CN101423576A - Method for making high water-absorbent resin - Google Patents
Method for making high water-absorbent resin Download PDFInfo
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- CN101423576A CN101423576A CNA2007101692230A CN200710169223A CN101423576A CN 101423576 A CN101423576 A CN 101423576A CN A2007101692230 A CNA2007101692230 A CN A2007101692230A CN 200710169223 A CN200710169223 A CN 200710169223A CN 101423576 A CN101423576 A CN 101423576A
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Abstract
The invention relates to a method for manufacturing resin with high hydroscopic property. The hygroscopic resin is obtained through superposition reaction within the range that the neutralization ratio is between 45 and 85 mol percent and the concentration of an unsaturated monomer aqueous solution is between 20 and 55 weight portions; and the hygroscopic resin is subjected to coating treatment through a surface crosslinking agent and an inorganic salt aqueous solution to obtain the resin with high hydroscopic property. The resin has the characteristics that the resin shows good physical property, has low dust yield and reduces agglomeration after moisture absorption.
Description
Technical field
Super absorbent resin is applied 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 the waterproof outer coating in the cable and sanitary product such as diaper, women sanitary articles, deserted wiping cloth etc.
Background technology
Absorbent resin is applied 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 the waterproof outer coating in the cable and sanitary product such as diaper, women sanitary articles, deserted wiping cloth etc.
The composition material of present known super absorbent resin has starch-vinyl cyanide (hydrolyzed starchacrylonitrile) graftomer (Japan's special permission communique clear 49 (1974)-43 of meeting the water decomposition type in the art, 395), neutral starch-acrylic acid-grafted polymkeric substance (the open communique clear 51 (1976)-125 of Japanese Patent, 468), saponification ethene acetic acid-propylene ester copolymer (the open communique clear 52 (1977)-14 of Japanese Patent, 689), hydrolyzed acrylonitrile multipolymer or acrylamide copolymer (Japanese patent gazette clear 53 (1978)-15,959), and partly and polyacrylic acid (Japanese Patent discloses communique clear 55 (1980)-84,304) etc.Wherein in the raw material of starch-acrylonitrile grafting polymkeric substance,, can cause the decomposition of putrescibility, so can't preserve for a long time because contain natural polymer-starch; Moreover, its manufacture method is very complicated again, so the preparation method of super absorbent resin all accounts for maximum partly also economical with the super absorbent resin that uses vinylformic acid and acrylate to carry out the crosslinking polymerization gained now, it is former because raw material-the vinylformic acid of acrylate multipolymer can be rapidly by buying on the market, and the super absorbent resin that makes has high water-retaining capacity, and the decomposition that has cheap for manufacturing cost and tool economic benefit and can not cause putrescibility, so become the super absorbent resin that generalizes most.
The method that polymeric acrylic acid and acrylate form super absorbent resin can be made by several known methods, as aqueous solution polymerization reaction, anti-phase suspension polymerization, emulsion polymerization reaction or with the monomer sprinkling or be coated on methods such as carrying out polyreaction on the fibre substrate.In these methods, anti-phase suspension polymerization and emulsion polymerization reaction must use organic solvent, but if the temperature when effectively controlled polymerization reacts, organic solvent will cause the temperature of reactive system and the increase of pressure, produce phenomenon on fire even explosion caused, and then threaten operation site personnel's safety and cause problem of environmental pollution, its finished product also has the doubt of organic solvent residual.
The particle of super absorbent resin is because of having the characteristic of high moisture absorption, no matter in the process that stores or be used for making sanitary product, can absorb airborne aqueous vapor and cause resin to stick together each other, thereby can't be smoothly from quantitatively charging the amount of the confession equipment of successive, in the feasible sanitary product that produces, the content inequality of super absorbent resin, therefore, agglomeration problems becomes a new research tendency after the moisture absorption of improvement super absorbent resin.
So far still have many scientists to be agglomeration problems effort after the moisture absorption that reduces super absorbent resin always, the method of agglomeration problems is developed after the moisture absorption of the existing many reduction super absorbent resins of skill circle, the sex change silicone oil that has amino or epoxy group(ing) as use mixes (international publication WO95/33558) with absorbent resin, add specific surface area 50m
2The hydrophobic silica (Japanese kokai publication sho 56-133028) in absorbent resin that the above median size 0.05um of/g is following, and there are the Silicon dioxide, hydrate of use, hydrated alumina or titanium oxide hydrate to make an addition to (Japanese kokai publication sho 59-80459) in the absorbent resin in addition, also have and use the cationic interfacial agent with at least 12 alkyl to be sprayed on after absorbent resin surface (Japanese kokai publication sho 61-69854) carries out surface treatment, the organic compound powder (as calcium stearate) that adds high melting-point again goes to reach and reduces agglomeration problems after the absorbent resin moisture absorption.
