CN107722163B - Acrylic acid water-absorbent resin, water-absorbent resin with low soluble component and application thereof - Google Patents
Acrylic acid water-absorbent resin, water-absorbent resin with low soluble component and application thereof Download PDFInfo
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- CN107722163B CN107722163B CN201711098937.7A CN201711098937A CN107722163B CN 107722163 B CN107722163 B CN 107722163B CN 201711098937 A CN201711098937 A CN 201711098937A CN 107722163 B CN107722163 B CN 107722163B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract
The invention discloses a preparation method and a preparation method of acrylic acid water-absorbent resin and acrylic acid water-absorbent resin with low soluble component, which is prepared by copolymerizing acrylic acid and comonomer, wherein the comonomer comprises comonomer (I) and/or comonomer (II); the preparation method comprises the following steps: the acrylic acid water-absorbent resin described above or the acrylic acid water-absorbent resin obtained by the above-mentioned method is subjected to surface crosslinking treatment. The present invention provides a water-absorbent resin having a low soluble component, a production method and use thereof, and provides a water-absorbent resin having a low soluble component.
Description
Technical Field
The invention belongs to the technical field of preparation methods of water-absorbent resins, and particularly relates to an olefine acid water-absorbent resin, a water-absorbent resin with low soluble components and application of the olefine acid water-absorbent resin and the water-absorbent resin.
Background
The high molecular water-absorbing resin can absorb and maintain (even under pressure) hundreds or thousands of times of pure water or tens of times of normal saline, so that the high molecular water-absorbing resin is widely applied to the fields of sanitary materials such as baby diapers, female sanitary napkins, adult incontinence products, disposable mattresses in hospitals and the like, soil water retention, food preservation and the like, and is greatly convenient for daily life of people.
The performance requirements of superabsorbent resins (SAP) in the sanitary field of diapers, feminine napkins and the like have gone through three stages, from the initial simple emphasis on saturated liquid absorption of the superabsorbent resin to the emphasis on pressurized liquid absorption until products with low soluble components are currently required.
Reducing soluble components can be achieved by controlling the drying conditions in addition to the general method of increasing internal crosslinking agents. Patent CN102731802 describes a method of adding an initiator during granulation and drying water-absorbent resin particles by means of stepwise temperature control, the drying process being divided into a temperature rising zone, a constant temperature zone and a temperature lowering zone and water vapor being introduced into the constant temperature zone. The drying method has low soluble component in the product. However, the drying method has too low temperature in the heating area and the cooling area, and the drying efficiency is slow; and the temperature in the constant temperature area is 190 ℃, and the possibility of excessive drying of surface colloidal particles also exists. The method has complex flow and high energy consumption.
Disclosure of Invention
In order to make up for the defects in the prior art, the invention provides an acrylic water-absorbent resin and a preparation method thereof, and also provides a preparation method and application of the acrylic water-absorbent resin for preparing the water-absorbent resin with low soluble components.
In order to achieve the above object, the present invention adopts the following technical solutions:
the present invention provides, in a first aspect, an acrylic water-absorbent resin obtained by copolymerizing raw materials comprising acrylic acid and a comonomer comprising one or more of compounds having the following structural formulae (i) and (ii):
wherein, -R1or-R3Is hydrogen or methyl;
-R2or-R4Is an aliphatic alkane radical, preferably C1-C10An aliphatic hydrocarbon group of (a);
-X1or-X2The group capable of reacting with a carboxyl group is preferably a hydroxyl group or an epoxy group.
Preferably, the comonomer having formula (i) comprises one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, pentaerythritol monoacrylate; comonomers of formula (II) include allyl glycidyl ether and/or pentaerythritol monoallyl ether.
The second aspect of the present invention provides a method for producing the acrylic water-absorbent resin described above by solution polymerization or reversed-phase suspension polymerization of acrylic acid and a comonomer, or by employing a method comprising the steps of:
a) adding acrylic acid into alkali liquor to obtain a neutralized solution containing acrylic acid, acrylate and water; the alkali liquor is preferably sodium hydroxide solution;
b) adding a comonomer and an internal crosslinking agent into the neutralized liquid obtained in the step a), uniformly stirring, adding an initiator, and polymerizing to obtain the acrylic acid water-absorbent resin.
