CN101173016A - Method for producing high-performance high absorbent resin - Google Patents
Method for producing high-performance high absorbent resin Download PDFInfo
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- CN101173016A CN101173016A CNA2006101382066A CN200610138206A CN101173016A CN 101173016 A CN101173016 A CN 101173016A CN A2006101382066 A CNA2006101382066 A CN A2006101382066A CN 200610138206 A CN200610138206 A CN 200610138206A CN 101173016 A CN101173016 A CN 101173016A
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Abstract
The invention relates to high water absorption resin in a powder shape with low soluble matter content, and the high water absorption resin is insoluble in water and can absorb water liquid, urine liquid or blood. The preparation method of the high water absorption resin at least comprises the following steps: (1) a monomer aqueous solution with acid radical having over 50mole percent of neutralization rate and polyreaction initiator are led to stay in a pipe line with a jacket, and prepolymer is obtained through free radical polymerization reaction; (2) a long chain and a multielement epoxy group with high hydrophilicity is added in the sticky prepolymer, and light starting polymerization manner is used to produce gelatinovs solid: (3) drying, crushing and screening are held at 100 to 250 DEG C; (4) a surface crosslinking agent is used for coating processing; (5) heating surface processing is acted at 80 to 230 DEG C.
Description
Technical field
The invention relates to a kind of manufacture method of super absorbent resin, the manufacture method of the absorbent resin that especially a kind of solubles content is low.
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 (the open communique clear 49 (1974)-43 of Japanese Patent of meeting the water decomposition type, 395), neutral starch acrylamide acid graftomer (the open communique clear 51 (1976)-125 of Japanese Patent, 468), saponification ethene acetate propylene ester copolymer (the open communique clear 52 (1977)-14 of Japanese Patent, 689), hydrolyzed acrylonitrile multipolymer or acrylamide copolymer (Japanese patent gazette clear 53 (1978)-15,959), and partly and polyacrylic acid (Japanese Patent openly announces clear 55 (1980)-84,304) etc.Wherein account for maximum partly also economical with the super absorbent resin that uses vinylformic acid and acrylate to carry out the crosslinking polymerization gained, its former because vinylformic acid can be obtained by commercially available rapidly, and the super absorbent resin that makes has high water-retaining capacity, and have cheap for manufacturing cost and tool economic benefit, so become the super absorbent resin that generalizes most.
Polymeric acrylic acid and acrylate form the method for super absorbent resin and are succeeded in developing by many-sided, and the multiple industry member production that has been applied to is arranged, its polymerization process has casting film polyreaction (the open communique clear 48 (1973)-42 of Japanese Patent, 466), on conveying belt, carry out polyreaction (the open communique clear 58 (1983)-49 of Japanese Patent, 714), carry out polyreaction (the open communique clear 57 (1982)-34 of Japanese Patent in the pug mill type mixer of the stirring blade of pulverizing, 101), carry out anti-phase suspension polymerization (the open communique clear 59 (1984)-37 of Japanese Patent, 003), or monomer sprayed or be coated on carry out polyreaction (the open communique clear 62 (1987)-53,309 of Japanese Patent) on the fibre substrate.
Above-mentioned polymerization process is reaction raw materials such as polymerization single polymerization monomer, polymerization starter and linking agent together to be carried out Raolical polymerizable form gelatinous solid mostly, and whole polyreaction like this is wayward, and solubles content is also higher.
Summary of the invention
The object of the present invention is to provide a kind of production method of high-performance super absorbent, its polymerization process is comparatively stable comparatively speaking, and it is too high that reaction heat also is unlikely, except improve operating environment, more improved quality product.
For achieving the above object, a kind of powdery provided by the invention, water insoluble can absorb the low production method of high-performance super absorbent of water liquid, urine or blood and solubles content, may further comprise the steps at least:
1) make neutralization ratio 50mole% above contain acidic group monomer solution and initiators for polymerization react and get sticky polymer by in a long lines that contains chuck, carrying out prepolymerization with about 100 liters of flow velocitys per hour;
2) control long tube outlet fluid temperature (F.T.) is 15-80 ℃, is good with 20-40 ℃;
3) the polynary epoxy compounds that adds long-chain, high-hydrophilic makes sticky prepolymer change into gelatinous solid in light starting polymerization mode in sticky prepolymer;
4) carry out drying, pulverizing, screening with 100 ℃ to 250 ℃ hot blasts of temperature again;
5) surface crosslinking agent coating processing;
6) made with 80 ℃ to 230 ℃ heating surface processing of temperature at last.