Above-mentioned use has the sex change silicone oil of amino or epoxy group(ing), because viscosity is higher, difficulty when causing cleaning easily, in addition, use the meeting of hydrophobic silica in absorbent resin to reduce the absorption rate of absorbent resin, and use Silicon dioxide, hydrate, hydrated alumina or titanium oxide hydrate to make an addition to the method for absorbent resin, though can not reduce absorption rate, but,, be easy to generate the problem of dust because this type of hydrate is by the infusion of inorganic salt powder institute; Utilize cationic interfacial agent to be sprayed on the method on absorbent resin surface, then can reduce the absorption multiplying power of absorbent resin.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of super absorbent resin.
For achieving the above object, the manufacture method with the respond well super absorbent resin of agglomeration resistance after low powder amount and the moisture absorption provided by the invention, this method comprises at least:
(a) use a kind of water-soluble unsaturated monomer that contains vinylformic acid (salt) and acrylamide (salt), neutralization ratio is in 45 to 85 moles of % scopes, and the concentration of unsaturated monomer solution overlaps reaction in 20 to 55 weight part scopes and generates gelinite;
(b) with gelinite, through 100 ℃ to 180 ℃ temperature warm air dryings, pulverizing, one-tenth particle;
(c) with surface crosslinking agent and inorganic salt solution coating processing;
(d) be treated to the manufacture method of the super absorbent resin of feature again with 80 ℃ to 230 ℃ heating surface of temperature.
The manufacture method of described super absorbent resin, wherein, the particle diameter after the gelinite chopping oven dry is preferable with 0.05mm to 1.50mm scope.
The manufacture method of described super absorbent resin, wherein, the inorganic salt of inorganic salt solution are Tai-Ace S 150, lime carbonate, magnesium oxide, zeolite, kaolin, titanium dioxide or SiO 2 powder, can use or merge two or more mixing separately and use.
The manufacture method of described super absorbent resin, wherein, inorganic salt solution adds scope between weight percent 0.01wt% to 10.0wt%.
The manufacture method of described super absorbent resin, wherein, inorganic salt solution viscosity scope between 10 to 1400cPs.
The manufacture method of described super absorbent resin, wherein, inorganic salt solution its pH value scope under acidic conditions is not less than 2 and be not more than 6.
The manufacture method of described super absorbent resin, wherein, inorganic salt solution its pH value scope under nonacid condition is not less than 7 and be not more than 12.
The manufacture method of described super absorbent resin, wherein, its pH value of inorganic salt solution is adjusted employed acid solution, can be the organic acids such as formic acid, vinylformic acid and acetic acid of carbon containing, hydrogen, oxygen or sulphur, or be mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, still can use other to have the water-soluble acid solution that two keys are closed in insatiable hunger in addition, as methacrylic acid, Malin's acid, fumaric acid, 2-allylamine-2-methyl propane sulfonic acid etc., this acid solution can be used alone or multiple mixing is used.
The manufacture method of described super absorbent resin, wherein, its pH value of inorganic salt solution is adjusted employed alkali lye, can be the oxyhydroxide or the carbonate compound of alkali metal group in the periodictable or alkaline earths, as sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniac compounds etc.; This alkali lye can be used alone or multiple mixing is used.
The manufacture method of super absorbent resin provided by the invention, this method at least also comprises:
(a) use a kind of water-soluble unsaturated monomer that contains vinylformic acid (salt) and acrylamide (salt), neutralization ratio is in 45 to 85 moles of % scopes, and the concentration of unsaturated monomer solution overlaps reaction generation gelinite in the scope of 20 to 55 weight parts;
(b) gelinite is through 100 ℃ of warm air dryings to 180 ℃ of temperature, pulverizing, one-tenth particle;
(c) with after the surface crosslinking agent coating processing;
(d) handle with 80 ℃ to 230 ℃ temperature heating surface;
(e) with the inorganic salt solution coating processing be the preparation method of high-hydroscopicity resin of feature again.
