CN100424101C - Preparation method of powdery, water-insoluble high hydroscopicity resin capable of adsorbing water, urine or blood and containing low content residue monomer not reacted - Google Patents
Preparation method of powdery, water-insoluble high hydroscopicity resin capable of adsorbing water, urine or blood and containing low content residue monomer not reacted Download PDFInfo
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Abstract
The invention discloses a making method of powder-shaped, insoluble, water, urine or blood absorbable low-residual remnant monomer high-hydroscopicity resin, which comprises the following steps: adding internal crosslinking agent in the acid group monomer liquid; aerating acid group monomer liquid in the pipe line with inert gas; adding initiator; starting polymerization reaction with free radical; cutting the polymerized gel; drying; sieving the solid with fixed grain size; adding surface crosslinking agent; proceeding heat disposal; adding inert inorganic powder.
Description
Technical field
The present invention relates to a kind of super absorbent resin, particularly relate to a kind of powdery, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer.
Background technology
Super absorbent resin has powerful moisture holding capacity, can absorb hundred times even thousand times to the water of weight own, and but swelling has and keeps immobilising state after the suction, can seepage even on super absorbent resin, exert pressure also not, and absorbed water can gently disengage in atmosphere.Owing to have above-mentioned characteristic, so super absorbent resin is used the water-loss reducer of soil as agricultural forest industry the earliest, in recent years the production technology because of super absorbent resin has sizable progress, so also be widely used in sanitary product, as the water-retaining agent of diaper, adult-incontinence articles and women sanitary articles and preserve fresh-keeping application that food uses etc.
Make the material of super absorbent resin, (Japanese Patent is communique clear 49 (1974)-43 openly for common starch acrylamide nitrile (hydrolyzed starch-acrylonitrile) graftomer of meeting the water decomposition type that has, 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 patents such as (Japanese Patent openly announce clear 55 (1980)-84,304).Wherein account for maximum partly also tool economic benefit with the super absorbent resin that uses vinylformic acid and acrylate to carry out the crosslinking polymerization gained, the super absorbent resin that its former because vinylformic acid can be buied from the market rapidly, make has higher water-retaining capacity, cheap for manufacturing cost and tool economic benefit, so become the super absorbent resin manufactured materials of generalization.
Polymeric acrylic acid and acrylate form the method for super absorbent resin and are succeeded in developing by many-sided, and there is several different methods to be applied to industry member production, its polymerization process is common has the casting film polyreaction (Japanese patent laid-open publication gazette is clear and 48 (1973)-42,466), (Japanese Patent discloses clear and 58 (1983)-49 to carry out polyreaction on conveying belt, 714), the pinching of the stirring blade of pulverizing mixed and carried out polyreaction in the base (Japanese Patent discloses clear and 57 (1982)-34,101), (Japanese Patent discloses clear and 59 (1984)-37 to carry out the anti-phase suspension polymerization, 003) sprays and with monomer or be coated on and carry out polyreaction (Japanese Patent disclose clear and 62 (1987)-53,309) or the like patent on the fibre substrate.
Super absorbent resin is the hydrophilic polymer that is not dissolved in water, general resin inside has inhomogeneity bridge formation structure, in order to improve quality, for example improve uptake rate, improve colloid intensity, improve anti-caking effect and hydraulic permeability etc., fixedly can remake further bridge formation on the surface of resin behind the particle diameter in screening, this surface-crosslinked processing promptly utilize have can with the multiple functional radical linking agent of acid-base reaction, existing many before this patents propose, for example: disperse super absorbent resin and linking agent to carry out surface-crosslinked processing (JP-A-56-131608 in organic solvent, 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 steam treatment (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 and ether (ether) compound (JP-A-2-153903) etc.Though these surface-treated methods can improve the uptake rate of resin or the water absorbent rate under the pressurize, will cause the too much adverse consequences of its confining force decline, reduce the performance of practical application.
In addition, when the super absorbent resin of the polyacrylic produced is used in sanitary product or food fresh keeping, might directly contact with human body and food, lower remaining monomer can promote the security in the use, and therefore requiring super absorbent resin to reduce its remaining monomeric residual quantity has in recent years become a kind of trend.
For reducing the level of residual monomers of super absorbent resin, existing many methods are developed, for example: (Japanese patent laid-open publication gazette is clear and 33 (1958)-2 to add ammonia and amine, 646 disclose clear and 50 (1975)-40 with Japanese Patent, 689) or add sulphite and hydrosulphite (United States Patent (USP) 2,960, No. 486 and 4,306, No. 955) reducing level of residual monomers, other has the low-temperature decomposition type of use and pyrolytic decomposition type initiator, and (Japanese patent laid-open publication gazette is clear and 50 (1975)-44,280, Japanese Patent disclose clear and 53 (1978)-141,388) or (Japanese Patent discloses clear and 50 (1975)-96,689 and United States Patent (USP) 3 merge to use redox initiator, 573, No. 263) so that remain in the monomer polymerization once more on super absorbent resin surface, and reach the purpose that reduces level of residual monomers.Also can use the microbiological degradation method to decompose residual monomer (Japanese patent laid-open publication gazette clear and 60 (1985)-29,523) and utilize the steam preheating mode to dry (Japanese patent laid-open publication gazette clear and 62 (1987)-104,764) again and reach the purpose of minimizing level of residual monomers.
