CN108192013A - The manufacturing method of polyacrylic acid water-absorbent resin - Google Patents
The manufacturing method of polyacrylic acid water-absorbent resin Download PDFInfo
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- CN108192013A CN108192013A CN201711416489.0A CN201711416489A CN108192013A CN 108192013 A CN108192013 A CN 108192013A CN 201711416489 A CN201711416489 A CN 201711416489A CN 108192013 A CN108192013 A CN 108192013A
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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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 polyacrylic acid water-absorbent resin manufacturing methods, include the following steps：It obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution；Blowing-agent particle and/or foaming agent solution are mixed with unsaturated acrylic monomer and cross-linking agent aqueous solution；Monomer solution is subjected to the step of polymerization forms porous gel shape cross-linked polymer；Aqueous porous gel shape cross-linked polymer is ground into gel particle through shearing and/or squeezing action power in the course of the polymerization process or after polymerization, the gel particle number average bead diameter is 0.5~20 millimeter, mass fraction of the gel particle grain size more than 2 millimeters is 10~100wt%, for the porous gel shape cross-linked polymer by shearing and/or squeezing action power, the porous structure destructive rate of gel particle is 0~70%；Manufactured gel particle is further dried, grain refined and screening.The imbibition characteristic of water-absorbing resins is not influenced, can efficiently be produced, be obtained a kind of water-absorbing resins with high speed rate of liquid aspiration and low monomer residue amount.
Description
Technical field
The present invention relates to the manufacturing methods of polyacrylic acid water-absorbent resin.More particularly to suitable for absorbent commodity, example
Such as：Paper nappy (disposable diaper), sanitary napkin, incontinence pad, mattress, pet pads, Wound care material, construction material, soil are protected
In the products such as water material, and polyacrylic acid water-absorbent resin and its manufacture with quick imbibition performance and low monomer residue amount
Method.
Background technology
High water absorbency polymer (Super absorbent polymer, SAP) is also known as high hydroscopic resin, is that one kind contains
Strongly hydrophilic group, it is not soluble in water, but the cross-linked polymer of tens of, hundreds of or even thousands of times of water of dead weight can be absorbed.High water absorption
Resin is now widely used in a variety of necks of the amenities and soil moisturizing agent etc. such as paper diaper, physiological hygiene cotton, adult-incontinence articles
Domain.Stage now, water-absorbing resin neutralized it has been known that there is polyacrylic acid part after crosslinked, Starch and Acrylic Acid graft polymers
Saponified, acrylonitrile copolymer crosslinked, the acrylamide copolymer of hydrolysate, vinyl acetate-acrylate copolymer
Crosslinked and cationic monomer crosslinked etc..
In recent years, paper diaper structure develops towards thinner direction, needs to reduce fiber content in product, improve simultaneously
Absorbent contents, thinner structure not only improves the comfort of dress, but also can reduce packaging, storage and transportation cost.More
Thin paper diaper structure proposes the performance of absorbent very big requirement, wherein it is important that water-absorbing resin conduction and distribution
Absorptive capacity under the ability of liquid, liquid-keeping property, pressure, particularly, absorption rate (the unit mass water absorbing agent of water-absorbing resin
Liquid absorption amount within the unit interval) it can be in its first time and liquid as paper diaper of the assessment with high-content water-absorbing resin
Quick absorbing liquid body major criterion when body contacts.However, there are mutual containing between the multiple performance of water-absorbing resin, if greatly
Width promotes its rate of liquid aspiration, necessarily leads to conduct and be distributed the bad of absorptive capacity under ability, liquid-keeping property or the pressure of liquid
Change, this becomes the development bottleneck with quick imbibition rate water-absorbing resin.
The technology of the existing absorption rate for improving water-absorbing resin mainly includes four kinds：(1) pass through the physically or chemically side of foaming
Method be prepared porous structure water-absorbing resin (such as EP0295438B, WO1994022502A, EP0644207B,
EP0538983B、US20050137546A、CN102225981A、US20120258851A、CN103857714A、
CN1140458A、CN1668343A、CN1296981A、CN101050244A、CN101143913A、CN101423588A、
CN104448155A、CN102311557A、CN104448102A、CN103214616A、CN103476811A、
CN103857714A、CN105377921A、CN102317329A、CN102010560A)；(2) it is granulated using micro mist and prepares agglomeration
Granular pattern water-absorbing resin (such as EP0591168A)；(3) logical fluidity enhancer (such as special crosslinking is added in water-absorbing resin
Agent) promoted water-absorbing resin logical fluidity, further improve its rate of liquid aspiration (such as WO2001089591A)；(4) it adds at surface
Reason agent (such as clay, inorganic material) come increase the rate of liquid aspiration of water-absorbing resin (such as US20050239942A,
WO2005120221A).Wherein, it is foamed polymer strategy to study more and more effective method.
In foamed polymer, it is known that have using carbonate, organic solvent, inert gas, heat decomposition type azo-compound,
The technologies such as insoluble inorganic powder, other thermal decomposable foaming agents also carry out foaming and crosslinked technology after polymerisation.
Patent CN103857714A is disclosed before initiator is added, and 10~900 microns of sodium carbonate particle of granularity is sent out
Infusion and can response type surfactant active 4 DEG C be added to monomer solution in, surfactant can stable sodium percarbonate particle and
Its gas generated after decomposing, bubble diameter smaller.After the completion of polymerization, surfactant participates in polymerisation and forms polymeric web
Network, effectively reduce resin in can extraction surface active agent content, meanwhile, soda decomposition generate gas effectively improve resin
Rate of liquid aspiration, the presence of surfactant further promotes rate of liquid aspiration.
Patent EP0538983B, which is disclosed, foams carbonic acid (hydrogen) salt of 0.2~2.5wt% in terms of acrylic monomers quality
Agent is dissolved or dispersed in 5 minutes in monomer solution for 15 minutes to after polymerizeing before polymerization, carries out causing at 0~20 DEG C poly-
It closes, the foaming agent being dissolved or dispersed in monomer solution decomposes in a heated condition, releases carbon dioxide, and it is poly- to carry out foaming
It closes, effectively improves the rate of liquid aspiration of water-absorbing resin.
Patent CN1140458A discloses a kind of acrylates solid blowing agent by the azo-compound containing amino and uses
In preparing quick absorption-type water-absorbing resin, which (and adds other as foaming agent and radical polymerization initiator simultaneously
Initiator), the foaming agent of 0.005~25wt% in terms of acrylic monomers quality is added into monomer solution, while add in propylene
The surfactant of 0~5wt% of acid monomers quality meter, foaming agent may be homogenously dispersed in monomer solution under static conditions,
Make polymerization of unsaturated monomers, and pass through thermal decomposition release gas, to promote the rate of liquid aspiration of resin.