Embodiment
Make super absorbent resin of the present invention, be to carry out polyreaction to cause free radical, what it was required contains the acidic group monomer except that vinylformic acid, still can use other to have the water-soluble monomer that two keys are closed in insatiable hunger, as methacrylic acid, Malin's acid, fumaric acid, 2-allylamine-2-methyl propane sulfonic acid etc.The monomeric specific limited of selecting for use is not used a kind of only, also can merge multiple monomer uses together, also can depending on the circumstances or the needs of the situation add and have other hydrophilic monomer of unsaturated double-bond, as acrylamide, Methacrylamide, vinylformic acid 2-alkyl ethyl ester, methacrylic acid 2-alkyl ethyl ester, methyl acrylate, ethyl propenoate, the dimethylamine acrylic acid-acrylamide, (United States Patent (USP)s 4 such as propylene dichloride amide group TMA (TriMethylAmine), 057, No. 521,4,062, No. 817,4,525, No. 527,4,286, No. 082 and 4,295, No. 987), but addition is a principle with the rerum natura of not destroying super absorbent resin.
Carry out Raolical polymerizable before, monomer solution concentration should be controlled between weight percent 20wt% to 55wt%, proper concn is between the 30wt% to 45wt%, concentration is when weight percent 20wt% is following, the hydration colloid is too soft and the unfavorable mechanical workout of stickiness arranged after the polymerization, add concentration more than weight percent 55wt%, difficult allotment problem is arranged during too near saturation concentration and react that too fast response heat is too much wayward.
Contain the monomeric carboxylic acid group of acidic group and should partly neutralize, make to be neutrality or subacidity with the pH value of control finished product.Neutralizing agent is the oxyhydroxide or the carbonate compound of alkali metal group or alkaline earths in the periodictable, as: sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniac compounds; Neutralizing agent can be used alone or multiple mixing is used.Contain the monomeric carboxylic acid group of acidic group and partly be neutralized into sodium salt or sylvite or ammonium salt, in and the concentration molar percentage be 45mol% to 85mol%, be preferably 50mol% to 75mol%, in and the concentration molar percentage be that the pH value of 45mol% finished product when following is understood on the low side, in and the concentration molar percentage be that the pH value of 85mol% finished product when above is understood higher, finished product pH value is non-when being neutrality or subacidity, if all not too suitable, also more dangerous when contacting with human body accidentally.
Also can add water-soluble high-molecular compound to reduce cost at the preceding monomer solution that carries out Raolical polymerizable, these water-soluble high-molecular compounds are as partly saponification or fully saponified polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid, polyacrylamide, starch or starch derivative such as methylcellulose gum, the vinylformic acid methylcellulose gum, polymkeric substance such as ethyl cellulose.The molecular weight of these water-soluble high-molecular compounds is not particularly limited, and wherein preferable water-soluble high-molecular compound is a starch, partly saponification or fully saponified polyvinyl alcohol etc. can be used alone or as a mixture.It is 0 to 20wt% that super absorbent resin contains these suitable weight percents that add water-soluble high-molecular compounds, but with 0 to 10wt% preferable, 0 to 5wt% is good especially, and adding when surpassing 20wt% to influence rerum natura, makes the rerum natura variation.
Before carrying out Raolical polymerizable, should add the Raolical polymerizable linking agent earlier in unreacted monomer solution, the optional usefulness of this Raolical polymerizable linking agent has the compound of two or more unsaturated double-bonds, as N, N '-two (2-propenyl) amine, 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, 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), as the sorbyl alcohol polyglycidyl ether, the polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, the Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers etc.After carrying out free radical reaction, just can make super absorbent resin have suitable degree of crosslinking and make the super absorbent resin colloid that suitable processibility be arranged.The Raolical polymerizable linking agent can be used alone or mixed use of two or more.Raolical polymerizable linking agent suitable additive amount is (is benchmark with the total solid of reactant) between weight percent 0.001wt% to 5wt%, more suitable consumption weight percent is between 0.01wt% to 3wt%, additive capacity hydrated body after the following polymerization of weight percent 0.001wt% is too soft and the unfavorable mechanical workout of stickiness arranged, additive capacity is too low in the above water-absorbent of weight percent 5wt%, reduces resin property.
Polyreaction is begun by the decomposition generation free radical of Raolical polymerizable initiator.Free radical starting agent can be selected thermolysis type initiator for use, the thermolysis type initiator that is fit to has superoxide, as hydrogen peroxide, two-Di tributyl superoxide, peroxidation acid amides or persulphate (ammonium salt, an alkali metal salt) etc., and azo-compound is as two (N, N-two the stretches the methyl NSC 18620) dihydrochlorides of two (2-amidine propane) dihydrochloride, the 2.2 '-azo-groups of 2.2 '-azo-group; Also can use reductive agent, making becomes the oxidation-reduction type initiator, as acid accumulator sulfite, thiosulphate, xitix or ferrous salt; Or with oxidation-reduction type initiator and thermolysis type initiator merging use, at first the redox initiator reacts the generation free radical earlier, when radical transfer is the carrying out of initiated polymerization to monomer, can discharge a large amount of heats when carrying out owing to polyreaction elevates the temperature, when temperature arrives the decomposition temperature of thermolysis type initiator, can cause the decomposition of second section thermolysis type initiator again, and whole polyreaction is more attained in fully.The general suitable consumption of Raolical polymerizable initiator be weight percentage for 0.001wt% to 10wt% (with in and acrylate weight be benchmark), more suitable consumption is then between 0.1wt% to 5wt%, when operating weight per-cent 0.001wt% is following, react too slow unfavorable economic benefit, when operating weight per-cent 10wt% is above, react that too fast response heat is wayward.
