CN102311557B - Method for preparing super absorbent resin - Google Patents
Method for preparing super absorbent resin Download PDFInfo
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- CN102311557B CN102311557B CN 201010226364 CN201010226364A CN102311557B CN 102311557 B CN102311557 B CN 102311557B CN 201010226364 CN201010226364 CN 201010226364 CN 201010226364 A CN201010226364 A CN 201010226364A CN 102311557 B CN102311557 B CN 102311557B
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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 manufacture method 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, such as 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.Store the ability of liquid in order to take full advantage of absorption layer, 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 impact to the distribution situation of liquid in absorption layer in the absorption layer.
When the super absorbent resin in the absorption layer or paper pulp fiber behind liquid-absorbing, 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 the zone of having been expanded by liquid-absorbent, this phenomenon appellation is that colloid blocks (Gel-blocking) again; This phenomenon one occurs, and liquid afterwards just can not penetrate cartridge again, and to edge flowing, causes the generation of leak case.
In addition, near the super absorbent resin of expansion area the phenomenon that colloid blocks has occured, remaining liquid just can't arrive the more part of deep layer, so that the ability of absorption layer storage liquid significantly reduces.
The method that reduction colloid known in the art blocks all is the uptake rate (United States Patent (USP) 4 that changes super absorbent resin, 548, No. 847), the so-called cation chelating agent of use that this patent discloses (Cationic Complexing Agent) is such as 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 to utilize the mode that lowers the water gel middle crosslink density, make the easier liquid-absorbing of super absorbent resin.
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, but the difference of absorption rate is also little.
United States Patent (USP) 5,115 is mentioned for No. 011, uses vitriol, acetate or nitrate compound with aluminium, calcium, magnesium, with 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 United States Patent (USP) 5,115, also mention the absorption agent of a kind of absorbing blood and liquid 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 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, such as the prepared material of antimony (Antimony), also can reduce the generation (United States Patent (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, although can produce the super absorbent resin of low absorption rate, but, owing to must could obtain via secondary processing, cause significantly reducing production efficiency (United States Patent (USP) 6,433,058,6,579, No. 958).
Use polyol compound and carbonate cpds in fluidised bed Spray Grain-make Drier (Fluid-bed spray granulator dryer) mixing granulation, then make an addition to unsaturated monomer and carry out polyreaction, though so can improve the absorption rate to liquid, but, use polyol compound to apply, the super absorbent resin of namely producing through a mode thus produces outside the xanthochromia (Yellow-coloring change) easily, still must mix about 60 to 120 minutes ability via the fluidised bed Spray Grain-make Drier obtains, cause production efficiency significantly to reduce (United States Patent (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 very important problem.One of method that solves this problem is the slow or absorption rate of 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 manufacture method of super absorbent resin, have defective in the known technology to overcome.
For achieving the above object, the manufacture method of super absorbent resin provided by the invention comprises:
(a) in a kind of water-soluble unsaturated monomer that contains the acidic group monomer, 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) with after the 0.005wt% that accounts for the resin total amount～5wt% surface crosslinking agent coating processing, re-use 80 ℃ to 230 ℃ heating surface of temperature and process.
The manufacture method of described super absorbent resin, wherein the whipping agent crossed of coating processing is the mixture of carbonate cpds and alum compounds.
The manufacture method of described super absorbent resin, wherein said carbonate cpds are to have carbonate or bicarbonate radical compound in the chemical structure.
The manufacture method of described super absorbent resin, wherein said alum compounds are potassium alum, sodium alum or the ammonla alum that contains crystal water.
The manufacture method of described super absorbent resin, wherein the weight mixture ratio of carbonate cpds and alum compounds is 5: 95 to 95: 5.
The manufacture method of described super absorbent resin, wherein the treatment temp during coating processing is 40 ℃ to 95 ℃.
The manufacture method of described super absorbent resin, the whirlpool disappearance index (VI value) of the super absorbent resin of wherein making is not more than 35sec/g.
