CN101045771A - Preparation method of water absorbtion resin - Google Patents
Preparation method of water absorbtion resin Download PDFInfo
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- CN101045771A CN101045771A CN 200610066539 CN200610066539A CN101045771A CN 101045771 A CN101045771 A CN 101045771A CN 200610066539 CN200610066539 CN 200610066539 CN 200610066539 A CN200610066539 A CN 200610066539A CN 101045771 A CN101045771 A CN 101045771A
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Abstract
This invention relates to manufacturing method of a hydroscopicity high water absorbent resin. Its neutralization ratio is between 45 to 85 mol percent, concentration of unsaturated monomer water solution is bentween 20 to 55 part by weight. In preparationg process add antidusting agent to reduce dust quantity of hydrophilia resion, obtain high water absorbent resin that possess good physical property, high retentivity and high absorbing magnification under higher pressure.
Description
Technical field
Super absorbent resin 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 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 the art has starch-vinyl cyanide (hydrolyzed starchacrylonitrile) graftomer (day disclosure special permission communique clear 49 (1974)-43 of meeting the water decomposition type, 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 the decomposition that has cheap for manufacturing cost and tool economic benefit and 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, to reduce absorbent resin is formed gel and cohesion by the wetting back of waterborne liquid tendency.When the absorbent resin surface forms gel, can block liquid from the absorbent resin surface to delivered inside, thereby reduced the receptivity of super absorbent resin to liquid, and gel also can make absorbent resin produce the phenomenon of cohesion, further reduces the receptivity of absorbent resin.
Summary of the invention
The object of the invention is to provide a kind of manufacture method of absorbent resin.
For achieving the above object, manufacture method 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) reacted gelinite chopping is in 100 ℃ of warm air dryings to 180 ℃ of scopes of temperature, pulverizing, screening;
(c) with surface crosslinking agent coating processing in addition; And
(d) 120 ℃ to 230 ℃ heat hot of temperature are handled.
Described manufacture method, the gelinite diameter of its screening is not more than 2.00mm.
Described manufacture method gained super absorbent resin, its particle size distribution range are between 0.10mm 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.
Described manufacture method, its surface crosslinking agent contain the alkylidene group sulfite compounds of alkoxyl group, its general formula as shown in the formula:
R is the alcoxyl alkylidene group of carbonatoms 2-10 in the formula.
Described surface crosslinking agent is glycol sulfite ester.
Described surface crosslinking agent, the scope of its addition is between weight percent 0.005wt% to 10.0wt%.
Its composition of a kind of super absorbent resin provided by the invention comprises:
(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 scope of 20 to 55 weight parts;
(b) with 100 ℃ of warm air dryings of temperature, pulverizing, screening gelinite to 180 ℃ of scopes;
(c) the inert inorganic salt powder of interpolation 0.005wt% to 10.0wt% scope;
(d) surface crosslinking agent 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 agglomeration resistance and handle.
Described super absorbent resin, its 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, the size of particles of its water-insoluble micro mist is not more than 0.6mm.
Described super absorbent resin, its sticking agent are Sorbitol Powder, polyoxyethylene glycol and propylene oxide ethylene oxide polymer.
Described sticking agent can use or merge two or more mixing separately and use, and the interpolation scope is between weight percent 0.005wt% to 10.0wt%.
In detail, existing many methods at the surface-crosslinked processing of super absorbent resin are developed on circle, present technique field, 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 add polyvalent alcohol as inert solvent (United States Patent (USP) 4,507,438,4,541, No. 871) absorbent resin carried out the method for crosslinking Treatment, 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 have use N-(hydroxyalkyl)--the methylamino propionic ester is sprayed on absorbent resin surface (United States Patent (USP) 5,229, No. 466) heat-treat, 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 United States Patent (USP) 4289814 about the surface-crosslinked processing of super absorbent resin, 4295978,4500670,4732968,4758617,4824901,4954562,5026800; Though these heat-treating methods can improve uptake rate, promptly water absorbent rate under the pressurize will cause the too much adverse consequences of confining force decline, reduce the performance of practical application.