Preferably, the first preparation method described above in the present invention comprises the steps of:
a) adding acrylic acid into a sodium hydroxide solution to obtain a neutralized solution containing acrylic acid, sodium acrylate and water, wherein the mass percentage concentration of the sodium hydroxide solution is preferably 20-40%;
b) adding a comonomer and an internal crosslinking agent into the neutralized liquid obtained in the step a), uniformly stirring, adding an initiator, and polymerizing to obtain the acrylic acid water-absorbent resin.
The second preparation method described above in the present invention comprises the steps of:
a) cooling the acrylic acid aqueous solution to 0-10 ℃, then adding a comonomer and an internal crosslinking agent, stirring uniformly, adding an initiator, and polymerizing to obtain a polymerization reaction solution; preferably, the mass percentage concentration of the acrylic acid aqueous solution is 25-45%, more preferably 30-40%, and the polymerization reaction time is 1-8 hours, preferably 3-6 hours;
b) adding a sodium hydroxide aqueous solution into the polymerization reaction liquid obtained in the step a), and carrying out neutralization reaction to obtain acrylic acid water-absorbent resin; preferably, the mass percentage concentration of the sodium hydroxide aqueous solution is 20-40%;
the third preparation method of the present invention comprises the following steps:
a) dissolving a surfactant in a petroleum hydrocarbon solvent and cooling to 20-50 ℃; the petroleum hydrocarbon solvent may be, for example, petroleum ether, n-hexane, cyclohexane, toluene, etc., but the present invention is not limited thereto;
b) adding acrylic acid and a comonomer into a sodium hydroxide aqueous solution for neutralization reaction, cooling, and adding an initiator and an internal crosslinking agent to obtain a reaction solution; the mass percentage concentration of the sodium hydroxide aqueous solution is preferably 20-40%;
c) adding the reaction liquid into the petroleum hydrocarbon solvent dissolved with the surfactant obtained in the step a), stirring and mixing under an anaerobic condition, and carrying out prepolymerization to obtain a prepolymerized suspension; preferably, nitrogen is introduced to remove oxygen in the reaction system in the prepolymerization process, so that no oxygen participates in the reaction process, and the prepolymerization temperature is preferably 60-90 ℃;
d) cooling the pre-polymerized suspension to 10-30 ℃, and then adding reaction liquid with the same mass as that in the step c) for final polymerization to obtain the acrylic water-absorbent resin.
Preferably, the comonomer is added in an amount of 0.001 to 10%, preferably 0.01 to 1%, by mass of acrylic acid.
Preferably, the internal crosslinking agent used for preparing the acrylic water-absorbent resin is one or more of N, N-methylene bisacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diacrylate, polyethylene glycol diglycidyl ether, glycerol triacrylate, ethoxylated glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol triallyl ether, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate; the addition amount of the internal crosslinking agent is 0.05 to 0.8%, preferably 0.1 to 0.4% by mass of acrylic acid.
Preferably, the initiator used for preparing the acrylic acid water-absorbent resin is one or more of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide and di-tert-butyl peroxide, and preferably ammonium persulfate; the amount of the initiator added is 0.01 to 1%, preferably 0.1 to 0.4% by mass of acrylic acid.
The third aspect of the present invention provides a method for producing an acrylic water-absorbent resin having a low soluble component, wherein the acrylic water-absorbent resin or the acrylic water-absorbent resin produced by the method is subjected to a surface crosslinking treatment.
Preferably, the acrylic water-absorbent resin is subjected to crushing, drying, grinding, and sieving in this order before the surface crosslinking treatment step. In a specific embodiment, the drying temperature is 100-250 ℃, the drying time is 10-300min, and the acrylic acid water-absorbent resin is cut into resin sections with the diameter of 2-20 mm; further preferably, the drying temperature is 150-.
