CN102311557A - Method for preparing super absorbent resin - Google Patents
Method for preparing super absorbent resin Download PDFInfo
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- CN102311557A CN102311557A CN2010102263643A CN201010226364A CN102311557A CN 102311557 A CN102311557 A CN 102311557A CN 2010102263643 A CN2010102263643 A CN 2010102263643A CN 201010226364 A CN201010226364 A CN 201010226364A CN 102311557 A CN102311557 A CN 102311557A
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Abstract
The invention discloses a simple and convenient method for preparing a super absorbent resin. The super absorbent resin prepared by a method for adding a foaming agent has high absorption rate.
Description
Technical field
The present invention relates to a kind of method of manufacture of super absorbent resin.
Background technology
Super absorbent resin applies to water retention agent, the anti-dewdrop condensing agent in the material of construction and the material that removes moisture content in the oil of agricultural or gardening aspect widely; Or waterproof outer coating and sanitary product in the cable; Like diaper, women sanitary articles, deserted wiping cloth etc., especially be used on the diaper the most large.
Ultrathin diaper is present main developing direction, is that the super absorbent resin of its this kind absorption layer and paper pulp fiber mixture must possess higher receptivity is arranged because ultrathin diaper must possess highdensity absorption layer.In order to make full use of the ability of absorption layer storing liquid, so that the distribution situation of liquid in absorption layer just becomes is very important.Generally speaking, the minimizing of paper pulp fiber has negative influence to the distribution situation of liquid in absorption layer in the absorption layer.
After the super absorbent resin in the absorption layer or paper pulp fiber are absorbing liquid; Cause void space or the interior hole of super absorbent resin in super absorbent resin and the paper pulp fiber to be closed because can expand rapidly; Thereby suppressed the conduction of liquid; Cause later liquid can not penetrate by liquid-absorbent and expansible is regional, this phenomenon appellation is that colloid blocks (Gel-blocking) again; This phenomenon one takes place, and liquid afterwards just can not penetrate cartridge again, and flows to the edge, causes the generation of leak case.
In addition, near the super absorbent resin of expansion area the phenomenon that colloid blocks has taken place, remaining liquid just can't arrive the more part of deep layer, makes the ability of absorption layer storing liquid significantly reduce.
The method that reduction colloid known in the art blocks all is the uptake rate (USP 4 that changes super absorbent resin; 548; No. 847); This patent discloses the so-called cation chelating agent (Cationic Complexing Agent) that uses like water-soluble cpdss such as Sodium hexametaphosphate 99, disodium EDTA or ammonium hydrogen phosphates; With contain the formed water gel of at least one divalent-metal ion, be the mode that utilize to lower the water gel middle crosslink density, make super absorbent resin absorb liquid more easily.
EP 0 631 768 A1 mention a kind of cartridge; This cartridge utilizes the super absorbent resin that different-grain diameter distributes, and (particle size range of Class1 is 600-850um; The particle size range of type 2 is less than 250um); Further produce the cartridge with different absorption, still, the difference of absorption rate is also little.
USP 5,115 is mentioned for No. 011, uses vitriol, acetate or nitrate compound with aluminium, calcium, magnesium, with the monovalent metal salt or the ammonium salt compound of sulfurous acid, to mix less than 10 weight parts, can reduce the generation of colloid choking phenomenon.
Above-mentioned USP 5; Also mention the absorption agent of a kind of absorbing blood and liquid 115, No. 011, this absorption agent has used super absorbent resin and the mixture with halogen compounds of phosphate, inferior sulfate radical or sulfate radical; What this type of mixture was claimed is that (state with flowing powder is kept at room temperature to water soluble mixt; Harmless to organism) be dissolved in unsaturated monomer and carry out polyreaction, so, can improve the velocity of diffusion of liquid.
In addition; Use has the water soluble anion compound of carboxylic acid group, sulfonic group and phosphate and the polyvalent metal that valence mumber is at least 3 valencys, like the prepared material of antimony (Antimony), also can reduce the generation (USP 5 of colloid choking phenomenon; 578, No. 318).
Moreover, use citrate or the polyvalent metal salts solution of sulfate radical mixes with super absorbent resin, though can produce the super absorbent resin that hangs down absorption rate; But,, cause significantly reducing production efficiency (USP 6 owing to must could obtain via secondary processing; 433; 058,6,579, No. 958).