Yet above-mentioned prior art has following shortcoming:
1. it is quite effective to lowering remaining monomer content to add ammonia, amine or sulphite, but can cause suction force to reduce, but if the addition deficiency is then very limited to reducing remaining monomeric effect;
2. in addition, the ammonia of use, amine or sulphite can be dissolved in the aqueous solution, will contact the infringement that causes human body with human body, reach the pollution to environment;
3. use the method for initiator, can only be reduced in the remaining monomer of super absorbent resin colloid surface, but the remaining monomer of super absorbent resin colloid inside is then had no effect, and the cost that will expend is higher;
4. rely on the microbiological degradation monomer methods, too high and consuming time too of a specified duration because of cost, and be unfavorable for being applied on the manufacturing processed;
5. the method for utilizing the preheating of steam elder generation to dry again has then that manufacturing processed is loaded down with trivial details, control difficulty and a high shortcoming of on-the-spot machinery equipment infringement ratio of depreciation.
Summary of the invention
Subject matter to be solved by this invention is to provide a kind of powdery, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer are to solve the ammonia that prior art exists, amine or sulphite are to the infringement of human body and to the pollution of environment, the cost that uses initiator can only be reduced in the remaining monomer of super absorbent resin colloid surface and expend is higher, loaded down with trivial details with the microbiological degradation monomer manufacturing processed that is unfavorable for production process too for a long time or utilizes the preheating of steam elder generation to dry again consuming time, control difficulty and the high problem of on-the-spot machinery equipment infringement ratio of depreciation.
Therefore, for reaching above-mentioned purpose, the invention discloses a kind of powdery, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, be included in to contain and feed the pipeline that adds rare gas element after the acidic group monomer solution adds internal crosslinking agent, to remove oxygen; Add initiator again, the beginning Raolical polymerizable; With the gelinite of Raolical polymerizable gained chopping, dry and filter out fixedly particle diameter, add surface crosslinking agent then and carry out heat treated, and add the inert inorganic salt powder again.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, the concentration range that wherein contains the acidic group monomer solution for example is weight percentage 20 to 55.And contain the acidic group monomer for example for vinylformic acid, have insatiable hunger and close the water-soluble monomer of two keys or the mix monomer in the above-mentioned group.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein neutralization contains the monomeric neutralization ratio scope of acidic group and for example is molar percentage more than 50.And neutralizing agent for example is lithium hydroxide, sodium hydroxide, potassium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus or ammonia.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein internal crosslinking agent is a benchmark with the total solid of reactant, and the additive capacity scope for example is weight percentage 0.001 to 5.And internal crosslinking agent is to have the water-soluble cpds that two or more participate in the functional group of free radical reaction, for example compound for having the compound of two or more unsaturated double-bonds or having two or more epoxy group(ing).
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein rare gas element is for example removed oxygen but is not influenced the gas that Raolical polymerizable carries out for having, and for example be nitrogen, carbonic acid gas, blunt gas family gas, the derivative of blunt gas family gas, mixture or other suitable gas of above-mentioned group.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, the pipeline that for example combines of pipeline wherein for general iron pipe, stainless steel tube, plastic lined piping, the pipeline that contains weighting material, the pipeline that contains rotating paddle, static mixer or connection.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein to contain acidic group monomer salt with neutralization be benchmark to initiator, and the additive capacity scope for example is weight percentage 0.001 to 10.And initiator for example is the mixture of thermolysis type initiator, oxidation-reduction type initiator or above-mentioned group.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein Shai Xuan fixedly particle size range for example is 0.05 to 1.00 millimeter.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein the interpolation pattern of surface crosslinking agent for example be directly add, the furnishing aqueous solution adds or the interpolation of the furnishing hydrophilic organic solvent aqueous solution.Surface crosslinking agent is a benchmark with the total solid of reactant, and the additive capacity scope more for example is weight percentage 0.005 to 5.0.And surface crosslinking agent for example is the mixture of polyvalent alcohol, polyamine, the compound with two or more epoxy group(ing), alkylene carbonate or above-mentioned group.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein the temperature range of heat treated for example is a 80-230 degree Celsius, and the time range of heat treated for example is 2-150 minute.
According to the described powdery of preferred embodiment of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, wherein the inert inorganic salt powder for example is the mixture of Tai-Ace S 150, silicon-dioxide, aluminum oxide, magnesium oxide, calcium oxide, kaolin, lime carbonate, magnesiumcarbonate or above-mentioned group.The particle size range of inert inorganic salt powder for example is 0.001 to 100 micron.
According to the manufacture method of the described low remaining monomeric super absorbent resin of preferred embodiment of the present invention, wherein the inert inorganic salt powder is a benchmark with the total solid of reactant, and the addition scope for example is weight percentage 0.005 to 10.0.The present invention feeds the pipeline that adds rare gas element because of adopting with containing the acidic group monomer solution, to remove the technique means of oxygen, therefore can reduce the remaining monomer content of super absorbent resin.