The manufacture method of described super absorbent resin, the confining force of the super absorbent resin of wherein making 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 fast absorption rate, and also has the higher absorption multiplying power property under higher pressure.
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 a kind of super absorbent resin that has quick absorption rate and have the higher absorption multiplying power property under high pressure for preparing, furtherly, the super absorbent resin of manufacturing of the present invention has fast absorption rate 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 manufacture method with super absorbent resin of quick absorption rate and comprises at least:
What (1) neutralization ratio 45 molar percentages were above containing in the acidic group monomer solution, describedly 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 manufacture method of the super absorbent resin of the characteristic that has the higher absorption multiplying power under quick absorption rate 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, carbonate cpds is to have carbonate or bicarbonate radical compound in the chemical structure, as: yellow soda ash, salt of wormwood, volatile salt, magnesiumcarbonate, calcium carbonate, barium carbonate, sodium bicarbonate, 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: methacrylic acid, Malin's acid, fumaric acid, 2-allylamine-2-methyl propane sulfonic acid, maleic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, FUMARIC ACID TECH GRADE acid anhydride etc.The specific limited of selecting not of monomer is used a kind of only, also can merge various of 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, such as acrylamide, Methacrylamide, vinylformic acid 2-carboxyl ethyl ester, methacrylic acid 2-carboxyl ethyl ester, methyl acrylate, ethyl propenoate, dimethylamine acrylic acid-acrylamide, propylene dichloride acrylamido TMA (TriMethylAmine), but addition is take the physical property of not destroying super absorbent resin as principle.
When carrying out Raolical polymerizable, the not special restriction of monomer solution concentration, 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, hydrogel after the polymerization is too soft and the unfavorable mechanical workout of stickiness arranged, add 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, if be lower than 5.5, the interior remaining monomer content of water gel is too high after the polymerization, causes the physical property 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, the water gel volume becomes large after the polyreaction, causes execute-in-place poor.
When the carbonate cpds weight ratio of the whipping agent of processing is lower than 5%, can't reach the present invention's desired result, when being higher than 96%, then system of Himdu logic vitriol compound amount is excessively low, effective carbon coated phosphate compounds, carbonate cpds is contacted with unsaturated monomer solution immediately and form carbon dioxide and overflow, also can't reach the present invention's desired result.The weight mixture ratio of the carbonate cpds that it is suitable and alum compounds is 5: 95 to 95: 5, is preferably 20: 80 to 80: 20.
Until carbonate cpds mix with the alum compounds finish 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 ℃ affect quality, and heat treatment time was advisable with 3 minutes to 20 minutes.Being applicable to 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 such as part saponification or fully saponified polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid, polyacrylamide, starch or starch derivative such as methylcellulose gum, the vinylformic acid methylcellulose gum, the polymkeric substance such as ethyl cellulose, the molecular weight of these water-soluble polymers is not particularly limited, its better water-soluble polymer is starch, part saponification or fully saponified polyvinyl alcohol etc., all can be used alone or as a mixture.It is 0wt% to 20wt% that super absorbent resin contains these suitable weight percents that add water-soluble polymer, but better with 0wt% to 10wt%, 0wt% to 5wt% is especially good, and adding when surpassing 20wt% to affect physical property, makes the physical property variation.
Before carrying out Raolical polymerizable, add first the Raolical polymerizable linking agent in unreacted monomer solution, the optional usefulness of this Raolical polymerizable linking agent has the compound of two or more unsaturated double-bonds, as: N, N '-two (2-propenyl) amine, N, N '-methyne bisacrylamide, N, the two Methacrylamides of N '-methyne, the vinylformic acid propylene, glycol diacrylate, polyethyleneglycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycerol tri-acrylate, the glycerine trimethacrylate, triacrylate or the trimethacrylate of glycerine additional ring oxidative ethane, triacrylate or the trimethacrylate of trihydroxymethyl propane additional ring oxidative ethane, the trihydroxymethyl propane trimethacrylate, the trihydroxymethyl propane triacrylate, N, N, N-three (2-propenyl) amine, ethylene glycol diacrylate, three vinylformic acid polyoxyethylene glycerides, three vinylformic acid diethyl polyoxyethylene glycerides, two propylene triethyleneglycol ester etc., also optional usefulness has the compound of two or more epoxy group(ing), such 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 suitable processibility.
