but claim of the present invention and technical scope are not limited by these embodiment.
Reference example:
1) gets in the 500c.c Conical flask of water that 48% aqueous sodium hydroxide solution 218.7g slowly adds 270g vinylformic acid and 291.6g, sodium hydroxide/acrylic acid dropping ratio is in 0.85 to 0.95 scope, the dropping time is 2 hours, and keeps bottle temperature of interior neutralization reaction system in 20 ℃ to 40 ℃ scopes; Get the monomer concentration 42wt% aqueous solution this moment, and wherein the vinylformic acid of 70mol% (mol ratio) partly neutralizes and becomes sodium acrylate.
2) add the N of 0.414g again, N '-methyne bisacrylamide is in water-soluble unsaturated monomer solution, and temperature maintenance is in about 20 ℃.
3) add the 0.144g hydrogen peroxide, 1.8g sodium bisulfite and the reaction of 1.8g ammonium persulphate initiator.
4) will react the gelinite that the back generates and utilize the chopping of cut pulverizer, and to filter out size be the following gelinite of 2mm diameter.
5) again with 130 ℃ of temperature dryings 2 hours; Utilize fixedly particle diameter screen cloth screening of 0.1mm～0.85mm, get the powdery absorbent resin, it measures confining force is 42.6g/g, 20g/cm
2Water absorbent rate 6.3g/g under the pressure, 49g/cm
2Water absorbent rate 6.1g/g under the pressure.
Embodiment one
Weigh the obtained absorbent resin 100g of reference example, (loose first finish company makes to add ethylene glycol and oxyethane alkylphosphonic, trade(brand)name: A-512A) mixed aqueous solution 1.5g, surface tension value=33.4mN/m, with 140 ℃ of temperature heat treated 1 hour, after the cooling, promptly get high-performance high absorbent resin.It measures confining force is 32.1g/g, 20g/cm
2Water absorbent rate 27.5g/g under the pressure, 49g/cm
2Water absorbent rate 19.3g/g under the pressure.
Embodiment two:
Repeat embodiment one, but add glycerine and oxyethane alkylphosphonic mixed aqueous solution 1.5g, surface tension value=32.5mN/m with 140 ℃ of temperature heat treated 1 hour, promptly gets high-performance high absorbent resin.It measures confining force is 31.4g/g, 20g/cm
2Water absorbent rate 26.8g/g under the pressure, 49g/cm
2Water absorbent rate 19.7g/g under the pressure.
Embodiment three:
Repeat embodiment one, but add Diethylene Glycol and oxyethane alkylphosphonic mixed aqueous solution 1.5g, surface tension value=31.3mN/m with 140 ℃ of temperature heat treated 1 hour, promptly gets high-performance high absorbent resin.It measures confining force is 30.1g/g, 20g/cm
2Water absorbent rate 25.2g/g under the pressure, 49g/cm
2Water absorbent rate 17.9g/g under the pressure.
Embodiment four:
Repeat embodiment one, but add ethylene carbonate and oxyethane alkylphosphonic mixed aqueous solution 1.5g, surface tension value=33.9mN/m with 140 ℃ of temperature heat treated 1 hour, promptly gets high-performance high absorbent resin.It measures confining force is 32.9g/g, 20g/cm
2Water absorbent rate 25.7g/g under the pressure, 49g/cm
2Water absorbent rate 16.5g/g under the pressure.
Embodiment five:
Repeat embodiment one, but add polyethyleneglycol diglycidylether (Nagase company makes, trade(brand)name: EX-810) and oxyethane alkylphosphonic mixed aqueous solution 1.5g, surface tension value=33.1mN/m, with 110 ℃ of temperature heat treated 1 hour, promptly get high-performance high absorbent resin.It measures confining force is 31.7g/g, 20g/cm
2Water absorbent rate 23.4g/g under the pressure, 49g/cm
2Water absorbent rate 15.2g/g under the pressure.
