CN107722163A - The water-absorbing resins and its application of acrylic water-absorbent resin and low soluble component - Google Patents
The water-absorbing resins and its application of acrylic water-absorbent resin and low soluble component Download PDFInfo
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- CN107722163A CN107722163A CN201711098937.7A CN201711098937A CN107722163A CN 107722163 A CN107722163 A CN 107722163A CN 201711098937 A CN201711098937 A CN 201711098937A CN 107722163 A CN107722163 A CN 107722163A
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Abstract
The invention discloses a kind of acrylic water-absorbent resin, low soluble component acrylic water-absorbent process for preparing resins and preparation method thereof, by being made comprising acrylic acid, comonomer, the comonomer includes comonomer (I) and/or comonomer (II)；Preparation method comprises the following steps：Acrylic water-absorbent resin made from above-mentioned acrylic water-absorbent resin or above-mentioned method is subjected to surface-crosslinked processing.The present invention provides a kind of water-absorbing resins of low soluble component, preparation method and applications, and provides a kind of water-absorbing resins with relatively low soluble constituent.
Description
Technical field
The invention belongs to the technical field of water-absorbing resins preparation method, more particularly to olefin(e) acid water-absorbing resins and low solvable
Property component water-absorbing resins and their application.
Background technology
Hydroscopic high-molecular resin is due to that can absorb and keep (or even under stress) sole mass hundreds times even thousands of times
Pure water or decades of times physiological saline, therefore be widely used in baby paper diaper, sanltary towel, adult-incontinence articles,
The hygienic material field and soil water-retaining, food fresh keeping etc. such as hospital's disposable mattress field, it is very easy to the day of people
Often life.
Super absorbent resin (SAP) is applied to the property of the super absorbent resin of the health field such as paper diaper, sanltary towel
It can require to experienced three phases, from the initial simple saturation liquid absorption for emphasizing water-absorbing resin, to the liquid absorption that pressurizes is emphasized, directly
To currently requiring that product has low soluble component.
Soluble component is reduced in addition to general increase internal crosslinker method, can also be by controlling drying condition come real
It is existing.Patent CN102731802 describes one kind and initiator is added in granulation process, and utilizes sectional temperature-controlled dry water suction tree
The method of fat particle, drying process are divided into heating zone, flat-temperature zone and cooling area and are passed through vapor in flat-temperature zone.The drying side
Method product soluble component is relatively low.But temperature of the drying means in heating zone and cooling area is too low, drying efficiency is slow；And
And the temperature in flat-temperature zone is 190 DEG C, there is also over-drying possibility for top layer micelle.This kind of method flow complexity, energy consumption
It is high.
The content of the invention
To make up the deficiencies in the prior art, the present invention provides a kind of acrylic water-absorbent resin and its preparation side
Method, also provide and utilize the acrylic water-absorbent resin-made for the preparation method of the water-absorbing resins of low soluble component and its answer
With, using the present invention acrylic water-absorbent resin the water-absorbing resins with relatively low soluble constituent can be made.
In order to realize an above-mentioned goal of the invention, present invention employs following technical scheme：
First aspect present invention provides acrylic water-absorbent resin, by the material copolymerization system comprising acrylic acid and comonomer
, the comonomer includes the one or more in the compound with following structural formula (I) and (II)：
Wherein ,-R1Or-R3For hydrogen or methyl；
-R2Or-R4For aliphatic alkane group, preferably C1-C10Aliphatic hydrocarbon group；
-X1Or-X2For the group that can be reacted with carboxyl, preferably hydroxyl or epoxide group.
Preferably, the comonomer with structural formula (I) includes hydroxy-ethyl acrylate, hydroxyethyl methacrylate, propylene
Sour hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, methacrylate, glycidyl ether, methyl
Glycidyl ether, glycerol mono-acrylate, glycerin monomethyl acrylic ester, one kind in pentaerythrite mono acrylic ester
It is or a variety of；Comonomer with structural formula (II) includes allyl glycidyl ether and/or pentaerythritol monoallyl ether.