Above-mentioned Raolical polymerizable linking agent can be used alone or mixed use of two or more.Raolical polymerizable linking agent suitable additive amount is (take the total solid of reactant as benchmark) 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.
The carboxylic acid group's part that contains the acidic group monomer should neutralize to control the pH value of finished product, make it be neutrality or subacidity, neutralizing agent is oxyhydroxide or the carbonate compound of periodictable alkali metal group or alkaline earths, as: sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniac compounds; This neutralizing agent can be used alone or multiple mixing is used.
The carboxylic acid group who contains the acidic group monomer partly is neutralized into sodium salt or sylvite or ammonium salt, its neutralization ratio molar percentage is between the 45mol% to 85mol%, be preferably between the 50mol% to 75mol%, the neutralization ratio molar percentage is that the pH value of 45mol% finished product when following can be on the low side, in and the concentration molar percentage be that the pH value of 85mol% finished product when above is understood higher, finished product pH value is non-when being neutrality or subacidity, if all not too suitable, also more dangerous when accidentally contacting with human body.
Prepolymerization is begun by the decomposition generation free radical that polyreaction causes (initial) agent.Initiators for polymerization can be selected thermolysis type initiator, 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 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: 2.2 '-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 is reacted the generation free radical in advance, 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 and elevate the temperature, when arriving the decomposition temperature of thermolysis type initiator, can cause again the decomposition of second segment thermolysis type initiator, and whole polyreaction is more attained in fully.
The suitable consumption of general Raolical polymerizable initiator be weight percentage for 0.001wt% to 10wt% (take in and acrylate weight as benchmark), more suitable 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 reacts on the conveyer belt type reactor, and the gelinite of reaction gained utilizes first pulverizer to be cut into the following little gelinite of diameter 2.00mm, 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 better between 0.05mm to 1.50mm, particle diameter is then again sent back in the reactor greater than the gelinite of 2.00mm and again shredded.The following gelinite of particle diameter 0.03mm is dried, pulverization process, easily produce the finished product fine powder amount and improve, when the above gelinite of particle diameter 2.00mm is dried, easily because thermal conduction effect is not good, cause finished product higher at remaining monomer, the shortcoming that physical property is performed poor.According to the present invention, the particle size dispersion of acrylate gelinite is more narrow better, not only can make gelinite physical property performance after oven dry reach optimum regime, and be conducive to control time and the temperature of oven dry, dries after screening is finished again.
Bake out temperature is dried with 100 ℃ to 180 ℃ of 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 ahead of time crosslinking reaction, so that in the follow-up drying process, can't effectively remove remaining monomer because degree of crosslinking is too high, reach the effect that reduces remaining monomer.
Pulverize, screen fixedly particle diameter after the drying, carry out again the surface crosslinking agent coating processing.Fixedly particle diameter is to be advisable between 0.06mm to 1.00mm in screening, and with better 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 more narrow better.
Super absorbent resin is the hydrophilic polymer of dissolving not, resin inside has inhomogeneity bridging structure, generally for improve quality as: improve uptake rate, improve colloid intensity, improve anti-caking effect, hydraulic permeability etc. and all can remake on the surface of resin further bridge formation, this surface-crosslinked processing namely utilize have can with the report of the multiple functional radical linking agent of acid-base reaction, existing many patent disclosures 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 (JP-A-1-292004, No. 6346569, United States Patent (USP)) uses organic solution, water, ether (ether) compound (JP-A-2-153903) etc.; Though these surface-treated methods can improve uptake rate, improve water absorbent rate under the pressure, 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 react simultaneously when surface treatment is polyvalent alcohol such as glycerol, ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol etc.; Maybe can use polyamine such as quadrol, two quadrols, Triethylene Diamine; Maybe can use compound with two or more epoxy group(ing) such as sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers etc.; Also can use alkylene carbonate such 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 linking agent can be used alone or mixed use of two or more, its suitable additive amount is (take the total solid of reactant as benchmark) between weight percent 0.001wt% to 10wt%, more suitable consumption is between 0.005wt% to 5wt%, the linking agent additive capacity can't show effect when weight percent 0.001wt% is following, the linking agent additive capacity is when weight percent 10wt% is above, water-absorbent is too low, reduces resin property.
