CN101050251A - Method for fabricating high water absorption resin - Google Patents
Method for fabricating high water absorption resin Download PDFInfo
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- CN101050251A CN101050251A CN 200610067100 CN200610067100A CN101050251A CN 101050251 A CN101050251 A CN 101050251A CN 200610067100 CN200610067100 CN 200610067100 CN 200610067100 A CN200610067100 A CN 200610067100A CN 101050251 A CN101050251 A CN 101050251A
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Abstract
This invention discloses a method for producing powdery and water-insoluble high-water-absorbent resin with low soluble content. The high-water-absorbent resin can absorb water, urine and blood. The method comprises: (1) adding crosslinking agent to acid-containing monomer aqueous solution with a neutralization rate higher than 50 mol.%, and performing free radical polymerization; (2) standing monomer solution, catalyst and water-absorbent resin (less than 100 mu.m) in a mixer with at least one screw for 3-600 s; (3) drying with 100-250 deg.C hot wind, pulverizing, and screening; (4) coating with surface crosslinking agent; (5) performing surface thermal treatment at 80-230 deg.C; (6) adding inert organic salt powder. The acid-containing monomer is selected from acrylic acid, methacrylic acid and 2-allylamine-2-methylpropane sulfonic acid, and the monomer aqueous solution contains 0-5 wt. % of water-soluble polymer.
Description
Technical field
The present invention mainly provides a kind of manufacture method of super absorbent resin, except making polyreaction more evenly to reduce the especially solvable of absorbent resin, more can improve the operability when reclaiming processing procedure or finished product fine powder through this manufacture method.
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 has starch acrylamide nitrile (hydrolyzedstarch-acrylonitrile) graftomer (day disclosure special permission communique clear 49 (1974)-43 of meeting the water decomposition type, 395), (day disclosure communique is clear and 51 (1976)-125 for neutral starch acrylamide acid graftomer, 468), (day disclosure special permission communique is clear and 52 (1977)-14 for saponification ethene acetate propylene ester copolymer, 689), hydrolyzed acrylonitrile multipolymer or acrylamide copolymer (day disclosure special permission communique clear and 531978)-15,959), and partly and polyacrylic acid (day disclosure specially permit communique clear and 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.
Succeeded in developing by many-sided so that the method for polymeric acrylic acid and acrylate formation super absorbent resin is existing at present, and the multiple industry member production that has been applied to is arranged, its polymerization process has; It is clear and 48 (1973)-42 that the Japanese katal of casting film polyreaction is permitted communique, 466, it is clear and 58 (1983)-49 to carry out the day disclosure special permission communique of polyreaction on conveying belt, 714, it is clear and 59 (1984)-37 to carry out the day disclosure special permission communique of anti-phase suspension polymerization, 003, or monomer sprayed or to be coated on the Japan's special permission communique that carries out polyreaction on the fibre substrate clear and 62 (1987)-53,309 etc.
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 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.
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 not ear per-cent be 45mol% to 85mol%, proper concn is 50mol% to 75mol%, in and concentration not ear per-cent be that the pH value of 45mol% finished product when following is understood on the low side, in and concentration not ear per-cent be that the pH value of 85mol% finished product 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.
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, two (2-propenyl) amine of N-, 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, 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 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 as: 2, two (2-amidine propane) dihydrochlorides, 2 of 2 '-azo-group, two (N, N-two the stretches the methyl NSC 18620) dihydrochlorides of 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 0.001wt% to 10wt% (with in and acrylate weight be benchmark), more suitable consumption is then between 0.1wt% to 5wt%, usage quantity is when 0.001wt% is following, react too slow unfavorable economic benefit, usage quantity is 10wt% when above, reacts that too fast response heat is wayward.
Monomer solution can be on the conveyer belt type reactor or is equipped with in the horizontal type reactor of paddle and carries out polyreaction, the superabsorbent gels body of preparing utilizes pulverizer to be cut into the following little gelinite of diameter 20mm earlier, better below the diameter 10mm, be beneficial to back segment exsiccant step.