Second aspect of the present invention provides a kind of method for preparing acrylic water-absorbent resin described above, by acrylic acid and
Comonomer prepares the acrylic water-absorbent resin by polymerisation in solution or inverse suspension polymerization, or by using including such as
The method of lower step prepares the acrylic water-absorbent resin：
A) acrylic acid is added into alkali lye, obtains the neutralizer containing acrylic acid, acrylates and water；The preferred hydrogen of alkali lye
Sodium hydroxide solution；
B) comonomer and internal crosslinker are added into the neutralizer obtained by step a), is stirring evenly and then adding into initiator,
Polymerization obtains acrylic water-absorbent resin.
Preferably, the first preparation method above-mentioned in the present invention comprises the following steps：
A) acrylic acid is added in sodium hydroxide solution, obtains the neutralizer containing acrylic acid, PAA and water, hydrogen-oxygen
The mass percentage concentration for changing sodium water solution is preferably 20-40%；
B) comonomer and internal crosslinker are added into the neutralizer obtained by step a), is stirring evenly and then adding into initiator,
Polymerization obtains acrylic water-absorbent resin.
Second above-mentioned of preparation method comprises the following steps in the present invention：
A) acrylic acid aqueous solution is cooled to 0-10 DEG C, then adds comonomer and internal crosslinker, added after stirring
Enter initiator, polymerize to obtain polymerization liquid；Preferably, the mass percentage concentration of acrylic acid aqueous solution is 25-45%, is entered
One step is preferably 30-40%, and polymerization reaction time is 1-8 hours, preferably 3-6 hours；
B) sodium hydrate aqueous solution is added in the polymerization liquid obtained to step a), neutralization reaction is carried out and obtains acrylic acid
Water-absorbing resins；Preferably, the mass percentage concentration of sodium hydrate aqueous solution is 20-40%；
The third above-mentioned preparation method comprises the following steps in the present invention：
A) surfactant is dissolved in petroleum hydrocarbon solvent and is cooled to 20-50 DEG C；The petroleum hydrocarbon solvent example
Can be such as petroleum ether, n-hexane, hexamethylene, toluene, but the invention is not limited in this；
B) acrylic acid and comonomer are added in sodium hydrate aqueous solution and carries out neutralization reaction, initiator is added after cooling
And internal crosslinker, obtain reaction solution；The mass percentage concentration of sodium hydrate aqueous solution is preferably 20-40%；
C) will be added in reaction solution in the petroleum hydrocarbon solvent dissolved with surfactant that is obtained in step a), anaerobic bar
It is stirred under part and carries out prepolymerization, obtains prepolymerized suspension；Nitrogen is preferably pressed into during prepolymerization to remove
Oxygen in dereaction system so that do not have oxygen to participate in reaction in course of reaction, prepolymerization temperature is preferably 60-90
℃；
D) by prepolymerized suspension cooling down to 10-30 DEG C, add and carried out with the reaction solution of the quality such as step c)
Final polymerization, obtain acrylic water-absorbent resin.
Preferably, the addition of comonomer is the 0.001-10%, preferably 0.01-1% of acrylic acid quality.
Preferably, it is N to prepare the internal crosslinker used in the acrylic water-absorbent resin, N- methylene-bisacrylamides,
Ethylene glycol, ethylene glycol diglycidylether, propane diols, propylene glycol diglycidylether, polyethylene glycol, polyethylene glycol diacrylate
Ester, polyethyleneglycol diglycidylether, glycerine, glycerol tri-acrylate, ethoxylated glycerol triacrylate, pentaerythrite,
Pentaerythritol triacrylate, pentaerythritol triallyl ether, trimethylolpropane trimethacrylate and the hydroxyl first of ethoxylation three
One or more in base propane triacrylate；The addition of internal crosslinker is the 0.05-0.8% of acrylic acid quality, preferably
For 0.1-0.4%.
Preferably, the initiator prepared used in the acrylic water-absorbent resin is hydrogen peroxide, sodium peroxydisulfate, persulfuric acid
One or more in potassium, ammonium persulfate, TBHP and di-tert-butyl peroxide, preferably ammonium persulfate；Draw
The addition of hair agent is the 0.01-1%, preferably 0.1-0.4% of acrylic acid quality.
Third aspect present invention provides a kind of preparation method of the acrylic water-absorbent resin of low soluble component, will be above-mentioned
Acrylic water-absorbent resin or the acrylic water-absorbent resin that is prepared using the above method carry out surface-crosslinked processing.