Described manufacture method wherein, contains the acidic group monomer water solubles and is selected from acrylic or methacrylic acid or 2-allylamine-2-methyl propane sulfonic acid or its mixture.
Described manufacture method, wherein, the viscosity of sticky prepolymer is 10～10000cps.
Described manufacture method, wherein, initiators for polymerization can be thermolysis type initiator or oxidation-reduction type initiator.
Described manufacture method, wherein, thermolysis type initiator can be the superoxide of hydrogen peroxide, hydrogen peroxide, two-Di tributyl superoxide, peroxidation acid amides or persulphate classes such as (ammonium salt, an alkali metal salts), or 2, azo-initiators such 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 '-azo-group.
Described manufacture method, wherein, the oxidation-reduction type initiator can be acid accumulator sulfite, thiosulphate, xitix, ferrous sulfate or persulfuric acid salt.
Described manufacture method, wherein, pipeline can be the pipeline that is connected with rare gas element, the pipeline that includes screw-blade, installs the pipeline or the gas-liquid static mixer that help the mixed effect weighting material.
Described manufacture method, wherein, the temperature of prepolymerization reaction is 5-80 ℃.
Described manufacture method, wherein, the prepolymerization reaction times is 0.5～16 hour.
Described manufacture method, wherein, the light starting polymerization was generally finished in 1～300 second, and is preferable with 5～30 seconds.
Described manufacture method, wherein, the oblong link oxycompound can be sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers etc.
Described manufacture method, wherein, screening, its screening back particle size distribution range is between 0.05mm to 1mm.
Described manufacture method, surface crosslinking agent are polyvalent alcohol or polyethyleneglycol diglycidylether or alkylene carbonate or its mixture.
Described manufacture method, it is 0.005wt%～5.0wt% at weight percent that surface crosslinking agent adds scope.
Above-mentioned prepolymerization reaction can be carried out in a pre-polymerization reactor, and this reactor need possess can be made the polyreaction raw material mix and carry out prepolymerized effect.Pre-polymerization reactor is except can adopting the vertical type reactive tank that stirring rake generally is installed, also can adopt a kind of horizontal cylindrical container, the center is equipped with and makes store list to mobile stirring arm, single screw rod or twin screw arranged side by side, the phenomenon that can guarantee unidirectional the travelling forward of reaction mass like this and not occur refluxing, thus polyreaction material overstand and form gelatinous solid in reactor avoided.Yet the reactor of the above-mentioned type adopts the mode of batch material feeding usually, is unfavorable for suitability for industrialized production.
In other words, but the invention provides the method that a kind of continuous production possesses the super absorbent resin of low solubles content, it is characterized in that: the first, make monomer solution and polymerization starter form the heavy-gravity polymer by in a long lines that contains chuck, carrying out Raolical polymerizable; The second, control pipeline outlet fluid temperature (F.T.) is 15-80 ℃; The 3rd, behind heavy-gravity prepolymer and the polynary epoxy compounds blended, can be added to continuously on the belt reactor, utilize high-intensity various light source (for example: ultraviolet ray, infrared rays or X-ray etc.) to carry out light starting polymerization mode above it and make it be transformed into gelatinous solid.