Use polyol compound and carbonate cpds in fluidised bed spray granulating and drying machine (Fluid-bed spray granulator dryer) mixing granulation; Make an addition to unsaturated monomer then and carry out polyreaction, though so can improve absorption rate to liquid, still; Use polyol compound to apply; The super absorbent resin of promptly producing through a mode thus is easy to generate outside the xanthochromia (Yellow-coloring change), still must mix about 60 to 120 minutes ability via fluidised bed spray granulating and drying machine and obtain, and causes production efficiency significantly to reduce (USP 7; 163, No. 966).
The problem that quasi-solution of the present invention is determined is that ultrathin diaper must possess highdensity absorption layer is arranged, and especially for the cartridge with multi-layer absorber layer, prevents the generation of its colloid choking phenomenon, is a crucial problem.One of method that solves this problem is the slow or absorption rate of a permeating speed super absorbent resin fast in cartridge, yet the above-mentioned practice also can't be produced gratifying super absorbent resin.
Summary of the invention
The object of the present invention is to provide a kind of method of manufacture of super absorbent resin, have defective in the known technology to overcome.
For realizing above-mentioned purpose, the method for manufacture of super absorbent resin provided by the invention comprises:
(a) in a kind of monomeric water-soluble unsaturated monomer of acidic group that contains, neutralization ratio is in the scope of 45mol% to 85mol%, and concentration is in the aqueous solution of the scope of 20wt% to 55wt%;
(b) add the whipping agent that the 0.01wt%～10wt% account for the resin total amount crosses via coating processing and carry out polyreaction;
(c) water gel of gained is sheared after the polyreaction, and granulation is also used 100 ℃ to 180 ℃ temperature warm air dryings, pulverizing, screening;
(d), re-use 80 ℃ to 230 ℃ heating surface of temperature and handle with after the 0.005wt%～5wt% surface crosslinking agent coating processing that accounts for the resin total amount.
The method of manufacture of described super absorbent resin, wherein the whipping agent crossed of coating processing is the mixture of carbonate cpds and alum compounds.
The method of manufacture of described super absorbent resin, wherein said carbonate cpds are to have carbonate or bicarbonate radical compound in the chemical structure.
The method of manufacture of described super absorbent resin, wherein said alum compounds are potassium alum, sodium alum or the ammonla alum that contains crystal water.
The method of manufacture of described super absorbent resin, wherein the weight mixture ratio of carbonate cpds and alum compounds is 5: 95 to 95: 5.
The method of manufacture of described super absorbent resin, wherein the treatment temp during coating processing is 40 ℃ to 95 ℃.
The method of manufacture of described super absorbent resin, the whirlpool disappearance index (VI value) of the super absorbent resin of wherein processing is not more than 35sec/g.
The method of manufacture of described super absorbent resin, the confining force of the super absorbent resin of wherein processing is not less than 20g/g, 49g/cm
2Water absorbent rate is not less than 12g/g under the pressure.
Powdery provided by the invention, water insoluble can absorb the super absorbent resin of water or urine and blood, and this resin has absorption rate fast, and under higher pressure, also has the higher absorption multiplying power property.
Description of drawings
Fig. 1 is the figure of SEM (scanning type electron microscope) the photograph gained of getting the high-performance high absorbent resin particle of embodiment 1 gained.
Fig. 2 is the figure of SEM (scanning type electron microscope) the photograph gained of getting the high-performance high absorbent resin particle of comparative example 1 gained.
Embodiment
The present invention provides the super absorbent resin that a kind of preparation has rapid absorption speed and under high pressure, has the higher absorption multiplying power property; Furtherly; The super absorbent resin of manufacturing of the present invention has absorption rate fast to liquid; 0.9% sodium chloride aqueous solution whirlpool disappearance index is not more than 35sec/g, and in 49g/cm
2Water absorbent rate under the pressure is not less than 12g/g.