Preferably, before surface-crosslinked processing step is carried out, acrylic water-absorbent resin is crushed successively, done
Dry, grinding, screening process.In a kind of embodiment, dry temperature is 100-250 DEG C, drying time 10-
300min, acrylic water-absorbent resin is cut into 2-20mm resin section；It is further preferred that the temperature dried is 150-
200 DEG C, such as 160 DEG C, 180 DEG C, drying time 10-300min, such as 180min, 220min, sheared length 8-15mm,
Such as 8mm, 12mm, 15mm.
Preferably, described surface-crosslinked processing is to spray surface cross-linking solution, institute to acrylic water-absorbent resin surface layer
The surface cross-linking solution stated preferably comprises water, polyalcohol and surface crosslinking agent；The dosage of surface cross-linking solution is preferably acrylic acid
The 2-10% of water-absorbing resins quality, preferably 2.5-6%；Surface-crosslinked processing is entered under the conditions of being preferably 80-300 DEG C in temperature
OK, time 10-240min, more preferably 100-200 DEG C progress, time 30-60min.
Preferably, described polyalcohol include ethylene glycol, 1,2-PD, 1,3-PD, glycerine, diethylene glycol,
One or more in triethylene glycol or 1,4- butanediols；The dosage of polyalcohol is preferably acrylic water-absorbent resin quality
0.1-5%, more preferably 0.5-2%.
Preferably, described surface crosslinking agent includes ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, third
Hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, the one or more of ethylene carbonate or propene carbonate；Surface
The dosage of crosslinking agent is preferably the 0.01-1% of acrylic water-absorbent resin quality, more preferably 0.05-0.5%.
Preferably, the quality of described surface cross-linking solution reclaimed water is the 0.1-10% of acrylic water-absorbent resin quality,
Preferably 1.0-6.0%.
Fourth aspect present invention provides a kind of hygienic material, includes low soluble component made from method as discussed above
Acrylic water-absorbent resin.
Using above-mentioned technical scheme, have the following technical effect that：
The present invention passes through to containing the carbon-carbon double bond that may occur from being polymerize by base and the group that can be reacted with carboxyl reaction
Copolymerization, a kind of water-absorbing resins of low soluble component and preparation method thereof, the water imbibition tree that the present invention is prepared are obtained
Fat can significantly reduce soluble component in product under conditions of keeping liquid absorbency rate and centrifuge retention rate essentially identical
Content.
Embodiment
In order to be better understood from the present invention, with reference to the embodiment content that the present invention is furture elucidated.
The performance of water-absorbing resin in following each examples is tested using following methods：
(1) liquid absorbency rate
0.2g samples are weighed, are accurate to 0.001g, and the quality is denoted as m, sample is all poured into tea bag, tea bag is sealed
Mouthful, be dipped to equipped with mass fraction for 0.9% physiological saline beaker in, soak 30min；Then, by the tea bag equipped with sample
Bring out, hung up with clip, after the 10min that dripped under inactive state, weigh the tea bag quality m1 equipped with sample；Finally, use
The tea bag for not having sample carries out blank value measure, weighs the quality of blank test tea bag, and the quality is denoted as into m2.
Then liquid absorbency rate=(m1-m2)/m
(2) centrifuge retention rate
The tea bag equipped with sample of the complete liquid absorbency rate of above-mentioned test is dehydrated 3min under the conditions of 250G centrifugal force, then claimed
Tea bag quality of the amount equipped with sample, and the quality is denoted as m3.Blank value measure is carried out using the tea bag of no sample, weighs sky
The quality is simultaneously denoted as m4 by the quality of white tea bag.
Then centrifuge retention rate=(m3-m4)/m
(3) residual acrylic monomer content in product
1.000g super absorbent resins are weighed, are put into 250mL beaker, 200mL physiological saline is added, is put into magnetic rotor
Afterwards, sealed with sealed membrane, be placed on magnetic stirring apparatus and be stirred (rotating speed is about 500rpm).After 1 hour, stop stirring, it is quiet
Put 10 minutes, supernatant liquor is filtered with filter, residual monomer content is carried out to filtrate using high performance liquid chromatography
Analysis.