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 temperature temperature 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 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.
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, this surface-crosslinked processing promptly utilize have can with the multiple functional radical linking agent of acid-base reaction, be suggested in this preceding existing many patents; 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 carry out surface treatment (JP-A-63-270741, JP-A-64-50707, JP-A-1-292004), use organic solution, water, ether (ether) compound (JP-A-2-153903) etc.; Though these surface-treated methods can improve water absorbent rate under the uptake rate pressurize, will cause the too much adverse consequences of confining force decline, reduce the performance of practical application.
Screening is fixedly behind the particle diameter, but according to the linking agent that can react simultaneously when the surface treatment of the present invention is 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 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 0.001wt% to 10wt%, more suitable consumption is between 0.005wt% to 5wt%, the surface crosslinking agent additive capacity can't show effect when weight percent 0.001wt% is following, the surface crosslinking 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 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 0.005wt% to 10.0wt%, and is wherein preferable with 0.01wt% to 4.0wt%.
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 0.005wt% to 10.0wt%, and is wherein preferable with 0.01wt% to 4.0wt%.The 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 value 12 above non-ionic surfactants for use, 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 polyoxyethylene bay ether etc., this interfacial agent or tool viscosity organic compound can be formulated into aqueous solution kenel and add or add separately, suitable interfacial agent or tool viscosity organic compound additive capacity between weight percent 0.001wt% to 5wt% (is benchmark with the total solid of reactant), more suitable consumption weight percent is between 0.01wt% to 3wt%.
1, present method with polymeric acrylic acid and acrylate formation super absorbent resin has the multiple industry member production that is applied to, comprise that the day disclosure special permission communique of casting film polyreaction is clear and 48 (1973)-42,466, it is clear and 58 (1983)-49 to carry out the day disclosure special permission communique of polyreaction on conveying belt, 714, it is clear and 59 (1984)-37 to carry out the day disclosure special permission communique of anti-phase suspension polymerization, 003, or monomer sprayed or be coated on day disclosure of carrying out polyreaction on the fibre substrate to specially permit communique clear and 62 (1987)-53,309 etc.But above-mentioned polymerization process all responds wayward and the unsettled shortcoming of processing procedure, and solvable part of the super absorbent resin of gained is higher relatively.
2, in general, dried super absorbent resin carries out the surface crosslinking agent coating processing after need pulverizing, screen fixedly particle diameter again.The screening fixedly particle diameter to be advisable between 60 μ m to 1000 μ m, with preferable between 100 μ m to 850 μ m.Particle diameter can make greater than the absorbent resin of 850 μ m that the finished product rate of water absorption was slack-off afterwards, need grind again; Particle diameter then can cause the finished powder dust quantity higher less than the absorbent resin of 100 μ m, so the step that need reclaim is to save cost and to enhance productivity.In general, the mode of recovery can be:
(1) is prerequisite not influence final product quality, particle diameter is done to mix less than the absorbent resin of 100 μ m with particle diameter at the absorbent resin of 100 μ m to 850 μ m in the proper ratio.
(2) in the mode of humidification, make particle diameter attach to the absorbent resin surface of particle diameter at 100 μ m to 850 μ m less than the absorbent resin of 100 μ m, reclaim and the effect that reduces dust to reach.
Above-mentioned two kinds of ways of recycling have operation to go up the shortcoming that Dust Capacity is higher or organic efficiency is relatively poor.