Preferably, the surface crosslinking treatment is spraying a surface crosslinking solution onto the surface layer of the acrylic water-absorbent resin, the surface crosslinking solution preferably containing water, a polyhydric alcohol and a surface crosslinking agent; the amount of the surface-crosslinking solution to be used is preferably 2 to 10%, preferably 2.5 to 6% by mass of the acrylic water-absorbent resin; the surface crosslinking treatment is preferably carried out at a temperature of 80 to 300 ℃ for 10 to 240min, more preferably at 100 ℃ to 200 ℃ for 30 to 60 min.
Preferably, the polyhydric alcohol comprises one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, diethylene glycol, triethylene glycol or 1, 4-butanediol; the amount of the polyhydric alcohol to be used is preferably 0.1 to 5%, more preferably 0.5 to 2% by mass of the acrylic water-absorbent resin.
Preferably, the surface cross-linking agent comprises one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene carbonate or propylene carbonate; the amount of the surface-crosslinking agent to be used is preferably 0.01 to 1%, more preferably 0.05 to 0.5% by mass of the acrylic water-absorbent resin.
Preferably, the mass of water in the surface cross-linking solution is 0.1 to 10%, preferably 1.0 to 6.0% of the mass of the acrylic water-absorbent resin.
The fourth aspect of the present invention provides a sanitary material comprising the acrylic acid water-absorbent resin having a low soluble component obtained by the above-mentioned method.
By adopting the technical scheme, the method has the following technical effects:
the invention obtains the water-absorbent resin with low soluble component by copolymerizing the carbon-carbon double bond which can generate free radical polymerization and the group which can react with carboxyl and the preparation method thereof.
Detailed Description
In order to better understand the present invention, the following examples are provided to further illustrate the content of the present invention.
The properties of the water absorbent resins in the following examples were measured by the following methods:
(1) liquid absorption rate
Weighing 0.2g of sample, accurately measuring the sample to 0.001g, recording the mass as m, pouring all the samples into a tea bag, sealing the tea bag, soaking into a beaker filled with 0.9% of physiological saline by mass for 30 min; then, the tea bag containing the sample is lifted out, suspended by a clamp, and dripped for 10min in a static state, and then the mass m1 of the tea bag containing the sample is weighed; finally, blank value measurement was performed using a tea bag without a sample, and the mass of the blank test tea bag was weighed and recorded as m 2.
The liquid absorption rate is (m1-m2)/m
(2) Centrifugal water retention
The tea bag with the sample having the above-described test absorbency was dehydrated under a centrifugal force condition of 250G for 3min, and then the mass of the tea bag with the sample was weighed and designated as m 3. Blank value determination was performed using tea bags without a sample, and the mass of the blank tea bag was weighed and recorded as m 4.
The centrifugal water retention rate is (m3-m4)/m
(3) Residual acrylic acid monomer content in the product
1.000g of super absorbent resin was weighed, placed in a 250mL beaker, added with 200mL of physiological saline, placed in a magnetic rotor, sealed with a sealing film, and placed on a magnetic stirrer to stir (the rotation speed was about 500 rpm). After 1 hour, the stirring was stopped, the mixture was allowed to stand for 10 minutes, the supernatant was filtered with a filter, and the filtrate was analyzed for the residual monomer content using high performance liquid chromatography.
High performance liquid chromatograph manufacturer: agilent; the model is as follows: type 1260
(4)0.3psi pressure imbibition factor
The used equipment is as follows: a. the inner diameter of the opening at two ends is 25mm, the outer diameter is 30mm, and a nylon net with 200 meshes is fixed at one end;
b. the outer diameter of the plastic piston is slightly smaller than 25mm, the plastic piston can be tightly connected with the plastic cylinder and can freely move up and down;
c. the weight is 100g of round weight;
d. the glass dish is internally provided with the porous plate, so that the plastic cylinder can be placed on the porous plate, does not contact the bottom of the glass dish and can freely absorb moisture.
The test method comprises the following steps: placing the glass dish on a platform, and pouring 0.9% physiological saline; weighing 0.16g of sample, and uniformly scattering the sample into the bottom of the cylinder; then, the plastic piston to which the weight was added to the plastic cylinder, and its mass was measured to be m 5. The plastic cylinder with the added sample was placed on a multi-well plate of a glass dish, and after 60 minutes, the plastic cylinder was lifted out of the glass dish, and when the mass of the plastic cylinder was measured to be m6 after water was dropped, the pressure suction ratio was (m6-m5)/0.16 at 0.3 psi.