In pipeline, carry out the prepolymerization reaction except general vertical type reactive tank or cylindrical container saving space, more can guarantee the principle of reaction monomers aqueous solution first outer, make in the pre-polymerization process reactionless monomer residue in pipeline, and then reduce polyreaction over-drastic situation and take place.The residence time of the reaction monomers aqueous solution in pipeline is one of important factor of control prepolymerization reaction, long as the residence time, then the prepolymerization reaction is complete more, and prepolymer viscosity and molecular weight are also high more, solvable part of finished product is also lower, but is easier to betide excessive polymeric phenomenon in the pipeline; Short as the residence time, then prepolymer viscosity and molecular weight are lower, and solvable part of finished product is higher, but it is less that excessive polymeric chance takes place.In addition, the reaction monomers aqueous solution and polymerization starter, so that the mixing uniformity of prepolymer before the irradiation reaction and bridging agent also is the important factor that influences prepolymerization reaction and irradiation reaction.In order to improve above-mentioned each fluid mixed effect each other, usually can use following method: (1) feeds rare gas element in pipeline, as: nitrogen or carbonic acid gas or helium or neon or its mixed gas, be convenient to obtain for saving cost and consideration in industry member, use nitrogen or carbonic acid gas or its mixed gas usually.In addition, the pressure of rare gas element will be higher than the pipeline internal pressure, rare gas element is injected smoothly contain in the monomer solution pipeline and make each reacting fluid reach blended effect (2) installs screw-blade or tool mixed effect additional in pipeline weighting material as: Raschig ring or ripple earrings (3) use vapour-liquid type static mixer.
The technical development of light starting polymerization is skillful, use also quite extensive, for example: application, press, PCB/LCD processing procedure, footwear industry or the like.Utilize the mode of irradiation initiated polymerization to have many advantages, as: shorten processing procedure, promote production capacity and save energy or the like.Light source is of a great variety, comprises ultraviolet ray, infrared rays, X-ray or gamma-radiation or the like, is generally used so that ultraviolet ray is the most popular, and it has wavelength and lacks (100-400nm), the characteristic that penetration power is strong.It should be noted that the UV-lamp source strength that general preparation technology uses is 160W/cm～200W/cm, this often causes serious consume to the conveying belt of carrying work piece.Thus, the just necessary regular replacing of conveying belt, production cost also and then increases.Given this, the present invention adopts the mode of chuck insulation heating, improves the temperature by the reacting fluid in long lines, to shorten the time of back segment photopolymerization reaction.Thus, not only irradiation time and light source use power to reduce the also relative prolongation with the time limit of service of irradiation assembly of conveying belt.
The most important thing is,,, cause the phenomenon of monomer " implode " most probably and blocking pipeline causes the whole preparation process paralysis if the reacting fluid temperature in the pipeline is too high because Raolical polymerizable speed is fast.Given this, shorten irradiation time and operational security in order to reach simultaneously, the temperature of the reacting fluid of pipeline outlet is advisable with 15-80 ℃, is good with 20-40 ℃ wherein.
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 the concentration molar percentage be 45mol% to 85mol%, proper concn is 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, if not when the finished product pH value is neutrality or subacidity, all not too be fit to also more dangerous when contacting with human body accidentally.
The prepolymerization reaction is begun by the decomposition generation free radical of polymerization starter.Polymerization starter can be selected thermolysis type initiator for use, the thermolysis type initiator that is fit to has superoxide, as: hydrogen peroxide, two-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% was above, reacting too, the wayward and easy polymerization of fast response heat excessively formed gelatinous solid.
Carry out to add linking agent in sticky prepolymer before the reaction of light starting polymerization, the optional usefulness of linking agent has the compound of two or more unsaturated double-bonds, as: N, 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.
Sticky prepolymer can be on the conveyer belt type reactor or is equipped with in the horizontal type reactor of paddle and carries out the reaction of light starting polymerization, the superabsorbent gels body of preparing utilizes pulverizer to be cut into the following little gelinite of particle diameter 20mm earlier, better below the particle diameter 10mm, dry again.
Bake out temperature can carry out drying under 100 ℃ to 250 ℃, drying temperature is then dried with 120 ℃ to 180 ℃ and is advisable, when 120 ℃ of bake out 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 low remaining monomeric effect.
Pulverize, screen fixedly particle diameter after the drying, carry out the surface crosslinking agent coating processing again.Fixedly particle diameter is to be advisable between 0.06mm to 1.00mm in screening, and with preferable between 0.10mm to 0.850mm, the following fine powder of particle diameter 0.06mm improves the finished product dust, and the above particle of particle diameter 1.00mm makes the finished product rate of water absorption slack-off.