Patent CN102311557A, which is disclosed, a kind of to be used to prepare quick absorption-type by the foaming agent that coating processing is crossed and absorbs water
Resin, the carbonate compound mixture that the foaming agent which crosses is crossed for alum class compound coating processing, alum packet
After covering carbonate compound, carbonate will not be contacted with monomer solution immediately, and then prevent it molten with monomer in early stage
Neutralization reaction occurs for liquid；With the progress of polymerisation, the carbonate compound in foaming agent can be released slowly, be finally obtained more
Hole resin structure, and the polyvalent metal ion in alum is further crosslinked resin inside, the absorption improved under pressure is held
Amount.
Patent CN103476811A is disclosed before initiator is added, and 300~700 microns of stratum granulosum structure of granularity is sent out
Infusion (carbonate) is added in monomer solution promoting resin rate of liquid aspiration.
Patent CN102317329A discloses dissolving and/or has disperseed the acrylic monomer aqueous solution of gas, is not depositing
It is polymerize under surfactant or there are 300ppm the following conditions, inert gas micro-bubble is suspended or dissolved in monomer water
In solution, polymerization process is rested in polymeric gel, and rate of liquid aspiration is promoted in the case where not influencing resin surface tension.
In addition, also some other known rate of liquid aspiration lift techniques.
Patent EP0591168A discloses the method for reacting surface crosslinking agent with primary granule, and small particle resin is attached
Time that is poly- to be carried out at the same time with surface-crosslinked, being started by control surface crosslinking is realized intergranular surface-crosslinked to promote suction
Liquid speed rate.It is surface-crosslinked due to occurring between particle when the primary granule of aggregation is contacted with liquid, be not in fine grained point
From situation, gel blocking reduces；Agglomeration increases specific surface area, improves absorption rate.
Patent US20050239942A discloses that clay is added in water absorbing resin particle in surface cross-linking step and uses
To improve rate of liquid aspiration and permeability.
Patent WO2001089591A, which is disclosed, is surface-treated resin with hydroxyalkyl amide, and treatment temperature 100~
160 DEG C, 90~150 minutes time improved absorption rate, absorbs amount of liquid and gel strength.
These technologies improve resin absorption speed to a certain extent, but in the actual production process, can bring liquid
Permeability or resin impact resistance declined, the reduction of apparent density, manufacture, transport or use during be also easy to produce it is micro-
The problems such as powder or dust.The better water-absorbing resin of foaming effect in order to obtain often needs to add in surface work in polymerization system
Property agent, to stablize Air Bubble Size, this can lead to the reduction of water-absorbing resin surface tension in use, can inhibit the suction of product
Liquid characteristic.
In addition, skill upgrading disclosed in the patent rate of liquid aspiration of water-absorbing resins, but still it is insufficient, it is attributed to
After forming porous structure gel, by the Strong shear in stages or squeezing action power such as granulations, lead to the established porous knot of gel
Structure and considerable damage, are finally unable to reach the effect for being effectively increased SAP specific surface areas.Simultaneously as gel particle porous structure
Presence, gel degree of crushing increases, and porous structure causes specific surface area to increase, bring gel surface moisture dissipation speed in itself
Too fast, level of residual monomers is significantly increased.
Invention content
It will not excessively be reduced present invention aims at a kind of buildup of resin density is provided, not influence its imbibition characteristic, it can be with
The efficiently method of water-absorbing resins of the production with high speed rate of liquid aspiration and low monomer residue amount, and obtain a kind of at a high speed
The water-absorbing resins of rate of liquid aspiration and low monomer residue amount.
The present invention provides a kind of monomer solution containing unsaturated monomer and crosslinking agent, by polymerizeing, being granulated, drying, grinding
Mill, screening obtain water-absorbing resins, which has high rate of liquid aspiration and relatively low level of residual monomers, while do not interfere with its its
His imbibition characteristic.
To achieve these goals, the present invention provides the manufacturing method of the polyacrylic acid water-absorbent resin, including
Following steps：
It obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution,
Blowing-agent particle and/or foaming agent solution are mixed with unsaturated acrylic monomer and cross-linking agent aqueous solution,
Monomer solution is subjected to polymerization and forms porous gel shape cross-linked polymer,
By aqueous porous gel shape cross-linked polymer in the course of the polymerization process or polymerization after through shearing and/or squeezing action power powder
It is broken into gel particle,
The gel particle number average bead diameter is 0.5~20 millimeter,
Mass fraction of the gel particle grain size more than 2 millimeters is 10~100wt%,
The porous gel shape cross-linked polymer is broken by shearing and/or squeezing action power, the porous structure of gel particle
Bad rate is 0~70%,
Gel particle after crushing is thermally dried to form aperture as 10~500 um porous structure cross-linked polymerics
Object,
Grain refined is carried out to porous structure cross-linked polymer after drying and is sieved.
The invention discloses a kind of water-absorbing resins and its manufacturing method with high rate of liquid aspiration, advantage is
It and stability and high efficiency is manufactured with high rate of liquid aspiration and low list by the way that porous gel shaped polymer is controlled to be granulated gel particle size
The water-absorbing resins of body residual quantity.
Specific embodiment
The polyacrylic acid water-absorbent resin and its manufacturing method of the present invention are described in detail below, but the present invention
Range is not limited to these explanations.
[1] manufacturing method of polyacrylic acid water-absorbent resin of the invention.
It obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution,
Blowing-agent particle and/or foaming agent solution are mixed with unsaturated acrylic monomer and cross-linking agent aqueous solution,
Monomer solution is subjected to polymerization and forms porous gel shape cross-linked polymer,
By aqueous porous gel shape cross-linked polymer in the course of the polymerization process or polymerization after through shearing and/or squeezing action power powder
It is broken into gel particle,
The gel particle number average bead diameter is 0.5~20 millimeter,
Mass fraction of the gel particle grain size more than 2 millimeters is 10~100wt%,
The porous gel shape cross-linked polymer is broken by shearing and/or squeezing action power, the porous structure of gel particle
Bad rate is 0~70%,
Gel particle after crushing is thermally dried to form aperture as 10~500 um porous structure cross-linked polymerics
Object,
Grain refined is carried out to porous structure cross-linked polymer after drying and is sieved.
1.1 monomer solution
Obtain the step of containing unsaturated acrylic monomer and cross-linking agent aqueous solution.It is specifically described below.