High performance liquid chromatograph producer：Agilent；Model：1260 types
(4) 0.3psi pressurizations liquid absorbency rate
Device therefor is：A. the internal diameter of both ends open is 25mm, external diameter 30mm plastic cylinder, and 200 purposes are fixed in one end
Nylon wire；
B. plastic piston, external diameter are slightly less than 25mm, can be closely connected with above-mentioned plastic cylinder, and can be freely movable up and down；
C. weight is 100g circle counterweights；
D. glass dish, an included porous plate, after plastic cylinder being placed on porous plate, does not contact glass dish
Bottom, moisture can be freely absorbed again.
Method of testing：Glass dish is placed on platform, pours into 0.9% physiological saline；Sample 0.16g is weighed, by sample
Uniformly it is sprinkled into bottom of cylinder；Then, the plastic piston for adding counterweight is added into plastic cylinder, it is m5 to determine its quality.It will add
The plastic cylinder for having entered sample is put on the porous plate of glass dish, is proposed plastic cylinder from glass dish after 60min, by water droplet
The quality of test plastic cylinder is m6 after net, then liquid absorbency rate=(m6-m5)/0.16 of being pressurizeed under 0.3psi.
(5) soluble component content
In 250mL beakers, the 184.3g 0.9wt%NaCl aqueous solution is weighed, 1.00g super absorbent resin samples are added
Enter into the solution, stir 16h to extract the soluble component in super absorbent resin sample.The solution of this extraction is filtered
Paper is filtered, and weighs filtrate obtained by 50.0g as measurement filtrate.First, (0.9wt%NaCl's is water-soluble for progress blank solution
Liquid) titration, titrated using the 0.1mol/LNaOH aqueous solution, until pH=10；Then by using 0.1mol/L hydrochloric acid
Solution titrates, and until pH=2.7, obtains blank titration amount respectively [bNaOH], [bHCl] mL.Sample extraction liquid is carried out
Same titration operation is stated, obtains titer respectively [NaOH], [HCl] mL.The soluble component of super absorbent resin sample
Content Ex and degree of neutralization DN can be calculated by following formula, and wherein Mw is mean molecule quantity.
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 is described in detail with reference to embodiments, but present disclosure is not only
It is limited only to the following examples.
Embodiment 1
A) 1027g sodium hydrate solids are dissolved in 4960g water in material-compound tank, then poured into sodium hydrate aqueous solution
In jacket reactor with agitator, add 2400g acrylic acid, control 80 DEG C of reactor temperature, obtain containing acrylic acid,
The neutralizer of PAA and water；
B) into the neutralizer obtained by step a) add 3.6g polyethyleneglycol diacrylates (mean molecule quantity 523) and
0.24g hydroxy-ethyl acrylates, the neutralizer in reactor is flowed into polymerization tank after stirring, and simultaneously in reactor exit
It is 10wt% ammonium persulfate aqueous solutions that the mass percentage concentrations that have prepared of 192g are added into neutralizer, polymerisation 15min
After obtain acrylic water-absorbent resin；
C) by the acrylic water-absorbent resin obtained by step b) successively by cutting into 8mm micelle, then at 180 DEG C
90min is dried in baking oven, then grinds successively, screening process, obtains acrylic water-absorbent resin powder；
D) counted using acrylic water-absorbent resin quality as 100g, the addition of water, ethylene glycol and ethylene glycol diglycidylether
Measure as 0.1g, 2g and 1g, surface cross-linking solution is prepared according to aforementioned proportion, to the acrylic absorbent resin surface obtained by step c)
Uniformly sprinkling, the dosage of surface cross-linking solution is that acrylic water-absorbent resin quality ratio is 3.1%, the temperature of surface-crosslinked processing
For 150 DEG C, surface-crosslinked processing time is 80min, is finally putting into 150 DEG C of baking oven and dries 80min, obtains water imbibition tree
Fat.