Produce the super absorbent resin of polyacrylic, its polyreaction generally is with in the conventional batch reaction vessel, or on the conveyer belt type reactor, react, the super absorbent resin of reaction gained, utilize pulverizer to be cut into the following little gelinite of diameter 20mm earlier, better below the diameter 10mm, screen again.
Fixedly the gelinite diameter of particle diameter is to be advisable below the 2.00mm in screening, and with preferable between 0.05mm to 1.50mm, particle diameter is then sent pulverizer again back to greater than the gelinite of 2.00mm and shredded once more.The following gelinite of particle diameter 0.03mm is dried, during pulverization process, easily produce high finished product fine powder amount, when the above gelinite of particle diameter 2.00mm is dried, easily because thermal conduction effect is not good, cause finished product higher, the shortcoming that rerum natura is performed poor at remaining monomer.According to the present invention, the particle size dispersion of acrylate gelinite is narrow more, not only can make gelinite rerum natura performance after oven dry reach optimum regime, and help controlling the time and the temperature of oven dry, dries after screening is finished again.
Bake out temperature is dried for 100 ℃ to 180 ℃ with temperature and is advisable, bake out temperature drying time below 100 ℃ is too of a specified duration, do not have an economic benefit, bake out temperature is dried more than 180 ℃ and is made linking agent carry out crosslinking reaction ahead of time, make in the subsequent drying process, can't effectively remove remaining monomer because of degree of crosslinking is too high, reach and reduce remaining monomeric effect.
Pulverize, screen fixedly particle diameter after the drying, carry out the surface crosslinking agent coating processing again.Fixedly particle diameter is to be advisable between 0.06mm to 1.00mm in screening, and with preferable between 0.10mm to 0.850mm, the following fine powder of particle diameter 0.06mm improves the finished product dust, and the above particle of particle diameter 1.00mm makes the finished product rate of water absorption slack-off.According to the present invention, the particle size dispersion of acrylate polymer is narrow more good more.
During the coating processing surface crosslinking agent, the addition manner of surface crosslinking agent is the kind according to surface crosslinking agent, be divided into surface crosslinking agent and directly add, or the interpolation of the furnishing surface crosslinking agent aqueous solution, 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 to get final product, and be wherein preferable with methyl alcohol, ethanol.
When surface crosslinking agent adds, can add the inert inorganic salt powder in the High hydrophilous resin, disperse to help solution.Its inert inorganic salt powder can be Tai-Ace S 150 or silicon-dioxide, or aluminum oxide, or magnesium oxide etc. or its mixture.Wherein preferable with Tai-Ace S 150, silicon-dioxide.The usage of inert inorganic salt powder can be used or merge two or more mixing separately and use.The inert inorganic salt powder adds scope between weight percent 0.005wt% to 10.0wt%, and is wherein preferable with 0.01wt% to 4.0wt%.
After carrying out the surface crosslinking agent coating processing,, make the surface crosslinking agent can be evenly and carry out crosslinking reaction fast, and make internal crosslinking agent carry out crosslinking reaction and reach effect of the present invention again to carry out heat treated in 80 ℃ to the 230 ℃ scopes.Thermal treatment temp cross-linking reaction time below 80 ℃ is too of a specified duration, do not have an economic benefit, thermal treatment temp more than 230 ℃ the easy deterioration of resin influence quality, heat treatment time was advisable with 2 minutes to 180 minutes, do the thermal treatment temp adjustment according to the surface treatment effect of desiring to acquire, thermal treatment temp height then heat treatment time is short, and when the thermal treatment temp temperature was hanged down, then the thermal treatment temp time was long.
Dry, be easy to generate during pulverization process high finished product fine powder dust quantity at its screening of the intermediate process of above-mentioned manufacturing super absorbent resin less than the gelinite below the 0.03mm particle diameter, disappearances such as particle diameter does not then cause finished product higher at remaining monomer because of thermal conduction is good more than 2.00mm easily, and the rerum natura performance is bad.The inventor etc. are through secular test and discover and utilize surface crosslinking agent and inorganic salt solution to spray or be coated on the super absorbent resin surface, or inorganic salt solution is coated on the super absorbent resin surface of finishing surfaction, again via the heating surface treating processes, the inorganic salt powder is attached to and the super absorbent resin surface fully completely, reduce the powder amount of production plant area and super absorbent resin finished product, reduce influence environment and organism.