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, a kind of powdery provided by the invention, water insoluble can absorb the low super absorbent resin of water liquid, urine or blood and solubles content, and its manufacture method comprises:
1) adds linking agent and carry out Raolical polymerizable containing more than neutralization ratio 50mole% in the acidic group monomer solution, contain the acidic group monomer and can be selected from vinylformic acid, methacrylic acid, 2-allylamine-2-methyl propane sulfonic acid or its mixture, and contain the water-soluble polymer of 0～5wt% in the monomer solution;
2) monomer solution, polymerization starter and particle diameter were detained 3～600 seconds in a mixing machine that has more than at least one the screw rod less than the absorbent resin of 100 μ m;
3) carry out drying, pulverizing, screening with 100 ℃ to 250 ℃ hot blasts of temperature;
4) surface crosslinking agent coating processing;
5) 80 ℃ to 230 ℃ heating surface of temperature are handled; And
6) add the inert inorganic salt powder.
Described method, its water-soluble polymer are polyvinyl alcohol or starch or starch derivative or its mixture.
Described method, its linking agent can be has the water-soluble cpds that two or more can participate in the functional group of free radical reaction.
Described method, its neutralizing agent can be lithium hydroxide or sodium hydroxide or potassium hydroxide or Quilonum Retard or yellow soda ash or salt of wormwood or lithium bicarbonate or sodium bicarbonate or saleratus or its mixture.
Described method, its initiators for polymerization can be thermolysis type initiator or oxidation-reduction type initiator.
Described method, in its initiators for polymerization, thermolysis type initiator can be hydrogen peroxide, hydrogen peroxide, two-Di tributyl superoxide, peroxidation acid amides or persulphate superoxide such as (ammonium salt, an alkali metal salts), or 2, two (N, N-two stretches the methyl NSC 18620) the dihydrochloride azo-initiators of two (2-amidine propane) dihydrochloride, the 2.2 '-azo-groups of 2 '-azo-group.
Described method, in its initiators for polymerization, the oxidation-reduction type initiator can be acid accumulator sulfite, thiosulphate, xitix, ferrous sulfate or persulfuric acid salt.
Described method, its mixing machine comprises following assembly:
1) contains the reaction monomers feeding pipe of linking agent;
2) polymerization starter feeding pipe;
3) fine grain size super absorbent resin feeding mouth;
4) screw rod more than;
5) mixing machine body;
6) reclaim the machine body;
7) reaction mass relief outlet.
Described method, its residence time is good with 20～30 seconds, and 20 seconds Nei Gengjia are especially with 10 seconds the bests.
Described method, its residence time mixed inhomogeneous with next reaction mass at 5 seconds, and back segment polymeric reaction temperature instability has the higher phenomenon of local temperature, and its solvable part is higher.
Described method,, the particle size distribution range after its screening is between 0.05mm to 1mm.
Described method, its surface crosslinking agent are polyvalent alcohol or polyethyleneglycol diglycidylether or alkylene carbonate or its mixture.
Described method, it is 0.005wt%～5.0wt% at weight percent that its surface crosslinking agent adds scope.
Described method, its inert inorganic salt powder can be Tai-Ace S 150 or aluminum oxide or magnesium oxide or calcium oxide or kaolin or silicon-dioxide or lime carbonate or magnesiumcarbonate or its mixture.15. according to the method for claim 14, it is 0.01wt%～4.0wt% at weight percent that its inert inorganic salt powder adds scope.
In detail, 1) preparation method of high-hydroscopicity resin provided by the present invention is to utilize one to have the above mixing machine of at least one screw rod, before polymerization, make the reaction mass uniform mixing, further be discharged to reactor again and finish polyreaction, below be its process description (asking for an interview Fig. 1): the reaction monomers that contains linking agent is entered in the mixing machine body by the reaction monomers feeding pipe 1 among Fig. 1, polymerization starter then enters body by polymerization starter feeding pipe 2, reaction monomers and polymerization starter are via the turning effort of the screw rod more than 3 subsequently, evenly, uniaxially is pushed ahead, and is discharged to enter in belt reactor or batch reactor by reaction mass relief outlet 7 at last and finishes polyreaction.Utilize the mode of production provided by the present invention, except can improving monomer solution and catalyst blended homogeneity, also can make temperature of reaction comparatively stable, improve the quality of production.In addition, use has the above mixing machine of at least one screw rod can guarantee that the phenomenon that refluxes does not appear in store list to travelling forward, thereby avoided polyreaction material overstand and form gelatinous solid in mixing machine, caused the inconvenience on the process operations.The length of residence time can influence reaction monomers and catalyst blended homogeneity, and then solvable part of content of influence reaction situation and finished product.In general, the residence time is long, and reaction monomers has the sufficient time to mix with catalyst, reaction can comparatively evenly and be stablized, solvable part relatively low, but the residence time also can not be long, forms excessive heavy-gravity prepolymer or gelatinous solid to avoid reaction mass in mixing machine.Length as for the residence time then can be controlled by the length and the rotating speed of screw rod.