Monomer (monomer) used in the present invention can be formed by free radical polymerization and be inhaled to contain unsaturated double-bond
Monomer of the Mono-olefinic unsaturation containing acid groups of water-base resin, is not particularly limited.It can be listed below：Acrylic acid, methyl
Acrylic acid, ethylacrylic acid, α-chloroacrylic acid, alpha-cyanoacrylate, Beta-methyl acrylic acid (crotonic acid), atropic acid,
β-acryloxy propionic, sorbic acid, α-chlorine sorbic acid, 2 '-methyl iso-crotonic acid, cinnamic acid, p- chloro-cinnamic acid, β-tristearin
Acid, itaconic acid, citraconic acid, mesaconic acid, glutaconate, aconic acid, maleic acid, cinnamic acid, fumaric acid, tricarboxylic ethylene and maleic acid
Acid anhydride, particularly preferred acrylic acid and methacrylic acid, most preferably acrylic acid.
It can be copolymerized using other class monomers with the monomer containing carboxyl.It can be listed below：Vinyl sulfonic acid, alkene
Propyltoluene sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, 2- (methyl)
The anionic properties such as acryloyl group ethanesulfonic acid, 2- (methyl) acryloyl groups propane sulfonic acid, (methyl) acryloyl group phosphoric acid 2- hydroxy methacrylates
Unsaturated monomer and its salt；Unsaturated monomer containing sulfydryl；The unsaturated monomer of phenolic hydroxy group；(methyl) acrylamide, N- second
The unsaturated monomer of the amide-containings such as base (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide；(methyl) acrylic acid
N, N- dimethyl amido ethyl ester, (methyl) acrylic acid N, N- dimethyl amido propyl ester, N, N- Dimethylaminopropyls (methyl) third
Amino-containing unsaturated monomer such as acrylamide etc..
These unsaturated monomers can be used alone, and can also be mixed with two or more, comprehensive absorbent resin powder
It is preferable to use contain acrylic acid and/or its salt (such as sodium salt, lithium salts, sylvite, ammonium salt, amine etc. for performance and cost
Salt), wherein in terms of cost, the polyacrylic acid water-absorbent resin of the acrylic monomer of more preferable sodium salt.
There is no particular restriction for the neutralization ratio of these undersaturated monomers containing acid groups, can be in part and/or complete
It neutralizes, preferably part neutralizes, and can also optionally neutralize polymeric gel after polymerisation.The unsaturation contains acid groups
The preferred degree of neutralization of monomer is 25~100mol%, particularly preferably reaches at least 40~95mol%, more preferably up to 50~
90mol%.The neutralization of monomer of the unsaturation containing acid groups can carry out before or after the polymerization.Alkali metal hydrogen can be used
Oxide, alkaline earth metal hydroxide, ammonia and carbonate and bicarbonate are neutralized.It is in addition it is possible to use any other
Can with it is described acid formed water soluble salt alkali.It can also be neutralized using a variety of alkali.It is preferable to use ammonia or alkali metal hydrogen-oxygens
Compound neutralizes, and is particularly preferably neutralized using sodium hydroxide.
As polyacrylic absorbent resin powder, the usage amount of acrylic acid and/or its salt relative to whole monomers into
Divide (except crosslinking agent), usually more than 60mol%, preferably more than 75mol%, preferably more than 90mol%, it is further excellent
It is selected as more than 95mol%.
Monomer concentration is also not particularly limited, and the unsaturated monomer containing acid groups and cross-linking agent aqueous solution a concentration of 25~
60wt%, preferably 30~55wt%, further preferred 35~50wt%.In the case of monomer concentration is less than 25wt%, energy is produced
Power can reduce, therefore not good enough.When monomer concentration is higher than in the case of 60wt%, crushing load increases, and production stability is caused to be deteriorated.
The solvent of monomer is water, can also and with a small amount of organic solvent.
As internal crosslinker, the compound for containing multiple vinyl selected from intramolecular, intramolecular contain at least one ethylene
Based compound and it is at least one can have with the compound for the functional group that carboxyl reacts on the unsaturated monomer, intramolecular it is multiple
Can with it is one or more in the compound for the functional group that carboxyl reacts on the unsaturated monomer.Previously many institute's weeks can be used
The internal crosslinking agent known.Specifically, it can for example enumerate：N, N '-methylene-bisacrylamide, trimethylolpropane tris (first
Base) acrylate, ethylene glycol two (methyl) acrylate, polyethyleneglycol diacrylate, polyethylene glycol two (methyl) acrylic acid
Ester, polyethylene glycol diallyl ether, pentaerythritol tetraacrylate, triarylamine, ethylene glycol diglycidylether, ethylene glycol,
1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediols, glycerine, pentaerythrite, polyethylene glycol and one kind in ethylene carbonate or
It is a variety of, these internal crosslinking agents, it is contemplated that reactivity can use one or more.Wherein, preferred trimethylolpropane tris
In (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol diglycidylether, polyethylene glycol, 1,4- butanediols
It is one or more, further preferred trimethylolpropane tris (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol two
It is one or more in glycidol ether.
The usage amount of internal crosslinker is determined according to the physical property of required water-absorbing resins, relative to content of monomer, preferably
0.001~5mol%, more preferably 0.005~2mol%, further preferably 0.01~1mol%.If the use of internal crosslinker
Amount is less than 0.001mol%, and the water soluble apparent extract of gained water-absorbing resins increases, and can not substantially ensure the suction under pressurization
Water.If the usage amount of internal crosslinking agent is more than 5mol%, chemical crosslinking density is too high, the absorbent resin powder of gained
Water absorption it is insufficient.In addition, internal crosslinking agent can be once added in reaction system, can also be added batch-wise to reaction system
In.
1.2 prepare foaming agent monomer solution
As foaming agent, occur physically and/or chemically to react in the manufacturing process of water-absorbing resins, decompose to give off gas
Body (such as carbon dioxide, oxygen, nitrogen, ammonia etc.), to increase the hole of resin surface.The foaming agent be selected from ammonium carbonate,
Ammonium hydrogen carbonate, sodium carbonate, sodium bicarbonate, calcium carbonate, potassium carbonate, saleratus, magnesium carbonate, two melon acid esters, azodiisobutyronitrile,
Azobisisoheptonitrile, azobisisovaleronitrile, azodicarbonamide, azo-bis-isobutyrate hydrochloride, diisopropyl azodiformate,
Two azoaminobenzenes, nitrourea, dinitrosopentamethylene tetramine, unifor, ketone hydrazone in tolysulfonyl, 4,4 '-
It is one or more in oxobenzenesulfonyl hydrazide, 2,4 methyl benzyl disulphonyl hydrazide, SODIUM PERCARBONATE, hydrogen peroxide, benzoyl peroxide.