The present invention because of adopt with rare gas element with contain the acidic group monomer solution and mix, and reduce the oxygen level that contains the acidic group monomer solution, so the remaining monomer of minimizing super absorbent resin inside had excellent effect.
The present invention sneaks into the technique means of rare gas element because of employing, and rare gas element is loss gradually in follow-up flow process, therefore can not contact the infringement that causes human body with human body, and rare gas element can not cause the pollution to environment yet.
The present invention can adopt general iron pipe, stainless steel tube, plastic lined piping, contain pipeline that the pipeline of weighting material, the pipeline that contains rotating paddle, static mixer or connection combine as the pipeline of sneaking into rare gas element, and the rare gas element that the derivative or the like that can use nitrogen, carbonic acid gas, blunt gas family gas, blunt gas family gas uses as reaction, therefore process structure is simple, materials used is cheap, can reduce manufacturing cost.
Embodiment
Below enumerate specific embodiment to describe content of the present invention in detail.
A kind of powdery disclosed by the invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, comprise prior to containing in the acidic group monomer solution and add internal crosslinking agent; Then, feed the pipeline that adds rare gas element with containing the acidic group monomer solution, to remove oxygen; Begin Raolical polymerizable again; Afterwards, with the gelinite drying of Raolical polymerizable gained, pulverize and filter out fixedly particle diameter; Then, carry out heat treated behind the interpolation surface crosslinking agent; And, add the inert inorganic salt powder mixes evenly after, get final product super absorbent resin.
The above-mentioned concentration range that contains the acidic group monomer solution should be controlled at for example weight percent 20 to 55, also can be weight percentage 30 to 45.Wherein, contain acidic group monomer solution concentration when weight percent 20 is following, the hydration colloid of super absorbent resin is too soft and stickiness arranged after the polymerization, unfavorable mechanical workout, concentration is when weight percent 55 is above, too, have the problem that is difficult for allotment and react the too too much and wayward reaction of fast response heat near saturation concentration.And contain the acidic group monomer for example for vinylformic acid, have insatiable hunger and close the water-soluble monomer of two keys or the mix monomer in the above-mentioned group.Close the water-soluble monomer of two keys and for example be methacrylic acid, Malin's acid, fumaric acid or 2-allylamine-2-methyl propane sulfonic acid and have insatiable hunger.
Above-mentioned contain the acidic group monomer solution and also can comprise having other hydrophilic monomer of unsaturated double-bond, its addition is a principle with the rerum natura of not destroying low remaining monomeric super absorbent resin.For example be acrylamide, Methacrylamide, vinylformic acid 2-alkyl ethyl ester, methacrylic acid 2-alkyl ethyl ester, methyl acrylate, ethyl propenoate, dimethylamine acrylic acid-acrylamide or propylene dichloride acrylamido TMA (TriMethylAmine) and have other hydrophilic monomer of unsaturated double-bond.
The above-mentioned acidic group monomer solution that contains also can add water-soluble high-molecular compound and reduces cost or obtain special rerum natura.Contain the amount that the acidic group monomer solution contains water-soluble high-molecular compound and for example be weight percentage below 20, more can for example be weight percentage below 10, can for example be weight percentage below 5 especially.And water-soluble high-molecular compound for example is the mixture of partly saponification or fully saponified polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid, polyacrylamide, starch, starch derivative or above-mentioned group.Starch derivative for example is a methylcellulose gum, vinylformic acid methylcellulose gum or ethyl cellulose or the like polymkeric substance.
Above-mentioned contain the monomeric carboxylic acid group of acidic group and should partly neutralize, make to be neutrality or subacidity with the pH value (potential of hydrogen) of control finished product.The neutralizing agent that neutralization is added, its neutralization contain the monomeric neutralization ratio scope of acidic group for example for molar percentage 45 to 85, more can for example be molar percentage 50 to 75.When in and concentration molar percentage (mol%) be 45 when following, the pH value of finished product is understood on the low side.When in and the concentration molar percentage be 85 when above, the pH value of finished product is understood higher.When being neutrality or subacidity, not too be fit to also more dangerous when it contacts with human body accidentally as if finished product pH value is non-.And neutralizing agent for example is lithium hydroxide, sodium hydroxide, potassium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus or ammonia.
Above-mentioned internal crosslinking agent is a benchmark with the total solid of reactant, and the additive capacity scope for example is weight percentage 0.001 to 5, more can for example be weight percentage 0.01 to 3.Add internal crosslinking agent, after carrying out Raolical polymerizable, just can make low remaining monomeric super absorbent resin have suitable degree of crosslinking, and make the super absorbent resin colloid that suitable processibility be arranged.Wherein, when the additive capacity of internal crosslinking agent when weight percent 0.001 is following, the super absorbent resin after the polyreaction is too soft and stickiness is arranged, and is unfavorable for mechanical workout.When additive capacity when weight percent 5 is above, the super absorbent resin water-absorbent is too low, reduces resin property.And internal crosslinking agent for example is the compound that has the compound of two or more unsaturated double-bonds or have two or more epoxy group(ing).Compound with two or more unsaturated double-bonds for example is 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 or two propylene triethyleneglycol ester.And the compound with two or more epoxy group(ing) for example is sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether or two glycerol polyglycidyl ether.