(5) Soluble component content
In a 250mL beaker, 184.3g of a 0.9 wt% NaCl aqueous solution was weighed, and 1.00g of a super absorbent resin sample was added to the solution, and stirred for 16 hours to extract soluble components in the super absorbent resin sample. The extracted solution was filtered through a filter paper, and 50.0g of the obtained filtrate was weighed as a measurement filtrate. First, titration of a blank solution (0.9 wt% NaCl in water) was performed using 0.1mol/l naoh in water until pH 10; subsequently, by titration using a 0.1mol/L hydrochloric acid solution until the pH becomes 2.7, blank titration amounts of [ bhnaoh ], [ bHCl ] mL were obtained, respectively. The sample extracts were subjected to the same titration as described above to obtain [ NaOH ] and [ HCl ] mL of the titrated amounts, respectively. The soluble component content Ex and the degree of neutralization DN of the super absorbent resin sample can be calculated by the following formula, wherein Mw is the average molecular weight.
DN(％)＝100*([NaOH]-[bNaOH])/([HCl]-[bHCl])；
Mw＝72.06*(1-DN/100)+94.04*DN/100；
Ex(wt％)＝([HCl]-[bHCl])*0.1*Mw*184.3*100/(1000*1.0*50.0)
The preparation method of the present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
a) Dissolving 1027g of sodium hydroxide solid in 4960g of water in a dosing tank, then pouring an aqueous solution of sodium hydroxide into a jacketed reaction kettle with a stirrer, adding 2400g of acrylic acid, and controlling the temperature in the reaction kettle to be 80 ℃ to obtain a neutralized solution containing acrylic acid, sodium acrylate and water;
b) adding 3.6g of polyethylene glycol diacrylate (average molecular weight 523) and 0.24g of hydroxyethyl acrylate into the neutralized liquid obtained in the step a), uniformly stirring, then making the neutralized liquid in the reaction kettle flow into a polymerization tank, simultaneously adding 192g of prepared ammonium persulfate aqueous solution with the mass percentage concentration of 10 wt% into the neutralized liquid at the outlet of the reaction kettle, and carrying out polymerization reaction for 15min to obtain acrylic water-absorbent resin;
c) shearing the acrylic acid water-absorbent resin obtained in the step b) into colloidal particles with the size of 8mm in sequence, drying the colloidal particles in a drying oven at the temperature of 180 ℃ for 90min, and then grinding and screening the colloidal particles in sequence to obtain acrylic acid water-absorbent resin powder;
d) and c) based on the mass of the acrylic acid water-absorbent resin as 100g, adding 0.1g, 2g and 1g of water, glycol and ethylene glycol diglycidyl ether into the acrylic acid water-absorbent resin, preparing a surface cross-linking solution according to the proportion, uniformly spraying the surface of the acrylic acid water-absorbent resin obtained in the step c), wherein the using amount of the surface cross-linking solution is 3.1 percent of the mass ratio of the acrylic acid water-absorbent resin, the temperature of surface cross-linking treatment is 150 ℃, the time of the surface cross-linking treatment is 80min, and finally, drying in an oven at 150 ℃ for 80min to obtain the water-absorbent resin.