2) method of recovery fine grain size absorbent resin provided by the invention, its method is described as follows: the reaction monomers that contains linking agent is entered in the mixing machine body by the reaction monomers feeding pipe 1 among Fig. 2, polymerization starter then enters body by polymerization starter feeding pipe 2, particle diameter then enters body by recovery machine mouth 6 via fine grain size absorbent resin feeding mouth 3 less than the absorbent resin of 100 μ m, reaction monomers subsequently, the absorbent resin of polymerization starter and fine grain size is by the screw rod turning effort more than, evenly, uniaxially is pushed ahead, discharge by reaction mass relief outlet 7 at last, enter in belt reactor or batch reactor and finish polyreaction.
The present invention will contain monomer, polymerization starter and the particle diameter of linking agent to be detained in a mixing machine that has more than at least one the screw rod less than the absorbent resin of 100 μ m before polyreaction, see through adjusting the residence time can make reaction monomers improve the reaction homogeneity with the catalyst thorough mixing, also can reach the effect of recovery fine grain size absorbent resin.Thus, the relative raising with stability of the uniformity coefficient of whole polyreaction is many, and has simplified the step that reclaims processing procedure or finished product fine powder.
For making the characteristic that processing procedure of the present invention is stable more, reduce solvable part and recovery fine grain size absorbent resin, must do following analysis and record:
(1) solubles content: weigh the 0.5g super absorbent resin earlier, add 0.9% salt solution 185g again, after stirring hour under the 500rpm rotating speed, go out the SAP extraction liquid with filter paper filtering.At last, weigh this extraction liquid 20g,, re-use 0.1N HCl and carry out back titration to obtain the content of SAP solvend earlier with 0.1N NaOH titration.
(2) processing procedure stability: then every 15min record primary first-order equation temperature, with foundation as judgement.In addition, attentive response material and fine grain size absorbent resin to mix and the situation that reclaims.
(3) uptake rate of finished product: weigh the super absorbent resin of 2g earlier, add 0.9% salt solution 50ml again, under the 600rpm rotating speed, observe and write down the wherein time of whirlpool disappearance.
(4) finished product is at 49g/cm
2Absorption multiplying power under the pressure.
Description of drawings
Fig. 1 is a screw mixer synoptic diagram of the present invention.
Fig. 2 reclaims the machine synoptic diagram for the bar mixing machine of spiral shell of the present invention in conjunction with fine powder.
Embodiment
Below with embodiment the present invention is described, but patent of the present invention and technical scope are not limited by these embodiment.
Embodiment one:
(1), under ice bath, vinylformic acid 22.53kg slowly added in the aqueous sodium hydroxide solution afterwards and neutralize prior to adding the water of 49% aqueous sodium hydroxide solution 17.35kg and 30.52kg in the 100L reactive tank; Get the monomer concentration 38.6wt% aqueous solution this moment, and wherein 68mole% vinylformic acid partly neutralizes and is sodium acrylate.
(2) the glycerol polyoxyethylene glycol triglycidyl ether (n=7) that adds 33.80g again is in part neutral acrylic acid aqueous solution, and holding temperature is in about 20 ℃.
(3) control aforesaid propylene acid sodium solution flow is 70.4kg/hr, and it is entered in the mixed organism by 1 among specification sheets Fig. 2 of the present invention.