Above-mentioned rare gas element is for example removed oxygen but is not influenced the gas that Raolical polymerizable carries out for having, and it for example is nitrogen, carbonic acid gas, blunt gas family gas, the derivative of blunt gas family gas or the mixture of above-mentioned group.Be convenient to obtain for saving cost and consideration in industry member, use nitrogen or carbonic acid gas or its mixed gas usually.Wherein, add the purpose of rare gas element and removing oxygen, to guarantee the reduction of monomer solution oxygen level, the Raolical polymerizable after making it can carry out smoothly, reduces remaining monomeric content.But, when if the oxygen level of the monomer solution after the deoxygenation is on the low side, then monomer solution can be presented in unsteady state, do not have a little delay if discharge monomer solution fully this moment, then easily produce Raolical polymerizable ahead of time, and cause manufacturing processed to carry out smoothly, and the uppity problem of Raolical polymerizable is arranged.If the oxygen level of monomer solution is higher after the deoxygenation, though Raolical polymerizable is carried out, its speed of reaction will become comparatively slow and cause the remaining monomer content of reacted super absorbent resin too high.
Therefore, the optimal oxygen that removes is: the oxygen level of control minimum quantity, but can make Raolical polymerizable be able to easy control.Control remove the oxygen quality aspect, except the rerum natura of the temperature that can observe Raolical polymerizable and super absorbent resin, also can after removing oxygen, install additional, for example a continous way or a segmentation contains the oxygen detector, unreacted monomer aqueous solution oxygen level before the common not deoxygenation is all at 10ppm (partsper million, 1,000,000/) more than, if oxygen level 2 to 4ppm then Raolical polymerizable can carry out smoothly, but its reacted remaining monomer content has higher trend, if oxygen level is lower than below the 2ppm, then except that polyreaction can be carried out smoothly, its remaining monomer content also had lower phenomenon.
The pipeline that above-mentioned pipeline for example combines for general iron pipe, stainless steel tube, plastic lined piping, the pipeline that contains weighting material, the pipeline that contains rotating paddle, static mixer or connection.Wherein, the advantage that in-line carries out deoxygenation monomer solution by can guarantee deoxygenation the time can be controlled by the principle of first outer, does not have the reaction monomers aqueous solution that is detained and make in the process of deoxygenation, and reduces the possibility that polyreaction takes place in advance.And the length of removing the oxygen pipeline also can influence the effect of deoxygenation, and the mixing time of rare gas element is longer when longer as pipeline, and the effect of deoxygenation is also preferable.In order to improve rare gas element and the mixed effect that contains the acidic group monomer solution, and then contain the oxygen level of acidic group monomer solution after the reduction deoxygenation, remove oxygen pipeline and also can install screw-blade additional or fill the weighting material that increases mixed effect, for example Raschig ring, ripple earrings or other weighting material that is fit to.Moreover, rare gas element also can influence deaerating effect at the dispersion effect that contains the acidic group monomer solution, good then deaerating effect is also better if dispersiveness heals, the pressure of common rare gas element will be higher than the pipeline internal pressure during operation, rare gas element is injected smoothly contain in the acidic group monomer solution pipeline and carries out the deoxygenation step smoothly.Deoxygenation step pipeline also can use vapour-liquid type static mixer except can using above-mentioned design, increase the effect of deoxygenation.
Above-mentioned Raolical polymerizable begins to produce free radical with the interpolation initiator and begins, and employed initiator contains acidic group monomer salt with neutralization is benchmark, the additive capacity scope for example is weight percentage 0.001 to 10, more can for example be weight percentage 0.1 to 5.Initiator is for example for the mixture of thermolysis type initiator, oxidation-reduction type initiator or above-mentioned group.Wherein, when using the mixture of oxidation-reduction type initiator and thermolysis type initiator, the redox initiator can react the generation free radical earlier.When radical transfer is on containing the acidic group monomer, the carrying out of initiated polymerization immediately.Can discharge a large amount of heats when carrying out and elevate 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 owing to polyreaction.
Above-mentioned thermolysis type initiator for example is superoxide or azo-compound.Superoxide for example is hydrogen peroxide, two-tert-butyl peroxide, peroxidation acid amides, persulphate, ammonium salt or an alkali metal salt.Azo-compound for example is 2, two (2-amidine propane) dihydrochlorides, 2 of 2 '-azo-group, two (N, N-two the stretches the methyl NSC 18620) dihydrochlorides of 2 '-azo-group.And the oxidation-reduction type initiator for example is acid accumulator sulfite, thiosulphate, xitix or ferrous salt.
Above-mentioned Raolical polymerizable can for example react in the conventional batch reaction vessel, or reacts on the conveyer belt type reactor.The gelinite of Raolical polymerizable gained utilizes for example pulverizer earlier, and the chopping super absorbent resin for example becomes the gelinite of diameter below 20 millimeters, more can shred to after becoming the little gelinite of diameter below 10 millimeters, dries again.