Example 2
a) Dissolving 1027g of sodium hydroxide solid in 4960g of water in a dosing tank, then pouring an aqueous solution of sodium hydroxide into a jacketed reaction kettle with a stirrer, adding 2400g of acrylic acid, and controlling the temperature in the reaction kettle to be 80 ℃ to obtain a neutralized solution containing acrylic acid, sodium acrylate and water;
b) adding 2.4g of polyethylene glycol diacrylate (average molecular weight 523) and 24g of hydroxybutyl acrylate into the neutralized liquid obtained in the step a), uniformly stirring, then making the neutralized liquid in the reaction kettle flow into a polymerization tank, simultaneously adding 24g of prepared 10 wt% ammonium persulfate aqueous solution into the neutralized liquid at the outlet of the reaction kettle, and carrying out polymerization reaction to obtain acrylic water-absorbent resin;
c) shearing the acrylic acid water-absorbent resin obtained in the step b) into colloidal particles with the size of 12mm in sequence, drying the colloidal particles in an oven at the temperature of 180 ℃ for 90min, and then grinding and screening the colloidal particles in sequence to obtain acrylic acid water-absorbent resin powder;
d) based on 100g of the mass of the acrylic acid water-absorbent resin, the addition amounts of water, glycerol and polyethylene glycol diglycidyl ether are 5g, 2g and 0.5g, a surface cross-linking solution is prepared according to the proportion, the surface of the acrylic acid water-absorbent resin obtained in the step c) is uniformly sprayed, the use amount of the surface cross-linking solution is 7.5 percent of the mass ratio of the acrylic acid water-absorbent resin, the temperature of surface cross-linking treatment is 80 ℃, the time of the surface cross-linking treatment is 150min, and finally the acrylic acid water-absorbent resin is dried in an oven at 180 ℃ for 80min to obtain the water-absorbent resin.
Example 3
a) Dissolving 640g of sodium hydroxide solid into 4960g of water in a dosing tank, then pouring an aqueous solution of sodium hydroxide into a jacketed reaction kettle with a stirrer, adding 2400g of acrylic acid, and controlling the temperature in the reaction kettle to be 80 ℃;
b) adding 9.6g of polyethylene glycol diacrylate (average molecular weight 523) and 12g of glycerol triacrylate into the neutralized liquid obtained in the step a), uniformly stirring, then making the neutralized liquid in the reaction kettle flow into a polymerization tank, simultaneously adding 96g of prepared tert-butyl hydroperoxide solution with the mass percentage concentration of 10 wt% into the neutralized liquid at the outlet of the reaction kettle, and obtaining acrylic acid water-absorbent resin after polymerization reaction;
c) shearing the acrylic acid water-absorbent resin obtained in the step b) into colloidal particles with the particle size of 10mm in sequence, drying the colloidal particles in a drying oven at the temperature of 200 ℃ for 10min, and then grinding and screening the colloidal particles in sequence to obtain acrylic acid water-absorbent resin powder;
d) based on 100g of the mass of the acrylic acid water-absorbent resin, adding 1g, 0.5g and 0.05g of water, glycerol and polyethylene glycol diglycidyl ether into the acrylic acid water-absorbent resin, preparing a surface cross-linking solution according to the proportion, uniformly spraying the surface of the acrylic acid water-absorbent resin obtained in the step c), wherein the using amount of the surface cross-linking solution is that the mass ratio of the acrylic acid water-absorbent resin is 1.55%, the temperature of surface cross-linking treatment is 80 ℃, the time of the surface cross-linking treatment is 150min, and finally, drying in an oven at 180 ℃ for 80min to obtain the water-absorbent resin.
Example 4
a) Dissolving 1027g of sodium hydroxide solid in 4960g of water in a dosing tank, then pouring an aqueous solution of sodium hydroxide into a jacketed reaction kettle with a stirrer, adding 2400g of acrylic acid, and controlling the temperature in the reaction kettle to be 80 ℃;
b) adding 3.6g of pentaerythritol triacrylate (average molecular weight 523) and 0.024g of hydroxybutyl acrylate into the neutralized liquid obtained in the step a), uniformly stirring, then making the neutralized liquid in the reaction kettle flow into a polymerization tank, simultaneously adding 192g of prepared 10 wt% ammonium persulfate aqueous solution into the neutralized liquid at the outlet of the reaction kettle, and carrying out polymerization reaction for 15min to obtain acrylic water-absorbent resin;
c) shearing the acrylic acid water-absorbent resin obtained in the step b) into colloidal particles with the size of 8mm, drying in an oven at the temperature of 150 ℃ for 100min, and then sequentially grinding and screening to obtain acrylic acid water-absorbent resin powder;
d) and c) based on the mass of the acrylic acid water-absorbent resin as 100g, adding 0.1g, 2g and 1g of water, glycol and ethylene glycol diglycidyl ether into the acrylic acid water-absorbent resin, preparing a surface cross-linking solution according to the proportion, uniformly spraying the surface of the acrylic acid water-absorbent resin obtained in the step c), wherein the using amount of the surface cross-linking solution is 3.1 percent of the mass ratio of the acrylic acid water-absorbent resin, the temperature of surface cross-linking treatment is 150 ℃, the time of the surface cross-linking treatment is 80min, and finally, drying in an oven at 150 ℃ for 80min to obtain the water-absorbent resin.