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 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 with methyl alcohol, ethanol better (No. 6849665, United States Patent (USP)).
Powdery provided by the invention, water insoluble can absorb the super absorbent resin of water or urine and blood, and this resin has fast absorption rate, and also has the higher absorption multiplying power property under higher pressure.Its manufacture method comprises:
(a) in using a kind of water-soluble unsaturated monomer that contains the acidic group monomer, in it and 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) with after the surface crosslinking agent coating processing, re-use 80 ℃ to 230 ℃ heating surface of temperature and process.
Above-mentioned technical characterictic, when using 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 thus the effect of quick absorption rate; Polyvalent metal ion in the Alum compounds, also with super absorbent resin in carboxylate radical produce bond, improve the intensity of super absorbent resin, so that have the characteristic that has the higher absorption multiplying power under the high pressure via the super absorbent resin of manufacturing of the present invention.
For the present invention, only must be when carrying out polyreaction, adding whipping agent that coating processing crosses namely produces super absorbent resin with the water-soluble unsaturated monomer aqueous solution in this polyreaction mode just can make and have fast uptake rate, 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 maximum 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 first not, and the blank group tea bag heavy (with the same steps as operation) of filling super absorbent resin heavily namely 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 section is arranged, to powder 20g/cm in addition
2And 49g/cm
2Pressure, then this right cylinder is placed on the absorptivity demand tstr, allow this super absorbent resin absorb 0.9% sodium chloride aqueous solution one hour, survey suction weight, after with the weight of institute's value divided by super absorbent resin, namely get pressurized and absorb the tuple value.
Whirlpool disappearance index of the present invention (Vortex Index, VI) is to carry out according to following described method, and with five measurements, behind removal maximum 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 electromagnetic mixer, 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 namely 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, to carry out according to following described method: weigh 5.000 ± 0.001 gram super absorbent resins (SAP) and place hot analytical balance glass disc and write down weight, setting analysis temperature is 140 ℃, 15 minutes analysis times, namely get the super absorbent resin water ratio after analysis is finished, unit is 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 the present patent application 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, namely get the whipping agent (A) that coating processing is crossed.
Reference example two
Get 800g calcium 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, namely get the whipping agent (B) that coating processing is crossed.
Reference example three
Get 500g sodium bicarbonate (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, namely 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, time for adding 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 is maintained at about 20 ℃.
3) add the 0.144g hydrogen peroxide, 1.8g sodium bisulfite and the reaction of 1.8g ammonium persulphate initiator.
4) gelinite that generates after will reacting utilizes the chopping of cut pulverizer, and to filter out size be the following gelinite of 2mm diameter.
5) again with dry 2 hours of 130 ℃ of temperature; 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 ethylene glycol, BDO (manufacturing of Taiwan plastic company) and by volume 1: 1: 0.5 mixed aqueous solution 2.5g of methyl alcohol, with 150 ℃ of temperature heat treated 1 hour, after the cooling, namely 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 that 0.92%, 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 that 1.12%, 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 that 1.23%, 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 that 1.08%, 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 that 1.14%, VI value is 25.71sec/g.
Embodiment six
Repeat embodiment one, use simultaneously 0.391g whipping agent (C) and 0.391g whipping agent (A).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 that 1.12%, 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, time for adding 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 is maintained at about 20 ℃.