Blowing-agent particle and/or foaming agent solution with acrylic monomer and cross-linking agent aqueous solution are mixed, prepare foaming
Agent monomer solution, foaming agent need Monodispersed in monomer solution under stirring or static condition.Dispersing mode can be that will send out
It is added in monomer solution after infusion dissolving, re-forms blowing-agent particle process, it can also be by blowing-agent particle directly by stirring
Mix or static conditions under be dispersed in monomer solution, can also previously prepared foaming agent emulsion, then by emulsion and monomer
Solution mixes.
Foaming agent is -10~120 DEG C in temperature, the time is in 1~60 minute, in 100 mass parts lists in monomer solution
0~10 mass parts can be dissolved in liquid solution, 0~1 mass parts of dissolving is preferably able to, can further preferably dissolve 0~0.5 matter
Measure part.Number average bead diameter of the blowing-agent particle in monomer solution be 0.1~900 micron, preferably 0.5~100 micron, further
Preferably 1~25 micron.
In order to effectively control dispersibility, solubility and grain size of the foaming agent in monomer solution, dissolving in foaming agent, point
Organic solvent can be used in scattered or emulsion mixed process, such as can be enumerated：Methanol, ethyl alcohol, glycerine, acetone, acetic acid second
Ester, dimethyl sulfoxide, (poly-) ethylene glycol, (poly-) propylene glycol, ethylene carbonate, ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,
4- butanediols etc..These organic solvents can use one or more.When using organic solvent, consumption of organic solvent is with water quality
Gauge is controlled in 20wt% hereinafter, preferably 10wt% is hereinafter, further preferably below 5wt%.Alternatively, it is also possible to by adding
Add foaming agent protection materials (such as non-in starch, starch derivatives, cellulose, cellulose derivative, inorganic salts, monomer solution
Dissolving polymer material etc.), dispersibility, the solubility of precipitating reagent, the methods of cooling control foaming agent in monomer solution
And grain size.
Above-mentioned foaming agent can discharge gas by chemistry and/or physical reactions, and the generation and release of gas are in resin system
Standby temperature-rise period realizes that gas release temperature is 20~200 DEG C, preferably 40~180 DEG C, further preferably 70~160 DEG C,
When gas release temperature is less than 20 DEG C, gas can not be rested on effectively in polymerization system, it is impossible to reach ideal pore
Effect, when gas release temperature is less than 200 DEG C, gas yield in entire resin manufacturing processes is seldom.
Foaming agent consumption is in terms of 100 parts by weight unsaturated monomers, in the range of 0.005~20 parts by weight, preferably 0.01~
10 parts by weight, further preferred 0.02~5 parts by weight, when foaming agent consumption is less than the situation of 0.005 parts by weight, it is impossible to obtain
Preferably high rate of liquid aspiration is obtained, when foaming agent consumption is higher than 20 parts by weight, resin property deterioration is produced, transports and used
Dust is serious in journey, and impact resistance declines, and production cost is higher.
Foaming agent disperses before prepared by unsaturated acrylic monomer and cross-linking agent aqueous solution, in preparation process or after preparing
To monomer solution.In addition, foaming agent initiator add in monomer solution before, in adition process or add in after be added to solution
In.
1.3 polymerization procedure
Polymerization procedure is the step of monomer solution is polymerize.Polymerization process can normal pressure, decompression or pressurization under into
Row, preferably carries out under normal pressure.
As the polymerization initiator used in this step, there is no particular restriction, can use and under polymerization conditions can
It forms free radical and is commonly used for preparing any initiator of water-absorbing resins.It can also be by acting on and can gather electron beam
The water-containing monomer solution of conjunction and cause polymerization.It can also be acted on by high-energy radiation in the presence of photoinitiators poly- to cause
It closes.According to monomeric species, polymerizing condition being polymerize etc., from the polymerization initiator utilized when usually manufacturing water-absorbing resins
Select one or more uses.
Polymerization initiator is preferably peroxide, hydroperoxides, hydrogen peroxide, persulfate and azo-compound.It is excellent
Choosing uses water soluble starter.Specifically enumerate：Heat decomposition type initiator, such as sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate over cure
Hydrochlorate；The peroxide such as hydrogen peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, azonitrile compound, azo amidification are closed
Object, cyclic annular azo amidine compound, azo amide compound, alkyl azo-compound, bis- (2- amidine propanes) disalts of 2,2 '-azo
The azo-compounds such as bis- [2- (2- imidazoline -2- bases) propane] dihydrochlorides of hydrochlorate, 2,2 '-azo；Or photolysis type initiator,
Such as Benzoin derivative, benzil derivatives, acetophenone derivs, benzophenone derivates, azo-compound.These cause
In agent, with regard to cost and for reducing the ability of residual monomer, preferably heat decomposition type initiator, further preferably persulfuric acid
Salt.
In addition, the decomposition of these polymerization initiators can be promoted by and with reducing agent.Therefore, it is possible to use redox
System initiator.It as the reducing agent, is not particularly limited, can be selected from：Sodium pyrosulfite, sodium sulfite, bisulfite
The sulfurous acid such as sodium (hydrogen) (salt), L-AA (salt), metal salt (such as iron (II) ion or silver ion), amine etc..In oxygen
In the case that change reduction series initiators use oxidative polymerization initiator and reducing agent in this way, it can be closed respectively with monomer solution
Reducing agent, can also be mixed in monomer solution by stream in advance.
When carrying out the polymerization, poly- second two can also be added in the reaction system before polymerization or in polymerization as needed
Alcohol, starch, starch derivatives, cellulose, cellulose derivative, polyvinyl alcohol, polyacrylic acid (salt), polyacrylic acid (salt) crosslinking
The hydrophilic polymers such as body；Or chain-transferring agents, the chelating agent such as ortho phosphorous acid (salt) etc..It, can be preferable as hydrophilic macromolecule
Ground uses water-soluble resin or water-absorbing resins, can improve the viscosity of reaction system.Relative to monomer, hydrophilic polymer
Usage amount is preferably 0~30wt%, more preferably 0.001~20wt%, further preferably 0.01~10wt%.
As the polymerization employed in this step, it is not particularly limited.Free radical polymerization in preferably homogeneous
(such as free radical polymerization in aqueous solution), the precipitation polymerization from organic solvent, suspension polymerisation, emulsion polymerization or mini-emulsion polymerization
Deng.It is preferred that the free radical polyalcohol in homogeneous system, the free radical polymerization in further preferred aqueous solution.Water solution polymerization process has
Make the standing polymerization that monomer solution is polymerize under static condition and the stirring polymerization being polymerize in agitating device
Method etc..In addition, polymerization is divided into batch method according to continuous production and continuity method polymerize.It is particularly suitable for the polymerization solved the problems, such as
It is aqueous solution polymerization, especially continuous conveyor polymerization or continuous kneader polymerization.