According to the present invention, the present invention prepares a kind of method of manufacture with super absorbent resin of rapid absorption speed and comprises at least:
What (1) neutralization ratio 45 molar percentages were above containing in the acidic group monomer solution, saidly contains the mixture that the acidic group monomer is selected from acrylic or methacrylic acid or 2-allylamine-2-methyl propane sulfonic acid or above-mentioned group;
(2) add whipping agent and the initiators for polymerization crossed via coating processing and carry out Raolical polymerizable generation high water absorbent resin gel body;
(3) water gel is cut into little water gel;
(4) again this gelinite is carried out drying, pulverizing, screening with 100 ℃ to 250 ℃ hot blasts of temperature;
(5) carry out surface-crosslinked reaction on the surface of super absorbent resin at last.
Above-mentioned preparation has the method for manufacture of the super absorbent resin of the characteristic that has the higher absorption multiplying power under rapid absorption speed and the high pressure; Wherein, Be used in that to carry out the whipping agent that coating processing that polyreaction adds crosses be carbonate cpds; And the mixture of alum compounds; The mixture ratio of its carbonate cpds and alum compounds is 5: 95 to 95: 5, and carbonate cpds is to have carbonate or bicarbonate radical compound in the chemical structure, as: yellow soda ash, salt of wormwood, volatile salt, magnesiumcarbonate, lime carbonate, barium carbonate, sodium hydrogencarbonate, saleratus, bicarbonate of ammonia, Magnesium hydrogen carbonate, Calcium hydrogen carbonate or barium bicarbonate etc.The alum compounds then is the compound that contains crystal water, as: potassium alum, sodium alum or ammonla alum etc.
The used water-soluble unsaturated monomer of general known manufacturing absorbent resin is except vinylformic acid; Still can use other water-soluble monomer with unsaturated double-bond of acidic-group, as: methylacrylic acid, Malin's acid, fumaric acid, 2-allylamine-2-methyl propane sulfonic acid, maleic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, FUMARIC ACID TECH GRADE acid anhydride etc.The monomeric specific limited of selecting for use is not used a kind of only; Also can merge multiple monomer uses simultaneously; Also can depending on the circumstances or the needs of the situation add and have other hydrophilic monomer of unsaturated double-bond; As: acrylic amide, USAF RH-1, vinylformic acid 2-carboxyl ethyl ester, methylacrylic acid 2-carboxyl ethyl ester, methyl acrylate, ethyl propenoate, n n dimetylaniline acrylic acid-acrylamide, propylene dichloride acrylamido TMA(TriMethylAmine), but addition is a principle with the rerum natura of not destroying super absorbent resin.
When carrying out Raolical polymerizable, monomer solution concentration does not have special restriction, but preferred concentration should be controlled between the weight percent 20wt% to 55wt%, and proper concn is between the 30wt% to 45wt%.Concentration is when weight percent 20wt% is following, and the hydrogel after the polymerization is too soft and the unfavorable mechanical workout of stickiness is arranged, and adds concentration more than weight percent 55wt%; Near saturation concentration; Be difficult for allotment and react that too fast response heat is wayward, the pH value of unsaturated monomer solution is not less than 5.5, as if being lower than 5.5; After the polymerization in the water gel remaining monomer content too high, cause the rerum natura of super absorbent resin not good.
In the monomer solution before carrying out Raolical polymerizable; The whipping agent that the interpolation coating processing is crossed carries out the absorption rate that polyreaction can improve super absorbent resin in this reaction; It is the 0.01-10wt% that accounts for water-soluble unsaturated monomer that the whipping agent that coating processing is crossed adds consumption; Additive capacity is not had an effect below weight percent 0.01wt%; Then polyreaction is too violent more than weight percent 10wt% for additive capacity, and the water gel volume becomes big after the polyreaction, causes execute-in-place property poor.
When the carbonate cpds weight ratio of the whipping agent of handling is lower than 5%; Can't reach the present invention's desired result; Be higher than at 96% o'clock, then system of Himdu logic vitriol compound amount is low excessively, effectively the carbon coated phosphate compounds; Carbonate cpds is contacted with unsaturated monomer solution immediately and form dioxide gas and overflow, also can't reach the present invention's desired result.The weight mixture ratio of carbonate cpds that it is suitable and alum compounds is 5: 95 to 95: 5, is preferably 20: 80 to 80: 20.