3) add the 0.144g hydrogen peroxide, 1.8g sodium bisulfite and the reaction of 1.8g ammonium persulphate initiator.
4) gelinite that generates after will reacting utilizes the chopping of cut pulverizer, and to filter out size be the following gelinite of 2mm diameter.
5) again with dry 2 hours of 130 ℃ of temperature; 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 ethylene glycol, 1,4-butyleneglycol (manufacturing of Taiwan plastic company) 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 process, namely 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 that 2.13%, 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 that 2.31%, VI value is 23.98sec/g.
Comparative example one
Repeat embodiment one, use 1.4g calcium 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 that 1.01%, VI value is 42.71sec/g.
Comparative example two
Repeat comparative example one, but with sodium bicarbonate (Chinese red triangle company, ProductName: AK-28) substitute calcium 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 that 1.03%, VI value is 43.55sec/g.
Comparative example three
Repeat comparative example two, but the addition of sodium bicarbonate 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 that 1.17%, VI value is 40.21sec/g.
Comparative example four
Repeat comparative example two, but potassium alum (Taiwan alum company) substitutes calcium 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 that 1.26%, VI value is 51.72sec/g.
Comparative example five
Repeat comparative example two, (company extensively is full of by China, ProductName: GF-60) substitute calcium 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 that 1.13%, VI value is 49.37sec/g.
Claims (7)
1. the manufacture method of a super absorbent resin comprises:
(a) in a kind of water-soluble unsaturated monomer that contains the acidic group monomer, 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 carbonate cpds that the 0.01wt%～10wt% account for the resin total amount crosses via coating processing and the mixture whipping agent of alum compounds 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) with after the 0.005wt% that accounts for the resin total amount～5wt% surface crosslinking agent coating processing, re-use 80 ℃ to 230 ℃ heating surface of temperature and process.
2. the manufacture method of super absorbent resin as claimed in claim 1, wherein, described carbonate cpds is to have carbonate or bicarbonate radical compound in the chemical structure.
3. the manufacture method of super absorbent resin as claimed in claim 1, wherein, described alum compounds is potassium alum, sodium alum or the ammonla alum that contains crystal water.
4. the manufacture method of super absorbent resin as claimed in claim 1, wherein, the weight mixture ratio of carbonate cpds and alum compounds is 5: 95 to 95: 5.
5. the manufacture method of super absorbent resin as claimed in claim 1, wherein, the treatment temp during coating processing is 40 ℃ to 95 ℃.
6. the manufacture method of super absorbent resin as claimed in claim 1, wherein, the whirlpool disappearance index of the super absorbent resin of making is not more than 35sec/g.
7. the manufacture method of super absorbent resin as claimed in claim 1, wherein, the confining force of the super absorbent resin of making 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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| CN1812818A (en) * | 2003-04-25 | 2006-08-02 | 施拖克豪森公司 | Superabsorbent polymer with high permeability |
| CN101143913A (en) * | 2007-09-06 | 2008-03-19 | 段梦麟 | Method for preparing water absorption polymer with high liquid absorption speed, dispersity and dried degree |
| CN102010560A (en) * | 2010-11-02 | 2011-04-13 | 南京工业大学 | Method for preparing foamy high water absorption resin |
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| US20040087926A1 (en) * | 2002-11-06 | 2004-05-06 | Ko Young C. | Absorbent articles comprising inverse HIPE foams other foams |
| US6863924B2 (en) * | 2002-12-23 | 2005-03-08 | Kimberly-Clark Worldwide, Inc. | Method of making an absorbent composite |
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| CN1812818A (en) * | 2003-04-25 | 2006-08-02 | 施拖克豪森公司 | Superabsorbent polymer with high permeability |
| CN101143913A (en) * | 2007-09-06 | 2008-03-19 | 段梦麟 | Method for preparing water absorption polymer with high liquid absorption speed, dispersity and dried degree |
| CN102010560A (en) * | 2010-11-02 | 2011-04-13 | 南京工业大学 | Method for preparing foamy high water absorption resin |
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