Utilize in the process that inorganic salt solution is sprayed on absorbent resin this, whether its solution sprays easily is an epochmaking key, if the viscosity of its solution is too high, be difficult in the process of spraying, being dispersed evenly to the absorbent resin surface, to make that the rerum natura performance of finished product is relatively poor behind the upgrading agglomeration resistance, moreover the viscosity of inorganic salt solution is to change along with the change of pH value, when the pH value 6 between 7 the time, viscosity can be more of the same type inorganic salt solution promote several times and even hundreds of times, reach 200cPs, even more than the 1400cPs, thereby cause in the process of sprinkling, inorganic salt solution can't be dispersed evenly to the surface of absorbent resin.
Adjust the acid solution of the pH value of inorganic salt solution, can be the organic acid of formic acid, vinylformic acid and the acetic acid etc. of carbon containing, hydrogen, oxygen or sulphur, or be the mineral acid of hydrochloric acid, sulfuric acid, nitric acid etc., still can use other to have the water-soluble acid solution that two keys are closed in insatiable hunger in addition, as: methacrylic acid, Malin's acid, fumaric acid, 2-allylamine-2-methyl propane sulfonic acid etc., its acid solution can be used alone or multiple mixing is used.And adjust the alkali lye of the pH value of inorganic salt solution, can be the oxyhydroxide or the carbonate compound of alkali metal group in the periodictable or alkaline earths, as sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniac compounds; This alkali lye can be used alone or multiple mixing is used.
Foundation inorganic salt solution used in the present invention is that the inorganic salt powder of Tai-Ace S 150, sal epsom, aluminum oxide, magnesium oxide, zinc oxide, lime carbonate, calcium phosphate, barium phosphate, diatomite, weak soil, clay, talcum powder, zeolite, kaolin, swollen soil, activated carbon, silicon-dioxide, titanium dioxide mixes the aqueous solution that is generated with water, and the inorganic salt powder can use or merge two or more mixing separately and use.The viscosity scope of inorganic salt solution is between 10 to 1400cPs, and the interpolation scope is between weight percent 0.01wt% to 20.0wt%, and is wherein preferable with 0.01wt% to 10wt%.The size of particles of inorganic salt powder preferably is not more than 10mm, and suitable size is below the 0.6mm.Employed pH value scope is 2 to 6 when acidity for inorganic salt solution, and employed pH value scope is between 7 to 12 when nonacid.Absorbent resin and inorganic salt solution can mix in mixing device.Used mixing device must can produce big mixing force, makes mixing full and uniform.Be applicable to that mixing device of the present invention can be V-type mixing tank, column mixer, high-speed stirring mixer, helical mixer, fluidized bed mixer, double arm kneading mixer, both arms cone mixer, ribbon blender, close wall type mixing tank, pulverize kneader, impeller and screw extrusion press.
Via the super absorbent resin of manufacturing of the present invention,,, can more be applicable to the sanitary product of various types, the water-retaining agent that agricultural is used and food fresh keeping is used again so can reduce influence to organism and environment owing to have the characteristic of low powder amount.
Be water absorbent rate under the pressure that shows super absorbent resin of the present invention, the present invention utilizes pressurized to absorb heavy (pressure load: 20g/cm
2) measure, the pressurized absorbed dose is to measure according to the method described in the 7th page in the European patent 0339461 A specification sheets; The super absorbent resin of initial weight is placed in the right cylinder of sieve shading portion, to powder 20g/cm in addition
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, will survey suction weight again with the weight of institute's value divided by super absorbent resin, promptly get pressurized absorption tuple value.
Confining force of the present invention is to average after utilizing the tea bag test method determination and removing maximum and Schwellenwert with five measurements; The super absorbent resin of 0.2g is contained in the tea bag, and was soaked in 0.9% sodium chloride aqueous solution 20 minutes, the tea bag after then this being soaked places whizzer (diameter 23cm, rotating speed 1400rpm) weighing after centrifugal three minutes.The numerical value of gained deducts not earlier, and the preceding blank group tea bag heavy (with the same steps as operation) of filling super absorbent resin heavily promptly gets confining force numerical value divided by polymkeric substance again.