Above-mentioned oven dry is advisable to dry under the temperature between 100 ℃ to 250 ℃, and drying temperature is then at 120 ℃ to 180 ℃.When bake out temperature below 100 ℃, drying time is too of a specified duration, does not have an economic benefit.And work as bake out temperature more than 250 ℃, and will make internal crosslinking agent carry out crosslinking reaction ahead of time, make and can't effectively remove remaining monomer because of degree of crosslinking is too high in the subsequent drying process, reach and reduce remaining monomeric effect.
Fixedly in the particle diameter process, the fixedly particle size range of screening super absorbent resin for example is 0.05 to 1.00 millimeter, more can for example be 0.10 millimeter to 0.850 millimeter for above-mentioned drying, pulverizing and screening.The fixedly particle size range of screening super absorbent resin is when particle diameter is below 0.06 millimeter, and fine powder will make the finished product dust improve, and particle size range is more than 1.00 millimeters the time, and particle will make the finished product rate of water absorption slack-off.
Above-mentioned surface crosslinking agent is a benchmark with the total solid of reactant, and the additive capacity scope more can for example be weight percentage 0.001 to 10, more can for example be weight percentage 0.005 to 5.The interpolation pattern of surface crosslinking agent for example is directly interpolation, the furnishing aqueous solution adds or the furnishing hydrophilic organic solvent aqueous solution adds.Wherein the furnishing hydrophilic organic solvent aqueous solution adds employed hydrophilic organic solvent for example for methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol, acetone, methyl ether or ether etc. do not have particular restriction, can form solution to get final product, and more often uses with methyl alcohol or ethanol.
Above-mentioned surface crosslinking agent for example is the mixture of polyvalent alcohol, polyamine, the compound with two or more epoxy group(ing), alkylene carbonate or above-mentioned group.Wherein polyvalent alcohol for example is glycerol, ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, 1,4 butyleneglycol, trialkyl methylpropane or sorbyl alcohol.Polyamine for example is quadrol, two quadrols, Triethylene Diamine or polyethyene diamine.Compound with two or more epoxy group(ing) for example is sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether or two glycerol polyglycidyl ether.Alkylene carbonate for example is 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.
Above-mentioned heat treated makes surface crosslinking agent can carry out crosslinking reaction, and makes internal crosslinking agent carry out crosslinking reaction and reach effect of the present invention, and the temperature range of heat treated for example is a 80-230 degree Celsius, and the time range of heat treated for example is 2-150 minute.Wherein, the following cross-linking reaction time of heat treated temperature 80 degree Celsius is not had economic benefit too for a long time, the heat treated temperature Celsius 230 the degree more than then the easy deterioration of resin influence quality, and the treatment time is according to the treatment temp adjustment, if the then crosslinked required time of treatment temp height shortens, if the low then crosslinked required time of treatment temp is longer.
The particle size range of above-mentioned inert inorganic salt powder for example is 0.001 micron to 100 microns.The inert inorganic salt powder is a benchmark with the total solid of reactant, and the addition scope for example is weight percentage 0.005 to 10.0, more can for example be weight percentage 0.01 to 4.0.Wherein, the addition of inert inorganic salt powder is relevant with its grain diameter size, when inert inorganic salt powder particle particle diameter hour, its surface-area is bigger, then inert inorganic salt powder consumption can be less.As if the inert inorganic salt powder of selecting for use grain diameter less than 0.001 micron, the too high suitability for industrialized production that is unfavorable for of the manufacturing cost of inert inorganic salt powder then, as if the inert inorganic salt powder of selecting for use grain diameter greater than 100 microns, then inert inorganic salt powder used in amounts is bigger, has the too high problem that influences the super absorbent resin absorbing power of addition.And the inert inorganic salt powder for example can use the mixture of Tai-Ace S 150, silicon-dioxide, aluminum oxide, magnesium oxide, calcium oxide, kaolin, lime carbonate, magnesiumcarbonate or above-mentioned group.
Above-mentioned inert inorganic salt powder can add or follow the organic compound of tensio-active agent or tool viscosity to add separately, and kenel or the interpolation of aqueous solution kenel separately of the organic compound of tensio-active agent or tool viscosity, it is that the additive capacity scope of benchmark for example is weight percentage 0.001 to 5 with the total solid of reactant, more can for example be weight percentage 0.01 to 3.Wherein, tensio-active agent for example is the mixture of nonionic surfactant, water soluble anion type tensio-active agent, cationic surfactant, negative and positive amphoteric surfactant or the above-mentioned group of HLB (hydroppile-lipophile balance, wetting ability-lipophilicity equilibrium) value more than 12.And the organic compound of tensio-active agent or tool viscosity for example is oneself six esters of glycerine, ethylene glycol, hexan-hexol, Volpo S 10, polyoxyethylene glycol, stearic acid macrogol ester, stearic acid polyoxyethylene glycol, polyoxyethylene nonylbenzene ether, the hot phenylate of polyoxyethylene, polyoxyethylene ten phenyl ether, polyethylene oxide alkyl ethers or polyoxyethylene bay ether.