The manufacturing device of water-absorbing resins as the present invention, is not particularly limited, preferably continuous conveyor polymerization dress
Put or continuously stir polyplant.
Continuous conveyor polyplant is preferably that the continuous of cyclic annular conveyer belt type stands polyplant, and conveyer belt is fluororesin
System or the conveyer belt to be formed with fluororesin-coated surface.Furthermore it is preferred that have heating unit or attemperator, and have
The device of system that the steam of water generated when polymerizeing and/or monomer solution is recycled and recycled.
It continuously stirs polyplant and uniaxial agitating device may be used, can also use continuous kneader etc. that there is multiple stir
The agitating device of axis is mixed, it is preferable to use multi-shaft stirring device for productive viewpoint.
When polymerization start temperature refers to that initiator adds to monomer solution, the real time temperature of polymerization system.The monomer is water-soluble
In the step of liquid is polymerize, in order to solve the problems in the invention and promote the progress of foaming process, polymerization start temperature is
20~120 DEG C, preferably 40~110 DEG C, further preferably preferably 60~100 DEG C.If polymerizeing start temperature is less than 20
DEG C, polymerization time is long, and production capacity is greatly reduced, and the physical property of water-absorbing resins may also reduce.If it polymerize start temperature
Higher than 120 DEG C, then there is the worry that the physical property of water-absorbing resins reduces.Polymerization time is not particularly limited, according to monomer and is gathered
Close initiator type, polymerization temperature etc. it is appropriate determine, but in terms of the production capacity for, the shorter polymerization time the better.
In addition, in order to promote to foam, preferably make peak temperature during polymerization higher, peak temperature is excellent in polymerization procedure
It is selected as 100 DEG C or more, more preferably 100~170 DEG C, further preferably 100~150 DEG C.
1.4 pulverising step
The step of aqueous gel shape cross-linked polymer of above-mentioned gained is crushed, pulverising step can polymerization when or
It is carried out after polymerization.Crushing process during polymerization can use kneader, and the crushing after polymerization can use cutting machine, meat grinder
Deng.Gel particle number average bead diameter is 0.5~20 millimeter, preferably 0.3~15 millimeter, further preferred 0.5~10 millimeter after crushing；
And gel particle grain size more than 2 millimeters mass fraction for 10~100wt%, preferably 20~100wt%, further preferred 30~
100wt%.Gel particle is more than 100 millimeters, and there are the possibility that water-absorbing resin moisture is difficult to control.
In order to effectively keep the porous structure of gel cross-linked polymer, by shearing, squeezing action power, gel particle
Porous structure destructive rate is 0~70%, preferably 0~60%, further preferred 0~50%.By controlling broken rear gel particle
The destructive rate of size and its porous structure can effectively prepare the quick absorption-type high hydroscopic resin with low monomer residue amount.
1.5 heat-drying step
Heat-drying step is that the aqueous gel shape cross-linked polymer is subject to drying, forms porous structure drying polymerization
Object.Drying is usually in 60~300 DEG C as heating medium temperature, preferably 80~250 DEG C, more preferable 100~220 DEG C of temperature
Lower progress.Drying time depends on surface area and the water content of polymer and drier type, is selected to obtain target and contains
Water (water content passes through in 105 DEG C of dry 3 hours weightless measurements).
Water content for water-absorbing resin of the present invention is not particularly limited, the more preferable 0.2~30wt% of water content, further
It is preferred that 0.3~15wt%, particularly preferred 0.5~10wt%.Too high-moisture not only damages mobility, and therefore influences production,
And make being crushed into for water-absorbing resin can not possibly and may be out of hand to specific size distribution.
It is not particularly limited as used drying means, a variety of methods can be used to obtain target water content, specifically
It enumerates：Heat drying, hot-air are dry, be dried under reduced pressure, infrared drying, microwave drying, by with hydrophobic organic solvent
Azeotropic mixture is dehydrated and using the drying of high-temperature steam high humility.
In addition, foaming agent can pass through further thermal decomposition under the drying temperature, further foaming process is realized.
1.6 grain refineds and screening step
In order to obtain the water-absorbing resins (adjusting grain size jointly with following micro mist granulation process) with specified particle size, need
The step of grain refined is carried out to porous structure cross-linked polymer after drying and is sieved.
For obtaining having irregular pulverized shape, and the absorbent resin that grain size can be controlled effectively, grain refined uses
Machine include shearing crude pulverizer, impact powder pulverizer and high-speed rotation type powder pulverizer.It is and right after grain refined
Resin particle is further sieved.
The Mass median diameter (D50) of water-absorbing resins, is preferably regulated as 200~650 microns, is more preferably adjusted to 200
~550 microns, further preferably it is adjusted to 300~500 microns.Particle fraction control of the diameter less than 150 microns for 0~
8wt%, preferably 0~5wt%, more preferable 0~2wt%.In addition, the fewer diameter the better higher than 850 microns of particle fraction, control
For 0~8wt%, preferably 0~5wt%, more preferable 0~2wt%.In the present invention, it is preferred in 150~850 microns of particle
Ratio carries out surface-crosslinked under conditions of being more than 95wt%, more preferably more than 98wt%.The logarithmic scale of size distribution is inclined
Poor (σ ζ) is preferably controlled to 0.20~0.40, more preferable 0.20~0.38, further preferred 0.20~0.36.
The recycling of 1.7 fine grained water-absorbing resins
In the present invention, small particle fine grained is controlled (less than 150 by the way that fine grained water-absorbing resins are recycled
The particle of micron) yield.
The small particle water absorbing resin particle (particle for being less than 106 microns) obtained by grain refined and screening can pass through return
Polymerize again to monomer solution or mixed with a large amount of hot water carry out agglomeration (weight ratio of little particle water-absorbing resin and hot water be 2:
1~1:2), to revert to water-setting gum-like product again.Then by be granulated, dry and grain refined and etc. readjust as mesh
Mark grain size water absorbing resin particle.Amount of waste can be reduced by the particle for recycling and regenerating beyond target zone.
[2] physical property of polyacrylic acid water-absorbent resin
The polyacrylic acid water-absorbent resin of the present invention has the particulate water-absorbing agent of irregular pulverized shape, specific physical property
It is as follows.