(4) the control particle diameter is 1.02kg/hr less than the absorbent resin feeding of 100 μ m (following general designation fine powder), and is entered in the mixed organism by 6. among specification sheets Fig. 2 of the present invention.
(5) control L-xitix, Sodium Persulfate and 2 respectively, the flow of 2-azo-group two (2-amidine propane) is 12.99g/hr, 162.40g/hr and 162.40g/hr, and it is entered in the mixed organism via 2 among description of the invention Fig. 2.
(6) utilize one to have the above mixing machine of at least one screw rod, with aforesaid propylene acid sodium solution, polymerization starter and fine powder uniform mixing, it is 10 seconds that the control screw speed makes the residence time of reaction mass, and the reaction mass viscosity of discharge is 7.0cP (recording with the Type B viscosmeter).
(7) reaction mass behind the uniform mixing is entered in the belt reactor continuously finish polyreaction.The result shows that polymeric reaction temperature is stable, and on the screw rod or the outlet pipe bent position all do not have any colloid and generate.
(8) colloid is utilized the cut pulverizer be cut into gelinite below the 2mm diameter.
(9) with 170 ℃ of temperature dryings 1 hour; Utilize fixedly particle diameter of screen cloth screening 0.1mm～0.85mm, get the powdery super absorbent resin.
(10) weigh this super absorbent resin 100g, add ethylene carbonate/water/methyl alcohol=1/1/1 (weight ratio) solution 4g, with 215 ℃ of temperature heat treated 10 minutes.
(11) after the cooling, (platform is moulded company and produced the name of an article: NS-2000) and 20% aqueous glycerin solution 2g, promptly get high-performance high absorbent resin behind the uniform mixing, the analysis solubles content is 2.43%, and uptake rate is 75.24 seconds, 49g/cm to add 1g lime carbonate
2It is 25.48g/g that pressure absorbs multiplying power down.
Embodiment two:
Repeat embodiment one, but the feeding of step 4 changes 1.53kg/hr into.The result shows that reaction mass and fine powder mixed scenario are good, polymeric reaction temperature stable, and on the screw rod or the outlet pipe bent position all do not have any colloid generation.As for the reaction mass viscosity of discharging then is 7.2cP, and the finished product solubles content is 2.51%, and uptake rate is 71.75 seconds, 49g/cm
2It is 25.39g/g that pressure absorbs multiplying power down.
Embodiment three:
Repeat embodiment one, but the feeding of step 4 changes 2.04kg/hr into.The result shows that reaction mass and fine powder mixed scenario are good, polymeric reaction temperature stable, and on the screw rod or the outlet pipe bent position all do not have any colloid generation.As for the reaction mass viscosity of discharging then is 7.8cP, and the finished product solubles content is 2.49%, and uptake rate is 67.23 seconds, 49g/cm
2It is 25.17g/g that pressure absorbs multiplying power down.
Embodiment four:
Repeat embodiment one, but the feeding of step 4 changes 3.06kg/hr into.The result shows that reaction mass and fine powder mixed scenario are good, polymeric reaction temperature stable, and on the screw rod or the outlet pipe bent position all do not have any colloid generation.As for the reaction mass viscosity of discharging then is 8.5cP, and the finished product solubles content is 2.50%, and uptake rate is 61.02 seconds, 49g/cm
2It is 24.87g/g that pressure absorbs multiplying power down.
Embodiment five:
Repeat embodiment one, but the feeding of step 4 changes 4.08kg/hr into.The result shows, has the part fine powder to be suspended on the reaction mass and the temperature of reaction amplitude of more before having beated increases, but on the screw rod or the outlet pipe bent position still do not have any colloid and generate.As for the reaction mass viscosity of discharging then is 9.4cP, and the finished product solubles content is 2.71%, and uptake rate is 55.46 seconds, 49g/cm
2It is 24.01g/g that pressure absorbs multiplying power down.