Treat carbonate cpds mix with the alum compounds accomplish after, again to heat-treat in 40 ℃ to the 95 ℃ scopes, make the alum compounds can be evenly and apply with carbonate cpds fast and reach effect of the present invention.Thermal treatment temp applies required time below 40 ℃ too of a specified duration, do not have an economic benefit; Thermal treatment temp then applies poor effect more than 95 ℃ influence quality, and heat treatment time was advisable with 3 minutes to 20 minutes.Be applicable to that thermal treatment unit of the present invention comprises: tunnel like mixing drier, rotary drum dryer, desk-top moisture eliminator, fluidized bed dryer, pneumatic dryer and infrared dryer etc.
In the monomer solution before carrying out Raolical polymerizable; Also can add water-soluble polymer to reduce cost; These water-soluble polymers are like partly saponification or fully saponified Z 150PH, polyoxyethylene glycol, ROHM, SEPIGEL 305, starch or starch derivative such as methylcellulose gum; The vinylformic acid methylcellulose gum, polymkeric substance such as TKK 021, the molecular weight of these water-soluble polymers does not have special qualification; Its preferable water-soluble polymer is starch, partly saponification or fully saponified Z 150PH etc., separately or mix to use and all can.It is 0wt% to 20wt% that super absorbent resin contains these suitable weight percents that add water-soluble polymer, but preferable with 0wt% to 10wt%, 0wt% to 5wt% is good especially, and adding when surpassing 20wt% to influence rerum natura, makes the rerum natura variation.
Before carrying out Raolical polymerizable, 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 triacrylate of the triacrylate of the two USAF RH-1s of N '-methyne, vinylformic acid propylene ester, glycol diacrylate, polyethyleneglycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycerol tri-acrylate, glycerine trimethacrylate, glycerine additional ring oxidative ethane or trimethacrylate, trihydroxymethyl propane additional ring oxidative ethane or trimethacrylate, trihydroxymethyl propane trimethacrylate, trihydroxymethyl propane triacrylate, N; N; N-three (2-propenyl) amine, ethylene glycol diacrylate, three vinylformic acid polyoxyethylene glycerides, three vinylformic acid diethylammonium polyoxyethylene glycerides, two propylene triethyleneglycol ester etc.; Also optional usefulness has the compound of two or more epoxy group(ing); Like sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two USP Kosher polyglycidyl ethers etc., after carrying out free radical reaction, just can make super absorbent resin have suitable degree of crosslinking, and suitable processibility.
Above-mentioned Raolical polymerizable linking agent can use separately or two or more mixing is used.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%; The hydrated body of additive capacity after the following polyreaction 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.
Containing the monomeric carboxylic acid group of acidic group partly should neutralize with the pH value of control finished product; Make it be neutrality or subacidity; Neutralizing agent is the oxyhydroxide or the carbonate compound of periodictable alkali metal group or alkaline earths, as: sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus or ammoniac compounds; This neutralizing agent can use one or more to mix separately and use.
Contain the monomeric carboxylic acid group of acidic group and partly be neutralized into sodium salt or sylvite or ammonium salt; Its neutralization ratio molar percentage is between the 45mol% to 85mol%, is preferably between the 50mol% to 75mol%, and the neutralization ratio molar percentage is that the pH value of 45mol% finished product when following can be on the low side; In with 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.
The prepolymerization reaction is begun by the decomposition generation radical that polyreaction causes (initial) agent.Initiators for polymerization 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, peroxo-acid amides or persulphate (ammonium salt, an alkali metal salt) etc.; And azo cpd is like 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, make it become 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 being reacted the generation radical in advance, is the carrying out of initiated polymerization on radical transfer to monomer.Can discharge great amount of heat when carrying out and elevate the temperature, when arriving 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 owing to polyreaction.
The suitable consumption of general Raolical polymerizable initiator be weight percentage for 0.001wt% to 10wt% (with in acrylate weight be benchmark); More suitably consumption is then between weight percent 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.