The judgement of caking effect after the moisture absorption of the present invention, be to utilize 3.0 gram super absorbent resins, insert in the culture dish of 6 centimeters of diameters, culture dish is put into the bottom contain 300mL water purifying air extractor (vacuum desiccator), and utilize off-gas pump that pressure is evacuated to 200mmHg and bled 1 minute, close off-gas pump, after taking out culture dish and slow Rotate 180 degree after 7 minutes, weigh the super absorbent resin (W) that remains in the culture dish with analytical balance, agglomeration resistance is respond well after the W value restrains less than 0.4, represents moisture absorption, W value circle is between the 1.0-0.4 gram, after the expression moisture absorption agglomeration resistance effect still can, when W value greater than 1.0 grams, represent moisture absorption after the agglomeration resistance effect bad.
Powder amount of the present invention is in enclosed space, apart from bottom level is that a funnel is placed at the 60cm place, and utilize dividing plate to cover funnel bottom, the 100g absorbent resin is positioned in the funnel, opens dividing plate, absorbent resin is fallen, utilize dust gauge HAZ-DUST HD-1100 type instrument, scan method with laser light and measure dust concentration, and, average behind removal maximum and the Schwellenwert with five measurements.
Below with embodiment the present invention is described; But claim of the present invention and technical scope are not limited by these embodiment.
Embodiment one
1) gets in the 500c.c Conical flask that 48% aqueous sodium hydroxide solution 218.7g slowly adds 270g vinylformic acid and 291.6g water, sodium hydroxide/acrylic acid dropping ratio is in 0.85 to 0.95 scope, the dropping time is 2 hours, and keeps bottle temperature of interior neutralization reaction system in 20 ℃ to 40 ℃ scopes; Get the monomer concentration 42wt% aqueous solution this moment, and wherein 70mol% (mol ratio) vinylformic acid partly neutralizes and is sodium acrylate.
2) add the N of 0.414g again, N '-methyne bisacrylamide is in water-soluble unsaturated monomer solution, and holding temperature is in about 20 ℃.
3) add the 0.144g hydrogen peroxide, 1.8g sodium bisulfite and 1.8g ammonium persulphate are with initial action.
4) utilize the cut pulverizer that reacted gelinite is shredded, and to filter out size be the following gelinite of 2mm diameter.
5) with 130 ℃ of temperature dryings 2 hours; Utilize fixedly particle diameter of screen cloth screening 0.1mm～0.85mm, get the powdery super absorbent resin.
6) weigh this super absorbent resin 100g, add silicon-dioxide/water=1/9 (weight ratio) solution 4.0g (viscosity=40cPs, pH value=5.0), to be mixedly add ethylene carbonate/water/methyl alcohol=1/1/1 (weight ratio) solution 3.9g again after evenly, with 200 ℃ of temperature heat treated 15 minutes, after the cooling, promptly get high-performance high absorbent resin, the mensuration confining force is 31.2g/g, 20g/cm
2Water absorbent rate 29.6g/g under the pressure, W value=0.20g (agglomeration resistance is respond well after the moisture absorption), powder amount 0.72mg/m
3
Embodiment two
Weigh 100g super absorbent resin (name of an article: platform speed is protected BC286LE), add silicon-dioxide/water=1/9 (weight ratio) solution 4.0g (viscosity=40cPs, pH value=5.0), the mensuration confining force is 30.4g/g, 20g/cm
2Water absorbent rate 29.2g/g under the pressure, W value=0.11g (agglomeration resistance is respond well after the moisture absorption), powder amount 0.53mg/m
3
Embodiment three
Repeat embodiment two, but super absorbent resin is used the name of an article instead: platform speed is protected BC283, adds silicon-dioxide water=1/9 (weight ratio) solution 4.0g (viscosity=40cps pH value=5.0), and the mensuration confining force is 30.5g/g, 20g/cm
2Water absorbent rate 29.4g/g under the pressure, W value=0.07g (agglomeration resistance is respond well after the moisture absorption), powder amount 0.42mg/m
3
Embodiment four
Repeat embodiment two, adding silicon-dioxide water is silicon-dioxide/water=2/8 (weight ratio) solution 2.0g (viscosity=90cPs, pH value=11), and the mensuration confining force is 30.1g/g, 20g/cm
2Water absorbent rate 29.1g/g under the pressure, W value=0.09g (agglomeration resistance is respond well after the moisture absorption), powder amount 0.42mg/m
3
Embodiment five
Repeat embodiment two, but its silicon-dioxide is used kaolin/water=2/8 (weight ratio) solution 2.5g (viscosity=142cPs, pH value=8.5) instead, the mensuration confining force is 29.8g/g, 20g/cm