Embodiment 2
A) 1027g sodium hydrate solids are dissolved in 4960g water in material-compound tank, then poured into sodium hydrate aqueous solution
In jacket reactor with agitator, add 2400g acrylic acid, control 80 DEG C of reactor temperature, obtain containing acrylic acid,
The neutralizer of PAA and water；
B) into the neutralizer obtained by step a) add 2.4g polyethyleneglycol diacrylates (mean molecule quantity 523) and
24g hy-droxybutyls, the neutralizer in reactor is flowed into polymerization tank after stirring, and simultaneously reactor exit to
The 10wt% ammonium persulfate aqueous solutions that 24g has been prepared are added in neutralizer, acrylic water-absorbent resin is obtained after polymerisation；
C) by the acrylic water-absorbent resin obtained by step b) successively by cutting into 12mm micelle, then at 180 DEG C
Baking oven in dry 90min, then in turn through grinding, screening process, obtain acrylic absorbent resin powder；
D) counted using acrylic water-absorbent resin quality as 100g, water, glycerine and polyethyleneglycol diglycidylether add
Dosage is 5g, 2g, 0.5g, surface cross-linking solution is prepared according to aforementioned proportion, to the acrylic absorbent resin table obtained by step c)
Face is uniformly sprayed, and the dosage of surface cross-linking solution is that acrylic water-absorbent resin quality ratio is 7.5%, the temperature of surface-crosslinked processing
Spend for 80 DEG C, surface-crosslinked processing time is 150min, is finally putting into 180 DEG C of baking oven and dries 80min, obtains water imbibition tree
Fat.
Embodiment 3
A) 640g sodium hydrate solids are dissolved in 4960g water in material-compound tank, then poured into sodium hydrate aqueous solution
In jacket reactor with agitator, 2400g acrylic acid is added, controls 80 DEG C of reactor temperature；
B) into the neutralizer obtained by step a) add 9.6g polyethyleneglycol diacrylates (mean molecule quantity 523) and
12g glycerol tri-acrylates, the neutralizer in reactor is flowed into polymerization tank after stirring, and simultaneously in reactor exit
It is 10wt% TBHP solution that the mass percentage concentrations that have prepared of 96g are added into neutralizer, after polymerisation
Obtain acrylic water-absorbent resin；
C) by the acrylic water-absorbent resin obtained by step b) successively by cutting into 10mm micelle, then at 200 DEG C
Baking oven in dry 10min, then in turn through grinding, screening process, obtain acrylic absorbent resin powder；
D) counted using acrylic water-absorbent resin quality as 100g, water, glycerine and polyethyleneglycol diglycidylether add
Dosage is 1g, 0.5g, 0.05g, surface cross-linking solution is prepared according to aforementioned proportion, to the acrylic absorbent resin obtained by step c)
Surface is uniformly sprayed, and the dosage of surface cross-linking solution is that acrylic water-absorbent resin quality ratio is 1.55%, surface-crosslinked processing
Temperature be 80 DEG C, surface-crosslinked processing time be 150min, is finally putting into 180 DEG C of baking oven drying 80min, is absorbed water
Property resin.
Embodiment 4
A) 1027g sodium hydrate solids are dissolved in 4960g water in material-compound tank, then poured into sodium hydrate aqueous solution
In jacket reactor with agitator, 2400g acrylic acid is added, controls 80 DEG C of reactor temperature；
B) into the neutralizer obtained by step a) add 3.6g pentaerythritol triacrylates (mean molecule quantity 523) and
0.024g hy-droxybutyls, the neutralizer in reactor is flowed into polymerization tank after stirring, and exported simultaneously in reactor
Place adds the 10wt% ammonium persulfate aqueous solutions that 192g has been prepared into neutralizer, and acrylic acid is obtained after polymerisation 15min
Water-absorbing resins；
C) acrylic water-absorbent resin obtained by step b) is passed through to the micelle for cutting into 8mm, then in 150 DEG C of baking oven
Middle dry 100min, then grind successively, screening process, obtain acrylic water-absorbent resin powder；
D) counted using acrylic water-absorbent resin quality as 100g, the addition of water, ethylene glycol and ethylene glycol diglycidylether
Measure as 0.1g, 2g and 1g, surface cross-linking solution is prepared according to aforementioned proportion, to the acrylic absorbent resin surface obtained by step c)
Uniformly sprinkling, the dosage of surface cross-linking solution is that acrylic water-absorbent resin quality ratio is 3.1%, the temperature of surface-crosslinked processing
For 150 DEG C, surface-crosslinked processing time is 80min, is finally putting into 150 DEG C of baking oven and dries 80min, obtains water imbibition tree
Fat.