2.1 surface apertures
Water-absorbing resins surface porosity is observed by scanning electron microscope, in order to effectively promote the suction of resin
Liquid speed rate controls the apparent density of resin and improves the impact resistance crushing performance of resin, and the porous structure average pore size is preferred
It is 10~500 microns, more preferably 10~300 microns, more preferably 10~200 microns, especially preferably 10~150 microns.
2.2 centrifuge retention multiplying powers (CRC)
Centrifuge retention multiplying power (CRC) to the sodium-chloride water solution of 0.9wt% is preferably 10~60g/g, and more preferably 20
~55g/g, further preferably 25~50g/g, especially preferably 25~45g/g.For absorbability.The higher the better by CRC,
But it needs to be balanced with other physical property as the case may be in actual use.
2.3 swirl method infiltration rates
The swirl method infiltration rate of water-absorbing resins of the present invention is shorter than 60sec/g, preferably 1~55sec/g, more preferable 2~
45sec/g.Water absorbing agent of the infiltration rate more than 60sec/g may not achieve the effect that enough.
2.4 particle sizes and distribution
The median granularity of quality (D50) of water-absorbing resins of the present invention, is preferably regulated as 200~650 microns, more preferably adjusts
It is 200~550 microns, is further preferably adjusted to 300~500 microns.Particle fraction control of the diameter less than 150 microns is 0
~8wt%, preferably 0~5wt%, more preferable 0~2wt%.In addition, the fewer diameter the better higher than 850 microns of particle fraction, control
It is made as 0~8wt%, preferably 0~5wt%, more preferable 0~2wt%.In the present invention, it is preferred in 150~850 microns of particle
Ratio be more than 95wt%, more preferably carry out under conditions of more than 98wt% it is surface-crosslinked.The logarithmic scale of size distribution
Deviation (σ ζ) is preferably controlled to 0.20~0.40, more preferable 0.20~0.38, further preferred 0.20~0.36.
2.5 water content
Water content is to determine the parameter of the volatile materials such as water included in water-absorbing resins.Water imbibition tree of the present invention
The water content of fat is preferably 1~10wt%, more preferable 2~10wt%.
2.6 level of residual monomers
The level of residual monomers of water-absorbing resins of the present invention is preferably 0~600ppm, more preferably 0~500ppm.
[3] purposes of polyacrylic acid water-absorbent resin
The application of particle-shape water-absorbing resin of the present invention is not particularly limited, and be can be used for paper diaper, physiological hygiene cotton, is lost
Prohibit the absorbent commodities such as protection pad, be preferred for for example thin absorbing articles of thin absorption base and absorbing articles.
In absorbent commodity, typically contain other absorbent materials (paper pulp fiber etc.), wherein water-absorbing resins contain
It measures as 30~100wt%, preferably 40~100wt%, more preferably 50~100wt%, further preferably 60~
100wt%.
[4] embodiment
The present invention will be illustrated with following embodiment and comparing embodiment, but the present invention is not limited to following embodiments.
The various performances of water-absorbing resins are measured through following methods.It is outer unless specified otherwise, water-absorbing resin, water absorbing agent and absorption
Article uses under conditions of 25 ± 2 DEG C and 50%RH (relative humidity).Used normal saline solution is the chlorine of 0.90wt%
Change sodium water solution.
4.1 surface apertures
Water-absorbing resins surface porosity and aperture are observed by scanning electron microscope, by particle-shape water-absorbing
Resin sample is adhered on sample stage, is tested after metal spraying.
4.2 centrifuge retention multiplying powers (CRC)
Centrifuge retention multiplying power (CRC) is represented under no pressurization to 0.90wt% sodium-chloride water solutions (also referred to as physiological saline
Water) water absorbent rate that is centrifuged after water suction 30 minutes.
0.20g water-absorbing resins are weighed, record weight is W0 (g), it uniformly is put into the cloth made of supatex fabric
In bag, sealing is immersed in normal saline solution of the control at 25 ± 2 DEG C.After 30 minutes by the bag containing water-absorbing resins from
It is taken out in saline solution.It is dehydrated 3 minutes under 250G using centrifuge, then weighs to obtain weight W2 (g).Without using any
The weight W1 (g) of bag is measured after the similar operations of water absorbing agent.Centrifuge retention multiplying power (g/g) is calculated according to the following formula.
Centrifuge retention multiplying power (g/g)=((W2 (g)-W1 (g))/W0 (g)) -1
4.3 swirl method infiltration rates
In 100 milliliters of beakers with stirrer, 50 ml NaCls are added in pipette, beaker is placed on magnetic
It on power blender, is stirred with 500 ± 50r/min rotating speeds, confirms that liquid level generates and stablize whirlpool.Accurately weigh 2.000 grams of water imbibitions
Resin is added in whirlpool, while starts timing with stopwatch, when liquid surface vortex disappears, and liquid level becomes horizontality, as
Terminal records the time.
4.4 particle sizes and distribution
Particle size and distribution are tested by sieve method.A certain amount of high-hydroscopicity powder by it is a series of in order
The standard screen of arrangement is separated into different grain size atmosphere.It weighs to the powder of each particle size range, and report that it accounts for total weight hundred
Divide ratio.
Ensure that sieve is dried.Whether each sieve there is into optical test damage or unclean part.Change the sieve of damage
Son.Make the residual particles that clean with a brush.Large face plate and each empty sieve (being accurate to 0.1 gram) weight, and record.By correct
Sequentially (850 microns, 600 microns, 300 microns, 150 microns, 45 microns) sieve is placed on the oscillator (it is fine
Bottom, coarse upper).It weighs in 100 grams of (being accurate to 0.1 gram) samples to beaker to be tested, m1.Load weighted sample is poured into
In uppermost sieve.By sifter cap on the indicating cover of manufacturer.Oscillator is sieved by following parameter setting：Oscillation intensity (70 ±
2) % (according to the setting of 1000 oscillators of Retsch VE), 1.0 millimeters of amplitude, duration of oscillation 10 minutes.Opening vibrator, 10
Each sieve and pallet are carefully removed after minute and weighed respectively, is accurate to 0.01 gram, m2.Calculate the percentage of every section of sample
(w) it is as follows：
It is determined as median granularity of quality (D50) corresponding to the grain size of R=50% weight.Logstandard deviation (σ ζ) is by following formula
It represents, the σ ζ of wherein smaller value mean relatively narrow size distribution.
σ ζ=0.5 × ln (X2/X1)
(wherein X1 and X2 are respectively the grain size of R=84.1% weight and R=15.9% weight)
4.5 water content
It is the ratio for representing particulate water-absorbing resin at 180 DEG C shared by volatile ingredient.
The assay method of water content is to proceed as follows.