In view of providing, the invention described above has lower thermal treatment temp and short heat treatment time, making super absorbent resin has under high absorbing power and the high pressure and absorbs multiplying power, and low gel blockage phenomenon, make absorbing products have easy drying property and low leaks.
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.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-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 in the monomer solution, also can add water-soluble polymer 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%, 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 arranged, 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 general suitable consumption of Raolical polymerizable initiator be weight percentage for 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 produce the finished product fine powder amount and improve, when the above gelinite of particle diameter 2.00mm is dried, easily because thermal conduction effect is not good, cause finished product higher, the shortcoming that other rerum natura is performed poor at remaining monomer.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 drying time below 100 ℃ is too of a specified duration, do not have an economic benefit, 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 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.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, when thermal treatment, to build bridge simultaneously and react, its surperficial linking agent is that general formula (1) is representative, contains the alkylidene group sulfite compounds of alkoxyl group,
R is expressed as the alcoxyl alkylidene group of carbonatoms 2-10 in the formula.
The surface crosslinking agent of above-mentioned general formula (1) expression is, the alkylidene group sulfite compounds that contains alkoxyl group, particularly for example: glycol sulfite ester, 4-methyl isophthalic acid, 3-dioxane penta oxazolidine-2-ketone, 4,5-dimethyl-1,3-dioxane penta oxazolidine-2-ketone, 1,3, the own oxazolidine of 2-dioxane-2-ketone, 4-methyl isophthalic acid, 3, the own oxazolidine of 2-dioxane-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.
During the surface crosslinking agent coating processing, the addition manner of surface crosslinking agent, being divided into surface crosslinking agent 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 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.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.
According to the present invention, crosslinking reaction is that carboxylate radical and the hydroxyl in the absorbent resin carries out esterification, when the existing of mineral acid arranged in the reaction system, can reduce the needed activation energy of esterification, to quicken the speed of reaction of esterification.
The mixing device that is utilized in mixing process is that requirement can produce big mixing force, makes the mixing can be full and uniform.Be applicable to 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.
After the surface-crosslinked thermal treatment, add the water-insoluble micro mist in High hydrophilous resin, carry out agglomeration resistance and handle, purpose is the crack between increasing between the High hydrophilous resin particle, makes High hydrophilous resin still have high workability after absorbing moisture.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 electricity is low, reduces resin property.
Embodiment
Purpose of the present invention is providing a kind of powdery, 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 after the reaction screening is in 100 ℃ of warm air dryings to 180 ℃ of scopes of temperature, pulverizing, screening;
(c) applied with surface crosslinking agent; And
(d) 120 ℃ to 230 ℃ heat hot of temperature are handled;
The general formula of surface crosslinking agent (1) is for containing the alkylidene group sulfite compounds of alkoxyl group:
R is the alcoxyl alkylidene group of carbonatoms 2-10 in the formula.
The chemical structure of surface crosslinking agent, under the pyritous reaction conditions, form sulfuric acid and ethylene glycol with water after the hydrolysis of sulfurous acid ester group, carboxylate radical in ethylene glycol and the absorbent resin carries out esterification, under the reaction conditions of sulfuric acid as catalyzer, and the reaction rate accelerates of its esterification, and can reduce temperature of reaction, the shortening heat treatment time, the usage quantity of the reduction production plant area energy, its reaction formula is as follows:
For the present invention, only must utilize the alkylidene group sulfite compounds that contains alkoxyl group to be sprayed on absorbent resin, and handle via 120 ℃ to 230 ℃ heat hot of temperature, can make and have high confining force, and the super absorbent resin that under higher pressure, has the higher absorption multiplying power.Be used for preparing closing and there is no special restriction in the step of above-mentioned water-soluble unsaturated monomer, the sanitary product, agricultural that can more be applicable to various types via the super absorbent resin of gained of the present invention with and the water-retaining agent used of food fresh keeping.
Show water absorbent rate under the pressure of super absorbent resin of the present invention for card, the inventor utilizes pressurized to absorb heavy (pressure load: 20g/cm
2And 49g/cm
2) measure, 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 on according in the right cylinder that sieve shading portion is arranged, 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 suction weight again, with the weight of institute's value, promptly get pressurized absorption tuple value divided by super absorbent resin.