Polyreaction of the present invention can be in the conventional batch reaction vessel, or on the conveyer belt type reactor drum, reacts, and the gelinite of reaction gained utilizes pulverizer to be cut into little gelinite below the diameter 2.00mm 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 back in the reactor drum again greater than the gelinite of 2.00mm and shredded once more.Gelinite below the particle diameter 0.03mm is dried, pulverization process; Be prone to 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 rerum natura is performed poor at remaining monomer.According to the present invention, the particle size dispersion of acrylate gelinite is narrow more good 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, and screening is dried after accomplishing 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, makes 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. and all can remake further bridge formation on the surface of resin; This surface-crosslinked processing promptly utilize have can with the report of the multiple functional radical linking agent of acid-base reaction, existing many patents openly disclose before the present invention; 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 (No. 6346569, JP-A-1-292004, USP) and use organic solution, water, ether (ether) compound (JP-A-2-153903) etc.; Though these surface-treated methods can improve water absorbent rate under uptake rate, the pressurize, also cause the too much adverse consequences of confining force decline, reduce the performance of practical application.
According to the present invention, the linking agent that can when surface treatment, can react simultaneously is a polyvalent alcohol like USP Kosher, terepthaloyl moietie, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, Ucar 35 etc.; Maybe can use polyamine like quadrol, two quadrols, Triethylene Diamine; Maybe can use compound like sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two USP Kosher polyglycidyl ethers etc. with two or more epoxy group(ing); Also can use alkylene carbonate like 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 linking agent can be used separately or two or more mixing is used; Its suitable additive amount 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 linking agent additive capacity can't show effect when weight percent 0.001wt% is following, and the linking agent additive capacity is when weight percent 10wt% is above; Water-absorbent is too low, reduces resin property.
The coating processing of surface crosslinking agent; The addition manner of its surface crosslinking agent is that the kind according to surface crosslinking agent is divided into surface crosslinking agent and directly adds; Or the interpolation of the furnishing surface crosslinking agent aqueous solution, or the interpolation of the furnishing surface crosslinking agent hydrophilic organic solvent aqueous solution, hydrophilic organic solvent for example methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol, acetone, methyl ether, ether etc. does not have particular restriction; Can form solution and get final product, wherein with methyl alcohol, ethanol preferable (No. 6849665, USP).
Powdery provided by the invention, water insoluble can absorb the super absorbent resin of water or urine and blood, and this resin has absorption rate fast, and under higher pressure, also has the higher absorption multiplying power property.Its method of manufacture comprises:
(a) in using a kind of monomeric water-soluble unsaturated monomer of acidic group that contains, wherein with ratio in the scope of 45mol% to 85mol%, concentration is in the aqueous solution of the scope of 20wt% to 55wt%;
(b) add the whipping agent of crossing via coating processing and carry out polyreaction;
(c) water gel of gained is sheared after the polyreaction, and granulation is also used 100 ℃ to 180 ℃ temperature warm air dryings, pulverizing, screening;
(d), re-use 80 ℃ to 230 ℃ heating surface of temperature and handle with after the surface crosslinking agent coating processing.
Above-mentioned technical characterictic; When being to use the whipping agent crossed via coating processing and water-soluble unsaturated monomer to carry out polyreaction; The carbonate cpds of whipping agent can discharge lentamente and make the super absorbent resin surface have porousness (asking detail drawing 1 and Fig. 2) effect of height, reaches the effect of rapid absorption speed thus; Polyvalent metal ion in the alum compound, also with super absorbent resin in carboxylate radical produce the key knot, improve the intensity of super absorbent resin, make that the super absorbent resin via manufacturing of the present invention has the characteristic that has the higher absorption multiplying power under the high pressure.
With regard to the present invention; Only must be when carrying out polyreaction; Adding whipping agent that coating processing crosses promptly produces super absorbent resin with the water-soluble unsaturated monomer aqueous solution in this polyreaction mode just can make and have uptake rate fast; And the super absorbent resin that under higher pressure, also has the characteristic of higher absorption multiplying power, make the present invention more can be applicable to the sanitary product of various types, the water-retaining agent that agricultural is used and food fresh keeping is used.
Be water absorbent rate under the pressure that shows super absorbent resin of the present invention, the present invention uses confining force tea bag test method determination, and with five measurements, behind removal mxm. and the Schwellenwert, averages; The super absorbent resin of 0.200 ± 0.001g 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 control 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.