Embodiment 5
A) acrylic acid aqueous solution that mass percentage concentration is 25% is cooled to 8 DEG C, then adds 0.24g acrylic acid hydroxyl second
Ester and 3.6g polyethyleneglycol diacrylates, it is 10wt% mistakes to be stirring evenly and then adding into the mass percentage concentration that 192g has been prepared
Ammonium sulfate solution, polymerization obtain polymerization liquid in 2 hours；
B) sodium hydrate aqueous solution that mass percentage concentration is 40% is added in the polymerization liquid obtained to step a), is entered
Row neutralization reaction obtains acrylic water-absorbent resin；
C) by the acrylic water-absorbent resin obtained by step b) successively by cutting into 8mm micelle, then at 180 DEG C
90min is dried in baking oven, then grinds successively, screening process, obtains acrylic water-absorbent resin powder；
D) counted using acrylic water-absorbent resin quality as 100g, the addition of water, ethylene glycol and ethylene glycol diglycidylether
Measure as 10g, 6g and 0.1g, surface cross-linking solution is prepared according to aforementioned proportion, to the acrylic absorbent resin table obtained by step c)
Face is uniformly sprayed, and the dosage of surface cross-linking solution is that acrylic water-absorbent resin quality ratio is 16.1%, surface-crosslinked processing
Temperature is 150 DEG C, and surface-crosslinked processing time is 80min, is finally putting into 150 DEG C of baking oven and dries 80min, obtains water imbibition
Resin.
Embodiment 6
A) 240g normal heptanes are added to tetra- mouthfuls of the 1L equipped with agitator, reflux condenser, thermometer and nitrogen inlet tube
In round-bottomed flask.0.46g sucrose fatty esters are added thereto, are warming up to 80 DEG C and are made its uniform with 350rpm mixing speed
Dissolving is scattered, is then cooled to 30 DEG C；
B) sodium hydrate aqueous solution that 60g mass percentage concentrations are 32% is added drop-wise under stirring condition while in cooling
Dissolved with the 250mL conical flasks of 46g acrylic monomers and 25g deionized waters, when temperature is down to below 30 DEG C, wherein adding
Containing 0.092g sodium peroxydisulfates, 0.046g ethylene glycol diglycidylethers, 0.046g hydroxyethyl methacrylates the aqueous solution
The acrylic acid neutralizer of prepolymerization is obtained after 18g, fully dissolving mixing；
C) prepolymerization is added in above-mentioned four round flask with acrylic acid neutralizer, it is abundant is passed through nitrogen while stirring
Deoxygenation；Then, 75 DEG C of reaction 2h are warming up to and carry out one section of W/O inverse suspension polymerization, are obtained containing prepolymerized water-absorbing resins
The suspension of micelle；
D) sodium hydrate aqueous solution that 60g mass percentage concentrations are 32% is added drop-wise under stirring condition while in cooling
Dissolved with the 250mL conical flasks of 46g acrylic monomers and 25g deionized waters, when temperature is down to below 30 DEG C, wherein adding
Containing 0.092g sodium peroxydisulfates, 0.046g ethylene glycol diglycidylethers, 0.046g hydroxyethyl methacrylates the aqueous solution
Final polymerization acrylic acid neutralizer is obtained after 18g, fully dissolving mixing；
E) suspension containing prepolymerized water-absorbing resins micelle is cooled to 50 DEG C, added in final polymerization acrylic acid
With liquid (now system temperature is down to 40 DEG C or so), 30min is stirred under nitrogen atmosphere so that two sections of neutralizer drops and one section
Water-absorbing resins micelle is adsorbed and assembled each other.Then, 75 DEG C of reaction 2h are continuously heating to and carry out final polymerization, are obtained containing poly- eventually
Close the suspension of water-absorbing resins micelle；
F) continue to raise temperature to 100-120 DEG C of progress azeotropic dehydration and cause normal heptane backflow, remove 148g water altogether.Will
System temperature is adjusted to 80 DEG C, and 0.092g ethylene glycol diglycidylethers are added into mixed liquor, and 2h carries out table at this temperature
Face cross-linking reaction；Then, remaining water in system is removed with normal heptane by distillation reaction, now it is observed that grape cluster
The water-absorbing resin particles of shape sink to drag, and it is dried into 1h at 130 DEG C；Finally, with the screen cloth of different pore size size
It is sieved, further obtains required particle diameter water-absorbing resins product.