For showing the low remaining monomer characteristic of super absorbent resin of the present invention, remaining monomeric mensuration is after filtering with the extraction liquid of super absorbent resin, utilize the liquid chromatography (LC) instrument to analyze, elder generation's essence weighs 0.500 gram super absorbent resin in 150 milliliters of Erlenmeyer flasks, one of the stirrer of adding 0.524% (per-cent) sodium-chlor (NaCl) aqueous solution 100 grams and 2 millimeters long, with 500rpm (revolution per minute, revolutions per minute) rotating speed stirred one hour, adding the stirring earlier of 20% aluminum sulfate aqueous solution, 5 grams left standstill 20 minutes after 1 minute, utilize 0.2 micron cellulose acetate filter paper filtering again, filtrate is squeezed into liquid chromatography (LC) instrument (type: C
18Tubing string) inner analysis compares the signal of gained and calibration curve and can obtain remaining amount of monomer.
Below at length list each experimental example and trial value thereof,, but be not limited to the present invention so that effect of the present invention is described.
Experimental example one
Step:
1) adds 3000 gram vinylformic acid and 3240 water that restrain in 100 milliliters of Conical flasks; Weigh 48% aqueous sodium hydroxide solution 2430 gram in addition again, under ice-cold environment, aqueous sodium hydroxide solution slowly added in the acrylic acid aqueous solution and neutralize; Must contain acidic group monomer concentration 42wt% (weight percent) aqueous solution this moment, and wherein 70mol% (molar percentage) vinylformic acid partly neutralizes and is sodium acrylate;
2) add 10 grams, three propenyl amine again in part neutral acrylic acid solution, and holding temperature is in about 20 ℃;
3) the unpolymerized acidic group monomer solution flow velocity that contains of control is 200 liters/hour, make it pass through the stainless steel tube of 1 meter of a diameter 5 millimeters long, stainless steel tube is gone into 5 millimeters at end and is located 0.5 millimeter stainless steel tube importing of diameter of side connection nitrogen, nitrogen flow is controlled to be 400 liters/hour, treat that the unreacted monomer aqueous solution is fully by behind the stainless steel tube, (label: WINLAB DATALINE OXYGEN METER) the analysis oxygen level is 3.8ppm (parts per million to contain oxygen, 1,000,000/), take static mixer apart and observe the inner no any polymkeric substance of finding;
4) add 40 gram hydrogen peroxide, behind 60 gram Sodium Persulfates and the two initial Raolical polymerizables of (2-amidine propane) dihydrochloride of 20 gram 2.2-azo-groups, place and made it form colloidal naturally in 1 hour;
5) after the reaction, utilize the cut pulverizer to be cut into gelinite below 2 mm dias this gelinite;
6) with 170 ℃ of temperature dryings 1 hour; Utilize screen cloth to screen 0.1 millimeter ~ 0.85 millimeter fixedly particle diameter, get the powdery super absorbent resin;
7) weigh this super absorbent resin 100 grams, add ethylene carbonate: water: methyl alcohol=1: 1: 1 (weight ratio) solution 4 grams, with 215 ℃ of temperature heat treated 10 minutes;
8) after the cooling, (platform is moulded company and produced the name of an article: NS-2000) and 20% aqueous glycerin solution, 2 grams, promptly get high-performance high absorbent resin behind the uniform mixing, analyzing remaining monomer is 356ppm to add 1 gram lime carbonate.
Experimental example two
Step:
Repeated experiments example one is 2.7ppm but the stainless steel tube length that step 3) is passed through changes 4 meters, oxygen level analysis into, takes static mixer apart and observes the inner no any polymkeric substance of finding; All the other steps are 160ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
Experimental example three
Step:
Repeated experiments example one is 2.1ppm but the stainless steel tube length that step 3) is passed through changes 7 meters, oxygen level analysis into, takes static mixer apart and observes the inner no any polymkeric substance of finding; All the other steps are 130ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
Experimental example four
Step:
1) adds 3000 gram vinylformic acid and 3240 water that restrain in 100 milliliters of Conical flasks; Weigh 48% aqueous sodium hydroxide solution 2430 gram in addition again, under ice-cold environment, aqueous sodium hydroxide solution slowly added in the acrylic acid aqueous solution and neutralize; Must contain the acidic group monomer concentration 42wt% aqueous solution this moment, and wherein 70mol% vinylformic acid partly neutralizes and is sodium acrylate;
2) add 10 grams, three propenyl amine again in part neutral acrylic acid solution, and holding temperature is in about 20 ℃;
3) the unpolymerized acidic group monomer solution flow velocity that contains of control is 200 liters/hour, make it pass through the stainless steel tube of 1 meter of a diameter 5 millimeters long, be full of 5 millimeters Raschig rings of diameter in stainless steel tube inside, stainless steel tube is gone into 5 millimeters at end and is located 0.5 millimeter stainless steel tube importing of diameter of side connection nitrogen, nitrogen flow is controlled to be 400 liters/hour, treat that the unreacted monomer aqueous solution is fully by behind the stainless steel tube, (label: WINLAB DATALINE OXYGEN METER) the analysis oxygen level is 1.8ppm, takes static mixer apart and observes the inner no any polymkeric substance of finding to contain oxygen;
4) add 40 gram hydrogen peroxide, after 60 gram Sodium Persulfates and two (2-amidine propane) the dihydrochloride starting polymerization reactions of 20 gram 2.2-azo-groups, place and made it form colloidal naturally in 1 hour;
5) utilize the cut pulverizer to be cut into gelinite below 2 mm dias this gelinite after the reaction;
6) with 170 ℃ of temperature dryings 1 hour; Utilize screen cloth to screen 0.1 millimeter ~ 0.85 millimeter fixedly particle diameter, get the powdery super absorbent resin;
7) weigh this super absorbent resin 100 grams, add ethylene carbonate: water: methyl alcohol=1: 1: 1 (weight ratio) solution 4 grams, with 215 ℃ of temperature heat treated 10 minutes;
8) after the cooling, (platform is moulded company and is produced the name of an article: NS-2000) and 20% aqueous glycerin solution, 2 grams, promptly get high-performance high absorbent resin behind the uniform mixing, analyze remaining monomer 94ppm to add 1 gram lime carbonate.