Example 5
a) Cooling an acrylic acid aqueous solution with the mass percentage concentration of 25% to 8 ℃, then adding 0.24g of hydroxyethyl acrylate and 3.6g of polyethylene glycol diacrylate, stirring uniformly, adding 192g of a prepared ammonium persulfate aqueous solution with the mass percentage concentration of 10 wt%, and polymerizing for 2 hours to obtain a polymerization reaction liquid;
b) adding a sodium hydroxide aqueous solution with the mass percentage concentration of 40% into the polymerization reaction liquid obtained in the step a), and carrying out neutralization reaction to obtain acrylic acid water-absorbent resin;
c) shearing the acrylic acid water-absorbent resin obtained in the step b) into colloidal particles with the size of 8mm in sequence, drying the colloidal particles in a drying oven at the temperature of 180 ℃ for 90min, and then grinding and screening the colloidal particles in sequence to obtain acrylic acid water-absorbent resin powder;
d) taking the mass of the acrylic acid water-absorbent resin as 100g, adding 10g, 6g and 0.1g of water, glycol and glycol diglycidyl ether into the acrylic acid water-absorbent resin, preparing a surface cross-linking solution according to the proportion, uniformly spraying the surface of the acrylic acid water-absorbent resin obtained in the step c), wherein the using amount of the surface cross-linking solution is 16.1 percent of the mass ratio of the acrylic acid water-absorbent resin, the temperature of the surface cross-linking treatment is 150 ℃, the time of the surface cross-linking treatment is 80min, and finally drying in an oven at 150 ℃ for 80min to obtain the water-absorbent resin.
Example 6
a) 240g of n-heptane was charged into a 1L four-necked round bottom flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube. Adding 0.46g of sucrose fatty acid ester, heating to 80 ℃, uniformly dissolving and dispersing at a stirring speed of 350rpm, and then cooling to 30 ℃;
b) dropwise adding 60g of 32 mass percent sodium hydroxide aqueous solution into a 250mL conical flask dissolved with 46g of acrylic acid monomer and 25g of deionized water under the condition of stirring while cooling, adding 18g of aqueous solution containing 0.092g of sodium persulfate, 0.046g of ethylene glycol diglycidyl ether and 0.046g of hydroxyethyl methacrylate when the temperature is reduced to be below 30 ℃, and fully dissolving and mixing to obtain acrylic acid neutralizing solution for prepolymerization;
c) adding acrylic acid neutralization solution for prepolymerization into the four-neck round-bottom flask, and introducing nitrogen while stirring to remove oxygen fully; then, heating to 75 ℃ for reaction for 2h to carry out a section of W/O reversed-phase suspension polymerization to obtain a suspension containing pre-polymerized water-absorbent resin colloidal particles;
d) dropwise adding 60g of 32 mass percent aqueous solution of sodium hydroxide into a 250mL conical flask dissolved with 46g of acrylic acid monomer and 25g of deionized water under the condition of stirring while cooling, adding 18g of aqueous solution containing 0.092g of sodium persulfate, 0.046g of ethylene glycol diglycidyl ether and 0.046g of hydroxyethyl methacrylate when the temperature is reduced to be below 30 ℃, and fully dissolving and mixing to obtain acrylic acid neutralizing liquid for final polymerization;
e) the suspension containing the pre-polymerized water-absorbent resin colloidal particles was cooled to 50 ℃, an acrylic acid neutralizing solution for final polymerization was added (at this time, the system temperature was lowered to about 40 ℃), and stirring was carried out for 30 minutes under a nitrogen atmosphere, so that the droplets of the second-stage neutralizing solution and the first-stage water-absorbent resin colloidal particles adsorbed to each other and aggregated. Then, continuously heating to 75 ℃ to react for 2h for final polymerization to obtain suspension containing final polymerization water-absorbent resin colloidal particles;
f) the temperature was further raised to 100-120 ℃ for azeotropic dehydration and n-heptane was refluxed to remove 148g of water in total. Adjusting the temperature of the system to 80 ℃, adding 0.092g of ethylene glycol diglycidyl ether into the mixed solution, and carrying out surface crosslinking reaction at the temperature for 2 h; then, the remaining water in the system was removed by distillation reaction with n-heptane, at which time it was observed that the water-absorbent resin particles in the form of grape bunches settled at the bottom of the flask, which was dried at 130 ℃ for 1 hour; finally, sieving the mixture by using sieves with different pore sizes to further obtain the water-absorbent resin product with the required particle size.