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, existing before this many patents propose; 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 the linking agent that can react simultaneously when surface treatment according to the present invention 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 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 linking agent can be used alone or mixed use of two or more.The suitable additives amount of surface 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%, surface linking agent additive capacity can't show effect when weight percent 0.001wt% is following, surface 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 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%, wherein preferable with 0.01wt% to 4.0wt%, its particle diameter of inert inorganic salt powder is 0.001 μ M to 100 μ M, if select for use particle less than the inorganic salt powder of the 0.001 μ M too high suitability for industrialized production that is unfavorable for of cost then, if select for use particle the too high problem that influences the super absorbent resin absorbing power of addition then to be arranged greater than the inorganic salt powder of 100 μ M.The inert inorganic salt powder can add separately maybe can follow interfacial agent or tool viscosity organic compound to add, its interfacial agent or tool viscosity organic compound can be selected HLB 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 this interfacial agent such as polyoxyethylene bay ether 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%.
Embodiment
But the present invention provides the mode of the super absorbent resin of the low solubles content of a kind of continuous production tool, it is characterized in that: the first, make monomer solution and polymerization starter form the heavy-gravity polymer by in a long lines that contains chuck, carrying out Raolical polymerizable; The second, control pipeline outlet fluid temperature (F.T.) is 15-80 ℃; The 3rd, behind heavy-gravity prepolymer and the polynary epoxy compounds blended, can be added to continuously on the belt reactor, utilize high-intensity various light source (for example: ultraviolet ray, infrared rays or X-ray etc.) to carry out light starting polymerization mode above it and make it be transformed into gelatinous solid.See through the mode of production provided by the present invention, have following advantage: (1) prepolymer obviously improves with respect to the viscosity of liquid reactions material, the mobile reduction, easier and after the belt reactor be complementary, and whole polyreaction stability is improved, reaction heat is unlikely to too high (2) uses a long lines reactor except saving the space, and more can guarantee the principle of reacting fluid first outer, uses chuck to heat the reacting fluid in the pipeline and control its temperature out to be 15-80 ℃, can to shorten the back segment irradiation time and prolong conveying belt and the work-ing life of irradiation assembly and reach purpose (3) that continous way produces.Preparation method of high-hydroscopicity resin provided by the present invention is except improving production operation and Working environment, and quality product also improves greatly, especially has clearly effect for the reduction solubles content.
For showing the characteristic of the low solubles content of super absorbent resin among the present invention, the determination step of solubles content is as follows: weigh the 0.5g super absorbent resin earlier, add 0.9% salt solution 185g again, after stirring one hour under the 500rpm rotating speed, go out the SAP extraction liquid with filter paper filtering.At last, 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.
Below with embodiment the present invention is described, but technology of the present invention and claim are not limited by these embodiment.
Embodiment one
(1), under ice bath, the aqueous sodium hydroxide solution (concentration is 45%) of 1476.3 weight parts is slowly added in the aforesaid propylene aqueous acid afterwards prior to adding the water of 1760 parts by weight of acrylic and 2263.7 weight parts in the neutralizing well.Obtain the aqueous solution that monomer concentration is 38.6wt% this moment, wherein has the vinylformic acid neutralization of 68mol% to be sodium acrylate.
(2) in and after program finishes, utilizing water temperature adjustment control section neutral sodium acrylate salt brine solution is about 20 ℃.
(3) flow of adjusting above-mentioned monomer solution is 100 liters/hour, and making it contain chuck, diameter by one is that 5 centimeters, total length are 26.35 meters stainless steel tube.In addition, stainless steel tube is gone into 5 centimeters at end and is located the stainless steel tube that side is connected a diameter 0.5 and 0.9 centimeter respectively with 10 centimeters.The former imports nitrogen, and flow control is 200 liters/hour, and the latter then feeds Potassium Persulphate/sodium bisulfite=1/1 (weight ratio), and flow control is 2 milliliters/hour.