Embodiment six:
Repeat embodiment one, but, promptly get high-performance high absorbent resin with 180 ℃ of temperature heat treated 10 minutes.It measures confining force is 33.1g/g, 20g/cm
2Water absorbent rate 22.9g/g under the pressure, 49g/cm
2Water absorbent rate 16.3g/g under the pressure.
Embodiment seven:
Weigh reference example one obtained super absorbent resin 100g, add Aluminium Sulphate usp (powder) 1.0g, to be mixedly add ethylene carbonate and oxyethane alkylphosphonic mixed aqueous solution 1.5g again after evenly, with 140 ℃ of temperature heat treated 1 hour, after the cooling, promptly get high-performance high absorbent resin.It measures confining force is 30.1g/g, 20g/cm
2Water absorbent rate 24.5g/g under the pressure, 49g/cm
2Water absorbent rate 18.3g/g under the pressure.
Embodiment eight:
Repeat embodiment one, but (loose first finish company makes trade(brand)name: A-512B) mixed aqueous solution 1.5g, surface tension value=31.4mN/m to add ethylene carbonate and oxyethane alkylphosphonic, with 140 ℃ of temperature heat treated 1 hour, promptly get high-performance high absorbent resin.It measures confining force is 33.8g/g, 20g/cm
2Water absorbent rate 23.2g/g under the pressure, 49g/cm
2Water absorbent rate 15.4g/g under the pressure.
Comparative example one:
Repeat embodiment one, but add aqueous glycol solution 1.5g, surface tension value=50.5mN/m with 140 ℃ of temperature heat treated 1 hour, after the cooling, promptly gets high-performance high absorbent resin.It measures confining force is 41.1g/g, 20g/cm
2Water absorbent rate 9.3g/g under the pressure, 49g/cm
2Water absorbent rate 6.8g/g under the pressure.
Comparative example two:
Repeat comparative example one, improved temperature to 180 ℃ heat treated 1 hour, after the cooling, promptly get high-performance high absorbent resin.It measures confining force is 40.9g/g, 20g/cm
2Water absorbent rate 9.4g/g under the pressure, 49g/cm
2Water absorbent rate 7.0g/g under the pressure.
Claims (5)
1. the manufacture method of a super absorbent resin, this method comprises at least:
(a) use a kind of water-soluble unsaturated monomer that contains vinylformic acid and acrylamide, neutralization ratio is in the scope of 45 to 85 moles of %, and the concentration of unsaturated monomer solution is in the scope of 20 to 55 weight %; With the total solid of reactant is benchmark, adds 0.001wt%-5wt% polyreaction linking agent and carries out polyreaction;
(b) the gelinite chopping of reaction back generation is in 100 ℃ of warm air dryings to 180 ℃ of scopes of temperature, pulverizing, screening;
(c) carry out surface-crosslinked coating processing with cross-linking compounds and the phosphatic mixed aqueous solution of epoxy alkyl; And
(d) 120 ℃ to 230 ℃ heat hot of temperature are handled.
2. according to the manufacture method of the described super absorbent resin of claim 1, wherein, the gelinite diameter of chopping is not more than 2.00mm.
3. according to the manufacture method of the described super absorbent resin of claim 1, wherein, cross-linking compounds is selected from diglycidyl ether compounds, alkylene carbonate compound or polyol compound.
4. according to the manufacture method of the described super absorbent resin of claim 1, wherein, the epoxy alkyl phosphate compounds is an oxyethane alkylphosphonic acid carboxylic acid salt compound, and the surface tension value of the aqueous solution is not more than 36mN/m.
5. according to the manufacture method of the described super absorbent resin of claim 3, wherein, the scope of surface crosslinking agent addition is that benchmark is between weight percent 0.005wt% to 10.0wt% with the total solid of reactant.
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| CN1970588A (en) * | 2005-11-25 | 2007-05-30 | 台湾塑胶工业股份有限公司 | Preparation method of powdery, water-insoluble high hydroscopicity resin capable of adsorbing water, urine or blood and containing low content soluble substance |
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