Comparative example 1
A) 1027g sodium hydrate solids are dissolved in 4960g water in material-compound tank, then poured into sodium hydrate aqueous solution
In jacket reactor with agitator, add 2400g acrylic acid, control 80 DEG C of reactor temperature, obtain containing acrylic acid,
The neutralizer of PAA and water；
B) into the neutralizer obtained by step a) add 3.6g polyethyleneglycol diacrylates (mean molecule quantity 523) and
0.24g hydroxy-ethyl acrylates, the neutralizer in reactor is flowed into polymerization tank after stirring, and simultaneously in reactor exit
It is 10wt% ammonium persulfate aqueous solutions that the mass percentage concentrations that have prepared of 192g are added into neutralizer, polymerisation 15min
After obtain acrylic water-absorbent resin；
C) by the acrylic water-absorbent resin obtained by step b) successively by cutting into 8mm micelle, then at 180 DEG C
90min is dried in baking oven, then grinds successively, screening process, obtains acrylic water-absorbent resin powder.
Comparative example 2
A) 1027g sodium hydrate solids are dissolved in 4960g water in material-compound tank, then poured into sodium hydrate aqueous solution
In jacket reactor with agitator, add 2400g acrylic acid, control 80 DEG C of reactor temperature, obtain containing acrylic acid,
The neutralizer of PAA and water；
B) 3.6g polyethyleneglycol diacrylates (mean molecule quantity 523) are added into the neutralizer obtained by step a), are stirred
The neutralizer in reactor is flowed into polymerization tank after mixing uniformly, and has added 192g into neutralizer in reactor exit simultaneously
The mass percentage concentration prepared is 10wt% ammonium persulfate aqueous solutions, and acrylic water-absorbent tree is obtained after polymerisation 15min
Fat；
C) by the acrylic water-absorbent resin obtained by step b) successively by cutting into 8mm micelle, then at 180 DEG C
90min is dried in baking oven, then grinds successively, screening process, obtains acrylic water-absorbent resin powder；
D) counted using acrylic water-absorbent resin quality as 100g, the addition of water, ethylene glycol and ethylene glycol diglycidylether
Measure as 0.1g, 2g and 1g, surface cross-linking solution is prepared according to aforementioned proportion, to the acrylic absorbent resin surface obtained by step c)
Uniformly sprinkling, the dosage of surface cross-linking solution is that acrylic water-absorbent resin quality ratio is 3.1%, the temperature of surface-crosslinked processing
For 150 DEG C, surface-crosslinked processing time is 80min, is finally putting into 150 DEG C of baking oven and dries 80min, obtains water imbibition tree
Fat.
The properties of product contrast for the acrylic water-absorbent resin that above-described embodiment and comparative example are prepared see the table below 1.
Table 1
By upper table data, containing may occur from by base polymerization carbon-carbon double bond and can be with the base of carboxyl reaction
The comonomer (I) of group, can be under conditions of liquid absorbency rate and centrifuge retention rate be essentially identical, and effectively reduce product can
Molten component.
Claims (13)
- A kind of 1. acrylic water-absorbent resin, it is characterised in that：It is made by the material copolymerization comprising acrylic acid and comonomer, institute Stating comonomer includes the one or more in the compound with following structural formula (I) and (II)：Wherein ,-R1Or-R3For hydrogen or methyl；-R2Or-R4For aliphatic alkane group, preferably C1-C10Aliphatic hydrocarbon group；-X1Or-X2For the group that can be reacted with carboxyl, preferably hydroxyl or epoxide group.
- 2. acrylic water-absorbent resin according to claim 1, it is characterised in that：Comonomer with structural formula (I) Including hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, Methacrylate, glycidyl ether, methyl propenoic acid glycidyl ether, glycerol mono-acrylate, glycerine list Methacrylate, the one or more in pentaerythrite mono acrylic ester；Comonomer with structural formula (II) includes alkene Propyl glycidyl ether and/or pentaerythritol monoallyl ether.