The particulate water-absorbing agent (weight W7 [g]) for weighing about 1g is placed in measuring cup (weight W6 [g]), in 105 DEG C of nothing
3 hours are stood in wind drying machine, is subject to drying.Measure total weight (W8 of dried measuring cup and particulate water-absorbing resin
[g]), it is calculated according to the following formula.
Water content [wt%]={ (W8-W6-W7)/W7 } × 100.
4.6 level of residual monomers
1.000 grams of water-absorbing resins are weighed, and record the quality of sample in a clean weighing boat.By load weighted sample
Product are transferred in a clean beaker.The sodium chloride solution for taking 200 milliliter 0.9% with graduated cylinder is added in beaker.Magnetic force is put into stir
Son is mixed, beaker liquid level or the mouth with bottle stopper envelope conical flask are sealed with paraffin.With 500 ± 50r/min rate stirred samples.60 minutes
Stop stirring afterwards.Sample is made to stand 5 minutes.With 0.45 urn filter filtered sample, HPLC tests are carried out.
Production Example 1
By pipeline acrylic acid/sodium acrylate mixed monomer solution, (acrylic acid/sodium acrylate molar ratio is 2.2/
7.8), acrylic acid/sodium acrylate monomer concentration is 44.0wt%, and monomer solution flow is 8689kg/h.Monomer solution temperature is
80~90 DEG C.Polyethyleneglycol diacrylate (the molecule of a concentration of 11.3wt% is delivered at monomer solution pipeline branch mouth
It measures 522), flow 72kg/h.It is in addition, water-soluble by the azo-bis-isobutyrate hydrochloride that delivery pump melting concn is 6.17wt%
The sodium persulfate aqueous solution (flow 60kg/h) of liquid (flow 50kg/h) and a concentration of 4wt% forms initiator mixing turbid, and
The mixing turbid is delivered to by monomer solution pipeline branch mouth in monomer, carries out polymerisation.Reaction solution is sprayed onto reaction bed, shape
Into monomer solution (the suspended particulate grain size containing suspended particulate<100 microns, in 80~90 DEG C of monomer solutions, in 1 minute
Insoluble, meltage is less than 0.01wt%), temperature of reaction system increases rapidly, and temperature change is 90~150 DEG C, and foaming agent exists
It is decomposed under the temperature condition, obtains porous structure aqueous gel shaped polymer.
Embodiment 1
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, fine grained gel, gel are shredded into using scissors
2~15 millimeters of particle diameter distribution, the porous structure destructive rate of gel particle are less than 20%.And gel particle is spread over into woven wire
On be dried, drying temperature be 190 DEG C, the time be 1 hour, obtaining cross linked porous structural polymer, (aperture 100~200 is micro-
Rice).Grain refined is carried out to porous crosslinked polymeric after drying using broken cooking machine, and is sieved, obtain grain size for 300~
425 microns, moisture 3.9wt%, CRC 40.3g/g, swirl method infiltration rate be 28sec/g, levels of residual monomers is
The particulate porous structure water-absorbing resins of 285ppm, 100~200 microns of aperture.
Embodiment 2
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, a diameter of 5 centimetres solidifying is shredded into using scissors
Film, the porous structure destructive rate of gel particle are less than 5%.And gel is spread over and is dried on woven wire, dry temperature
It is 190 DEG C to spend, and the time is 1 hour, obtains cross linked porous structural polymer (100~200 microns of aperture).Using broken cooking machine
Grain refined is carried out, and sieved to porous crosslinked polymeric after drying, it is 300~425 microns, moisture to obtain grain size
The granular porous knot that 4.5wt%, CRC 39.5g/g, swirl method infiltration rate are 25sec/g, levels of residual monomers is 197ppm
Structure water-absorbing resins, 100~200 microns of aperture.
Embodiment 3
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, fine grained gel, gel are shredded into using scissors
2~5 millimeters of particle diameter distribution, the porous structure destructive rate of gel particle are less than 30%.And gel particle is spread over into woven wire
On be dried, drying temperature be 190 DEG C, the time be 1 hour, obtaining cross linked porous structural polymer, (aperture 100~200 is micro-
Rice).Grain refined is carried out to porous crosslinked polymeric after drying using broken cooking machine, and is sieved, obtain grain size for 300~
425 microns, moisture 3.3wt%, CRC 41.1g/g, swirl method infiltration rate be 31sec/g, levels of residual monomers is
The particulate porous structure water-absorbing resins of 325ppm, 100~200 microns of aperture.
Embodiment 4
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, fine grained gel, gel are shredded into using scissors
5~10 millimeters of particle diameter distribution, the porous structure destructive rate of gel particle are less than 20%.And gel particle is spread over into woven wire
On be dried, drying temperature be 190 DEG C, the time be 1 hour, obtaining cross linked porous structural polymer, (aperture 100~200 is micro-
Rice).Grain refined is carried out to porous crosslinked polymeric after drying using broken cooking machine, and is sieved, obtain grain size for 300~
425 microns, moisture 3.5wt%, CRC 40.6g/g, swirl method infiltration rate be 29sec/g, levels of residual monomers is
The particulate porous structure water-absorbing resins of 298ppm, 100~200 microns of aperture.
Embodiment 5
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, fine grained gel is broken into using meat grinder, is coagulated
0.5~15 millimeter of glue particle diameter distribution, the porous structure destructive rate of gel particle are less than 40%.And gel particle is spread over into metal
Be dried on silk screen, drying temperature be 190 DEG C, the time be 1 hour, obtain cross linked porous structural polymer (aperture 100~
200 microns).Grain refined is carried out, and sieved to porous crosslinked polymeric after drying using broken cooking machine, obtaining grain size is
300~425 microns, moisture 3.9wt%, CRC 40.1g/g, swirl method infiltration rate be 30sec/g, levels of residual monomers
For the particulate porous structure water-absorbing resins of 212ppm, 100~200 microns of aperture.
Embodiment 6
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, fine grained gel is broken into using meat grinder, is coagulated
0.5~5 millimeter of glue particle diameter distribution, the porous structure destructive rate of gel particle are less than 50%.And gel particle is spread over into metal
Be dried on silk screen, drying temperature be 190 DEG C, the time be 1 hour, obtain cross linked porous structural polymer (aperture 100~
200 microns).Grain refined is carried out, and sieved to porous crosslinked polymeric after drying using broken cooking machine, obtaining grain size is
300~425 microns, moisture 3.2wt%, CRC 40.1g/g, swirl method infiltration rate be 33sec/g, levels of residual monomers
For the particulate porous structure water-absorbing resins of 412ppm, 100~200 microns of aperture.