Comparative example 1
a) Dissolving 1027g of sodium hydroxide solid in 4960g of water in a dosing tank, then pouring an aqueous solution of sodium hydroxide into a jacketed reaction kettle with a stirrer, adding 2400g of acrylic acid, and controlling the temperature in the reaction kettle to be 80 ℃ to obtain a neutralized solution containing acrylic acid, sodium acrylate and water;
b) adding 3.6g of polyethylene glycol diacrylate (average molecular weight 523) and 0.24g of hydroxyethyl acrylate into the neutralized liquid obtained in the step a), uniformly stirring, then making the neutralized liquid in the reaction kettle flow into a polymerization tank, simultaneously adding 192g of prepared ammonium persulfate aqueous solution with the mass percentage concentration of 10 wt% into the neutralized liquid at the outlet of the reaction kettle, and carrying out polymerization reaction for 15min to obtain acrylic water-absorbent resin;
c) shearing the acrylic acid water-absorbent resin obtained in the step b) into colloidal particles with the size of 8mm in sequence, drying the colloidal particles in an oven at the temperature of 180 ℃ for 90min, and then grinding and screening the colloidal particles in sequence to obtain acrylic acid water-absorbent resin powder.
Comparative example 2
a) Dissolving 1027g of sodium hydroxide solid in 4960g of water in a dosing tank, then pouring an aqueous solution of sodium hydroxide into a jacketed reaction kettle with a stirrer, adding 2400g of acrylic acid, and controlling the temperature in the reaction kettle to be 80 ℃ to obtain a neutralized solution containing acrylic acid, sodium acrylate and water;
b) adding 3.6g of polyethylene glycol diacrylate (average molecular weight 523) into the neutralized liquid obtained in the step a), uniformly stirring, then making the neutralized liquid in the reaction kettle flow into a polymerization tank, simultaneously adding 192g of prepared ammonium persulfate aqueous solution with the mass percentage concentration of 10 wt% into the neutralized liquid at the outlet of the reaction kettle, and carrying out polymerization reaction for 15min to obtain acrylic acid water-absorbent resin;
c) shearing the acrylic acid water-absorbent resin obtained in the step b) into colloidal particles with the size of 8mm in sequence, drying the colloidal particles in a drying oven at the temperature of 180 ℃ for 90min, and then grinding and screening the colloidal particles in sequence to obtain acrylic acid water-absorbent resin powder;
d) and c) based on the mass of the acrylic acid water-absorbent resin as 100g, adding 0.1g, 2g and 1g of water, glycol and ethylene glycol diglycidyl ether into the acrylic acid water-absorbent resin, preparing a surface cross-linking solution according to the proportion, uniformly spraying the surface of the acrylic acid water-absorbent resin obtained in the step c), wherein the using amount of the surface cross-linking solution is 3.1 percent of the mass ratio of the acrylic acid water-absorbent resin, the temperature of surface cross-linking treatment is 150 ℃, the time of the surface cross-linking treatment is 80min, and finally, drying in an oven at 150 ℃ for 80min to obtain the water-absorbent resin.
The product properties of the acrylic water-absorbent resins prepared in the above examples and comparative examples are compared as shown in Table 1 below.
TABLE 1
As can be seen from the data in the above table, the comonomer (I) containing a carbon-carbon double bond capable of undergoing radical polymerization and a group capable of reacting with a carboxyl group can effectively reduce the soluble component of the product under the conditions of basically the same liquid absorption rate and centrifuge retention rate.