(4) locate the stainless steel tube that side connects 0.9 centimeter of two diameter apart from 85 centimeters of pipeline exit end, one imports green grass or young crops of the different moon in heptan of azo two, flow control is 20 milliliters/hour, and another then imports glycerol polyoxyethylene glycol triglycidyl ether (n=7), and flow control is 15 milliliters/hour.At last, pipeline outlet fluidic temperature is 20 ℃
(5) the described reacting fluid of step 4 is joined on the travelling belt, travelling belt top device has the high-intensity ultraviolet irradiating machine, utilizes 25 seconds (illumination=15.18J/cm of this device above-mentioned mixing liquid of irradiation
2) crosslinking reaction of carrying out that makes forms colloid.
(6) utilize the cut pulverizer to be cut into the following gelinite of 2mm diameter.
(7) with 130 ℃ of temperature dryings 2 hours; Utilize fixedly particle diameter of screen cloth screening 0.1mm～0.85mm, get the powdery super absorbent resin.
(8) weigh this super absorbent resin 100g, add Aluminium Sulphate usp (powder) 1g, to be mixedly add ethylene carbonate/water/methyl alcohol=1/1/1 (weight ratio) solution 4g again after evenly, with 215 ℃ of temperature heat treated 10 minutes.
(9) after the cooling, (platform is moulded company and is 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 to add 1g lime carbonate.Measure confining force=33.6g/g, 49g/cm
2Water absorbent rate=22.8g/g under the pressure, solubles content=13.4%.
Embodiment two
(1) repeats embodiment one, be adjusted into 20 seconds (illumination=13.99J/cm but the pipeline temperature out is 25 ℃ and back segment irradiation time
2), the confining force=31.5g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=23.7g/g under the pressure, solubles content=10.0%.
Embodiment three
(1) repeats embodiment one, be adjusted into 15 seconds (illumination=9.35J/cm but the pipeline temperature out is 30 ℃ and back segment irradiation time
2), the confining force=30.7g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=23.9g/g under the pressure, solubles content=8.1%.
Embodiment four
(1) repeats embodiment one, be adjusted into 10 seconds (illumination=6.36J/cm but the pipeline temperature out is 35 ℃ and back segment irradiation time
2), the confining force=30.1g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=24.1g/g under the pressure, solubles content=7.3%.
Embodiment five
(1) repeats embodiment one, be adjusted into 5 seconds (illumination=3.03J/cm but the pipeline temperature out is 40 ℃ and back segment irradiation time
2), the confining force=29.5g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=23.2g/g under the pressure, solubles content=5.4%.
Embodiment six
(1) repeat embodiment one, but the stainless steel tube total length changes 52 meters long into.The confining force of super absorbent resin then is 35.2g/g, 49g/cm
2Water absorbent rate=22.3g/g under the pressure, solubles content=11.2%.
Embodiment seven
(1) repeats embodiment six, be adjusted into 20 seconds (illumination=13.99J/cm but the pipeline temperature out is 25 ℃ and back segment irradiation time
2), the confining force=32.7g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=23.2g/g under the pressure, solubles content=8.3%.
Embodiment eight
(1) repeats embodiment six, be adjusted into 15 seconds (illumination=9.35J/cm but the pipeline temperature out is 30 ℃ and back segment irradiation time
2), the confining force=32.0g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=24.0g/g under the pressure, solubles content=6.4%.
Embodiment nine
(1) repeats embodiment six, be adjusted into 10 seconds (illumination=6.36J/cm but the pipeline temperature out is 35 ℃ and back segment irradiation time
2), the confining force=31.8g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=24.5g/g under the pressure, solubles content=5.1%.
Embodiment ten
(1) repeats embodiment six, be adjusted into 5 seconds (illumination=3.03J/cm but the pipeline temperature out is 40 ℃ and back segment irradiation time
2), the confining force=30.9g/g of gained water-absorbing resin as a result, 49g/cm
2Water absorbent rate=24.1g/g under the pressure, solubles content=3.8%.
Comparative example one:
(1) repeats embodiment one, but the described reaction monomers solution of step (3) injects always the vertical response groove under logical nitrogen (flow control is at 200 liters/hour) and under the high-speed stirring about reaction response 30min, gained prepolymer viscosity is 140cps, but finds on the agitating vane a little polymkeric substance is arranged after the discharging.The confining force of super absorbent resin then is 33.4g/g, 49g/cm
2Water absorbent rate=23.1g/g under the pressure, solubles content=13.7%.