The confining force that the present invention is alleged is to utilize 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.
Embodiment
Below with preferred embodiment explanation the present invention, but patent 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 70mol% (mol ratio) vinylformic acid partly neutralizes and is sodium acrylate.
2) add the N of 0.414g again, N '-methyne bisacrylamide is in water-soluble unsaturated monomer solution, and its 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) reacted gelinite is utilized cut pulverizer chopping, 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 super absorbent resin, the mensuration 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 super absorbent resin 100g of reference example, add glycol sulfite ester/water/methyl alcohol=1/1/1 (weight ratio) solution 1.5g, with 140 ℃ of temperature heat treated 1 hour, after the cooling, promptly get high-performance high absorbent resin, the mensuration confining force is 35.1g/g, 20g/cm
2Water absorbent rate 21.5g/g under the pressure, 49g/cm
2Water absorbent rate 15.3g/g under the pressure.
Embodiment two:
Repeat embodiment one, but add glycol sulfite ester/water/methyl alcohol=1/1/1 (weight ratio) solution 6.0g, with 140 ℃ of temperature heat treated 1 hour, promptly get high-performance high absorbent resin, the mensuration confining force is 3 1.6g/g, 20g/cm
2Water absorbent rate 24.8g/g under the pressure, 49g/cm
2Water absorbent rate 18.7g/g under the pressure.
Embodiment three:
Repeat embodiment one, but with 180 ℃ of temperature heat treated 10 minutes, promptly get high-performance high absorbent resin, the mensuration confining force is 34.6g/g, 20g/cm
2Water absorbent rate 21.7g/g under the pressure, 49g/cm
2Water absorbent rate 15.9g/g under the pressure.
Embodiment four:
Repeat example one, but add glycol sulfite ester/water/methyl alcohol=1/3/1 (weight ratio) solution 2.5g, with 140 ℃ of temperature heat treated 1 hour, promptly get high-performance high absorbent resin, the mensuration confining force is 34.9g/g, 20g/cm
2Water absorbent rate 21.9g/g under the pressure, 49g/cm
2Water absorbent rate 15.3g/g under the pressure.
Embodiment five:
Weigh reference example one obtained super absorbent resin 100g, add Aluminium Sulphate usp (powder) 1.0g, to be mixedly add glycol sulfite ester/water/methyl alcohol=1/1/1 (weight ratio) solution 1.5g again after evenly, with 140 ℃ of temperature heat treated 1 hour, after the cooling, promptly get high-performance high absorbent resin, the mensuration confining force is 33.6g/g, 20g/cm
2Water absorbent rate 23.7g/g under the pressure, 49g/cm
2Water absorbent rate 17.5g/g under the pressure.
Comparative example one:
Repeat embodiment one, but add water/methyl alcohol=1/1 (weight ratio) solution 1.5g, with 140 ℃ of temperature heat treated 1 hour, after the cooling, promptly get high-performance high absorbent resin, the mensuration confining force is 42.4g/g, 20g/cm
2Water absorbent rate 6.2g/g under the pressure, 49g/cm
2Water absorbent rate 5.9g/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, the mensuration confining force is 42.3g/g, 20g/cm
2Water absorbent rate 6.3g/g under the pressure, 49g/cm
2Water absorbent rate 5.9g/g under the pressure.
Comparative example three:
Repeat embodiment five, but add water/methyl alcohol=1/1 (weight ratio) solution 1.5g, with 140 ℃ of temperature heat treated 1 hour, after the cooling, promptly get high-performance high absorbent resin, the mensuration confining force is 41.5g/g, 20g/cm
2Water absorbent rate 6.5g/g under the pressure, 49g/cm
2Water absorbent rate 6.1g/g under the pressure.
Claims (11)
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 (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) reacted gelinite chopping is in 100 ℃ of warm air dryings to 180 ℃ of scopes of temperature, pulverizing, screening;
(c) with surface crosslinking agent coating processing in addition; And
(d) 120 ℃ to 230 ℃ heat hot of temperature are handled.
2. manufacture method according to claim 1, the gelinite diameter of its screening is not more than 2.00mm.