2Water absorbent rate 28.9g/g under the pressure, W value=0.14g (agglomeration resistance is respond well after the moisture absorption), powder amount 0.37mg/m
3
Embodiment six
Repeat embodiment four, the addition of its silicon-dioxide aqueous solution is increased to 6.0g (viscosity=90cPs, pH value=11) by 2.0g, and the mensuration confining force is 28.9g/g, 20g/cm
2Water absorbent rate 28.7g/g under the pressure, W value=0.09g (agglomeration resistance is respond well after the moisture absorption), powder amount 0.11mg/m
3
Comparative example one
Repeat embodiment two, but add SiO 2 powder 0.4g earlier, to be mixed evenly after, add Sorbitol Powder/water=1/9 (weight ratio) solution 3.8g (viscosity=20cps, pH value=7.4) again, the mensuration confining force is 29.4g/g, 20g/cm
2Water absorbent rate 28.3g/g under the pressure, W value=0.81g (after the moisture absorption agglomeration resistance effect still can), powder amount 6.71mg/m
3
Comparative example two
Repeat embodiment two, add kaolin powder 0.4g earlier, to be mixed evenly after, add Sorbitol Powder/water=1/9 (weight ratio) solution 3.8g (viscosity=20cPs, pH value=7.4) again, the mensuration confining force is 27.2g/g, 20g/cm
2Water absorbent rate 26.3g/g under the pressure, W value=0.96g (after the moisture absorption agglomeration resistance effect still can), powder amount 8.44mg/m
3
Comparative example three
Repeat comparative example one, it adds Sorbitol Powder/water and uses polyoxyethylene glycol (PEG-8000)/water=1/9 (weight ratio) solution instead, and the mensuration confining force is 26.3g/g, 20g/cm
2Water absorbent rate 24.1g/g under the pressure, W value=0.92g (after the moisture absorption agglomeration resistance effect still can), powder amount 9.16mg/m
3
Comparative example four
Repeat embodiment two, but its silicon-dioxide changes silicon-dioxide/water=1/9 (weight ratio) solution 4.0g (viscosity=240cPs, pH value=6.4) into, the mensuration confining force is 27.4g/g, 20g/cm
2Water absorbent rate 25.1g/g under the pressure, W value=0.95g (after the moisture absorption agglomeration resistance effect still can), powder amount 10.12.mg/m
3
Comparative example five
Repeat embodiment two, but its silicon-dioxide changes kaolin/water=1/9 (weight ratio) solution 6.0g (viscosity=410cPs, pH value=6.7) into, the mensuration confining force is 26.2g/g, 20g/cm
2Water absorbent rate 24.3g/g under the pressure, W value=10.66g (after the moisture absorption agglomeration resistance effect still can), powder amount 14.14mg/m
3
Claims (10)
1, a kind of manufacture method with the respond well super absorbent resin of agglomeration resistance after low powder amount and the moisture absorption, this method comprises at least:
(a) use a kind of water-soluble unsaturated monomer that contains vinylformic acid (salt) and acrylamide (salt), neutralization ratio is in 45 to 85 moles of % scopes, and the concentration of unsaturated monomer solution overlaps reaction in 20 to 55 weight part scopes and generates gelinite;
(b) with gelinite, through 100 ℃ to 180 ℃ temperature warm air dryings, pulverizing, one-tenth particle;
(c) with surface crosslinking agent and inorganic salt solution coating processing;
(d) be treated to the manufacture method of the super absorbent resin of feature again with 80 ℃ to 230 ℃ heating surface of temperature.
2, the manufacture method of super absorbent resin according to claim 1, wherein, the particle diameter after the gelinite chopping oven dry is with 0.05mm to 1.50mm scope.
3, the manufacture method of super absorbent resin according to claim 1, wherein, the inorganic salt of inorganic salt solution are Tai-Ace S 150, lime carbonate, magnesium oxide, zeolite, kaolin, titanium dioxide or SiO 2 powder, can use or merge two or more mixing separately and use.
4, the manufacture method of super absorbent resin according to claim 1, wherein, inorganic salt solution adds scope between weight percent 0.01wt% to 10.0wt%.
5, the manufacture method of super absorbent resin according to claim 1, wherein, inorganic salt solution viscosity scope between 10 to 1400cPs.
6, the manufacture method of super absorbent resin according to claim 1, wherein, inorganic salt solution its pH value scope under acidic conditions is not less than 2 and be not more than 6.
7, the manufacture method of super absorbent resin according to claim 1, wherein, inorganic salt solution its pH value scope under nonacid condition is not less than 7 and be not more than 12.