Embodiment six:
Repeat embodiment one, but the feeding of step 4 changes 5.12kg/hr into.The result shows that the fine powder amount that is suspended on the reaction mass increases and the temperature of reaction instability, and also has the colloid that is partly formed by fine powder suction back to stick on it on the screw rod.As for the reaction mass viscosity of discharging then is 11.2cP, and the finished product solubles content is 3.42%, and uptake rate is 50.89 seconds, 49g/cm
2It is 22.89g/g that pressure absorbs multiplying power down.
Embodiment seven:
(1), under ice bath, vinylformic acid 32.00kg slowly added in the aqueous sodium hydroxide solution afterwards and neutralize prior to adding the water of 49% aqueous sodium hydroxide solution 23.93kg and 44.07kg in the 100L reactive tank; Get the monomer concentration 38.44wt% aqueous solution this moment, and wherein 66mole% vinylformic acid partly neutralizes and is sodium acrylate.
(2) the glycerol polyoxyethylene glycol triglycidyl ether (n=20) that adds 98.45g again is in part neutral acrylic acid aqueous solution, and holding temperature is in about 20 ℃.
(3) control aforesaid propylene acid sodium solution flow is 60.5kg/hr, and it is entered in the mixed organism by 1. among specification sheets Fig. 2 of the present invention.
(4) the control particle diameter is 0.88kg/hr less than the absorbent resin feeding of 100 μ m (following general designation fine powder), and is entered in the mixed organism by 6. among specification sheets Fig. 2 of the present invention.
(5) flow of controlling L-xitix, two-Di tributyl hydrogen peroxide and Potassium Persulphate respectively is 11.25g/hr, 139.13g/hr and 139.13g/hr, and it is entered in the twin screw mixing body via 2. in the explanatory view 2 of the present invention.
(6) utilize the above mixing machine of at least one screw rod with aforesaid propylene acid sodium solution, polymerization starter and fine powder uniform mixing, it is 10 seconds that the control screw speed makes the residence time of reaction mass, and the reaction mass viscosity of discharge is 13.1cP (recording with the Type B viscosmeter).
(7) reaction mass behind the uniform mixing is entered in the belt reactor continuously finish polyreaction.The result shows that reaction mass mixes situation with fine powder good, but because of viscosity higher slightly, on the belt reactor dispersion more difficult, the hot higher phenomenon of minority local reaction is arranged.
(8) colloid is utilized the cut pulverizer be cut into gelinite below the 2mm diameter.
(9) with 170 ℃ of temperature dryings 1 hour, utilize fixedly particle diameter of screen cloth screening 0.1mm～0.85mm, must the powdery super absorbent resin.
(10) weigh this super absorbent resin 100g, add ethylene carbonate/water/methyl alcohol=1/1/1 (weight ratio) solution 4g, with 215 ℃ of temperature heat treated 10 minutes.
(11) after the cooling, (platform is moulded company and produced the name of an article: NS-2000) and 20% aqueous glycerin solution 2g, promptly get high-performance high absorbent resin behind the uniform mixing, the analysis solubles content is 4.2%, and uptake rate is 70.85 seconds, 49g/cm to add 1g lime carbonate
2It is 24.63g/g that pressure absorbs multiplying power down.
Embodiment eight:
Repeat embodiment one, but the feeding of step 4 changes 1.32kg/hr into.The result shows, has the part fine powder to be suspended on the reaction mass and the temperature of reaction amplitude of more before having beated increases, but on the screw rod or the outlet pipe bent position still do not have any colloid and generate.As for the reaction mass viscosity of discharging then is 13.4cP, and the finished product solubles content is 4.7%, and uptake rate is 67.41 seconds, 49g/cm
2It is 24.21g/g that pressure absorbs multiplying power down.