3. manufacture method according to claim 1, gained super absorbent resin, its particle size distribution range are between 0.10mm 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.
4. manufacture method according to claim 1, its surface crosslinking agent contain the alkylidene group sulfite compounds of alkoxyl group, its general formula as shown in the formula:
R is the alcoxyl alkylidene group of carbonatoms 2-10 in the formula.
5. surface crosslinking agent according to claim 4 is glycol sulfite ester.
6. according to claim 4 or 5 described surface crosslinking agents, the scope of its addition is between weight percent 0.005wt% to 10.0wt%.
7. its composition of super absorbent resin comprises:
(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 scope of 20 to 55 weight parts;
(b) with 100 ℃ of warm air dryings of temperature, pulverizing, screening gelinite to 180 ℃ of scopes;
(c) the inert inorganic salt powder of interpolation 0.005wt% to 10.0wt% scope;
(d) surface crosslinking agent 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 agglomeration resistance and handle.
8. super absorbent resin according to claim 7, its 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%.
9. super absorbent resin according to claim 8, the size of particles of its water-insoluble micro mist is not more than 0.6mm.
10. super absorbent resin according to claim 7, its sticking agent are Sorbitol Powder, polyoxyethylene glycol and propylene oxide ethylene oxide polymer.
11. sticking agent according to claim 10 can use or merge two or more mixing separately and use, the interpolation scope is between weight percent 0.005wt% to 10.0wt%.
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| CN101735377B (en) * | 2009-12-25 | 2012-04-18 | 中国科学院长春应用化学研究所 | Method for preparing membranous absorbent material |
| CN104140491A (en) * | 2014-02-28 | 2014-11-12 | 重庆文理学院 | Preparation method of salt-tolerant super absorbent polymer (SAP) |
| CN106133031A (en) * | 2014-08-04 | 2016-11-16 | 株式会社Lg化学 | Super absorbent resin and preparation method thereof |
| CN107511037A (en) * | 2017-09-04 | 2017-12-26 | 无锡普爱德环保科技有限公司 | A kind of drying machine water absorbing agent |
| CN108659434A (en) * | 2017-03-31 | 2018-10-16 | 台湾塑胶工业股份有限公司 | Water-absorbent resin and method for producing same |
| CN108976841A (en) * | 2018-08-01 | 2018-12-11 | 安徽富瑞雪化工科技股份有限公司 | A method of improving super absorbent resin powder flowbility |
| CN110586049A (en) * | 2019-01-26 | 2019-12-20 | 江苏斯尔邦石化有限公司 | Polyacrylate high water absorption resin with high gel bed permeability and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101735377B (en) * | 2009-12-25 | 2012-04-18 | 中国科学院长春应用化学研究所 | Method for preparing membranous absorbent material |
| CN104140491A (en) * | 2014-02-28 | 2014-11-12 | 重庆文理学院 | Preparation method of salt-tolerant super absorbent polymer (SAP) |
| CN106133031A (en) * | 2014-08-04 | 2016-11-16 | 株式会社Lg化学 | Super absorbent resin and preparation method thereof |
| CN106133031B (en) * | 2014-08-04 | 2019-01-08 | 株式会社Lg化学 | High water absorbency polymer and preparation method thereof |
| CN108659434A (en) * | 2017-03-31 | 2018-10-16 | 台湾塑胶工业股份有限公司 | Water-absorbent resin and method for producing same |
| CN108659434B (en) * | 2017-03-31 | 2020-10-20 | 台湾塑胶工业股份有限公司 | Water-absorbent resin and method for producing same |
| CN107511037A (en) * | 2017-09-04 | 2017-12-26 | 无锡普爱德环保科技有限公司 | A kind of drying machine water absorbing agent |
| CN108976841A (en) * | 2018-08-01 | 2018-12-11 | 安徽富瑞雪化工科技股份有限公司 | A method of improving super absorbent resin powder flowbility |
| CN110586049A (en) * | 2019-01-26 | 2019-12-20 | 江苏斯尔邦石化有限公司 | Polyacrylate high water absorption resin with high gel bed permeability and preparation method thereof |
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| CN100543053C (en) | 2009-09-23 |
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