Water absorbent rate under the pressure of super absorbent resin of the present invention is to use pressurized to absorb heavy (pressure load: 20g/cm
2(0.3psi) and 49g/cm
2(0.7psi)) measure, the pressurized absorbed dose is according to the method described in the 7th page in the European patent 0339461A specification sheets; The super absorbent resin that just weighs 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, let this super absorbent resin absorb 0.9% sodium chloride aqueous solution one hour, survey suction weight, after with the weight of institute's value divided by super absorbent resin, promptly get pressurized absorption tuple value.
(Vortex Index VI), is to carry out according to following described method to whirlpool disappearance index of the present invention, and with five measurements, behind removal mxm. and the Schwellenwert, averages; Add 0.9% sodium chloride aqueous solution 50mL in the beaker of 100mL; Put into magnetic stirring bar and beaker is placed the induction stirring machine, rotating speed is 600rpm, weighs 2.000 ± 0.001 gram super absorbent resins with analytical balance; Be poured in the beaker and start stopwatch, record whirlpool disappearance required time.The numerical value of gained promptly gets whirlpool disappearance exponential number divided by the weight of actual super absorbent resin.
The weight of actual super absorbent resin of the present invention; Be to carry out: weigh 5.000 ± 0.001 gram super absorbent resins (SAP) and place hot analytical balance glass disc and write down weight according to following described method; Setting analysis temperature is 140 ℃; 15 minutes analysis times, analysis promptly gets the super absorbent resin water ratio after accomplishing, and unit is a per-cent.Super absorbent resin weight is multiplied by the weight that the numerical value of deduction behind the per-cent is actual super absorbent resin.
Below with optimal reference and embodiment the present invention is described; But the interest field of application of the present invention is not limited by these embodiment.
Reference example one
Get 200g yellow soda ash (Taiwan plastic company, ProductName: FP-100A) with the ammonla alum (Taiwan alum company) of 800g with 50 ℃ of temperature heat treated 15 minutes, after the cooling, promptly get the whipping agent (A) that coating processing is crossed.
Reference example two
Get 800g lime carbonate (Taiwan plastic company, ProductName: FP-100A) with the potassium alum (Taiwan alum company) of 200g with 80 ℃ of temperature heat treated 25 minutes, after the cooling, promptly get the whipping agent (B) that coating processing is crossed.
Reference example three
Get 500g sodium hydrogencarbonate (Chinese red triangle company, ProductName: AK-28) with the potassium alum (Taiwan alum company) of 500g with 60 ℃ of temperature heat treated 30 minutes, after the cooling, promptly get the whipping agent (C) that coating processing is crossed.
Embodiment one
1) gets in the 3000c.c Conical flask of water that 48% aqueous sodium hydroxide solution 218.7g slowly adds 270g vinylformic acid and 291.6g; Sodium hydroxide/acrylic acid dropping ratio is in 0.85 to 0.95 scope; The dropping time is 2 hours, and keeps bottle temperature of interior neutralization reaction system in 20 ℃ to 40 ℃ scopes; Get the monomer concentration 42wt% aqueous solution this moment, and wherein the vinylformic acid of 70mol% (mol ratio) partly neutralizes and becomes sodium acrylate.
2) N of adding 0.414g, N '-methyne bisacrylamide and 0.781g whipping agent (A) are in water-soluble unsaturated monomer solution, and temperature maintenance is in about 20 ℃.
3) add the 0.144g ydrogen peroxide 50,1.8g sodium sulfite anhy 96 and the reaction of 1.8g ammonium persulphate initiator.
4) will react the gelinite that the back generates and utilize the chopping of cut kibbler, and to filter out size be the gelinite below the 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.
6) get the powdery super absorbent resin 100g that above-mentioned steps 5 makes; Add terepthaloyl moietie, 1,4-butyleneglycol (Taiwan plastic manufactured) and by volume 1: 1: 0.5 mixed aqueous solution 2.5g of methyl alcohol were with 150 ℃ of temperature heat treated 1 hour; After the cooling, promptly get high-performance high absorbent resin.It measures confining force is 32.7g/g, 20g/cm
2Water absorbent rate 29.6g/g under the pressure, 49g/cm
2Water absorbent rate 19.4g/g under the pressure, water ratio are 0.92%, and the VI value is 28.56sec/g.