Comparative example 1
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, is repeatedly rubbed using meat grinder, is broken into thin
Grain gel, 0.1~1 millimeter of gel particle diameter distribution, the porous structure destructive rate of gel particle are more than 80%.And gel particle is spread
Exhibition is dried on a wire mesh, and drying temperature is 190 DEG C, and the time is 1 hour, obtains cross linked porous structural polymer (hole
100~200 microns of diameter).Grain refined is carried out, and sieved to porous crosslinked polymeric after drying using broken cooking machine, is obtained
Grain size be 300~425 microns, moisture 2.2wt%, CRC 43.5g/g, swirl method infiltration rate are 42sec/g, residual
Stay the particulate porous structure water-absorbing resins that amount of monomer is 1790ppm, 100~200 microns of aperture.
Comparative example 2
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, is repeatedly rubbed using meat grinder, is broken into thin
Grain gel, 0.5~2 millimeter of gel particle diameter distribution, the porous structure destructive rate of gel particle are more than 70%.And gel particle is spread
Exhibition is dried on a wire mesh, and drying temperature is 190 DEG C, and the time is 1 hour, obtains cross linked porous structural polymer (hole
100~200 microns of diameter).Grain refined is carried out, and sieved to porous crosslinked polymeric after drying using broken cooking machine, is obtained
Grain size be 300~425 microns, moisture 2.4wt%, CRC 42.5g/g, swirl method infiltration rate are 41sec/g, residual
Stay the particulate porous structure water-absorbing resins that amount of monomer is 1766ppm, 100~200 microns of aperture.
Comparative example 3
Porous structure aqueous gel shaped polymer in Production Example 1 is taken, is repeatedly rubbed using meat grinder, is broken into thin
Grain gel, 0.5~10 millimeter of gel particle diameter distribution, the porous structure destructive rate of gel particle are more than 70%.And by gel particle
It spreads over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 1 hour, obtains cross linked porous structural polymer
(100~200 microns of aperture).Grain refined is carried out, and sieved to porous crosslinked polymeric after drying using broken cooking machine,
Obtain grain size be 300~425 microns, moisture 3.1wt%, CRC 42.5g/g, swirl method infiltration rate be 40sec/g,
Particulate porous structure water-absorbing resins of the levels of residual monomers for 450ppm, 100~200 microns of aperture.
By Examples 1 to 6 and the comparison of comparative example 1~3 it is found that being granulated the particle size of gel particle by control and coagulating
Glue porous structure destructive rate, can obtain while have high rate of liquid aspiration and the high hydroscopic resin of low monomer residue amount.
It these are only the embodiment of the present invention, be not intended to limit the scope of the invention, it is every to be said using the present invention
The equivalent structure or equivalent flow shift that bright book content is made directly or indirectly is used in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (6)
1. a kind of manufacturing method of polyacrylic acid water-absorbent resin, which is characterized in that it includes the following steps：
(a) it obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution,
(b) step for mixing blowing-agent particle and/or foaming agent solution with unsaturated acrylic monomer and cross-linking agent aqueous solution
Suddenly,
(c) monomer solution is subjected to the step of polymerization forms porous gel shape cross-linked polymer,
(d) by aqueous porous gel shape cross-linked polymer in the course of the polymerization process or polymerization after through shearing and/or squeezing action power powder
The step of being broken into gel particle,
(d1) the gel particle number average bead diameter is 0.5~20 millimeter,
(d2) mass fraction of the gel particle grain size more than 2 millimeters is 10~100wt%,
(d3) the porous gel shape cross-linked polymer is broken by shearing and/or squeezing action power, the porous structure of gel particle
Bad rate is 0~70%,
(e) gel particle after crushing is thermally dried to form aperture as 10~500 um porous structure cross-linked polymers
The step of,
(f) the step of grain refined is carried out to porous structure cross-linked polymer after drying and is sieved.
2. the manufacturing method of water-absorbing resins according to claim 1, which is characterized in that the unsaturation acrylic monomer
The mixed solution for being the water soluble salt of acrylic acid and/or acrylic acid as principal component with the aqueous solution of crosslinking agent.
3. the manufacturing method of water-absorbing resins according to claim 1, which is characterized in that the crosslinking agent is included selected from molecule
Have the compound of multiple vinyl, intramolecular contain at least one vinyl compound and it is at least one can with it is described unsaturated single
Carboxyl reacts on body the compound of functional group, intramolecular have it is multiple can be with carboxyl reacts on the unsaturated monomer function
It is one or more in the compound of group.
4. the manufacturing method of water-absorbing resins according to claim 1, which is characterized in that the gel particle number average bead diameter is
0.5~20 millimeter, preferably 0.3~15 millimeter, further preferred 0.5~10 millimeter.
5. the manufacturing method of water-absorbing resins according to claim 1, which is characterized in that the gel particle grain size is more than 2
The mass fraction of millimeter is 10~100wt%, preferably 20~100wt%, further preferred 30~100wt%.
6. the manufacturing method of water-absorbing resins according to claim 1, which is characterized in that the porous gel shape cross-linked polymeric
For object by shearing, squeezing action power, the porous structure destructive rate of gel particle is 0~70%, preferably 0~60%, further excellent
Select 0~50%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372891A (en) * | 2019-06-17 | 2019-10-25 | 宜兴丹森科技有限公司 | The manufacturing method of polyacrylic water-absorbing resin |
| CN115044094A (en) * | 2022-06-22 | 2022-09-13 | 湖北工业大学 | Super absorbent resin with sponge structure and preparation method thereof |
| CN115057957A (en) * | 2022-08-18 | 2022-09-16 | 山东诺尔生物科技有限公司 | Preparation method of super water-absorbing material and super water-absorbing material |
-
2017
- 2017-12-25 CN CN201711416489.0A patent/CN108192013A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372891A (en) * | 2019-06-17 | 2019-10-25 | 宜兴丹森科技有限公司 | The manufacturing method of polyacrylic water-absorbing resin |
| CN110372891B (en) * | 2019-06-17 | 2022-06-24 | 宜兴丹森科技有限公司 | Method for producing polyacrylic acid water-absorbent resin |
| CN115044094A (en) * | 2022-06-22 | 2022-09-13 | 湖北工业大学 | Super absorbent resin with sponge structure and preparation method thereof |
| CN115057957A (en) * | 2022-08-18 | 2022-09-16 | 山东诺尔生物科技有限公司 | Preparation method of super water-absorbing material and super water-absorbing material |
| CN115057957B (en) * | 2022-08-18 | 2022-11-04 | 山东诺尔生物科技有限公司 | Preparation method of super water-absorbing material and super water-absorbing material |
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