- A kind of 3. method for preparing the acrylic water-absorbent resin described in claim any one of 1-2, it is characterised in that：By propylene Acid and comonomer prepare the acrylic water-absorbent resin by polymerisation in solution or inverse suspension polymerization, or by using bag The method for including following steps prepares the acrylic water-absorbent resin：A) acrylic acid is added into alkali lye, obtains the neutralizer containing acrylic acid, acrylates and water；The preferred hydroxide of alkali lye Sodium solution；B) comonomer and internal crosslinker are added into the neutralizer obtained by step a), is stirring evenly and then adding into initiator, is polymerize Obtain acrylic water-absorbent resin.
- 4. according to the method for claim 3, it is characterised in that：The addition of comonomer is the 0.001- of acrylic acid quality 10%, preferably 0.01-1%.
- 5. according to the method for claim 3, it is characterised in that：Prepare the interior crosslinking used in the acrylic water-absorbent resin Agent be N,N methylene bis acrylamide, ethylene glycol, ethylene glycol diglycidylether, propane diols, propylene glycol diglycidylether, Polyethylene glycol, polyethyleneglycol diacrylate, polyethyleneglycol diglycidylether, glycerine, glycerol tri-acrylate, ethoxylation Glycerol tri-acrylate, pentaerythrite, pentaerythritol triacrylate, pentaerythritol triallyl ether, trimethylolpropane tris One or more in acrylate and ethoxylated trimethylolpropane triacrylate；The addition of internal crosslinker is propylene The 0.05-0.8% of sour quality, preferably 0.1-0.4%.
- 6. according to the method described in claim any one of 3-5, it is characterised in that：Prepare used in the acrylic water-absorbent resin Initiator be hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, TBHP and di-tert-butyl peroxide In one or more, preferably ammonium persulfate；The addition of initiator is the 0.01-1% of acrylic acid quality, preferably 0.1- 0.4%.
- A kind of 7. preparation method of the acrylic water-absorbent resin of low soluble component, it is characterised in that：Comprise the following steps：Will Third made from the method described in acrylic water-absorbent resin or claim any one of 3-6 described in claim any one of 1-2 Olefin(e) acid water-absorbing resins carry out surface-crosslinked processing.
- 8. according to the method for claim 7, it is characterised in that：Before surface-crosslinked processing is carried out, in addition to following step Suddenly：The acrylic water-absorbent resin is crushed successively, dried, ground, screening process.
- 9. the method according to claim 7 or 8, it is characterised in that：Described surface-crosslinked processing is to acrylic water-absorbent Property resin surface layer sprinkling surface cross-linking solution, described surface cross-linking solution preferably comprises water, polyalcohol and surface crosslinking agent；Table The dosage of face crosslinker solution is preferably the 2-10% of acrylic water-absorbent resin quality, preferably 2.5-6%；Surface-crosslinked processing It is preferred that being carried out under the conditions of being 80-300 DEG C in temperature, time 10-240min, more preferably 100-200 DEG C progress, the time is 30-60min。
- 10. according to the method for claim 9, it is characterised in that：Described polyalcohol include ethylene glycol, 1,2- propane diols, One or more in 1,3- propane diols, glycerine, diethylene glycol, triethylene glycol or 1,4- butanediols；The dosage of polyalcohol is excellent Choosing is the 0.1-5% of acrylic water-absorbent resin quality, more preferably 0.5-2%.
- 11. according to the method for claim 9, it is characterised in that：Described surface crosslinking agent shrinks sweet including ethylene glycol two Oily ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, polypropylene glycol diglycidyl ether, ethylene carbonate Or the one or more of propene carbonate；The dosage of surface crosslinking agent is preferably the 0.01- of acrylic water-absorbent resin quality 1%, more preferably 0.05-0.5%.
- 12. according to the method for claim 9, it is characterised in that：The quality of described surface cross-linking solution reclaimed water is propylene The 0.1-10% of sour water-absorbing resins quality, preferably 1.0-6.0%.
- A kind of 13. hygienic material, it is characterised in that：Include low solvable made from the method described in claim any one of 7-12 The acrylic water-absorbent resin of property component.
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| CN109485879A (en) * | 2018-10-25 | 2019-03-19 | 万华化学集团股份有限公司 | A kind of acrylic absorbent resin and its preparation method and application that high temperature resistant is dry |
| 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 |
| CN116655943A (en) * | 2023-05-16 | 2023-08-29 | 深圳市嘉卓成科技发展有限公司 | Preparation method of antibacterial and antiviral water-based hydroxy acrylate emulsion |
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