Embodiment nine:
Repeat embodiment one, but the feeding of step 4 changes 1.75kg/hr into.The result shows that the fine powder amount that is suspended on the reaction mass increases and the temperature of reaction instability, and also has the colloid that is partly formed by fine powder suction back to stick on it on the screw rod.As for the reaction mass viscosity of discharging then is 14.5cP, and the finished product solubles content is 5.1%, and uptake rate is 63.97 seconds, 49g/cm
2It is 23.85g/g that pressure absorbs multiplying power down.
Embodiment ten:
Repeat embodiment one, but the feeding of step 4 changes 3.51kg/hr into.The result shows except the fine powder amount that is suspended on the reaction mass increases and the temperature of reaction instability, and also have the block that is formed by fine powder suction back to stick on it with the outlet pipe bent position on the screw rod.As for the reaction mass viscosity of discharging then is 14.1cP, and the finished product solubles content is 6.4%, and uptake rate is 61.11 seconds, 49g/cm
2It is 24.14g/g that pressure absorbs multiplying power down.
Comparative example one:
Repeat embodiment four, but sodium polyacrylate, polymerization starter and fine powder are stranded in the mixing machine that has only a screw rod.Found that have a large amount of fine powders to be suspended on the reaction mass, and all have block colloid slowly to generate with the outlet pipe bent position on the screw rod.As for the reaction mass viscosity of discharging then is 8.8cP, and the finished product solubles content is 8.1%, and uptake rate is 68.81 seconds, 49g/cm
2It is 25.12g/g that pressure absorbs multiplying power down.
Comparative example two:
Repeat embodiment four, but sodium polyacrylate, polymerization starter and the fine powder center that is stranded in has the vertical type steel basin of paddle.Found that the temperature of reaction amplitude of beating is big, and has the part fine powder to attach to the steel basin cell wall, promptly need clear up once every 2-4hr approximately.As for the reaction mass viscosity of discharging then is 8.3cP, and the finished product solubles content is 10.3%, and uptake rate is 68.27 seconds, 49g/cm
2It is 24.91g/g that pressure absorbs multiplying power down.
Claims (15)
1. a powdery, water insoluble can absorb the low super absorbent resin of water liquid, urine or blood and solubles content, and its manufacture method comprises:
1) adds linking agent and carry out Raolical polymerizable containing more than neutralization ratio 50mole% in the acidic group monomer solution, contain the acidic group monomer and be selected from vinylformic acid, methacrylic acid, 2-allylamine-2-methyl propane sulfonic acid or its mixture, and contain the water-soluble polymer of 0～5wt% in the monomer solution;
2) monomer solution, polymerization starter and particle diameter were detained 3～600 seconds in a mixing machine that has more than at least one the screw rod less than the absorbent resin of 100 μ m;
3) carry out drying, pulverizing, screening with 100 ℃ to 250 ℃ hot blasts of temperature;
4) surface crosslinking agent coating processing;
5) 80 ℃ to 230 ℃ heating surface of temperature are handled; And
6) add the inert inorganic salt powder.
2. according to the method for claim 1, its water-soluble polymer is polyvinyl alcohol or starch or starch derivative or its mixture.
3. according to the method for claim 1, its linking agent is to have the water-soluble cpds that two or more can participate in the functional group of free radical reaction.
According to the process of claim 1 wherein and agent be lithium hydroxide or sodium hydroxide or potassium hydroxide or Quilonum Retard or yellow soda ash or salt of wormwood or lithium bicarbonate or sodium bicarbonate or saleratus or its mixture.
5. according to the method for claim 1, its initiators for polymerization is thermolysis type initiator or oxidation-reduction type initiator.
6. according to the method for claim 5, in its initiators for polymerization, thermolysis type initiator is hydrogen peroxide, hydrogen peroxide, two-Di tributyl superoxide, peroxidation acid amides or persulphate superoxide such as (ammonium salt, an alkali metal salts), or 2, two (N, N-two stretches the methyl NSC 18620) the dihydrochloride azo-initiators of two (2-amidine propane) dihydrochloride, the 2.2 '-azo-groups of 2 '-azo-group.