Experimental example five
Step:
Repeated experiments example four is 0.8ppm but the stainless steel tube length that step 3) is passed through changes 4 meters, oxygen level analysis into, takes static mixer apart and observes the inner no any polymkeric substance of finding; All the other steps are 70ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
Experimental example six
Step:
Repeated experiments example one is 0.4ppm but the stainless steel tube length that step 3) is passed through changes 7 meters, oxygen level analysis into, takes static mixer apart and observes the inner no any polymkeric substance of finding; All the other steps are 65ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
Experimental example seven
Step:
1) adds 3000 gram vinylformic acid and 3240 water that restrain in 100 milliliters of Conical flasks; Weigh 48% aqueous sodium hydroxide solution 2430 gram in addition again, under ice-cold environment, aqueous sodium hydroxide solution slowly added in the acrylic acid aqueous solution and neutralize; Must contain the acidic group monomer concentration 42wt% aqueous solution this moment, and wherein 70mol% vinylformic acid partly neutralizes and is sodium acrylate;
2) add 10 grams, three propenyl amine again in part neutral acrylic acid solution, and holding temperature is in about 20 ℃;
3) the unpolymerized acidic group monomer solution flow velocity that contains of control is 200 liters/hour, (label: NORITAKE) its screw-blade mixing portion length is 30 millimeters to make it pass through a gas-liquid static mixer, nitrogen flow is controlled to be 400 liters/hour, treat that the unreacted monomer aqueous solution is fully by behind the stainless steel tube, (label: WINLAB DATALINE OXY gram EN METER) analyzing oxygen level is the 0.8p millimeter, takes static mixer apart and observes the inner no any polymkeric substance of finding to contain oxygen;
4) add 40 gram hydrogen peroxide, behind 60 gram Sodium Persulfates and the two initial Raolical polymerizables of (2-amidine propane) dihydrochloride of 20 gram 2.2-azo-groups, place and made it form colloidal naturally in 1 hour;
5) utilize the cut pulverizer to be cut into gelinite below 2 mm dias this gelinite after the reaction;
6) with 170 ℃ of temperature dryings 1 hour; Utilize screen cloth to screen 0.1 millimeter ~ 0.85 millimeter fixedly particle diameter, get the powdery super absorbent resin;
7) weigh this super absorbent resin 100 grams, add ethylene carbonate/water/methyl alcohol=1/1/1 (weight ratio) solution 4 grams, with 215 ℃ of temperature heat treated 10 minutes;
8) after the cooling, (platform is moulded company and is produced the name of an article: NS-2000) and 20% aqueous glycerin solution, 2 grams, promptly get high-performance high absorbent resin behind the uniform mixing, analyze remaining monomer 68ppm to add 1 gram lime carbonate.
Experimental example eight
Step:
Repeated experiments example four is 0.3ppm but its screw-blade mixing portion length of the gas-liquid static mixer that step 3) is passed through changes 60 millimeters, oxygen level analysis into, takes static mixer apart and observes the inner no any polymkeric substance of finding; All the other steps are 40ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
Experimental example nine
Step:
Repeated experiments example one is 0.1ppm but its screw-blade mixing portion length of the gas-liquid static mixer that step 3) is passed through changes 90 millimeters, oxygen level analysis into, takes static mixer apart and observes the inner no any polymkeric substance of finding; All the other steps are 25ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
Comparative example one
Step:
Repeated experiments example one, but step 3) control nitrogen flow is 400 liters/hour, and change into and use the logical nitrogen of homogenizer to mix 15 minutes, take out the back and find on the agitating vane a little polymkeric substance is arranged, its polymer weight of weighing is 3.68 grams after separating, the analysis of unreacted monomer aqueous solution oxygen level is 0.6ppm, and all the other steps are 72ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
Comparative example two
Step:
Repeated experiments example one, but step 3) control nitrogen flow is 400 liters/hour, and change into and use the logical nitrogen of homogenizer to mix 60 minutes, take out the back and find on the agitating vane polymkeric substance is arranged, its polymer weight of weighing is 1200 grams after separating, the analysis of unreacted monomer aqueous solution oxygen level is 0.6ppm, and all the other steps are 72ppm with the remaining monomer of experimental example one its gained super absorbent resin by analysis.
In sum, powdery of the present invention, water insoluble, can absorb water liquid, urine or blood and have the manufacture method of the super absorbent resin of low remaining unreacted monomer, have the following advantages at least:
The prepared super absorbent resin of the present invention confirms to have lower remaining monomer content through various tests, therefore can promote the security on using when being used in sanitary product or food fresh keeping.