Claims (13)
1. A method for preparing acrylic acid water-absorbent resin with low soluble components is characterized in that: the method comprises the following steps: carrying out surface crosslinking treatment on the acrylic acid water-absorbent resin;
the acrylic acid water-absorbent resin is prepared by copolymerizing raw materials containing acrylic acid and a comonomer, wherein the comonomer is hydroxyethyl acrylate; the addition amount of the comonomer is 0.01 percent of the mass of the acrylic acid;
the acrylic water-absorbent resin was prepared by a method employing the following steps:
a) adding acrylic acid into alkali liquor to obtain a neutralized solution containing acrylic acid, acrylate and water;
b) adding a comonomer and an internal crosslinking agent into the neutralized liquid obtained in the step a), uniformly stirring, adding an initiator, and polymerizing to obtain acrylic acid water-absorbent resin; the internal crosslinking agent is polyethylene glycol diacrylate; the addition amount of the internal crosslinking agent is 0.1-0.4% of the mass of the acrylic acid;
the surface cross-linking treatment is to spray a surface cross-linking solution on the surface layer of the acrylic acid water-absorbent resin, wherein the surface cross-linking solution contains water, polyhydric alcohol and a surface cross-linking agent; wherein, the polyhydric alcohol is glycol, and the surface cross-linking agent is ethylene glycol diglycidyl ether;
the dosage of the surface cross-linking solution is 2-10% of the mass of the acrylic acid water-absorbent resin; the surface cross-linking treatment is carried out at 80-300 deg.C for 10-240 min.
2. The method of claim 1, wherein: before the surface cross-linking treatment, the method also comprises the following steps: and sequentially crushing, drying, grinding and screening the acrylic acid water-absorbent resin.
3. The production method according to claim 1 or 2, characterized in that: the dosage of the surface cross-linking solution is 2.5 to 6 percent of the mass of the acrylic acid water-absorbent resin; the surface cross-linking treatment is carried out at a temperature of 100 ℃ and 200 ℃ for 30-60 min.
4. The method of claim 1, wherein: the amount of the polyhydric alcohol is 0.1 to 5% by mass of the acrylic water-absorbent resin.
5. The method of claim 4, wherein: the amount of the polyhydric alcohol is 0.5 to 2% by mass of the acrylic water-absorbent resin.
6. The method of claim 1, wherein: the amount of the surface-crosslinking agent is 0.01 to 1% by mass based on the mass of the acrylic water-absorbent resin.
7. The method of claim 6, wherein: the amount of the surface-crosslinking agent is 0.05 to 0.5% by mass of the acrylic water-absorbent resin.
8. The method of claim 1, wherein: the mass of water in the surface cross-linking solution is 0.1-10% of that of the acrylic acid water-absorbent resin.
9. The method of claim 8, wherein: the mass of water in the surface cross-linking solution is 1.0-6.0% of the mass of the acrylic acid water-absorbent resin.
10. The production method according to claim 1, wherein the alkali solution is a sodium hydroxide solution.
11. The production method according to any one of claims 1 to 10, characterized in that: the initiator used for preparing the acrylic acid water-absorbent resin is one or more of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide and di-tert-butyl peroxide; the addition amount of the initiator is 0.01-1% of the mass of the acrylic acid.
12. The method of claim 11, wherein: the initiator used for preparing the acrylic acid water-absorbent resin is ammonium persulfate; the addition amount of the initiator is 0.1-0.4% of the mass of the acrylic acid.
13. A sanitary material characterized by: an acrylic water-absorbent resin comprising a low-soluble component obtained by the production method as claimed in any one of claims 1 to 12.
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| CN110559124A (en) * | 2019-08-26 | 2019-12-13 | 广州科莱瑞迪医疗器材股份有限公司 | Ice pack for chemotherapy |
| CN113383622A (en) * | 2021-06-09 | 2021-09-14 | 江苏沿海地区农业科学研究所 | Coating agent for improving germination rate of purslane seeds and use method thereof |
| CN114773622A (en) * | 2022-03-25 | 2022-07-22 | 浙江卫星新材料科技有限公司 | Method for improving apparent density of high-absorptivity resin |
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