Comparative example two
(1) repeats embodiment one, but the described reaction monomers solution of step (3) injects always the vertical response groove under logical nitrogen (flow control is at 200 liters/hour) and under the high-speed stirring about reaction response 60min, gained prepolymer viscosity is 255cps, but finds in agitating vane and the reactive tank the residual phenomenon of partial polymer is arranged after the discharging.The confining force of super absorbent resin then is 36.1g/g, 49g/cm
2Water absorbent rate=23.4g/g under the pressure, solubles content=13.5%.
Claims (14)
1. a powdery, water insoluble can absorb the low production method of high-performance super absorbent of water liquid, urine or blood and solubles content, may further comprise the steps at least:
1) make neutralization ratio 50mole% above contain acidic group monomer solution and initiators for polymerization react and get sticky polymer by in a long lines that contains chuck, carrying out prepolymerization with about 100 liters of flow velocitys per hour;
2) control long tube outlet fluid temperature (F.T.) is 15-80 ℃, is good with 20-40 ℃;
3) the polynary epoxy compounds that adds long-chain, high-hydrophilic makes sticky prepolymer change into gelatinous solid in light starting polymerization mode in sticky prepolymer;
4) carry out drying, pulverizing, screening with 100 ℃ to 250 ℃ hot blasts of temperature again;
5) surface crosslinking agent coating processing;
6) made with 80 ℃ to 230 ℃ heating surface processing of temperature at last.
2. manufacture method according to claim 1 wherein, contains the acidic group monomer water solubles and is selected from acrylic or methacrylic acid or 2-allylamine-2-methyl propane sulfonic acid or its mixture.
3. manufacture method according to claim 1, wherein, the viscosity of sticky prepolymer is 10～10000cps.
4. manufacture method according to claim 1, wherein, initiators for polymerization is thermolysis type initiator or oxidation-reduction type initiator.
5. manufacture method according to claim 4, wherein, thermolysis type initiator is the superoxide of hydrogen peroxide, hydrogen peroxide, two-Di tributyl superoxide, peroxidation acid amides or persulfuric acid salt, or 2, azo-initiators such 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 '-azo-group.
6. manufacture method according to claim 4, wherein, the oxidation-reduction type initiator is acid accumulator sulfite, thiosulphate, xitix, ferrous sulfate or persulfuric acid salt.
7. manufacture method according to claim 1, wherein, pipeline is pipeline or the gas-liquid static mixer that the pipeline that is connected with rare gas element, the pipeline that includes screw-blade, installing help the mixed effect weighting material.
8. manufacture method according to claim 1, wherein, the temperature of prepolymerization reaction is 5-80 ℃.
9. manufacture method according to claim 1, wherein, the prepolymerization reaction times is 0.5～16 hour.
10. manufacture method according to claim 1, wherein, the light starting polymerization was generally finished in 1～300 second.
11. manufacture method according to claim 1, wherein, the oblong link oxycompound can be sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers etc.
12. manufacture method according to claim 1, wherein, screening back particle size distribution range is between 0.05mm to 1mm.
13. manufacture method according to claim 1, surface crosslinking agent are polyvalent alcohol or polyethyleneglycol diglycidylether or alkylene carbonate or its mixture.
14. manufacture method according to claim 13, it is 0.005wt%～5.0wt% at weight percent that surface crosslinking agent adds scope.
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| EP0605215B1 (en) * | 1992-12-25 | 1998-03-25 | Nippon Shokubai Co., Ltd. | Absorbent and method for production of absorbent resin |
| US6927268B2 (en) * | 2000-06-21 | 2005-08-09 | Nippon Shokubai Co., Ltd. | Production process for water-absorbent resin |
| JP3939988B2 (en) * | 2002-01-16 | 2007-07-04 | 住友精化株式会社 | Method for producing water absorbent resin |
| CN1208352C (en) * | 2003-11-01 | 2005-06-29 | 山东省科源石油化工生产力促进中心 | Method for producing high absorptive resin |
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