The present invention mixes rare gas element in pipeline with monomer solution, can reduce the oxygen level that contains the acidic group monomer solution and arrive the minimum content of control Raolical polymerizable easily, and monomer solution can be controlled by the principle of first outer in the time of can guaranteeing deoxygenation, making does not have the reaction monomers aqueous solution that is detained in the process of deoxygenation, reduce the possibility that polyreaction takes place in advance.
Pipeline of the present invention also can install screw-blade additional or fill the weighting material that increases mixed effect, improves the degree of mixing of rare gas element and monomer solution, and the remaining monomer that reduces super absorbent resin inside is had excellent effect.
Rare gas element loss gradually in follow-up manufacturing process that the present invention uses, and the pH value of finished product is neutrality or subacidity, so can not cause the infringement of human body when contacting with human body, and rare gas element can not cause the pollution to environment yet;
The present invention can use cheap piping material and rare gas element and device structure simple, therefore can effectively reduce manufacturing cost;
Low remaining monomeric super absorbent resin of the present invention can not cause suction force to reduce and not have the phenomenon of luming after the moisture absorption yet.
Though the present invention with aforesaid preferred embodiment openly as above; but be not in order to limit the present invention; any those of ordinary skill in the art; without departing from the spirit and scope of the present invention; when can doing a little change and modification, therefore scope of patent protection of the present invention must be looked this specification sheets appending claims person of defining and is as the criterion.
Claims (10)
1. a powdery, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin is characterized in that this method comprises at least:
Add internal crosslinking agent in more than neutralization ratio 50 molar percentages contain the acidic group monomer solution after, add the pipeline of rare gas element by inside, carry out Raolical polymerizable again and get gelinite, wherein this contains the mixture that the acidic group monomer is selected from vinylformic acid, methacrylic acid, 2-allylamine-2-methyl propane sulfonic acid or above-mentioned group, and this contains the water-soluble high-molecular compound that the acidic group monomer solution contains 0～5 weight percent; And
With this gelinite with 100 ℃ to 250 ℃ dryings of temperature, pulverizing, screening, interpolation surface crosslinking agent, with 80 ℃ to 230 ℃ of temperature do heating surface handle and add the inert inorganic salt powder after become super absorbent resin.
2. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that this water-soluble high-molecular compound is the mixture of partly-hydrolysed or fully saponified polyvinyl alcohol, starch or starch derivative or above-mentioned group.
3. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that this internal crosslinking agent is to have the water-soluble cpds that two or more participate in the functional group of free radical reaction.
4. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that neutralizing this, to contain the used neutralizing agent of acidic group monomer solution be lithium hydroxide, sodium hydroxide, potassium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate or saleratus.
5. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that this pipeline is the pipeline that iron pipe, stainless steel tube, plastic lined piping or pipeline, static mixer or the connection that contains filler combine.
6. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that particle size distribution range is between 0.05 to 1 millimeter after the screening of this super absorbent resin.
7. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that this surface crosslinking agent is the mixture of polyvalent alcohol, polyethyleneglycol diglycidylether or alkylene carbonate or above-mentioned group.
8. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that this surface crosslinking agent adds scope between 0.005 to 5.0 weight percent.
9. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that this inert inorganic salt powder is the mixture of Tai-Ace S 150, aluminum oxide, magnesium oxide, calcium oxide, kaolin, silicon-dioxide, lime carbonate or magnesiumcarbonate or above-mentioned group.
10. powdery according to claim 1, water insoluble, the manufacture method that can absorb water liquid, urine or blood and containing low content residue monomer not reacted super absorbent resin, it is characterized in that, this inert inorganic salt powder, its interpolation scope is between 0.01 to 4.0 weight percent.
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| CN104788871A (en) * | 2015-04-16 | 2015-07-22 | 江门市高力依科技实业有限公司 | Preparation method of surface-treated super absorbent resin |
| CN108641045A (en) * | 2018-05-07 | 2018-10-12 | 浙江卫星新材料科技有限公司 | The preparation method of height water conservation super absorbent resin |
Citations (3)
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| US5866678A (en) * | 1992-12-25 | 1999-02-02 | Nippon Shokubai Co., Ltd. | Absorbent and method for production of absorbent resin |
| CN1383432A (en) * | 2000-06-21 | 2002-12-04 | 株式会社日本触媒 | Process for prodn. of water-absorbent resin |
| CN1391582A (en) * | 1999-11-20 | 2003-01-15 | 巴斯福股份公司 | Method for continuously producing cross-linked fine-particle geleous polymerizates |
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|---|---|---|---|---|
| US5866678A (en) * | 1992-12-25 | 1999-02-02 | Nippon Shokubai Co., Ltd. | Absorbent and method for production of absorbent resin |
| CN1391582A (en) * | 1999-11-20 | 2003-01-15 | 巴斯福股份公司 | Method for continuously producing cross-linked fine-particle geleous polymerizates |
| CN1383432A (en) * | 2000-06-21 | 2002-12-04 | 株式会社日本触媒 | Process for prodn. of water-absorbent resin |
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