7. according to the method for claim 5, in its initiators for polymerization, the oxidation-reduction type initiator is acid accumulator sulfite, thiosulphate, xitix, ferrous sulfate or persulfuric acid salt.
8. according to the method for claim 1, its mixing machine comprises following assembly:
1) contains the reaction monomers feeding pipe of linking agent;
2) polymerization starter feeding pipe;
3) fine grain size super absorbent resin feeding mouth;
4) screw rod more than;
5) mixing machine body;
6) reclaim the machine body;
7) reaction mass relief outlet.
9. according to the method for claim 1, its residence time is good with 20～30 seconds, and 20 seconds Nei Gengjia are especially with 10 seconds the bests.
10. according to the method for claim 1, its residence time mixed inhomogeneous with next reaction mass at 5 seconds, and back segment polymeric reaction temperature instability has the higher phenomenon of local temperature, and its solvable part higher.
11. according to the method for claim 1,, the particle size distribution range after its screening is between 0.05mm to 1mm.
12. according to the method for claim 1, its surface crosslinking agent is polyvalent alcohol or polyethyleneglycol diglycidylether or alkylene carbonate or its mixture.
13. according to the method for claim 12, it is 0.005wt%～5.0wt% at weight percent that its surface crosslinking agent adds scope.
14. according to the method for claim 1, its inert inorganic salt powder is Tai-Ace S 150 or aluminum oxide or magnesium oxide or calcium oxide or kaolin or silicon-dioxide or lime carbonate or magnesiumcarbonate or its mixture.
15. according to the method for claim 14, it is 0.01wt%～4.0wt% at weight percent that its inert inorganic salt powder adds scope.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104918964A (en) * | 2014-07-11 | 2015-09-16 | 住友精化株式会社 | Manufacturing method for water absorbing resin |
| CN109312082A (en) * | 2016-10-28 | 2019-02-05 | 株式会社Lg化学 | Super absorbent polymer and method for manufacturing it |
| CN111068099A (en) * | 2019-12-11 | 2020-04-28 | 杭州千芝雅卫生用品有限公司 | High molecular absorption polymer, preparation method and application thereof |
| CN111302575A (en) * | 2019-10-22 | 2020-06-19 | 袁国明 | Coagulant, preparation method and application thereof |
| CN112789297A (en) * | 2018-09-27 | 2021-05-11 | 株式会社日本触媒 | Process for producing water-absorbent resin and water-absorbent resin |
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- 2006-04-04 CN CNB2006100671001A patent/CN100558760C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104918964A (en) * | 2014-07-11 | 2015-09-16 | 住友精化株式会社 | Manufacturing method for water absorbing 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 |
| CN109312082A (en) * | 2016-10-28 | 2019-02-05 | 株式会社Lg化学 | Super absorbent polymer and method for manufacturing it |
| CN109312082B (en) * | 2016-10-28 | 2021-08-10 | 株式会社Lg化学 | Superabsorbent polymer and method for making same |
| US11406962B2 (en) | 2016-10-28 | 2022-08-09 | Lg Chem, Ltd. | Super absorbent polymer and method for producing same |
| CN112789297A (en) * | 2018-09-27 | 2021-05-11 | 株式会社日本触媒 | Process for producing water-absorbent resin and water-absorbent resin |
| CN112789297B (en) * | 2018-09-27 | 2023-09-12 | 株式会社日本触媒 | Method for producing water-absorbent resin, and water-absorbent resin |
| CN111302575A (en) * | 2019-10-22 | 2020-06-19 | 袁国明 | Coagulant, preparation method and application thereof |
| CN111068099A (en) * | 2019-12-11 | 2020-04-28 | 杭州千芝雅卫生用品有限公司 | High molecular absorption polymer, preparation method and application thereof |
| CN111068099B (en) * | 2019-12-11 | 2021-04-06 | 杭州千芝雅卫生用品有限公司 | High molecular absorption polymer, preparation method and application thereof |
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