Embodiment two
Repeat embodiment one, but the addition of whipping agent (A) is increased to 11.72g.All the other get high-performance high absorbent resin with embodiment one, and the mensuration confining force is 31.5g/g, 20g/cm
2Water absorbent rate 30.2g/g under the pressure, 49g/cm
2Water absorbent rate 19.7g/g under the pressure, water ratio are 1.12%, and the VI value is 20.75sec/g.
Embodiment three
Repeat embodiment one, but use whipping agent (B) to substitute whipping agent (A).All the other get high-performance high absorbent resin with embodiment one, and the mensuration confining force is 30.9g/g, 20g/cm
2Water absorbent rate 29.4g/g under the pressure, 49g/cm
2Water absorbent rate 18.7g/g under the pressure, water ratio are 1.23%, and the VI value is 21.47sec/g.
Embodiment four
Repeat embodiment three, but the addition of whipping agent (B) is increased to 3.91g.All the other can get high-performance high absorbent resin with embodiment three, and the mensuration confining force is 31.5g/g, 20g/cm
2Water absorbent rate 29.1g/g under the pressure, 49g/cm
2Water absorbent rate 18.7g/g under the pressure, water ratio are 1.08%, and the VI value is 20.02sec/g.
Embodiment five
Repeat embodiment one, but use whipping agent (C) to substitute whipping agent (A).All the other get high-performance high absorbent resin with embodiment one, and the mensuration confining force is 31.2g/g, 20g/cm
2Water absorbent rate 28.9g/g under the pressure, 49g/cm
2Water absorbent rate 19.1g/g under the pressure, water ratio are 1.14%, and the VI value is 25.71sec/g.
Embodiment six
Repeat embodiment one, use 0.391g whipping agent (C) and 0.391g whipping agent (A) simultaneously.All the other get high-performance high absorbent resin with embodiment one, measure 32.1g/g, 20g/cm
2Water absorbent rate 29.2g/g under the pressure, 49g/cm
2Water absorbent rate 18.9g/g under the pressure, water ratio are 1.12%, and the VI value is 26.45sec/g.
Embodiment seven
1) gets in the 3000c.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 monomer concentration 42 weight parts water solution this moment, and wherein the vinylformic acid of 70mol% (mol ratio) partly neutralizes and becomes sodium acrylate.
2) N of adding 0.414g, N '-methyne bisacrylamide and 0.781g whipping agent (C) are in water-soluble unsaturated monomer solution, and temperature maintenance is in about 20 ℃.
3) add the 0.144g ydrogen peroxide 50,1.8g sodium sulfite anhy 96 and the reaction of 1.8g ammonium persulphate initiator.
4) will react the gelinite that the back generates and utilize the chopping of cut kibbler, and to filter out size be the gelinite below the 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.
6) get super absorbent resin 100g, add terepthaloyl moietie, 1,4-butyleneglycol (Taiwan plastic manufactured) and methyl alcohol 1/1/0.5 mixed aqueous solution 2.5g; With 150 ℃ of temperature heat treated 1 hour, after the cooling, weigh this super absorbent resin 10g; Add SiO 2 powder 0.1g; The polymine that adds again after evenly to be mixed: water=1: 3 (weight ratio) solution 1.2g, carry out agglomeration resistance and handle, promptly get high-performance high absorbent resin.It measures confining force is 31.5g/g, 20g/cm
2Water absorbent rate 28.4g/g under the pressure, 49g/cm
2Water absorbent rate 19.1g/g under the pressure, water ratio are 2.13%, and the VI value is 24.37sec/g.
Embodiment eight
Repeat embodiment seven, but use whipping agent (B) to substitute whipping agent (C).All the other get high-performance high absorbent resin with embodiment one, and the mensuration confining force is 30.9g/g, 20g/cm
2Water absorbent rate 29.4g/g under the pressure, 49g/cm
2Water absorbent rate 19.3g/g under the pressure, water ratio are 2.31%, and the VI value is 23.98sec/g.
Comparative example one
Repeat embodiment one, use 1.4g lime carbonate (Taiwan plastic company, ProductName: FP-100A).All the other get high-performance high absorbent resin with embodiment one, and the mensuration confining force is 32.2g/g, 20g/cm
2Water absorbent rate 28.7g/g under the pressure, 49g/cm
2Water absorbent rate 17.4g/g under the pressure, water ratio are 1.01%, and the VI value is 42.71sec/g.