8, the manufacture method of super absorbent resin according to claim 1, wherein, its pH value of inorganic salt solution is adjusted employed acid solution, organic acid for formic acid, vinylformic acid and the acetic acid of carbon containing, hydrogen, oxygen or sulphur, or be the mineral acid of hydrochloric acid, sulfuric acid, nitric acid, still can use other to have the water-soluble acid solution that two keys are closed in insatiable hunger in addition, as methacrylic acid, Malin's acid, fumaric acid, 2-allylamine-2-methyl propane sulfonic acid, this acid solution can be used alone or multiple mixing is used.
9, the manufacture method of super absorbent resin according to claim 1, wherein, its pH value of inorganic salt solution is adjusted employed alkali lye, for the oxyhydroxide or the carbonate compound of alkali metal group in the periodictable or alkaline earths, as sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniac compounds; This alkali lye can be used alone or multiple mixing is used.
10, a kind of manufacture method of super absorbent resin, this method comprises at least:
(a) use a kind of water-soluble unsaturated monomer that contains vinylformic acid (salt) and acrylamide (salt), neutralization ratio is in 45 to 85 moles of % scopes, and the concentration of unsaturated monomer solution overlaps reaction generation gelinite in the scope of 20 to 55 weight parts;
(b) gelinite is through 100 ℃ of warm air dryings to 180 ℃ of temperature, pulverizing, one-tenth particle;
(c) with after the surface crosslinking agent coating processing;
(d) handle with 80 ℃ to 230 ℃ temperature heating surface;
(e) with the inorganic salt solution coating processing be the preparation method of high-hydroscopicity resin of feature again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101692230A CN101423576A (en) | 2007-11-02 | 2007-11-02 | Method for making high water-absorbent resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101692230A CN101423576A (en) | 2007-11-02 | 2007-11-02 | Method for making high water-absorbent resin |
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| CN101423576A true CN101423576A (en) | 2009-05-06 |
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| CNA2007101692230A Pending CN101423576A (en) | 2007-11-02 | 2007-11-02 | Method for making high water-absorbent resin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311551A (en) * | 2010-07-05 | 2012-01-11 | 台湾塑胶工业股份有限公司 | Manufacturing method of high-hydroscopicity resin |
| CN105294920A (en) * | 2015-12-10 | 2016-02-03 | 湖北乾峰新材料科技有限公司 | Preparation method of high-water-absorption polymer |
| CN105561370A (en) * | 2015-04-28 | 2016-05-11 | 安徽省科晟生物科技有限公司 | Novel hemostatic material and preparation method thereof |
| CN105949391A (en) * | 2016-06-12 | 2016-09-21 | 山东诺尔生物科技有限公司 | Method for preparing special water-absorbing resin for adult diaper |
| CN115007122A (en) * | 2022-06-30 | 2022-09-06 | 东莞市鼎兴实业有限公司 | Drying agent and preparation method thereof |
| CN115418067A (en) * | 2022-09-09 | 2022-12-02 | 万华化学集团股份有限公司 | Preparation method and application of insoluble antibacterial super absorbent resin |
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2007
- 2007-11-02 CN CNA2007101692230A patent/CN101423576A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311551A (en) * | 2010-07-05 | 2012-01-11 | 台湾塑胶工业股份有限公司 | Manufacturing method of high-hydroscopicity resin |
| CN105561370A (en) * | 2015-04-28 | 2016-05-11 | 安徽省科晟生物科技有限公司 | Novel hemostatic material and preparation method thereof |
| CN105561370B (en) * | 2015-04-28 | 2019-02-15 | 安徽省科晟生物科技有限公司 | A kind of hemostatic material and preparation method thereof |
| CN105294920A (en) * | 2015-12-10 | 2016-02-03 | 湖北乾峰新材料科技有限公司 | Preparation method of high-water-absorption polymer |
| CN105949391A (en) * | 2016-06-12 | 2016-09-21 | 山东诺尔生物科技有限公司 | Method for preparing special water-absorbing resin for adult diaper |
| CN105949391B (en) * | 2016-06-12 | 2018-05-25 | 山东诺尔生物科技有限公司 | A kind of preparation method of the special water-absorbing resin of adult diaper |
| CN115007122A (en) * | 2022-06-30 | 2022-09-06 | 东莞市鼎兴实业有限公司 | Drying agent and preparation method thereof |
| CN115418067A (en) * | 2022-09-09 | 2022-12-02 | 万华化学集团股份有限公司 | Preparation method and application of insoluble antibacterial super absorbent resin |
| CN115418067B (en) * | 2022-09-09 | 2023-05-30 | 万华化学集团股份有限公司 | Preparation method and application of insoluble antibacterial super absorbent resin |
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