Comparative example two
Repeat comparative example one, but with sodium hydrogencarbonate (Chinese red triangle company, ProductName: AK-28) substitute lime carbonate.All the other get high-performance high absorbent resin with comparative example one, and the mensuration confining force is 32.8g/g, 20g/cm
2Water absorbent rate 28.4g/g under the pressure, 49g/cm
2Water absorbent rate 17.1g/g under the pressure, water ratio are 1.03%, and the VI value is 43.55sec/g.
Comparative example three
Repeat comparative example two, but the addition of sodium hydrogencarbonate is to 2.8g.All the other get high-performance high absorbent resin with comparative example two, and the mensuration confining force is 32.5g/g, 20g/cm
2Water absorbent rate 25.6g/g under the pressure, 49g/cm
2Water absorbent rate 10.7g/g under the pressure, water ratio are 1.17%, and the VI value is 40.21sec/g.
Comparative example four
Repeat comparative example two, but potassium alum (Taiwan alum company) substitutes lime carbonate.All the other get high-performance high absorbent resin with comparative example two, and the mensuration confining force is 28.7g/g, 20g/cm
2Water absorbent rate 29.4g/g under the pressure, 49g/cm
2Water absorbent rate 19.8g/g under the pressure, water ratio are 1.26%, and the VI value is 51.72sec/g.
Comparative example five
Repeat comparative example two, (company extensively is full of by China, ProductName: GF-60) substitute lime carbonate but utilize calcined kaolin.All the other get high-performance high absorbent resin with comparative example two, and the mensuration confining force is 29.1g/g, 20g/cm
2Water absorbent rate 27.6g/g under the pressure, 49g/cm
2Water absorbent rate 16.2g/g under the pressure, water ratio are 1.13%, and the VI value is 49.37sec/g.
Claims (8)
1. the method for manufacture of a super absorbent resin comprises:
(a) in a kind of monomeric water-soluble unsaturated monomer of acidic group that contains, neutralization ratio is in the scope of 45mol% to 85mol%, and concentration is in the aqueous solution of the scope of 20wt% to 55wt%;
(b) add the whipping agent that the 0.01wt%～10wt% account for the resin total amount crosses via coating processing and carry out polyreaction;
(c) water gel of gained is sheared after the polyreaction, and granulation is also used 100 ℃ to 180 ℃ temperature warm air dryings, pulverizing, screening;
(d), re-use 80 ℃ to 230 ℃ heating surface of temperature and handle with after the 0.005wt%～5wt% surface crosslinking agent coating processing that accounts for the resin total amount.
2. the method for manufacture of super absorbent resin as claimed in claim 1, wherein, the whipping agent that coating processing is crossed is the mixture of carbonate cpds and alum compounds.
3. the method for manufacture of super absorbent resin as claimed in claim 2, wherein, said carbonate cpds is to have carbonate or bicarbonate radical compound in the chemical structure.
4. the method for manufacture of super absorbent resin as claimed in claim 2, wherein, said alum compounds is potassium alum, sodium alum or the ammonla alum that contains crystal water.
5. the method for manufacture of super absorbent resin as claimed in claim 2, wherein, the weight mixture ratio of carbonate cpds and alum compounds is 5: 95 to 95: 5.
6. the method for manufacture of super absorbent resin as claimed in claim 1, wherein, the treatment temp during coating processing is 40 ℃ to 95 ℃.
7. the method for manufacture of super absorbent resin as claimed in claim 1, wherein, the whirlpool disappearance index of the super absorbent resin of processing is not more than 35sec/g.
8. the method for manufacture of super absorbent resin as claimed in claim 1, wherein, the confining force of the super absorbent resin of processing is not less than 20g/g, 49g/cm
2Water absorbent rate is not less than 12g/g under the pressure.
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| CN107722329A (en) * | 2017-11-03 | 2018-02-23 | 宜兴丹森科技有限公司 | Polyacrylic acid water-absorbent resin, composition and its manufacture method |
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| US20020007166A1 (en) * | 1998-10-28 | 2002-01-17 | Mitchell Michael A. | Continuous manufacture of superabsorbent/ion exchange sheet material |
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